WO2018061217A1 - 積層塗膜及び塗装物 - Google Patents
積層塗膜及び塗装物 Download PDFInfo
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- WO2018061217A1 WO2018061217A1 PCT/JP2016/079177 JP2016079177W WO2018061217A1 WO 2018061217 A1 WO2018061217 A1 WO 2018061217A1 JP 2016079177 W JP2016079177 W JP 2016079177W WO 2018061217 A1 WO2018061217 A1 WO 2018061217A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/065—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/02—Inorganic fillers used for pigmentation effect, e.g. metallic effect
- B05D2601/08—Aluminium flakes or platelets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/02—Inorganic fillers used for pigmentation effect, e.g. metallic effect
- B05D2601/10—Other metals
Definitions
- the present invention relates to a multilayer coating film comprising a pigment layer and a colored layer (color clear layer) containing a pigment on a glitter layer (metallic base layer) containing a glitter material, and the multilayer coating film. It relates to the provided paint.
- Patent Document 1 describes obtaining a design with a sense of depth regarding a laminated sheet for molding useful for automobile-related members and the like. It is a laminated sheet in which a colored layer is superimposed on a metallic luster layer, the lightness L * of transmitted light of the colored layer is 20 to 80, the gloss value of the metallic luster layer is 200 or more, and regular reflection of 45 degrees. The light saturation C * is 150 or more.
- the document also describes the addition of aluminum flakes to the metallic luster layer and the use of perylene red as a pigment in the colored layer.
- FF property flip-flop property
- the FI value represents the intensity of lightness at the highlight (near the regular reflection direction) with respect to the lightness at the shade
- the FI value also decreases when the lightness of the highlight is low.
- the amount of the glittering material is increased in order to increase the brightness at the highlight, the diffuse reflection by the glittering material also increases, and at the same time, the brightness is increased even in the shade, and a remarkable FF property cannot be obtained.
- An object of the present invention is to realize a metallic color having a high design property in a laminated coating film in which a warm color is produced by a glittering layer and a colored layer having translucency.
- high reflection flakes and low reflection flakes are used in combination as a bright material for the bright layer.
- the laminated coating film disclosed herein includes a glittering layer containing a glittering material formed directly or indirectly on the surface of an object to be coated, and a warm pigment based on the glittering layer.
- a colored layer having properties The glitter layer is a mixture of high-reflection flakes having a visible light reflectance of 90% or more and low-reflection flakes having a visible light reflectance of 1 ⁇ 2 or less of the high-reflection flakes as the glitter material. Contains, When both the high reflection and low reflection flakes are projected onto the bottom surface of the glitter layer, the ratio of the projected area of both the flakes in the bottom surface is 100%.
- highly reflective flakes such as aluminum flakes are effective in increasing the brightness of highlights, they have diffuse reflections due to minute irregularities on the surface of the flakes and diffuse reflections at the edges of the flakes. There is a diffuse reflection. Therefore, the brightness of the shade cannot be adjusted to the desired darkness only by adjusting the density of the highly reflective flakes. Therefore, in the present invention, high reflection flakes and low reflection flakes are used in combination, and the reflection characteristics of the shade can be adjusted using the light absorption function and concealment ability of the low reflection flakes.
- the ratio of the projected area of both the flakes on the bottom surface of the glittering layer is 100%, most of the incident light transmitted through the gap between the highly reflective flakes is blocked by hitting the low reflective flakes. Therefore, reflection of light by the ground is almost eliminated. The light diffusely reflected by the high reflection flakes is shielded or absorbed by the low reflection flakes, and the brightness of the shade is lowered. Therefore, even if a black underlayer is not provided under the glitter layer, a reflection characteristic having a high FI value can be obtained only by the glitter layer, which is advantageous for realizing a metallic color having a high design property.
- the low reflection flakes are thinner than the high reflection flakes.
- the diffuse reflection at the edge of the flake-like glitter material becomes stronger as the flake becomes thicker, and the low reflection flake is thinner than the high reflection flake, and thus the diffuse reflection is weak. Therefore, it is advantageous for reducing the brightness of the shade. Further, since the low reflection flakes contribute to the background concealment, it is not necessary to add a large amount of high reflection flakes having strong diffuse reflection at the edge.
- the visible light reflectance of the low-reflection flakes is 1 ⁇ 4 or less of the visible light reflectance of the high-reflection flakes, and the total area of both the high-reflection and low-reflection flakes is The ratio of the stated area of the highly reflective flakes occupied is 25% or more and 75% or less.
- the high reflection flakes are aluminum flakes, and the low reflection flakes are chrome oxide flakes.
