JP2000336284A - Mica coated with titanium-cobalt-aluminum compound oxide and product coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a multi-color changing pigment which changes its color according to the observation direction by coating a flaky mica substrate with a compound oxide containing titanium, cobalt and aluminum. SOLUTION: Preferably a flat-shaped mica powder having a particle size of 1-150 μm is firstly coated with titanium dioxide, then coated with a compound oxide of cobalt and aluminum and baked at 700-1,100 deg.C. Preferable blending composition is titanium oxide: 50-91.5 mol%, cobalt: 7.5-49 mol%, aluminum: 1-20 mol%, which exhibits yellowish green. When white light 18 is radiated to the mica coated with Ti-Co-Al compound oxide 10, a part of the light is reflected at the surface of the Ti-Co-Al compound oxide layer 16 as reflected light 20. The rest of the light 18 which is not reflected goes in, gives reflected light 22 at the titan dioxide layer, reflected light 24 at the mica surface and reflected interference light 26 having a specific color. Accordingly, different colors can be seen according to the angle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored mica titanium and a coated body using the same, and more particularly to improvement of the color tone.

[0002]

2. Description of the Related Art Many mica titanium pigments produce interference colors and are widely used as pearl pigments and the like.
And, in order to give a specific color tone to the mica titanium-based pigment, a colored pigment or the like may coexist,
These colored pigments generally have poor light fastness. For this reason, a part of the titanium dioxide layer of the mica titanium-based pigment is reduced to darkened low-order titanium oxide, and the interference color inherent in the mica titanium-based pigment is emphasized to obtain a colored appearance color (Japanese Patent Publication No. −
61032) has been developed. These inorganic colored pigments have the advantage of being extremely chemically stable and of being excellent in light resistance.

In recent years, pigments have been required to have not only a specific beautiful color tone but also various functions. For example, a pigment which can easily obtain a multi-color change property having a different color tone depending on a viewing angle is also used as a color copy. It is attracting attention from the viewpoint of obtaining a coated body that is difficult to duplicate by using a method.

[0004]

However, general pigments can usually be observed only in the same color tone when viewed from any direction, and the presence of an interfering substance causes the interference color to be slightly observable depending on the viewing direction. Only discoloration was obtained. The present invention has been made in view of the above-mentioned problems of the related art, and an object of the present invention is to provide a multicolor pigment having a color tone that changes depending on a viewing direction.

[0005]

In order to achieve the above object, a mica coated with a Ti—Co—Al-based composite oxide according to the present invention comprises: a flaky mica substrate; a composite oxide coated on the mica substrate; , Wherein titanium, cobalt, and aluminum are contained as metals constituting the composite oxide. In the present invention, it is preferable that the mica is coated with titanium dioxide, and the surface of the mica is coated with a composite oxide of cobalt and aluminum.

Further, in the present invention, the mixing molar ratio of the metal constituting the composite oxide is such that titanium dioxide is 50 to 9%.
Preferably, 1.5%, cobalt is 7.5-49% and aluminum is 1-20%. In the present invention, the compounding molar ratio of the metal constituting the composite oxide is as follows:
50 to 96.5% titanium dioxide, 2.5 to cobalt
It is preferred that the content is 7.5% and the content of aluminum is 1 to 47.5%. In the present invention, the compounding molar ratio of the metal constituting the composite oxide is such that titanium dioxide is 50 to 7%.
It is preferred that 2.5%, cobalt is 7.5 to 30%, and aluminum is 20 to 42.5%. Further, in the present invention, the mixing molar ratio of the metal constituting the composite oxide is 50 to 98% for titanium dioxide and 1 to 9 for cobalt.
It is preferred that 2.5% and aluminum be 1 to 49%.

In the present invention, when the hue of the appearance color of the mica coated with the Ti—Co—Al-based composite oxide is represented by the Hunter Lab value, the value of a is −31.13 to 1.13.
It is preferable that the value of 1.35 and b be in the range of -29.46 to 31.22, and the value of L be in the range of 30.82 to 88.23. Further, the coated body in the present invention is the Ti-Co-Al
A composition comprising a mica-based composite oxide-coated mica is applied to a substrate.

Further, in the present invention, the Ti-Co-Al
It is preferable that the color tone of the substrate coated with the composition containing the system composite oxide-coated mica be within a gray scale range of white to black. In the present invention, it is preferable that the color tone of the base material coated with the composition containing the composite oxide-coated mica is blue. In the present invention, it is preferable that the thickness of the composition containing mica coated with the Ti—Co—Al-based composite oxide applied on the substrate is 5 μm or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies conducted by the present inventors to achieve the object of the present invention, titanium,
By forming a composite oxide layer of cobalt and aluminum, it has been found that it is possible to obtain excellent color tone and multicoloring property, and the present invention has been completed. That is, the Ti-Co-Al-based composite oxide-coated mica in the present invention includes a flaky mica substrate and a composite oxide coated on the mica substrate, and titanium as a metal constituting the composite oxide, It is characterized by containing cobalt and aluminum.

The mica used in the present invention may be of any type, and is generally commercially available muscovite mica (muscov
It is possible to use biotite, etc. in some cases. The particle size is not particularly limited, but when used as a pearlescent pigment, among commercially available mica, those having a small particle size and as flat a particle shape as possible are preferable because beautiful colors and pearly luster are easily exhibited.
Therefore, the particle size of mica is preferably 1 μm to 150 μm, and more preferably 5 μm to 60 μm.

The mica coated with a Ti—Co—Al composite oxide according to the present invention may be a titanium mica coated with titanium dioxide, which is obtained by coating a composite oxide of cobalt and aluminum on mica titanium coated with titanium dioxide. It is suitable.

For this reason, as a method for producing the mica coated with a Ti—Co—Al based composite oxide of the present invention, it can be produced by various methods for coating cobalt and aluminum on titanium mica. FIG. 1 illustrates three methods, a solid phase method, a liquid phase method (urea method), and a sodium hydroxide neutralization decomposition method.

As shown in FIG. 1 (a), in the solid phase method, together with titanium mica, a cobalt compound such as cobalt carbonate, cobalt oxalate, cobalt hydroxide and cobalt oxide, aluminum carbonate, aluminum oxalate, and hydroxide An aluminum compound such as aluminum or aluminum oxide is mixed and fired at 700 ° C. to 1100 ° C. to obtain the Ti—Co—Al-based composite oxide-coated mica of the present invention.

In the liquid phase method (urea method), as shown in FIG. 1B, aluminum chloride or aluminum sulfate, cobalt chloride or cobalt sulfate, urea and water are mixed, and titanium mica is added thereto. After refluxing at 100 ° C. for 4 hours, drying, and firing at 700 ° C. to 1100 ° C., the mica coated with a Ti—Co—Al-based composite oxide of the present invention can be obtained.

