WO2016088295A1 - 積層塗膜及び塗装物 - Google Patents
積層塗膜及び塗装物 Download PDFInfo
- Publication number
- WO2016088295A1 WO2016088295A1 PCT/JP2015/005509 JP2015005509W WO2016088295A1 WO 2016088295 A1 WO2016088295 A1 WO 2016088295A1 JP 2015005509 W JP2015005509 W JP 2015005509W WO 2016088295 A1 WO2016088295 A1 WO 2016088295A1
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- WIPO (PCT)
- Prior art keywords
- colored
- flakes
- layer
- coating film
- glitter
- Prior art date
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Images
Classifications
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- 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
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- 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
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
- C09C1/64—Aluminium
- C09C1/642—Aluminium treated with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- 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
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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
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
-
- 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
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- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/66—Additives characterised by particle size
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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
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/414—Translucent
Definitions
- the present invention relates to a laminated coating film and a painted product.
- the present invention employs colored flakes as a glittering material for the glittering layer in order to solve the above problems.
- the color flake colorant when light enters the glittering layer, the color flake colorant reflects light having a wavelength specific to the colorant, and light of other wavelengths is absorbed by the colorant. The Therefore, even if the thickness of the colored layer is non-uniform, the light transmitted through the colored layer and incident on the glitter layer is absorbed and reflected by the colored flakes colored in the same color as the colored layer. The occurrence of uneven color is suppressed.
- the glittering flakes are partially exposed means that there is no coloring material in the part, and the part has translucent particles such as acrylic beads or glass beads or the like. The presence of a translucent film is not excluded.
- the exposed area ratio of the glitter flakes in the colored flakes is preferably 20% or more and 85% or less.
- the FI (flop index) value can be increased, which is advantageous in improving flip-flop performance.
- light is strongly absorbed in the portion where the colorant having a low total light transmittance is attached to the colored flakes, while light is absorbed by the colorant in a portion where the colorant having a high total light transmittance is attached. Since it is easy to transmit and reach the glittering frame, the regular reflection of light by the glittering flakes becomes stronger. Also in this embodiment, when the reflection angle of light increases, the reflected light is blocked by the coloring material having a low total light transmittance scattered and adhered to the glitter flakes, and the reflected light becomes weak. In particular, on the shade side, the reflected light intensity decreases. Therefore, the flip-flop property becomes strong.
- the colorant includes two colorants having different total light transmittances, and the area ratio of the colorant having high total light transmittance in the colored flakes is 25% or more and 80% or less. It is. This makes it possible to increase the FI value while using colored flakes, which is advantageous for improving flip-flop properties.
- the colored layer is colored black with a black pigment
- the colored flakes of the glitter layer are colored black with the coloring material.
- black color is developed by adding a black pigment to the colored layer, the degree of light absorption in the colored layer varies partially due to uneven thickness of the colored layer, and color unevenness (particularly shading) is likely to occur. Since the light is also absorbed by the black coloring material of the colored frame of the conductive layer, the occurrence of the uneven color is suppressed.
- the glitter layer is laminated on a colored underlayer having the same color as the colored layer.
- the underlayer is a colored underlayer having the same color as that of the colored layer. As a result, the turbidity of the coating color is suppressed, and the denseness, depth, and metal texture are enhanced.
- the brightness difference in the Munsell value of the comparison target color is 5.0 or less.
- the Munsell hue circle is divided into 100 and one hue of the comparison target color is set as a reference (0 position), and the counterclockwise rotation is displayed at +50 and clockwise rotation at -50, It is desired that the other hue is within a hue range of ⁇ 10.
- a transparent clear layer is laminated on the colored layer. Thereby, acid resistance and scratch resistance can be obtained.
- Examples of the coated object provided with the above-mentioned laminated coating film on the object to be coated include an automobile body, a motorcycle, other vehicle bodies, and other metal products. .
- the surface of the glittering flake is used as the glittering material. Since colored flakes formed by coloring with a colorant having the same color as the pigment are employed, the occurrence of uneven color due to uneven thickness of the colored layer can be suppressed. In addition, by using colored flakes, the amount of pigment added for suppressing color unevenness to the glittering layer can be reduced or reduced to zero, thereby suppressing occurrence of color unevenness due to uneven distribution of pigment on the glittering material. In addition, the orientation of the glittering material is less disturbed by the pigment, which is advantageous for securing the luminance.