- the glitter layer has an absolute value of an average value of a reflectance in a wavelength range of 450 nm to 700 nm with respect to a standard white plate measured at a light incident angle of 45 ° and a light receiving angle of 110 °. 003 or more and 0.045 or less. As a result, a high FI can be achieved, which is advantageous in obtaining a strong shading feeling.
- the pigment of the colored layer is a red pigment.
- a metallic red color can be realized.
- red pigment organic pigments such as perylene red, dibromanthrone red, azo red, anthraquinone red, quinacridone red, diketopyrrolopyrrole and the like can be preferably used.
- a transparent clear layer is directly laminated on the glitter layer.
- the transparent clear layer can provide acid resistance and scratch resistance.
- Examples of the coated object having the above-mentioned laminated coating film on the object to be coated include an automobile body, a motorcycle, other vehicle bodies, or other metal products and plastic products. May be.
- the glittering layer has a high reflectance with a visible light reflectance of 90% or more.
- flakes and low reflection flakes having a visible light reflectance of 1 ⁇ 2 or less of the high reflection flakes are contained in a mixed state, and both the high reflection and low reflection flakes are projected onto the bottom surface of the glitter layer.
- the ratio of the projected area of the two flakes occupying the bottom surface is 100%, it is advantageous for realizing a metallic color with high design by shielding or absorbing light by the low reflection flakes.
- Sectional drawing which shows a laminated coating film typically. Explanatory drawing of the reflected light which concerns on calculation of FI value.
- the graph which shows an example of the angle dependence of Y (10 degrees) in the state which does not contain the pigment of a glittering layer.
- Explanatory drawing which shows the measuring method of Y value.
- the graph which shows the spectral reflectance of each brilliant layer of the Example and comparative example which were measured with the incident angle of light 45 degrees, and the light reception angle 110 degrees.
- the graph which shows the relationship between the aluminum area rate in the combination of an aluminum flake and a low reflection flake, and the average reflectance in the light reception angle of 110 degrees of a glittering layer.
- the figure which expanded a part of FIG. The graph which shows the relationship between the inclination of the tangent of the spectrum in wavelength 620nm, and saturation C * .
- concentration C in the coefficient k 0.35.
- concentration C in the coefficient k 0.2.
- concentration C in the coefficient k 0.05.
- FIG. The graph which shows the range where FI value becomes 20 or more regarding Y (10 degrees), the coefficient k, and the pigment concentration C.
- a laminated coating film 12 provided on the surface of a vehicle body 11 of the present embodiment includes a glittering layer (first base) 14, a translucent colored layer (second base) 15, and The transparent clear layer 16 is laminated in order.
- An electrodeposition coating film 13 is formed on the surface of the vehicle body 11 by cationic electrodeposition coating, and the laminated coating film 12 is provided on the electrodeposition coating film 13.
- the glitter layer 14 includes a high-reflection flake 21 as a flake-like glitter material, a low-reflection flake 22 that is thinner than the high-reflection flake 21, a warm color pigment 23 as a pigment, and an ultraviolet ray. Contains shielding materials.
- the colored layer 15 contains a warm color pigment 25 of the same color as the warm color pigment 23 of the glitter layer 14, an ultraviolet shielding material, and the like.
- the flake-like glitter materials 21 and 22 are oriented so as to be substantially parallel to the surface of the glitter layer 14 (so that the orientation angle of the glitter materials 21 and 22 with respect to the surface of the glitter layer 14 is 3 degrees or less). Yes. After applying a paint containing the glitter materials 21 and 22 and the pigment 23 on the electrodeposition coating film 13, the glitter material 21 is utilized by utilizing the fact that the coating film is contracted and thinned by evaporation of the solvent by baking. , 22 are arranged so that the orientation angle is 3 degrees or less (preferably 2 degrees or less).
- pigments of various hues such as red pigments such as perylene red can be employed.
- perylene red having an average particle diameter of 2 nm to 160 nm.
- organic compound-based ultraviolet absorbers organic compound-based ultraviolet absorbers, inorganic compound-based ultraviolet scattering agents and the like can be employed, and among these, metal oxide nanoparticles such as iron oxide are preferably employed.
- an acrylic resin can be employed, and as the resin component of the transparent clear layer 16, for example, a carboxylic acid group-containing acrylic resin, a polyester resin, and an epoxy-containing resin can be used.
- a carboxylic acid group-containing acrylic resin for example, a polyester resin, and an epoxy-containing resin can be used.
- Combinations of acrylic resins, combinations of acrylic resins and / or polyester resins and polyisocyanates, and the like can be employed.