In the sodium hydroxide neutralization decomposition method, titanium mica is dispersed in water as shown in FIG.
After the temperature was raised to about 0 ° C., aluminum chloride or aluminum sulfate and cobalt chloride or cobalt sulfate were added dropwise, and sodium hydroxide was added dropwise to adjust the pH to 9, followed by filtration, washing with water, and drying. By firing at 1100 ° C., the mica coated with a Ti—Co—Al-based composite oxide of the present invention can be obtained.

Further, in the method of FIG.
The method of the present invention is also applicable to a method in which sodium hydroxide is added dropwise to titanium mica dispersion water whose temperature has been raised back and forth to adjust the pH to 9, and aluminum chloride or aluminum sulfate and cobalt chloride or cobalt sulfate are simultaneously added dropwise. -Co-
Al-based composite oxide-coated mica can be obtained.

Here, the method of simultaneously coating aluminum and cobalt on the surface of mica titanium has been described. However, these methods may be a method in which aluminum is coated and then cobalt is coated, or a method in which cobalt is coated and then aluminum is coated. Furthermore, the materials used are cobalt carbonate, cobalt oxalate, cobalt hydroxide, cobalt oxide, cobalt chloride, cobalt sulfate and aluminum carbonate, aluminum oxalate, aluminum hydroxide, aluminum oxide,
The combination of aluminum chloride and aluminum sulfate
There is no particular limitation. When aluminum and cobalt are separately coated, the solid phase method, liquid phase method, and sodium hydroxide neutralization decomposition method described above may be combined.

As described above, the method for obtaining the Ti—Co—Al-based composite oxide-coated mica of the present invention is as follows.
Since it is obtained by firing at 0 ° C., it is not limited to the method shown here, but can be obtained by various methods capable of coating aluminum and cobalt on the surface of mica titanium.

When aluminum and cobalt are separately coated, immediately after the coating, aluminum and cobalt form separate layers. However, by firing, aluminum and cobalt become one composite oxide layer. Becomes

FIG. 2 is a schematic view of the Ti-Co-Al-based composite oxide-coated mica of the present invention. As shown in the figure, the mica 10 coated with a Ti—Co—Al-based composite oxide of the present invention has a mica 12 at the center, a titanium dioxide layer 14 formed on the outer periphery, and a Co—Al Based composite oxide layer 1
6 are formed. The T of the present invention having such a form
i-Co-Al-based composite oxide-coated mica is titanium dioxide,
It was found that various appearance colors were exhibited depending on the mixing ratio of aluminum and cobalt.

The mixing molar ratio of the metal constituting the composite oxide coated on the mica surface of the Ti—Co—Al type composite oxide-coated mica is 50 to 91.5% for titanium dioxide and 7.5 to 5% for cobalt. When the content of aluminum is 49% and the content of aluminum is 1% to 20%, the appearance color of the obtained mica coated with a Ti—Co—Al-based composite oxide is as follows:
0.00 to 5.00, b is 0 to 30.00, L is 40.
It was yellow-green with a value of 00 to 70.00.

The mixing ratio of the metal constituting the composite oxide coated on the mica surface of the mica surface of the Ti-Co-Al-based composite oxide is 50 to 96.5% for titanium dioxide and 2.5 for cobalt. ~ 7.5%, aluminum is 1-47.5
%, The appearance color of the obtained Ti-Co-Al-based composite oxide-coated mica is a in terms of a-in terms of the Hunter's Lab.
20.00 to 5.00, b is -30.00 to -8.0
It exhibited a blue color in which 0 and L were 50.00 to 80.00. Further, the mixing molar ratio of the metal constituting the composite oxide coated on the mica surface of the mica surface of the Ti-Co-Al-based composite oxide is 50 to 72.5% for titanium dioxide and 7.5 to 30% for cobalt. 20 to 42.5 aluminum
%, And when the content of titanium dioxide is 50 to 98%, the content of cobalt is 1 to 2.5%, and the content of aluminum is 1 to 49%, the appearance color of the obtained mica coated with a Ti-Co-Al-based composite oxide is obtained. Is -20 in terms of Hunter's Lab.
00 to 5.00, b is -8.00 to 0, L is 40.00
Green to turquoise, such as ~ 85.00.
Table 1 below summarizes the above results.

[0023]

[Table 1]

FIG. 3 is a diagrammatic representation of Table 1. It has been found that by changing the mixing ratio of TiO ₂ -Al-Co in this manner, it is possible to obtain an appearance color having a wide range of yellow to blue colors. Even if the appearance color of the same system is changed, the appearance color is slightly changed by changing the mixing ratio of TiO ₂ -Al-Co.
The mica surface coated with TiO ₂ -Al-Co coated with TiO ₂ -Al-Co exhibits a unique property that its color changes depending on the viewing angle.
Referring again to FIG. 2, the Ti—Co—Al of the present invention
The multi-color change property of the system composite oxide-coated mica will be described.

As described above, the mica 10 coated with a Ti—Co—Al-based composite oxide of the present invention has a mica 12 at the center, a titanium dioxide layer 14 formed on the outer periphery, and a Co—Al A system composite oxide layer 16 is formed.
When the Ti—Co—Al-based composite oxide-coated mica 10 is irradiated with white light 18, a part of the white light 18 is reflected on the surface of the Co—Al-based composite oxide layer 16 to become reflected light 20.
The reflected light 20 has a color tone of the appearance color inherent in the mica 10 coated with the Ti—Co—Al-based composite oxide.

The white light 18 not reflected on the surface of the Co—Al-based composite oxide layer 16 proceeds inside the mica 10 coated with the Ti—Co—Al-based composite oxide, and
4 and the mica 12 surface generate a reflected light due to a large change in the refractive index. The reflected light 22 on the titanium dioxide layer 14 and the reflected light 24 on the surface of the mica 12 produce reflected interference light 26 of a specific color due to an optical path difference caused by the thickness of the titanium dioxide layer 14.

Therefore, from the angle at which the reflected interference light 26 is not observed, the reflected light 20 is observed in the color tone inherent to the mica 10 coated with the Ti—Co—Al-based composite oxide, and the reflected interference light 26 is observed. From the angle, the color in a state where the reflected interference light 26 and the normal reflected light 20 are mixed can be recognized.