- Sectional drawing which shows the prior art example of a laminated coating film typically typically.
- Sectional drawing which shows another prior art example typically Sectional drawing which shows typically the laminated coating film which concerns on Embodiment 1, 2 of this invention.
- Sectional drawing which shows an example of colored flakes typically.
- Sectional drawing which shows another example of colored flakes typically.
- the figure which shows the Munsell hue ring Sectional drawing which shows typically the laminated coating film which concerns on Embodiment 3 of this invention.
- Sectional drawing which shows an example of colored flakes typically.
- the top view which shows the same coloring frame typically.
- Sectional drawing which shows another example of colored flakes typically.
- the top view which shows the same coloring frame typically.
- the laminated coating film 12 provided on the surface of the vehicle body (steel plate) 11 of the automobile of the present embodiment is a colored base layer 14, a glittering layer 15, and a colored layer (black) 16 having translucency.
- the transparent clear layer 17 is laminated
- An electrodeposition coating (undercoat) 13 is formed on the surface of the vehicle body 11 by cationic electrodeposition coating, and the laminated coating 12 is provided on the electrodeposition coating 13.
- the colored underlayer 14 corresponds to an intermediate coating
- the glitter layer 15, the colored layer 16, and the transparent clear layer 17 correspond to an overcoat.
- the first pigment 21 is dispersed in the colored base layer 14.
- colored flakes 22 as a glittering material are dispersed.
- the second pigment 23 is dispersed in the colored layer 16.
- the first pigment 21 for example, commercially available carbon black having a particle size distribution having a peak in a particle size range of 300 nm or more and 500 nm or less, or black pigment such as graphite or iron tetroxide can be used.
- the second pigment 23 the same black pigment as that of the first pigment 21 can be employed.
- fine powder carbon black can be obtained by wet-grinding commercially available carbon black using a grinding medium such as glass beads. The structure is mechanically ground by this wet grinding to reduce the particle size.
- the colored flakes 22 of the glitter layer 15 are oriented so as to be substantially parallel to the surface of the glitter layer. After the paint containing the colored flakes 22 is applied on the colored base layer 14, the colored flakes 22 are physically arranged in a flat manner by utilizing the fact that the coating film is contracted and thinned by evaporation of the solvent by baking. .
- FIG. 4 shows an example of the colored flakes 22.
- the surface of the aluminum flakes 25 as glitter flakes is covered with an amorphous inner silica layer 26, and the silica layer 26 is covered with a metal oxide layer such as tin or zinc.
- a large number of silver particles uniformly adhere to the surface of the physical layer to form a silver particle layer 27, and an outer silica layer 28 is provided so as to cover the silver particle layer 27.
- a black visual effect is obtained by interference between reflected light on the surface of the inner silica layer 26 and reflected light on the surface of the silver particle layer 27. That is, the inner silica layer 26 and the silver particle layer 27 constitute a coloring material for the colored flakes 22, and the coloring flakes 22 are colored in the same color as the colored layer 16 by the coloring material.
- the colored layer 16 is colored in an achromatic color such as black as in the first embodiment, in order for the colored flakes 22 to be colored in the same color system as the colored layer 16, the brightness difference between the two Munsell values. Is desired to be 5.0 or less.
- the aluminum flake 25 has a particle size of 10 ⁇ m or more and 30 ⁇ m or less, a thickness of 0.5 ⁇ m or more and 2 ⁇ m or less, an inner silica layer 26 thickness of 10 nm or more and 100 nm or less, a metal oxide layer thickness of 10 nm or less, and an average of silver particles
- the particle diameter is preferably 20 nm or more and 40 nm or less
- the thickness of the outer silica layer 28 is preferably 10 nm or more and 100 nm or less.
- the colored flakes 22 can be manufactured by the following method, for example.
- An inner silicon layer 26 is formed by hydrolyzing an organosilicon compound in a solvent in which the aluminum flakes 25 are dispersed to precipitate silica on the surface of the aluminum flakes 25, and further on the surface of the inner silica layer 26.
- a metal oxide is deposited to form a metal oxide layer.
- silver particles are uniformly deposited over the entire surface of the metal oxide layer by electroless plating to form a silver particle layer 27.
- the silver particle layer 27 is formed, and the flakes are placed in a silicon-containing solution and stirred to form a hydrated film on the surface of the flakes.
- the outer silica layer 28 is formed by heating.
- Example- Table 1 shows the constitution of the laminated coating film of the example.