- the pigment concentration of the glittering layer 14 is preferably 3% by mass or more and 20% by mass or less, and the pigment concentration of the colored layer 15 is preferably 1% by mass or more and 17% by mass or less.
- the film thickness of the glitter layer 14 is preferably 5 ⁇ m or more and 8 ⁇ m or less, and the film thickness of the colored layer 15 is preferably 8 ⁇ m or more and 15 ⁇ m or less.
- the laminated coating film 12 is required to have high brightness in highlight and low brightness in shade, that is, high FI value.
- the FI value is a light receiving angle (positive angle) when light is incident on the surface of the multilayer coating film 12 at an incident angle of 45 ° (an angle inclined by 45 ° from the normal to the surface).
- a lightness index L * 45 ° tilt angle 45 ° reflected light from the reflecting direction toward the light source (45 ° reflected light), lightness of acceptance angles 15 ° reflected light (15 ° reflected light) L * 15 °
- a lightness index L * 110 ° of reflected light having a light receiving angle of 110 ° (110 ° reflected light) is a value obtained by the following equation.
- FIG. 3 shows an example of the angle-dependent characteristics of the Y value calibrated with an XYZ color system standard white plate of a glittering layer not containing a pigment.
- FIG. 4 shows a method for measuring the Y value.
- the incident angle of the light source 41 with respect to the glittering layer 15 is 45 °.
- the light receiving angle by the sensor 42 is 0 ° in the regular reflection direction.
- a three-dimensional variable angle spectral colorimetry system GCMS-4 manufactured by Murakami Color Research Co., Ltd. was used.
- the coefficient k is a reduction rate of the reflection intensity when the light receiving angle is changed from 10 ° to 25 °.
- the average value of the reflectance in the wavelength range of 450 nm to 700 nm with respect to a standard white plate measured at a light incident angle of 45 ° and a light receiving angle of 110 ° (typical shade direction) “Average reflectance at a light receiving angle of 110 °”) is 0.003 or more and 0.045 or less (expressed as a percentage, 0.3% or more and 4.5% or less).
- the highly reflective flakes 21 such as aluminum flakes are effective in increasing the brightness of highlights, but have diffuse reflection due to minute irregularities on the surface of the flakes and diffuse reflection at the edges of the flakes. There is diffuse reflection at the film 13. Therefore, the brightness of the shade cannot be adjusted to the desired darkness only by adjusting the density of the highly reflective flake 21. Therefore, in the present embodiment, the high reflection flake 21 and the low reflection flake 22 are used in combination, and the reflection characteristics of the shade are adjusted using the light absorption function and the concealment ability of the low reflection flake 22.
- FIG. 5 shows the spectral reflectance of each of the glittering layers of Examples and Comparative Examples measured at a light incident angle of 45 ° and a light receiving angle of 110 ° with respect to a standard white plate.
- the reflectances in Tables 1 to 3, FIGS. 7 and 8, and the transmittances in FIGS. 9 and 10 are the same.
- the variable angle spectrocolorimetry system GCMS-4 manufactured by Murakami Color Research Laboratory was used.
- Table 1 shows the specifications and average reflectance of the glittering layers of Examples and Comparative Examples.
- the aluminum flakes correspond to the high reflection flakes 21 and the chrome oxide flakes correspond to the low reflection flakes 22.
- the spectral reflectance rises from around 580 nm, and red coloring is recognized even in the shade having a light receiving angle of 110 °.
- the spectral reflectance is a little higher from around 660 nm, and no substantial color development is observed in the shade.
- the high-reflection flakes 21 and the low-reflection flakes 22 are provided such that a plurality of each of the high-reflection flakes 21 and the low-reflection flakes 22 overlap with each other in the thickness direction of the glitter layer 14.
- FIG. 6 is a photograph of the glitter layer according to the above example taken from the surface side.
- the whitish particles in the figure are aluminum flakes, and the other particles are chromium oxide flakes.
- the ratio of the projected area of both flakes occupying the bottom surface hereinafter referred to as “projected area occupation ratio” is 100%. is there.
- the present embodiment is characterized in that, instead of providing such an absorption layer, two types of flakes 21 and 22 having different reflection characteristics are used as the glitter material of the glitter layer 14.
- a preferred highly reflective flake 21 is an aluminum flake having a visible light reflectance of 90% or more.
- the aluminum flakes preferably have an average particle diameter of 5 ⁇ m to 15 ⁇ m, a thickness of 20 nm to 200 nm, and a surface roughness Ra of 100 nm or less.
- the concentration of such highly reflective flakes 21 is expressed as a ratio with respect to the resin contained in the glitter layer 14 and is 8% by mass or more and 20% by mass or less, thereby obtaining the desired highlight brightness.