The characteristic feature of the present invention is that C
The o-Al-based composite oxide layer 16 has extremely high transparency,
The present invention has almost no effect on the reflected interference light 26 and the color tone of the reflected interference light 26 can be manipulated by adjusting the layer thickness of the titanium dioxide layer 14 covering the surface of the mica 12. The Ti-Co-Al-based composite oxide-coated mica 10 according to the present invention is capable of obtaining multicoloring properties of various colors by combining the appearance color and the color of the reflected interference light 26.

Further, even if the mica coated with a Ti-Co-Al-based composite oxide is not in the above-mentioned range of the mixing ratio of TiO ₂ -Al-Co, it is inferior in polychromic property, but has a beautiful luster. Since it has a color tone, it can be sufficiently used as a pigment.

The reason why the mica coated with the Ti-Co-Al-based composite oxide of the present invention uses titanium dioxide and cobalt aluminate as materials for coating the mica surface will be described.
The reason why titanium dioxide is used for the Ti-Co-Al-based composite oxide-coated mica of the present invention is that the interference interference color can be generated by coating the mica with titanium dioxide as described above. The reason for using cobalt aluminate is that by coating cobalt dioxide on titanium dioxide, the outermost layer of cobalt aluminate is stable against concentrated acids and alkalis and has excellent heat resistance. Since it is a highly transparent and highly saturated blue pigment, it can exhibit high multicoloring properties by being combined with the interference color of titanium dioxide-coated mica.

There is no limitation that the titanium dioxide layer 14 and the Co—Al-based composite oxide layer 16 must be continuous, but if a layer having a lower refractive index than the titanium dioxide layer is provided between them, Since the thickness of the optically controlled titanium oxide changes, the color tone of the reflection interference color may change, or the saturation of the reflection interference color may be significantly reduced. It is better not to provide a layer.

It is preferable that mica, titanium dioxide, and cobalt aluminate are applied from the inside in the order of coating on mica. For example, when coating in the order of mica, cobalt aluminate, and titanium dioxide, the reflection interference color is not generated well, which has a significant adverse effect on the multicoloring property. In addition, since the Ti-Co-Al-based composite oxide-coated mica is coated with an inorganic compound to form a powder, the mica has a feature of being extremely excellent in light resistance, stability over time, and chemical stability. are doing.

When the mica coated with a Ti-Co-Al-based composite oxide of the present invention is used as a pigment, the mica coated with the Ti-Co-Al-based composite oxide of the present invention may be used by blending it in an appropriate amount in a coating composition. Can be. T to paint composition
The blending amount of the i-Co-Al-based composite oxide-coated mica is not particularly limited because it depends on the object to which the composition is to be used. T
If the amount of the i-Co-Al-based composite oxide-coated mica is small, the hiding power is reduced, and if the amount is too large, the dispersion of the Ti-Co-Al-based composite oxide-coated mica is uneven in the composition. Or the appearance of the composition-coated body may be mottled, or the viscosity of the composition may be increased to adversely affect workability, printability, and the like.

The coating composition is not particularly limited.
Examples thereof include those in which a binder resin, a solvent, and the like are blended. The binder resin is a resin capable of stably adhering the Ti-Co-Al-based composite oxide-coated mica onto the substrate, and after the coating composition is applied on the substrate, the solvent in the composition volatilizes. A film is formed on the substrate in a state where the mica coated with the Ti-Co-Al-based composite oxide is embedded. The binder resin is not particularly limited because it is selected according to the compatibility with the base material, the strength of the formed coating film, the film thickness, and the like, but those usually used as binders for paints and printing inks can be used. For example, Gilsonite, maleic acid resin, cyclized rubber, cured rosin, petroleum resin, nitrocellulose, acrylic resin, polyurethane resin, chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride , Polyester resin, alkyd resin, linseed oil, modified phenol resin, fumaric acid resin, epoxy ester resin, epoxy amino resin, epoxy phenol resin, polyester resin, vinyl resin, polyamide resin, mineral oil varnish, ketone resin, chloride rubber, ethyl cellulose, Urea resins, melamine resins and the like can be mentioned.

As the solvent to be mixed with the mica coated with the Ti—Co—Al-based composite oxide according to the present invention, a solvent generally used for paints and inks can be used. It is not particularly limited as long as it dissolves to improve the workability and the glittering colored pigment can be dispersed and blended well in this resin solution. For example,
Toluene, xylene, n-hexane, cyclohexane,
Methyl acetate, ethyl acetate, isopropyl acetate, n-acetic acid
Propyl, n-butyl acetate, isobutyl acetate, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, ethylene glycol monomethyl acetate, ethylene Glycol monoethyl ether, ethylene glycol monoethyl ether acetate and the like. As the solvent, a volatile organic solvent is often used. In some cases, water or the like may be blended.

When a coating composition containing the Ti-Co-Al-based composite oxide-coated mica of the present invention is used, the properties of the composition are adjusted as long as the effects of the present invention are not impaired. In addition to the components, various additives blended in ordinary paints and inks may be blended. For example, plasticizers, waxes, wetting agents, stabilizers, dyes and pigments, antistatic agents, defoamers,
Examples include an antioxidant, a leveling agent, a polymerization inhibitor, and a filler.

The base material coated with the coating composition containing the above-described Ti-Co-Al-based composite oxide-coated mica of the present invention includes paper, paperboard, cloth, leather, metal, plastic, and the like. The shape is not particularly limited, and various shapes can be applied. Of course, a substrate that has been previously painted, printed, or coated may be used.

In the present invention, in order to obtain a high color brilliant feeling and an excellent color tone, Ti-Co-Al in the coating composition is required.
The weight ratio between the mica and the binder resin is 1:
It is preferable that the ratio is 20 to 3.5: 10. When such a coating composition is applied on a substrate, the solvent in the composition is volatilized by drying, and a binder resin film is formed on the substrate. The mica coated with the Ti-Co-Al-based composite oxide is coated with this coating composition. Held therein to form a coating. Therefore, in the coating film on the base material, the weight ratio between the Ti-Co-Al-based composite oxide-coated mica and the binder resin is in the range of 1:20 to 3.5: 10. A coating film having such a composition ratio gives a colored appearance color and high glitter to the substrate, and develops a good color tone.

The substrate to which the coating composition containing the Ti-Co-Al-based composite oxide-coated mica of the present invention is to be applied has an achromatic color in the range of white to black gray scale, Alternatively, those having a yellowish-green to blue-blue color are suitable for sufficiently exhibiting the multicolor-changing property of the Ti-Co-Al-based composite oxide-coated mica of the present invention. The Ti-Co-A of the present invention
It is preferable to apply a coating composition containing the l-based composite oxide-coated mica at a coating thickness of 5 μm or more in order to sufficiently exhibit the multicolor-changing properties of the Ti-Co-Al-based composite oxide-coated mica of the present invention. .