- Each paint of the colored base layer, the glitter layer, the colored layer, and the transparent clear layer was applied to the steel material by wet on wet, and then baked (heated at 140 ° C. for 20 minutes).
- the glitter material of the glitter layer colored flakes using silver particles shown in FIG. 4 were employed.
- Comparative Example 1 employs aluminum flakes as a glittering material for the glittering layer, and other configurations are the same as those of the examples.
- Comparative Example 2 is obtained by adding commercially available carbon black (pigment) in addition to aluminum flakes (bright material) to the glitter layer, and other configurations are the same as those of the example.
- L * is measured by a spectrophotometer (for example, MA98 multi-angle spectrocolorimeter manufactured by X-Rite Co., Ltd.) defined in JIS Z 8722, illumination angle: 45 degrees, light receiving angle; 45 degrees from regular reflection angle ( Measured by vertical light reception.
- the lightness L * of Example and Comparative Examples 1 and 2 is shown in FIG. 5, and the color unevenness ⁇ L * is shown in FIG.
- ⁇ L * is 0.4 or less, it is difficult to feel color unevenness, and if ⁇ L * is 0.25 or less, color unevenness is hardly felt.
- FIG. 6 shows that in the example, the color unevenness is hardly felt.
- the color unevenness is hardly observed due to the use of the colored flakes 22.
- Embodiment 2 is a case where a chromatic color is obtained by a laminated coating film, and the layer structure of the laminated coating film is the same as that of Embodiment 1 shown in FIG. 3, but pigments 21, 23 and colored flakes 22 are examples. Is different.
- the pigments 21 and 23 for example, chromatic pigments such as perylene pigments, phthalocyanine blue pigments, diketopyrrolopyrrole pigments are employed. Therefore, the colored layer 16 is colored chromatic.
- the colored flakes 22 flakes obtained by coloring glitter flakes with a coloring material in a chromatic color similar to the colored layer 16 are employed.
- FIG. 7 shows an example of the colored flakes 22.
- the surface of the aluminum flakes 25 as glitter flakes is covered with a resin underlayer, and a large number of colorants adhere to the surface of the resin underlayer to form a colorant layer 29.
- a resin coat layer 30 is provided so as to cover the layer 29.
- the resin base layer and the resin coat layer 30 can be formed of, for example, a condensate of silica or polysiloxane, and a pigment having the same color as the pigments 21 and 23 can be used as the colorant.
- the Munsell hue ring is divided into 100, and the hue of the colored layer 16 is set as a reference (0 position), and is displayed as +50 counterclockwise and -50 clockwise. Then, it is desirable that the hue of the colored flakes 22 be in the hue range of ⁇ 10.
- the thickness of the resin underlayer is preferably 5 nm to 100 nm
- the primary particle diameter of the coloring material is preferably 20 nm to 100 nm
- the thickness of the resin coat layer 30 is preferably 10 nm to 100 nm.
- color unevenness is suppressed from occurring in the laminated coating film, and a desired luminance is obtained.
- L *, a *, and b * are measured with a spectrophotometer (for example, MA98 multi-angle spectrocolorimeter manufactured by X-Rite Co., Ltd.) specified in JIS Z 8722. Illumination angle: 45 degrees, light receiving angle; regular reflection It is performed at 45 degrees (vertical light reception) from the angle.
- the laminated coating film 12 provided on the surface of the vehicle body (steel plate) 11 of the automobile of this embodiment is formed by laminating a colored base layer 14, a glittering layer 15, and a transparent clear layer 17 in this order.
- An electrodeposition coating (undercoat) 13 is formed on the surface of the vehicle body 11 by cationic electrodeposition coating, and the laminated coating 12 is provided on the electrodeposition coating 13.
- the colored underlayer 14 corresponds to an intermediate coating
- the glitter layer 15 and the transparent clear layer 17 correspond to an overcoat.
- the colored flakes 22 of the glitter layer 15 are oriented so as to be substantially parallel to the surface of the glitter layer. After the paint containing the colored flakes 22 is applied on the colored base layer 14, the colored flakes 22 are physically arranged in a flat manner by utilizing the fact that the coating film is contracted and thinned by evaporation of the solvent by baking. .
- the resin component of the colored underlayer 14 for example, a polyester resin can be employed, and as the resin component of the glitter layer 15, for example, an acrylic resin can be employed, and the resin of the transparent clear layer 17.