- the low reflection flakes 22 preferably have a visible light reflectance of 1 ⁇ 2 or less of the high reflection flakes 21.
- the low reflection flakes 22 may have an average particle diameter of 5 ⁇ m or more and 20 ⁇ m or less, and from the viewpoint of suppressing diffuse reflection, the thickness is preferably 10 nm or more and 100 nm or less, and the surface roughness Ra is preferably 100 nm or less.
- the diffuse reflection at the edge of the flake-like glitter material becomes stronger as the thickness of the flake increases.
- the low reflection flake 22 has a smaller thickness, and thus the diffuse reflection is weak. Therefore, it is advantageous for reducing the brightness of the shade.
- FIG. 7 shows the total area of aluminum flakes and the low reflection flakes in each case where low reflection flakes A to D having different reflection characteristics are combined with aluminum flakes having a visible light reflectance of 90% or more as high reflection flakes.
- the relationship between the ratio of the total area of aluminum flakes to the total area (hereinafter referred to as “aluminum area ratio”) and the average reflectance of the glitter layer 14 at a light receiving angle of 110 ° is shown.
- the total area was calculated by a method in which the glittering layer was magnified and observed from the surface with a microscope, aluminum flakes and low reflection flakes were distinguished by brightness, and the total area of each flake was obtained by image processing.
- the low reflection flake A has a visible light reflectance of 3/4 of aluminum flake, and is a flake represented by chrome flake.
- the low reflection flake B has a visible light reflectance of 1 ⁇ 2 that of aluminum flake, and is a flake represented by stainless steel flake.
- the low reflection flake C has a visible light reflectance of 1 ⁇ 4 that of aluminum flake, and is a flake represented by chromium oxide flake.
- the low reflection flake D has a visible light reflectance of 1/18 that of aluminum flake, and is a flake represented by plate-like iron oxide ( ⁇ -Fe 2 O 3 ) flake and carbon flake.
- the projected area occupancy ratio of the aluminum flakes and the low reflection flakes to the bottom surface of the glitter layer is 100%. Further, the aluminum area ratio is changed by making the total amount (volume%) of the aluminum flakes and the low reflection flakes constant and changing the amounts of the aluminum flakes and the low reflection flakes relatively.
- the visible light reflectance of the low-reflection flakes needs to be 1 ⁇ 2 or less of the visible light reflectance of the aluminum flakes.
- low reflection flakes for example, chromium oxide flakes
- the aluminum area ratio is 25% or more and 75% or less
- light reception is performed. It can be seen that the average reflectance at an angle of 110 ° is 0.003 or more and 0.045 or less.
- an acrylic melamine resin was used as the resin for the glittering layer
- perylene red average particle size 200 nm
- the pigment concentration was 10% by mass.
- the colored layer was the same structure (perylene red (average particle diameter 30 nm); 5 mass%, acrylic resin; 58 mass%, melamine resin; 31 mass%, additive; remainder) in any painted plate.
- Table 2 shows the aluminum flake amount, chromium oxide flake amount, aluminum area ratio, and average reflectance at a light receiving angle of 110 ° of each coated plate.
- the measurement results are shown in FIG. According to the figure, when the average reflectance at a light receiving angle of 110 ° is 0.003 or more and 0.045 or less, the FI value is 20 or more, and the average reflectance is 0.005 or more and 0.035. When it is below, the FI value is 30 or more.
- the slope of the tangent line at 620 nm of the spectrum of the absolute value display spectral transmittance at an incident angle of 45 ° and a receiving angle of 25 ° is 0.012 nm ⁇ 1 or more and 0.03 nm ⁇ 1 .
- the spectral transmittance of the colored layer 15 is the spectral reflectance measured in a state where the colored layer 15 is laminated on the glittering layer 14 in a state where the colored layer 15 is removed and the surface of the glittering layer 14 is exposed. It is obtained by dividing by the measured spectral reflectance.
- FIG. 9 and 10 show the spectral transmittance spectra of the colored layers in the examples and comparative examples, respectively.
- the variable angle spectrocolorimetry system GCMS-4 manufactured by Murakami Color Research Laboratory was used.
- FIG. 9 shows each spectral transmittance spectrum in the measurement wavelength range of 420 to 740 nm
- FIG. 10 shows an enlarged version of each spectral transmittance spectrum in the range of 600 to 640 nm.
- Table 1 shows the specifications of the laminated coating films of Examples and Comparative Examples, and the tangential slope and chroma C * of the spectrum at a wavelength of 620 nm.
- the saturation C * is proportional to the slope of the tangent line of the spectrum at a wavelength of 620 nm, and the saturation C * becomes almost 100 at a slope of 0.02 nm ⁇ 1.