The coating method in the present invention is a method in which a composition containing the Ti-Co-Al-based composite oxide-coated mica of the present invention is applied to part or all of the surface of a substrate. This is a concept that also includes a typical printing method. As the coating method of the present invention, conventional coating methods, printing methods, and coating techniques can be used. For example, the printing methods include convex plate printing, concave plate printing, gravure printing, screen printing, and flexographic printing. , Offset printing, ink jet printing, electrostatic printing and the like can be used. Further, coating methods such as brush coating, spray coating, rolling coating, stencil coating, electrostatic coating, flow coating, dip coating, roller coating, and spray coating can also be used.

[0041]

【Example】Example 1  Based on FIG. 1 (c), according to one embodiment of the present invention, Ti-
Co-Al based composite oxide-coated mica was produced. Sand
That is, based on 100.00 parts by weight of titanium dioxide-coated mica,
One liter of water was added and dispersed by stirring. In addition to this,
Lut (CoCl₂・ 6H₂O) 11.89 parts by weight, containing water
Aluminum sulfate (Al₂(SO₄)₃・ 14H₂O)
Dissolve 72.27 parts by weight in water to make an aqueous solution and add dropwise,
The temperature was raised to 80 ° C. while stirring. 2 mol / l
Sodium hydroxide aqueous solution (NaOH)
The pH of the solution was adjusted to 9. Formed Ti-Co-Al complex
Filter and wash the mixed oxide-coated mica at 150 ° C for 12 hours.
After drying, it was baked at a temperature of 900 ° C. for 1 hour. What
Incidentally, the obtained Ti-Co-Al-based composite oxide-coated mica is
The molar ratio of the composite oxide is 67.6% titanium dioxide,
4.7% baltic, 27.7% aluminum and light blue
It had an appearance color and produced a yellow interference color.

[0042]Example 2  Based on FIG. 1 (c), according to one embodiment of the present invention, Ti-
Co-Al based composite oxide-coated mica was produced. Example 1
Is the content of titanium dioxide (titanium dioxide coating mica
Layer thickness) of titanium dioxide coated mica 100.00
1 liter of water was added to the parts by weight, and the mixture was stirred and dispersed. this
Hydrated cobalt chloride (CoCl₂・ 6H₂O) 12.
10 parts by weight, hydrous aluminum sulfate (Al₂(SO₄)
₃・ 14H₂O) 73.53 parts by weight of water dissolved in water
The mixture was added dropwise, and the temperature was raised to 80 ° C. while stirring. Sa
And a 2 mol / l sodium hydroxide aqueous solution (NaO
H) was added dropwise to adjust the pH of the solution to 9. Generated
The Ti-Co-Al-based composite oxide-coated mica is filtered, washed with water,
After drying at 150 ° C. for 12 hours, at 900 ° C. for 1 hour
Fired for hours. The obtained Ti-Co-Al-based composite acid
The oxide-coated mica has a different layer thickness of titanium dioxide from that of Example 1.
However, the compounding molar ratio of the composite oxide is the same as in Example 1.
67.6% titanium dioxide, 4.7% cobalt, aluminum
27.7% of Nium has light blue appearance color and red interference color
Was to occur.

[0043]Example 3  Based on FIG. 1 (c), according to one embodiment of the present invention, Ti-
Co-Al based composite oxide-coated mica was produced. Example
1 and 2 are the content of titanium dioxide (diacid coating mica)
Titanium dioxide-coated mica 10 having different thicknesses of titanium oxide)
1 liter of water is added to 0.00 parts by weight, and the mixture is stirred and dispersed.
Was. To this, hydrated cobalt chloride (CoCl₂・ 6H
₂O) 14.18 parts by weight, hydrous aluminum sulfate (Al
₂(SO₄)₃・ 14H₂O) 86.22 parts by weight in water
Dissolve into an aqueous solution and add dropwise, stirring up to 80 ° C
The temperature rose. 2 mol / l sodium hydroxide solution
The solution (NaOH) was added dropwise to adjust the pH of the solution to 9.
Was. The generated Ti-Co-Al-based composite oxide-coated mica is filtered.
After washing with water and drying at 150 ° C. for 12 hours, 900
Calcination was performed at a temperature of ° C. for 1 hour. The obtained Ti-Co-
The mica coated with an Al-based composite oxide was different from Examples 1 and 2 in that
Despite the different layer thickness of titanium, the compounding molar ratio of the composite oxide
Is 67.6% of titanium dioxide as in Examples 1 and 2,
4.7% aluminum and 27.7% aluminum with light blue appearance
And a green interference color was generated.

[0044]Example 4  Based on FIG. 1 (c), according to one embodiment of the present invention, Ti-
Co-Al based composite oxide-coated mica was produced. Example 1
Same content of titanium dioxide as titanium dioxide
100.00 weight by weight of titanium dioxide coated mica
1 liter of water was added to the mixture, and the mixture was stirred and dispersed. This includes
Cobalt chloride (CoCl₂・ 6H₂O) 8.91 weight
Part, hydrous aluminum sulfate (Al₂(SO₄)₃・ 14
H₂O) Dissolve 54.21 parts by weight in water to make an aqueous solution
The mixture was dropped and heated to 80 ° C. while stirring. 2m more
ol / l sodium hydroxide aqueous solution (NaOH)
The pH of the solution was adjusted to 9. Ti-Co- generated
The mica coated with the Al-based composite oxide is filtered, washed with water, and heated at 150 ° C.
After drying for 12 hours, bake at 900 ° C for 1 hour
Was. Note that the obtained Ti-Co-Al-based composite oxide-coated cloud was
In the mother, the compounding molar ratio of the composite oxide was 73.5 titanium dioxide.
%, Cobalt 3.9%, aluminum 22.6%, light blue
It has an appearance color of yellow and produces a yellow interference color.
Was.

[0045]Example 5  Based on FIG. 1 (c), according to one embodiment of the present invention, Ti-
Co-Al based composite oxide-coated mica was produced. Example 1
Same content of titanium dioxide as titanium dioxide
100.00 weight by weight of titanium dioxide coated mica
1 liter of water was added to the mixture, and the mixture was stirred and dispersed. This includes
Cobalt chloride (CoCl₂・ 6H₂O) 5.95 weight
Part, aqueous aluminum sulfate aqueous solution (Al₂(SO₄)₃
・ 14H₂O) 36.14 parts by weight of water dissolved in water
And the temperature was raised to 80 ° C. while stirring. Further
2mol / l sodium hydroxide aqueous solution (NaOH)
Was added dropwise to adjust the pH of the solution to 9. Generated Ti
-The mica coated with Co-Al-based composite oxide is filtered, washed with water,
After drying at 0 ° C for 12 hours, at 900 ° C for 1 hour
Fired. In addition, the obtained Ti-Co-Al-based composite oxide
In the coated mica, the compounding molar ratio of the composite oxide was 8%.
0.7%, cobalt 2.8%, aluminum 16.5%
Has a light blue appearance color and produces yellow interference color
there were.