- an acid epoxy curable acrylic resin can be employed.
- [Exposed colored flakes] 10 and 11 show an exposed colored flake 22A as the colored flake 22.
- FIG. The exposed colored flakes 22A are those in which the granular colorant (pigment) 31 is scattered and adhered to the surface of the aluminum flakes 25 as glitter flakes, and the aluminum flakes 25 are partially exposed. The entire aluminum flakes to which the coloring material 31 is adhered are covered with the resin coat layer 32. Since the colored flakes 22A are partially exposed, the aluminum flakes are referred to as “exposed colored flakes” for convenience.
- the exposed colored flakes 22A can be manufactured, for example, by the following immersion method or vapor deposition method.
- a coloring material, a silane coupling agent, and a solvent are mixed and dispersed by a ball mill.
- An aluminum flake paste and a solvent are added to the dispersion, and further, a dispersion treatment by a ball mill is performed.
- a solvent is added to the resulting slurry to remove the dispersing balls, and the slurry is left as it is to precipitate the aluminum flakes to which the coloring material has adhered, and the solvent is removed.
- monomers such as acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate and the like are dispersed in a slurry in which the colored aluminum flakes are dispersed in a hydrocarbon or alcohol solvent.
- a polymerization initiator such as benzoyl peroxide or isobutyl peroxide is added, and the mixture is heated and stirred to polymerize the monomer, thereby precipitating on the surface.
- carbon black is used as a coloring material, 1 g of carbon black, 0.5 g of silane coupling agent, 10 g of solvent (mineral split), aluminum flake paste (aluminum flake; average particle size: 30 ⁇ m, When the average thickness was set to 10 g, carbon black was scattered and adhered to the aluminum flakes, and the exposed area ratio of the aluminum flakes was 60%.
- a coloring material is evaporated and adhered to aluminum flakes while fluidizing the aluminum flakes in a vacuum vessel equipped with a powder fluidizing device and a resistance heating device.
- a powder fluidizer for example, a rotary fluidizer equipped with a barrel-type rotary vacuum chamber is used.
- the resistance heating device includes, for example, a DC power source, a pair of copper electrodes, and a stainless steel resistor, and the copper electrode is connected to a wire drawn from the DC power source into the vacuum chamber.
- the stainless steel resistor is bolted to the copper electrode so that it is located in the center of the vacuum chamber.
- a slurry in which aluminum flakes are dispersed in acetone is subjected to suction filtration, and then dried with hot air at 200 ° C. to obtain a dry powder of aluminum flakes.
- the vacuum degree in the vacuum chamber is lowered to 10 ⁇ 4 torr or less.
- a vacuum chamber is rotated by a rotor, and while flowing aluminum flakes, an electric current is applied to the electrodes to heat and evaporate the pigment. After the evaporation is complete, the aluminum flakes are cooled to near room temperature. Thereby, the aluminum flake which the colorant scattered and adhered is obtained.
- monomers such as acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate and the like are dispersed in a slurry in which the colored aluminum flakes are dispersed in a hydrocarbon or alcohol solvent.
- a polymerization initiator such as benzoyl peroxide or isobutyl peroxide is added, and the mixture is heated and stirred to polymerize the monomer, thereby precipitating on the surface.
- carbon black is used as a colorant
- carbon black is 10 g
- aluminum flakes average particle size: 30 ⁇ m, average thickness: 1 ⁇ m
- current supply to the electrode is 10 V, 40 A
- heat evaporation When the time was 60 minutes, carbon black was scattered and adhered to the aluminum flakes, and the exposed area ratio of the aluminum flakes was 50%.
- a coloring material and translucent beads such as acrylic beads may be mixed and adhered to the aluminum flakes so as to cover the entire surface. Even in this case, the coloring material is scattered and attached to the aluminum flakes, and the portion of the aluminum flakes to which the light-transmitting beads are attached is in a state where the aluminum flakes are optically exposed through the light-transmitting beads.
- the flakes can be called exposed colored flakes.
- [Mixed colored flakes] 12 and 13 show a mixed colored flake 22B as still another example of the colored flake 22.
- FIG. In the mixed colored flakes 22B the surface of the aluminum flakes 25 is covered with two types of granular coloring materials 33 and 34 having different visible light total light transmittances. Further, the entire aluminum flakes to which the coloring materials 33 and 34 are attached are covered with the resin coat layer 32. Two kinds of coloring materials 33 and 34 having different total light transmittances are attached to the surface of the aluminum flakes 25 as spots. Since these colored flakes 22B are mixed with a plurality of kinds of coloring materials, they are referred to as “mixed colored flakes” for convenience.