- the saturation C * is almost 150 (upper limit).
- the characteristics relating to the slope of the tangent line and the saturation C * shown in FIG. 11 were obtained as follows.
- a plurality of coated plates having the same structure as in the above-described embodiment are prepared, and the spectral spectrum of each coated plate is measured.
- the slope of tangent at 620 nm is obtained from the spectrum as described above, and the XY and Z values of the XYZ color system are obtained using a color matching function.
- the saturation C * is 50 or more.
- the inclination of the tangent line depends on the pigment particle size (average particle size) of the colored layer. According to FIG. 11 and FIG. 12, when the average particle diameter of the pigment particles is 2 nm or more and 160 nm or less, the slope of the tangent is 0.012 nm ⁇ 1 or more and 0.03 nm ⁇ 1 or less, which is less turbid and transparent. It can be seen that a high vivid red color can be obtained.
- the multilayer coating film 12 has a high FI by combining the reflection characteristics of the glitter layer 14 and the transmission characteristics of the colored layer 15. That is, the transmission characteristics of the colored layer 15 change depending on the pigment concentration C.
- the reflected light (particularly diffuse reflected light) from the glittering layer 14 is not so attenuated when passing through the colored layer 15, and the FI value does not increase.
- the pigment concentration C increases, the light is absorbed by the pigment particles when passing through the colored layer 15, and the light path length increases in order to pass through the pigment particles. FI value increases.
- the pigment concentration C is excessively high, the effect of shielding the reflected light by the pigment particles becomes large, and the FI value decreases.
- FIG. 13 is a graph showing the dependence of the FI value on Y (10 °) and the pigment concentration C of the colored layer based on the results of Table 3.
- the pigment concentration C expressed by mass% of the colored layer 15 is 1 or more and 17 or less, the FI value can be 20 or more.
- FIG. 17 plots the vertices a1 to h1, a2 to h2, and a3 to h3 of FIGS. 14 to 16 in a two-dimensional orthogonal coordinate system in which two variables of Y (10 °) and coefficient k are set as coordinate axes. This shows the relationship between Y (10 °) and coefficient k. Thus, the preferable range of the coefficient k differs depending on Y (10 °).
- FIG. 18 shows the relationship between the coefficient k and the pigment concentration C by plotting the vertices a1 to h1, a2 to h2, and a3 to h3 in a two-dimensional orthogonal coordinate system in which two variables of the coefficient k and the pigment concentration C are set as coordinate axes. This is what I saw. Thus, the preferable range of the pigment concentration C varies depending on the coefficient k.
- the range where the FI value is 20 or more is the three variables Y (10 °), k, and C as shown in FIG. Can be expressed in the three-dimensional orthogonal coordinate space placed on the X, Y, and Z coordinate axes.
- the polyhedron figure shown in FIG. 19 is formed by arranging the vertices a1 to d1, a2 to d2, and a3 to d3 in a three-dimensional orthogonal coordinate space.
- This polyhedron is surrounded by a total of ten planes A to J each including four vertices shown in Table 4.
- the polyhedron shown in FIG. 19 is an octahedron surrounded by a total of eight planes of A plane to H plane. Further, in this octahedron, the C surface and the F surface form a concave ridge angle, and the D surface and the G surface form a convex ridge angle.
- the polyhedron shown in FIG. 19 is surrounded by the planes represented by the eight formulas A to H shown in Table 3, and the plane represented by the formula C and the plane represented by the formula F form a concave ridge angle.
- the surface represented by Formula D and the surface represented by Formula G are octahedrons that form convex ridge angles.
- Y (10 °), coefficient k, and pigment concentration C the range in which the FI value is 30 or more is also represented by three variables Y (10 °), k, and C as shown in FIG.
- Y and Z coordinate axes can be represented by the three-dimensional orthogonal coordinate space. That is, the polyhedron figure is formed by arranging the vertices e1 to h1, e2 to h2, and e3 to h3 in a three-dimensional orthogonal coordinate space, and includes a total of 10 vertices each including four vertices shown in Table 5. Are surrounded by planes A ′ to J ′. Table 5 shows the above 10 plane equations.
- the polyhedron shown in FIG. 20 is an octahedron surrounded by a total of eight planes of A ′ plane to H ′ plane.
- the C ′ plane and the F ′ plane form a concave ridge angle
- the D ′ plane and the G ′ plane form a convex ridge angle.
- the polyhedron shown in FIG. 20 is surrounded by planes each represented by eight formulas A ′ to H ′ shown in Table 2, and a plane represented by formula C ′ and a plane represented by formula F ′ are It can be said that the concave ridge angle is formed, and the surface represented by the formula D ′ and the surface represented by the formula G ′ are octahedrons forming the convex ridge angle.