[0046]Example 6  Based on FIG. 1 (a), according to one embodiment of the present invention, Ti-
Co-Al based composite oxide-coated mica was produced. Example 1
The same content of titanium dioxide as that of titanium coating mica
Layer thickness) of 100.00 parts by weight of titanium dioxide-coated mica;
8.16 parts by weight of cobalt oxide (CoO), aluminum oxide
Um (Al₂O₃) 24.19 parts by weight and 900
Calcination was performed at a temperature of ° C. for 1 hour. The obtained Ti-Co-
Al-based composite oxide-coated mica has a compounding molar ratio of composite oxide
Is 55.6% titanium dioxide, 12.2% cobalt,
Minium 32.2% has a blue-green appearance color and yellow dried
It caused color interference.

[0047]Example 7  Based on FIG. 1 (b), according to one embodiment of the present invention, Ti-
Co-Al based composite oxide-coated mica was produced. 1 liter of water,
Hydrous cobalt chloride (CoCl₂・ 6H₂O) 25.91
Parts by weight, aqueous aluminum sulfate aqueous solution (Al₂(S
O₄)₃・ 14H₂O) 27.37 parts by weight, urea
Dissolve 8 parts by weight to make an aqueous solution, where it is the same as in Example 1.
Titanium dioxide content (layer thickness of titanium covering mica)
100.00 parts by weight of titanium dioxide coated mica of
The temperature was raised to 100 ° C. and refluxed for 4 hours. The resulting generation
The product was filtered, washed with water, and dried at 150 ° C. for 12 hours.
It was baked at a temperature of 900 ° C. for 1 hour. The obtained Ti
-Co-Al based composite oxide coated mica is compounded with composite oxide
Molar ratio: titanium dioxide 60.0%, cobalt 27.5
%, Aluminum 12.5% with yellow-green appearance color,
It produced a yellow interference color.

[0048]Example 8  Based on FIG. 1 (c), according to one embodiment of the present invention, Ti-
Co-Al based composite oxide-coated mica was produced. Sand
That is, based on 100.00 parts by weight of titanium dioxide-coated mica,
Add 1 liter of water and heat to 80 ° C while stirring and dispersing.
Was. To this, hydrated cobalt chloride (CoCl ₂・ 6H
₂O) 11.89 parts by weight, hydrous aluminum sulfate (Al
₂(SO₄)₃・ 14H₂O) 72.27 parts by weight in water
Dissolve and turn into an aqueous solution and add dropwise, while 2 mol / l water
Aqueous solution of sodium oxide (NaOH) should be dropped simultaneously
And adjust the pH of the solution to 9 with water.
Until the mixed aqueous solution containing aluminum sulfate
It was dropped. Cloud formed Ti-Co-Al-based composite oxide formed
The mother was filtered, washed with water and dried at 150 ° C. for 12 hours.
It was baked at a temperature of 900 ° C. for 1 hour. The obtained Ti
-Co-Al based composite oxide coated mica is compounded with composite oxide
Molar ratio: titanium dioxide 67.6%, cobalt 4.7
%, Aluminum is 27.7% and has a light blue appearance color,
It produced a yellow interference color.

Subsequently, the Ti-Co-Al-based composite oxidation of the present invention
The characteristics of the object-coated mica were examined.Experiment 1  The Ti-Co-Al-based composite oxide-coated mica according to the present invention
The blended paint composition is applied to the painted body painted on the substrate.
The Ti-Co-Al-based composite oxide-coated mica of the present invention
To achieve a sufficient effect, the base color,
I found it to resonate. This is a Ti-Co-Al based composite
Due to the high transparency of oxide-coated mica, Ti-Co-Al-based
The appearance color and interference color of the composite oxide-coated mica are base materials
Loses the underlying color of the Ti-Co-Al-based composite
The color tone and multi-color change of oxide-coated mica are impaired.
In order to live.

Accordingly, the present inventors have studied the relationship between the base color of the color tone of the base material and the degree of discoloration. First, 4.5 parts by weight of nitrocellulose as a binder resin and 10 to 20% of butyl acetate, 5 to 10% of xylene, 5 to 10% of ethyl acetate, 5 to 10% of methyl ethyl ketone, and 10 to 40% of toluene Use 5 parts by weight,
This binder resin and a solvent were mixed, and Example 1 was added thereto.
Ti-Co-Al with light blue appearance color and yellow interference color
4 parts by weight of the base composite oxide-coated mica were mixed and dispersed to prepare a coating composition. This is called sample 1.

Further, the same binder resin and solvent as in Sample 1 were used in the same amounts, and the appearance of Example 2 was changed to Ti-Co-A having a light blue appearance and a red interference color in this binder resin and solvent.
4 parts by weight of the l-based composite oxide-coated mica were mixed and dispersed to prepare a coating composition. This is called Sample 2.

The samples 1 and 2 were screen-printed on colored paper of each color with a thickness of about 110 μm, and the color was measured by a gonio-colorimeter to measure the degree of discoloration. FIG. 4 shows the Ti of the present invention.
FIG. 2 is an explanatory diagram of a method for measuring the degree of discoloration of a mica coated with a -Co-Al-based composite oxide. As shown in FIG.
On the basis of the vertical axis 32 with respect to the test object 30 on which the coating composition containing the mica coated with the o-Al-based composite oxide was printed,
The white light 36 is irradiated from the 45 degree direction by the white light source 34, and the light receivers 38 and 40 arranged at -25 degrees and 35 degrees are provided.
Colorimetrically measures the light received by
The determination was made by conversion with the ab value.

The measurement at -25 degrees and 35 degrees is -25 degrees.
In the degree, the interference color of the Ti-Co-Al-based composite oxide-coated mica was hardly affected, and only the appearance color could be observed.
The interference color of the mica coated with -Co-Al-based composite oxide has a strong effect, and a mixed color of the appearance color and the interference color can be observed.
This is because it can be determined that the greater the difference in the color observed at a point, the greater the degree of discoloration.

Some of the results of this measurement are shown in Table 2 for Sample 1 and Table 3 for Sample 2. The ab diagram in Table 2 is shown in FIG. 5A, and the ab diagram in Table 3 is shown in FIG.
(B) shows each.