- This mixed colored flake 22B can also be prepared by the dipping method or the vapor deposition method.
- the dipping method it is different from the case of exposed colored flakes in that multiple types of coloring materials are mixed with a silane coupling agent and a solvent and subjected to dispersion treatment with a ball mill.
- Colored flakes can be prepared.
- the vapor deposition method When the vapor deposition method is employed, mixed colored flakes can be prepared in the same manner except that a plurality of kinds of coloring materials are mixed and wrapped in a stainless steel mesh, which is different from the case of exposed colored flakes.
- carbon black and aniline black which have different total light transmittance, are used as coloring materials, carbon black 0.5g, aniline black 0.5g, silane coupling agent 0.5g, solvent (mineral split) ) And 10 g of aluminum flake paste (aluminum flake; average particle size: 30 ⁇ m, average thickness: 1 ⁇ m), carbon black and aniline black adhere to the flakes and occupy the surface of the aluminum flakes The area ratio of aniline black was 60%.
- carbon black and aniline black are used as coloring materials
- carbon black is 15 g
- aniline black is 15 g
- aluminum flakes (average particle size: 30 ⁇ m, average thickness: 1 ⁇ m) is 20 g
- the electrode is energized.
- the heating evaporation time was 60 minutes with 10V and 40A
- carbon black and aniline black adhered to the aluminum flakes
- the area ratio of aniline black occupying the surface of the aluminum flakes was 50%.
- the refractive index of carbon black is 1.8
- the refractive index of aniline black is 1.58. Since the total light transmittance is higher when the refractive index is smaller, the reflected light characteristics of the mixed colored flakes can be adjusted by controlling the occupation area ratio of the colorant having a different refractive index in the aluminum flakes.
- FIG. 14 shows a case using perylene red having a refractive index of 2.02 as a red pigment
- FIG. 15 shows a case using carbon black having a refractive index of 1.8 as a black pigment.
- the reflectivity increases as the exposed area ratio increases, and the reflectivity greatly decreases when the average particle size exceeds 200 nm.
- the obtained samples have different average particle diameters of exposed coloring flakes contained in the glitter layer and aluminum flake exposed area ratios. Then, the FI (flop index) value of each sample was measured.
- the FI value is reflected light inclined by 45 ° from the regular reflection direction to the incident direction side when light is incident on the surface of the sample 35 at an angle inclined by 45 ° from the normal to the surface.
- Lightness index L * 45 ° of (45 ° reflected light) brightness index L * 15 ° of reflected light (15 ° reflected light) tilted 15 ° from the regular reflection direction to the incident direction side, and incident direction from the regular reflection direction
- the value is obtained by the following equation.
- the FI value increases as the exposed area ratio increases from zero. This is because the 15 ° reflected light becomes stronger as the exposed area of the aluminum flakes increases. On the other hand, the FI value peaks at an exposed area ratio of about 50% to 60%, and thereafter the FI value decreases as the exposed area ratio increases. If the exposure of the aluminum flakes becomes too large, the coloring material This is considered to be due to a decrease in the degree of shielding of 110 ° reflected light due to.
- the obtained samples are different in the average particle diameter of the coloring material of the exposed colored flakes contained in the glittering layer and the area ratio of aniline black. Then, the FI value of each sample was measured.