- coefficient k, and pigment concentration C are in a relationship satisfying the condition that coordinates (Y (10 °), k, C) exist within the range defined by the octahedron,
- the FI value is 30 or more.
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Abstract
Description
上記光輝性層は、上記光輝材として、可視光線反射率が90%以上である高反射フレークと、可視光線反射率が上記高反射フレークの1/2以下である低反射フレークとを混合状態で含有し、
上記高反射及び低反射の両フレークを上記光輝性層の底面に投影したときに該底面に占める上記両フレークを合わせた投影面積の割合が100%であることを特徴とする。
図1に示すように本実施形態の自動車の車体11の表面に設けられた積層塗膜12は、光輝性層(第1ベース)14、透光性を有する着色層(第2ベース)15及び透明クリヤ層16を順に積層してなる。車体11の表面にはカチオン電着塗装によって電着塗膜13が形成され、電着塗膜13の上に上記積層塗膜12が設けられている。
金属調カラーを実現するには、ハイライトでの明度が高く、シェードでの明度が低いこと、すなわち、FI値が高いことが積層塗膜12に求められる。ここに、FI値は、図2に示すように、積層塗膜12の表面に対して光が入射角45゜(該表面の垂線から45゜傾けた角度)入射したときの、受光角(正反射方向から光源側への傾き角度)45゜の反射光(45゜反射光)の明度指数L*45°と、受光角15゜の反射光(15゜反射光)の明度指数L*15°と、受光角110゜の反射光(110゜反射光)の明度指数L*110°とに基いて、次式により求められる値である。
図3は顔料を含まない光輝性層のXYZ表色系の標準白色板で校正したY値の角度依存特性の一例を示す。図4にY値の測定方法を示す。光源41の光輝性層15に対する入射角は45゜である。センサ42による受光角は正反射方向を0゜としている。測定には株式会社村上色彩研究所製三次元変角分光測色システムGCMS-4を用いた。受光角10゜で測定した反射光のY値をY(10゜)、受光角25゜で測定した反射光のY値をY(25゜)とすると、図4の例では、Y(10゜)=510、Y(25゜)=120である。
光輝性層14に上述の如きの反射特性を得るために、本実施形態では、上述の反射特性が異なる2種類のフレーク、すなわち、高反射フレーク21と低反射フレーク22を採用している。
好ましい高反射フレーク21は、可視光線反射率が90%以上であるアルミフレークである。このような高い反射特性を得るために、アルミフレークは、その平均粒径が5μm以上15μm以下、厚さが20nm以上200nm以下、表面粗さRaが100nm以下であることが好ましい。このような高反射フレーク21の濃度を、光輝性層14が含有する樹脂に対する比率で表して、8質量%以上20質量%以下とすることにより、所期のハイライトの明度を得ている。
高反射フレークとしてアルミフレークを採用し、低反射フレークとして酸化クロムフレークを採用し、アルミ面積率を調整することによって、受光角110゜での平均反射率が相違する複数の光輝性層を作成した。それら各光輝性層に着色層を積層してなる複数の塗装板a~eを作成し、各塗装板のFI値を測定した。
本実施形態の着色層15は、光の入射角45゜及び受光角25゜における絶対値表示の分光透過率のスペクトルの620nmでの接線の傾きが0.012nm-1以上0.03nm-1である。ここに、着色層15の分光透過率は、光輝性層14に着色層15を積層した状態で測定した分光反射率を、着色層15が除かれて光輝性層14表面を露出させた状態で測定した分光反射率で除することで求められるものである。
<光輝性層の反射特性と着色層の透過特性との組み合わせ>
本発明の重要な特徴の一つは、光輝性層14の反射特性と着色層15の透過特性との組み合わせによって、積層塗膜12の高FI化を図った点にある。すなわち、着色層15の透過特性は、その顔料濃度Cによって変化する。顔料濃度Cが薄い場合は、光輝性層14からの反射光(特に拡散反射光)が着色層15を透過するときにあまり減衰されず、FI値は高くならない。そして、顔料濃度Cが高くなるにしたがって、光が着色層15を透過するときに、顔料粒子に吸収され、また、顔料粒子を透過するために光路長が長くなるため、シェードの明度が落ちる(FI値が高くなる。)。但し、顔料濃度Cが過度に高くなると、顔料粒子による反射光の遮蔽効果が大きくなってFI値が下がる。
試作実験によれば、図14に示すように、k=0.35であるときは、130≦Y(10゜)≦950であり、且つ質量%で表した顔料濃度Cが5≦C≦17であるときに、FI値が20以上となる。また、150≦Y(10゜)≦900であり、且つ7≦C≦12であるときに、FI値が30以上となる。同図の好ましい範囲を示す図形の頂点a1~h1に与えた座標(X,Y,Z)は、Y(10゜)、k及びCの3つの変数をX、Y及びZの各座標軸におく三次元直交座標空間の座標を表示したものである。この座標(X,Y,Z)に関しては、図15及び図16も同じである。
12 積層塗膜
13 電着塗膜
14 光輝性層
15 着色層
16 透明クリヤ層
21 高反射フレーク(光輝材)
22 低反射フレーク(光輝材)
23 顔料
25 顔料
Claims (7)
- 被塗物の表面に直接又は間接的に形成された光輝材を含有する光輝性層と、該光輝性層の上に重ねられ暖色系顔料を含有し透光性を有する着色層とを備え、