[0055]

[Table 2]

[0056]

[Table 3]

Table 2, FIG. 5 (a) and Table 3, FIG. 5 (b)
As shown in FIG. 7, it can be seen that even the Ti-Co-Al-based composite oxide-coated mica showing the same color tone shows a different color tone depending on the base color which is the base color. And Ti-C of the present invention
It can be seen that the multi-color change characteristic of the mica coated with the o-Al-based composite oxide is also affected.

However, as can be seen from FIGS. 5 (a) and 5 (b), in the case of the base material having the undercolor in the gray scale range of achromatic white to black, the light received at −25 ° and 35 ° was measured. It was found that there was a large difference in the color values and the discoloration was high. In addition, even in the case of a base material of a light blue base color, which is the same color as the object color of the powder, there was a large difference between the colorimetric values received at -25 degrees and 35 degrees, indicating high discoloration. In addition, when a base material having a light blue undercolor, which is the same color as the object color of the powder, is used, the undercolor affects the appearance color of the mica coated with the Ti-Co-Al-based composite oxide, thereby producing a synergistic effect. It was found that the appearance color to be obtained became vivid.

Accordingly, the color tone of the substrate to which the coating composition containing the Ti—Co—Al based composite oxide-coated mica of the present invention is applied is in the range of achromatic white to black gray scale, and The effect of the Ti-Co-Al-based composite oxide-coated mica of the present invention is irrelevant if it is a yellowish-green to blue-blue color system that is the same color system as the appearance color of the Ti-Co-Al-based composite oxide-coated mica Demonstrated and preferred.

On the other hand, when a base color having a base color other than the above-mentioned base color is used, the base color of the base material of the present invention is Ti-Co-
It overcomes the appearance color and interference color of the mica coated with an Al-based composite oxide, and destroys its discoloration. As examples of other colors, lemon color is shown in Table 2, FIG. 5 (a), and Table 3, FIG. 5 (b). 5 (a) and 5 (b), the difference between the colorimetric values received at -25 degrees and 35 degrees is small, and the mica coated with a Ti-Co-Al-based composite oxide of the present invention is a feature. The discoloration of the film.

[0061]Experiment 2  Further, the present inventors have proposed the Ti-Co-Al-based composite oxidation of the present invention.
Between Coating Thickness and Degree of Discoloration of Paint Compositions Containing Oxide-coated Mica
We examined the staff. Sample 1 from Experiment 1 was grayed out.
-Change the film thickness to a substrate with a base color within the scale range.
And then apply it with a doctor blade.
As shown, white light was irradiated from -45 degrees,
The colorimetric value received at 5 degrees is converted to the hunter's Lab value.
And calculate the distance between the two points of -25 degrees and 35 degrees in the ab diagram.
The thickness of the film is determined by calculating the degree of discoloration
Color of powder and powder is not affected by background color
It was confirmed that.

FIG. 6 shows the relationship between the degree of discoloration and the film thickness. As shown in FIG. 6, in the range where the film thickness does not become extremely thick, it can be seen that the degree of discoloration increases continuously as the film thickness increases. As a result of the experiment, when the coating film was thinner than 30 μm, a good degree of discoloration was exhibited on a substrate having a color ranging from white to L: 31.83a: −0.01b: 1.86. When the film had a thickness of 30 μm or more, a high degree of discoloration was obtained in the entire range from white to black without being affected by the underlying color.

Therefore, the coating thickness of the coating composition containing the Ti—Co—Al-based composite oxide-coated mica of the present invention is preferably 5 μm or more, more preferably 20 μm or more within a common sense. Yes, if it is 30 μm or more, it is possible to obtain a degree of discoloration that is not affected by the color of the base material, which is preferable.

From the results of Experiments 1 and 2, the color tone of the substrate to which the coating composition containing the Ti—Co—Al-based composite oxide-coated mica of the present invention is to be applied is achromatic white to black. If the color is not within the gray scale range and is not a yellowish green to indigo blue color, the substrate color is previously colored to a similar color by paint, paint, or other coloring means, or the Ti- It is preferable to apply a coating composition containing a mica coated with a Co—Al-based composite oxide at a coating thickness of 30 μm or more.

[0065]Experiment 3  Subsequently, Sample 1, which is a coating composition using Example 1, was used.
Substrate with white and gray base color so that film thickness is 30 μm
Was applied. Below the coating film of the coating composition of Sample 1 was formed
The base material having a white ground color was coated with the coating composition of the coating composition of Sample 3 and Sample 1.
The base material having a gray background color is referred to as Sample 4.
I do. Samples 3 and 4 were used for the measurement method shown in FIG.
Similarly, irradiate white light from the −45 degree direction to −25 degree.
And the wavelength distribution of the reflected light at 35 degrees were measured. Also ratio
For comparison, the titanium mica used in Example 1 was
Same binder as sample 1 without coating with cobaltate
Mixed with the base resin and the solvent, and
Comparative Sample 1 was applied to a white base material. At -25 degrees
FIG. 7A shows the wavelength distribution of reflected light at 35 degrees.
FIG. 7B shows the wavelength distribution of reflected light.

Since almost no interference light is detected, Ti-C
The appearance color of mica coated with o-Al complex oxide is observed-
In the wavelength distribution at 25 degrees, as shown in FIG. 7A, the reflectance of the samples 3 and 4 is mainly high on the short wavelength side and low on the long wavelength side. Then, it can be seen that the difference between the reflectance on the short wavelength side and the reflectance on the long wavelength side is very large. On the other hand, Comparative Sample 1, which is a coating film of titanium mica, tends to have a high wavelength on the short wavelength side and a low wavelength on the long wavelength side, but the difference between the reflectance on the long wavelength side and the reflectance on the short wavelength side is as follows. It can be seen that it is not so large and is observed whitish as a whole.

Further, since the interference light is strongly detected, Ti
As shown in FIG. 7 (b), the wavelength distribution at 35 degrees at which the mixed color of the appearance color and the interference color of the mica coated with -Co-Al-based composite oxide was observed was mainly at the short wavelength side for both samples 3 and 4. Has a low reflectance, and the reflectance on the long wavelength side changes high. Also, it can be seen that the difference between the reflectance on the short wavelength side and the reflectance on the long wavelength side is also very large. On the other hand, Comparative Sample 1, which is a coating film of titanium mica, also has a low wavelength on the short wavelength side and a high wavelength on the long wavelength side.

Examination of the discoloration from FIGS. 7 (a) and 7 (b) shows that both samples 3 and 4 change from a blue color to a yellow to orange color. Is very large. On the other hand, although the comparative sample 1 has changed from a whitish color to a yellow to orange color, the color change from white to yellow to orange when visually observed is poor in discoloration degree and is difficult to observe. there were.