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Abstract
Description
上記光輝性層は、上記光輝材として、光輝性フレークの表面を着色材によって上記着色層と同色系に着色してなる着色フレークを含有することを特徴とする。
図3に示すように本実施形態の自動車の車体(鋼板)11の表面に設けられた積層塗膜12は、着色下地層14、光輝性層15、透光性を有する着色層(黒色)16及び透明クリヤ層17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(下塗り)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。この積層塗膜12において、着色下地層14は中塗りに相当し、光輝性層15、着色層16及び透明クリヤ層17は上塗りに相当する。
-実施例-
実施例の積層塗膜の構成を表1に示す。
比較例1の積層塗膜の構成を表2に示す。
比較例2の積層塗膜の構成を表3に示す。
実施例及び比較例1,2の積層塗膜の色むらを評価した。すなわち、測色器を積層塗膜上で一方向に直線状に移動させて1cm刻みで明度L*を測定し、各位置の明度L*とその平均値(L*(平均))の差の絶対値を色むら度ΔL*(=|L*(平均)-L*|)として求めた。ここに、L*は、JIS Z 8722に規定する分光測光器(例えば、エックスライト株式会社製MA98 多角度分光測色計)により、照明角度;45度、受光角度;正反射角より45度(垂直受光)で測定した。実施例及び比較例1,2の明度L*を図5に、色むら度ΔL*を図6にそれぞれ示す。ここに、ΔL*が0.4以下であれば、色むらを感じにくく、ΔL*が0.25以下であれば、色むらをほぼ感じない。
実施形態2は積層塗膜によって有彩色の塗色を得るケースであり、積層塗膜の層構造は図3に示す実施形態1と同じあるが、顔料21,23及び着色フレーク22が実施例とは相違する。
図9に示すように本実施形態の自動車の車体(鋼板)11の表面に設けられた積層塗膜12は、着色下地層14、光輝性層15及び透明クリヤ層17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(下塗り)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。この積層塗膜12において、着色下地層14は中塗りに相当し、光輝性層15及び透明クリヤ層17は上塗りに相当する。
図10及び図11に着色フレーク22としての露出型着色フレーク22Aを示す。露出型着色フレーク22Aは、光輝性フレークとしてのアルミフレーク25の表面に、粒状着色材(顔料)31が散らばって付着し、アルミフレーク25が部分的に露出したものである。着色材31が付着したアルミフレーク全体が樹脂コート層32で覆われている。この着色フレーク22Aはアルミフレークが部分的に露出しているから、これを便宜上「露出型着色フレーク」という。この露出型着色フレーク22Aは例えば次の浸漬法や蒸着法によって製造することができる。
着色材、シランカップリング剤及び溶剤を混合し、ボールミルによる分散処理を行なう。その中にアルミフレークのペースト及び溶剤を添加し、さらにボールミルによる分散処理を行なう。得られたスラリーに溶剤を加えて分散用ボールを除き、そのまま放置することにより、着色材が付着したアルミフレークを沈澱させ、溶剤を除去する。
これは、粉体流動化装置及び抵抗加熱装置を備えた真空容器内において、アルミフレークを流動化させながら、着色材を蒸発させてアルミフレークに付着せしめる方法である。粉体流動化装置としては、例えば、バレル型回転式真空チャンバーを備えた回転式流動化装置を使用する。抵抗加熱装置は、例えば、直流電源、一対の銅電極及びステンレス網の抵抗体から構成し、銅電極は直流電源から真空チャンバー内部に引き込まれた電線に接続する。ステンレス網の抵抗体は、真空チャンバーの中央に位置するように、銅電極にボルトで固定する。
図12及び図13に着色フレーク22のさらに別の例として混在型着色フレーク22Bを示す。混在型着色フレーク22Bは、アルミフレーク25の表面が可視光線の全光線透過率の相違する2種類の粒状着色材33,34によって覆われている。さらに、着色材33,34が付着したアルミフレーク全体が樹脂コート層32で覆われている。全光線透過率が相違する2種類の着色材33,34はアルミフレーク25の表面に斑になって付着している。この着色フレーク22Bは複数種の着色材が混在しているから、これを便宜上「混在型着色フレーク」という。
露出型着色フレークに関し、アルミフレークの露出面積率及び着色材粒径が光線反射率に及ぼす影響を調べた。光線反射率は、着色フレークの表面の垂線を基準とする入射角度10゜での正反射率(反射角度10゜)であり、入射光の波長は630nmとした。
着色材として、平均粒径が200nmのカーボンブラックと、平均粒径が400nmのカーボンブラックの2種類を準備し、光輝性フレークとしてアルミフレークを準備し、露出面積率が異なる複数種の露出型着色フレークを作成した。それらの露出型着色フレークを用いて基板上に光輝性層を形成し、その上に透明クリヤ層を形成した複数のサンプルを作成した。光輝性層は、着色フレークを分散させたアクリル系ベース塗料をスプレー塗装することによって形成した。着色フレークは光輝性層表面と略平行に配向するようにし、且つ基板が個々の着色フレークの間から露出しないようにした。透明クリヤ層はアクリル系クリヤ塗料のスプレー塗装によって形成した。