上記光輝性層は、上記光輝材として、可視光線反射率が90%以上である高反射フレークと、可視光線反射率が上記高反射フレークの1/2以下である低反射フレークとを混合状態で含有し、
上記高反射及び低反射の両フレークを上記光輝性層の底面に投影したときに該底面に占める上記両フレークを合わせた投影面積の割合が100%であることを特徴とする積層塗膜。 - 請求項1において、
上記低反射フレークは、上記高反射フレークよりも、厚さが薄いことを特徴とする積層塗膜。 - 請求項1又は請求項2において、
上記低反射フレークの可視光線反射率が上記高反射フレークの可視光線反射率の1/4以下であり、
上記高反射及び低反射の両フレークの延べ面積の合計に占める上記高反射フレークの述べ面積の比率が25%以上75%以下であることを特徴とする積層塗膜。 - 請求項1乃至請求項3のいずれか一において、
上記高反射フレークがアルミフレークであり、上記低反射フレークが酸化クロムフレークであることを特徴とする積層塗膜。 - 請求項1乃至請求項4のいずれか一において、
上記光輝性層は、光の入射角45゜及び受光角110゜で測定した標準白色板に対する反射率の波長450nm~700nm範囲の平均値が絶対値表示で0.003以上0.045以下であることを特徴とする積層塗膜。 - 請求項1乃至請求項5のいずれか一において、
上記着色層の顔料が赤系顔料であることを特徴とする積層塗膜。 - 請求項1乃至請求項6のいずれか一の積層塗膜を備えていることを特徴とする塗装物。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109683443A (zh) * | 2019-01-30 | 2019-04-26 | 广州悦荣欣科技有限公司 | 一种新型复合涂层 |
JP7005823B1 (ja) * | 2020-10-13 | 2022-01-24 | 関西ペイント株式会社 | 複層塗膜形成方法 |
WO2022054709A1 (ja) * | 2020-09-14 | 2022-03-17 | 日本ペイント・オートモーティブコーティングス株式会社 | 複層塗膜および複層塗膜の形成方法 |
WO2022079958A1 (ja) * | 2020-10-13 | 2022-04-21 | 関西ペイント株式会社 | 複層塗膜形成方法 |
WO2022102380A1 (ja) | 2020-11-13 | 2022-05-19 | マツダ株式会社 | 積層塗膜及び塗装物 |
Families Citing this family (2)
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CN110100192B (zh) * | 2016-12-22 | 2021-02-09 | 富士胶片株式会社 | 光学膜及光学膜的制造方法 |
CN111052410B (zh) * | 2017-09-05 | 2023-06-13 | 夏普株式会社 | 发光器件 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001232283A (ja) * | 2000-02-28 | 2001-08-28 | Nippon Paint Co Ltd | 光輝性塗膜形成方法および塗装物 |
JP2005169385A (ja) * | 2003-11-17 | 2005-06-30 | Kansai Paint Co Ltd | 塗装方法 |
JP2005177541A (ja) * | 2003-12-16 | 2005-07-07 | Nippon Yushi Basf Coatings Kk | 積層塗膜の形成方法、積層塗膜および塗装物 |
JP2007167720A (ja) * | 2005-12-20 | 2007-07-05 | Honda Motor Co Ltd | 複層塗膜の形成方法 |
JP2007182527A (ja) * | 2005-12-07 | 2007-07-19 | Honda Motor Co Ltd | 自動車内装材用水性メタリック塗料および塗装物品 |
JP2012232236A (ja) * | 2011-04-28 | 2012-11-29 | Kansai Paint Co Ltd | 複層塗膜形成方法 |
JP2016193385A (ja) * | 2015-03-31 | 2016-11-17 | 関西ペイント株式会社 | 複層塗膜形成方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0576833A (ja) | 1991-09-19 | 1993-03-30 | Mazda Motor Corp | 塗膜構造 |
JP2000271536A (ja) | 1999-03-25 | 2000-10-03 | Nippon Paint Co Ltd | メタリック塗膜の形成方法 |
JP2000319521A (ja) | 1999-05-14 | 2000-11-21 | Dainichiseika Color & Chem Mfg Co Ltd | フリップフロップ性メタリック感を有する成形品用熱可塑性樹脂組成物 |
JP2001164191A (ja) * | 1999-12-07 | 2001-06-19 | Nippon Paint Co Ltd | 光輝性塗料組成物、塗膜形成方法および塗装物 |
JP2004209458A (ja) * | 2002-11-12 | 2004-07-29 | Kansai Paint Co Ltd | 模様塗膜形成方法及び塗装物品 |