[0069]Experiment 4  Sample 1 which is a coating composition using Example 1 was coated to a film thickness of 3
The substrate was applied to a white base material so that the base color was 0 μm. sample
A base material having a white base under which a coating film of the coating composition of 1 is formed
It is referred to as sample 5. The same binder as in sample 1
Resin and solvent have the same appearance color and interference color as Example 1
Is TiO₂Examples 4 and 4 in which the mixing ratios of Co, Co and Al are different, and
And 5 are mixed to form a base material with the same film thickness as sample 5 and a base color of white.
Applied. A substrate on which a coating film including Example 4 was formed was used as a sample.
6. The substrate on which the coating film including Example 5 was formed was referred to as Sample 7.
I will do it. The samples 5 to 7 were measured as shown in FIG.
Irradiating white light from -45 degree direction,
The reflected light is received at intervals of 5 degrees from 25 degrees to 65 degrees.
Investigate the degree of discoloration by converting the colorimetric values to the hunter's Lab
Was. The results are shown in Table 4 below.

[0070]

[Table 4]

As is clear from Table 4, samples 5 to 7
Since the Lab value changes as the angle is increased from -25 degrees, it can be understood that the color changes each time the angle changes. In particular, when the degree of discoloration is considered as a difference from the value at −25 degrees, it shows that the degree of discoloration is the largest around 45 degrees, and when the angle is further increased, the color returns to the original color again. . Considering the largest difference from -25 degrees, it can be understood how the Ti-Co-Al-based composite oxide-coated mica of the present invention has great discoloration.

[0072]Experiment 5  Sample 1 which is a coating composition using Example 1 was coated to a film thickness of 3
Base material with white base color and gray base material so as to have a thickness of 0 μm
Applied. Base on which the coating film of the coating composition of Sample 1 was formed
The base material having a white color has the shape of the coating film of the coating composition of Sample 8 and Sample 1.
The base material having a gray background color is referred to as Sample 9.
You. Example 1 was prepared using the same binder resin and solvent as in Sample 1.
Has the same appearance color but a different interference color,₂, C
o, mixing Examples 2 and 3 with the same Al compounding ratio,
Substrates having the same film thickness as Samples 8 and 9 with a white base color and a gray base
The material was applied. Base color on which a coating film including Example 2 was formed
A white base material is formed into a coating film including Sample 10 and Example 2.
A base material having a gray base color was coated on Sample 11 including Example 3.
The base material with the white underlayer on which the film was formed was used as the sample 12, Example 3
The base material on which the coating film containing
It will be referred to as 3.

The discoloration degree of each of Samples 8 to 13 was determined according to Experiment 4 described above.
Similarly, in the measurement method shown in FIG. 4, white light is irradiated from the -45 degree direction, reflected light is received at intervals of 5 degrees from -25 degrees to 65 degrees, and the colorimetric values are converted into Hunter Lab values. I checked.

Samples 8, 10, and 1 having a white base color
2 is shown in Table 5 below, and FIG. 8A shows the result of converting Table 5 into an ab diagram. Table 6 below shows the results of Samples 9, 11, and 13 in which the base color is a gray base material, and FIG. 8B shows the result of converting Table 6 into an ab diagram.

[0075]

[Table 5]

[0076]

[Table 6]

From the above results, it can be seen that different discoloration properties are exhibited when the titanium dioxide layer thickness is different even if they have the same appearance color. Then, it can be understood that the discoloration is large.

[0078]Experiment 6  Normally, the paint applied to the substrate changes color depending on the viewing angle
When observing the light source, change the light source position and the observation position.
Often observed by rotating the substrate surface
No. This means that when a person holds a substrate and observes it,
In most cases, other light sources are fixed.
And holding the hand rather than changing the observation angle by moving the head
This is because it is easier to rotate the material. In this state
It is assumed that the light source position and the observation position hardly move.
The incident angle of the irradiation light and the reflected light from the substrate.
It is assumed that the sum of the light receiving angles to be observed is kept constant.
Let In this way, the sum of the incident angle and the light receiving angle was kept constant
It was examined whether the degree of discoloration was sufficiently exhibited in the state.

FIG. 9 is an explanatory diagram showing an outline of the measuring method in Experiment 6. As shown in FIG. 9, the sum of the angles formed by the optical axis 46 of the white light source 42 and the light receiving direction axis 48 of the light receiver 44 is 4
It is fixed at 5 degrees, the substrate 50 is inclined from -25 degrees to 65 degrees with respect to the vertical axis of the ground, and the colorimetric value of the reflected light received by the light receiver 44 is converted into the hunter's Lab value. The degree of discoloration was measured. Samples 8 to 13 used in Experiment 5 were used as measurement targets.

Samples 8, 10, and 1 having a white base color
2 is shown in Table 7 below, and FIG. 10 (a) shows the result of converting Table 7 into an ab diagram. The results of Samples 9, 11, and 13 in which the base color is a gray base material are shown in Table 8 below and Table 8 is ab.
FIG. 10B shows the result of the conversion.

[0081]

[Table 7]

[0082]

[Table 8]

From the above results, the present invention can be applied to the case of observing the base color while the sum of the incident angle of the irradiation light and the light receiving angle for observing the reflected light from the substrate is kept constant. It was confirmed that the Ti-Co-Al-based composite oxide-coated mica has a large discoloration property.

[0084]Experiment 7  Ti-Co-Al-based composite of the present invention obtained in Example 1
Multi-color change property of oxide-coated mica Ti-Co-A
Is it possible to obtain it unless it is coated with l-based composite oxide?
Was compared.

For comparison, titanium mica (Comparative Example 1), cobalt-coated mica (Comparative Example 2), aluminum-coated mica (Comparative Example 3), cobalt-coated mica titanium (Comparative Example 4), and aluminum-coated mica titanium (Comparative Example 1) Example 5) and only a Ti-Co-Al-based composite oxide (Comparative Example 6) were used. The amounts of the respective metals of titanium dioxide, cobalt and aluminum coated on the mica surface contained in these comparative examples were adjusted to be the same as the amounts of the respective metals contained in Example 1.

The color tone was compared by setting each test object to a composition shown in Table 9 below, and setting the composition to a film thickness of 30 μm.
After coating with a doctor blade on black paper, and drying the resulting colored paper, as shown in FIG. 4, irradiate light from -45 degrees,
Observation was performed visually at -25 degrees and 35 degrees. When the color change was good when observed with the naked eye, the result was evaluated as ○, when the color changed but it was difficult to understand, and Δ when the color did not change.

[0087]

[Table 9]

Table 10 shows the results.