測定結果を図17に示す。平均粒径が200nmのケース及び400nmのケースのいずれも、露出面積率が零から大きくなるに従ってFI値が大きくなり、露出面積率50%~60%付近でFI値がピークになった後は露出面積率が大きくなるに従ってFI値が低下するという傾向になった。
2種の着色材混在型着色フレークに関し、全光線透過率が高い着色材の面積率(アルミフレークの表面積に占める当該着色材の面積率)及び当該2種の着色材の粒径が光線反射率に及ぼす影響を調べた。光線反射率の測定条件は先の露出型着色フレークの場合と同じである。
着色材として、各々平均粒径が200nmのカーボンブラック及びアニリンブラックと、各々平均粒径が400nmのカーボンブラック及びアニリンブラックを準備し、光輝性フレークとしてアルミフレークを準備し、着色材の平均粒径及びアニリンブラックの面積率が異なる複数種のカーボンブラック・アニリンブラック混在型着色フレークを作成した。それらの露出型着色フレークを用いて基板上に光輝性層を形成し、その上に透明クリヤ層を形成した複数のサンプルを作成した。光輝性層は、着色フレークを分散させたアクリル系ベース塗料をスプレー塗装することによって形成した。着色フレークは光輝性層表面と略平行に配向するようにし、且つ基板が個々の着色フレークの間から露出しないようにした。透明クリヤ層はアクリル系クリヤ塗料のスプレー塗装によって形成した。
12 積層塗膜
13 電着塗膜
14 着色下地層
15 光輝性層
16 着色層
17 透明クリヤ層
21 第1顔料
22 着色フレーク
22A 露出型着色フレーク
22A 混在型着色フレーク
23 第2顔料
25 アルミフレーク
26 内側シリカ層(着色材を構成)
27 銀粒子層(着色材を構成)
29 着色材層
31 着色材
32 樹脂コート層
33 着色材(全光線透過率が低い)
34 着色材(全光線透過率が高い)
Claims (11)
- 光輝材を含有する光輝性層の上に透光性を有する着色層が積層されてなる積層塗膜であって、
上記光輝性層は、上記光輝材として、光輝性フレークの表面を着色材によって上記着色層と同色系に着色してなる着色フレークを含有することを特徴とする積層塗膜。 - 請求項1において、
上記着色フレークは、上記光輝性フレークの表面に上記着色材が散らばって付着し、当該光輝性フレークが部分的に露出していることを特徴とする積層塗膜。 - 請求項2において、
上記着色フレークにおける上記光輝性フレークの露出面積率が20%以上85%以下であることを特徴とする積層塗膜。 - 請求項1において、
上記着色フレークは、上記着色材として、可視光線の全光線透過率の相違する複数種の着色材を有し、
上記全光線透過率が相違する複数種の着色材は上記光輝性フレークの表面に斑になって付着していることを特徴とする積層塗膜。 - 請求項4において、
上記着色材として、全光線透過率が相違する2種の着色材を備え、
上記着色フレークにおける上記全光線透過率が高い着色材の面積率が25%以上80%以下であることを特徴とする積層塗膜。 - 請求項2において、
上記着色材は、粒状であって、その平均粒子径が300nm以下であることを特徴とする積層塗膜。 - 請求項1において、
上記光輝性フレークがアルミフレークであることを特徴とする積層塗膜。 - 請求項1において、
上記着色層が黒色顔料によって黒色に着色され、
上記光輝性層の上記着色フレークが上記着色材で黒色に着色されていることを特徴とする積層塗膜。 - 請求項1において、
上記光輝性層が上記着色層と同色系の着色下地層の上に積層されていることを特徴とする積層塗膜。 - 請求項1において、
上記着色層の上に透明クリヤ層が積層されていることを特徴とする積層塗膜。 - 請求項1に記載された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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DE112015004592.9T DE112015004592B4 (de) | 2014-12-03 | 2015-11-02 | Mehrschichtiger Beschichtungsfilm und beschichteter Gegenstand |
CN201580049255.XA CN107000411B (zh) | 2014-12-03 | 2015-11-02 | 叠层涂膜和涂装物 |
MX2017003778A MX2017003778A (es) | 2014-12-03 | 2015-11-02 | Pelicula de recubrimineto de multicapa y objeto recubierto. |
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CN108146039A (zh) * | 2017-12-25 | 2018-06-12 | 广州钰鑫新材料有限公司 | 一种base底银色膜及其制备方法 |
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CN107000411A (zh) | 2017-08-01 |
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