US7851026B2 (en) | 2003-11-17 | 2010-12-14 | Kansai Paint Co. Ltd. | Method of forming a multi-layer coating including a metallic base coating and a colored clear coating on a substrate |
JP4844803B2 (ja) | 2005-03-31 | 2011-12-28 | Dic株式会社 | 成形用積層シート |
JP2011162732A (ja) | 2010-02-15 | 2011-08-25 | Kansai Paint Co Ltd | メタリック塗料組成物及び塗膜形成方法 |
JP2012017364A (ja) | 2010-07-06 | 2012-01-26 | Kansai Paint Co Ltd | メタリック塗料組成物及び塗膜形成方法 |
JP2013169507A (ja) * | 2012-02-21 | 2013-09-02 | Kansai Paint Co Ltd | 塗膜形成方法 |
EP2837432A4 (en) * | 2012-04-13 | 2016-04-20 | Kansai Paint Co Ltd | METHOD FOR FORMING COATING FILM |
-
2016
- 2016-09-30 EP EP16917767.2A patent/EP3421144B1/en active Active
- 2016-09-30 WO PCT/JP2016/079177 patent/WO2018061217A1/ja active Application Filing
- 2016-09-30 CN CN201680083505.6A patent/CN109715299B/zh active Active
- 2016-09-30 RU RU2018132233A patent/RU2720000C1/ru active
- 2016-09-30 MX MX2018011670A patent/MX2018011670A/es unknown
- 2016-09-30 US US16/087,020 patent/US10676622B2/en active Active
- 2016-09-30 JP JP2018541864A patent/JP6766875B2/ja active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001232283A (ja) * | 2000-02-28 | 2001-08-28 | Nippon Paint Co Ltd | 光輝性塗膜形成方法および塗装物 |
JP2005169385A (ja) * | 2003-11-17 | 2005-06-30 | Kansai Paint Co Ltd | 塗装方法 |
JP2005177541A (ja) * | 2003-12-16 | 2005-07-07 | Nippon Yushi Basf Coatings Kk | 積層塗膜の形成方法、積層塗膜および塗装物 |
JP2007182527A (ja) * | 2005-12-07 | 2007-07-19 | Honda Motor Co Ltd | 自動車内装材用水性メタリック塗料および塗装物品 |
JP2007167720A (ja) * | 2005-12-20 | 2007-07-05 | Honda Motor Co Ltd | 複層塗膜の形成方法 |
JP2012232236A (ja) * | 2011-04-28 | 2012-11-29 | Kansai Paint Co Ltd | 複層塗膜形成方法 |
JP2016193385A (ja) * | 2015-03-31 | 2016-11-17 | 関西ペイント株式会社 | 複層塗膜形成方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3421144A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109683443A (zh) * | 2019-01-30 | 2019-04-26 | 广州悦荣欣科技有限公司 | 一种新型复合涂层 |
WO2022054709A1 (ja) * | 2020-09-14 | 2022-03-17 | 日本ペイント・オートモーティブコーティングス株式会社 | 複層塗膜および複層塗膜の形成方法 |
JP7005823B1 (ja) * | 2020-10-13 | 2022-01-24 | 関西ペイント株式会社 | 複層塗膜形成方法 |
WO2022079958A1 (ja) * | 2020-10-13 | 2022-04-21 | 関西ペイント株式会社 | 複層塗膜形成方法 |
TWI773559B (zh) * | 2020-10-13 | 2022-08-01 | 日商關西塗料股份有限公司 | 複層塗膜形成方法 |
CN115989089A (zh) * | 2020-10-13 | 2023-04-18 | 关西涂料株式会社 | 多层涂膜形成方法 |
WO2022102380A1 (ja) | 2020-11-13 | 2022-05-19 | マツダ株式会社 | 積層塗膜及び塗装物 |
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