[0089]

[Table 10]

As is clear from Table 10, Ti-Co-A
The l-based composite oxide-coated mica has a color different from that of the composite oxide-coated mica alone or of the composite oxide-coated mica, which is an intermediate. Alternatively, the composite oxide-coated mica containing two types hardly exhibits multicolor change in color tone, while Ti-Co-
In the mica coated with the Al-based composite oxide, a multicolor change in color tone was clearly observed. Accordingly, the mica coated with a Ti—Co—Al-based composite oxide of the present invention can provide a color tone and multi-color change property that can be specifically obtained by coating a composite oxide of three metals of Ti, Co, and Al on the mica. It is understood to have

Hereinafter, the formulation examples of the present invention will be further described.
The present invention is not limited by these. What
Unless otherwise specified, the amount is expressed in% by weight.Formulation Example 1 Gravure ink  Ti-Co-Al composite oxide-coated mica 30.0% Ethylene-vinyl acetate copolymer resin 7.5 Chlorinated polypropylene 5.5 Toluene 28.0 Ethyl acetate 8.5 Methyl ethyl ketone 17.0 Isopropyl alcohol 2.5 Polyethylene Wax 0.8 Antistatic agent 0.2

[0092]Formulation Example 2 Gravure ink  Ti-Co-Al-based composite oxide-coated mica 15.0% Polyamide resin 15.0 Rosin ester 4.0 Nitrocellulose 3.0 Isopropyl alcohol 46.0 Ethyl acetate 5.0 Toluene 10.0 Polyethylene wax 2.0

[0093]Formulation Example 3 Gravure ink  Ti-Co-Al-based composite oxide-coated mica 20.0% cured rosin 15.0 Petroleum-based resin 10.0 Toluene 55.0

[0094]Formulation Example 4 Gravure ink  Ti-Co-Al-based composite oxide-coated mica 30.0% Nitrocellulose 10.0 Butyl cellosolve 10.0 Naphtha 25.0 Cyclohexane 25.0

[0095]Formulation Example 5 Gravure ink  Ti-Co-Al-based composite oxide-coated mica 14.0% ethylene-vinyl acetate copolymer resin 7.2 chlorinated polypropylene 5.8 toluene 58.0 ethyl acetate 11.0 isopropyl alcohol 3.0 polyethylene wax 0.8 Antistatic agent 0.2

[0096]Formulation Example 6 Screen Ink  Ti-Co-Al-based composite oxide-coated mica 15.0% acrylic resin 20.0 naphtha 35.0 butyl cellosolve 30.0

[0097]Formulation 7 Screen ink  Ti-Co-Al-based composite oxide-coated mica 15.0% nitrocellulose 15.0 cyclohexanone 40.0 isophorone 10.0 naphtha 10.0 dibutyl phthalate 10.0

[0098]Formulation 8 Screen ink  Ti-Co-Al-based composite oxide-coated mica 20.0% Nitrocellulose 20.0 Cyclohexanone 45.0 Isophorone 10.0 Dioctyl phthalate 5.0

[0099]

As described above, according to the present invention, Ti
-According to the mica coated with Co-Al-based composite oxide, the composite oxide layer containing titanium, cobalt and aluminum is formed on the mica, so that it is possible to see different colors depending on the observation angle. Become. Further, the coated body according to the present invention, by blending the Ti-Co-Al-based composite oxide-coated mica into a coating composition or the like, imparts multicolored color tone to a substrate coated with the composition. Becomes possible.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a method for synthesizing a mica coated with a Ti—Co—Al-based composite oxide of the present invention.

FIG. 2 is a schematic view of a mica coated with a Ti—Co—Al-based composite oxide of the present invention.

FIG. 3 is an explanatory view showing a relationship between a mixing ratio of a metal mixed in a mica coated with a Ti—Co—Al-based composite oxide of the present invention and a color tone.

FIG. 4 is an explanatory diagram of a method for measuring the degree of discoloration of a mica coated with a Ti—Co—Al-based composite oxide according to the present invention.

FIG. 5 is an ab diagram showing the results of measuring the degree of discoloration of the Ti—Co—Al-based composite oxide-coated mica of the present invention.

FIG. 6 is an explanatory diagram showing the relationship between the film thickness and the degree of discoloration of a coating composition containing the Ti-Co-Al-based composite oxide-coated mica of the present invention.

FIG. 7 is a wavelength distribution diagram of reflected light from a substrate to which a coating composition containing Example 1, which is a Ti-Co-Al-based composite oxide-coated mica of the present invention, is applied.

FIG. 8 is a diagram showing the results of Tables 5 and 6 in an ab diagram.

FIG. 9 is an explanatory diagram showing an outline of a measurement method in Experiment 6.

FIG. 8 is a diagram showing the results of Tables 7 and 8 in an ab diagram.

[Explanation of symbols]

 REFERENCE SIGNS LIST 10 Ti-Co-Al-based composite oxide-coated mica 12 Mica 14 Titanium dioxide layer 16 Co-Al-based composite oxide layer 18 White light 20 Reflected light 22 Reflected light 24 Reflected light 26 Reflected interference light

Claims (11)

[Claims] 1. A flaky mica substrate, and a composite oxide coated on the mica substrate, wherein titanium, cobalt, and aluminum are contained as a metal constituting the composite oxide. Ti-C
o-Al-based composite oxide-coated mica. 2. The mica coated with a Ti—Co—Al composite oxide according to claim 1, wherein the mica is coated with titanium dioxide and the surface of the mica is coated with a composite oxide of cobalt and aluminum. A mica coated with a Ti-Co-Al-based composite oxide, which is titanium. 3. The composite mica coated with a composite oxide according to claim 1, wherein the compounding molar ratio of the metal constituting the composite oxide is 50 to 91.5% for titanium dioxide and 7 for cobalt. .5-49
% And aluminum in an amount of 1 to 20%. 4. The composite oxide-coated mica according to claim 1 or 2, wherein the molar ratio of the metal constituting the composite oxide is 50 to 96.5% for titanium dioxide and 2 for cobalt. 0.5-7.
A Ti-Co-Al composite oxide-based mica comprising 5% and aluminum in an amount of 1 to 47.5%. 5. The composite oxide-coated mica according to claim 1, wherein the molar ratio of a metal constituting the composite oxide is 50 to 72.5% for titanium dioxide and 7 for cobalt. 0.5-30
%, And 20 to 42.5% of aluminum. 6. The composite mica coated with a composite oxide according to claim 1, wherein the mixing ratio of metal constituting the composite oxide is 50 to 98% for titanium dioxide and 1 to 2 for cobalt. 0.5% and aluminum in an amount of 1 to 49%.
Co-Al-based composite oxide-coated mica. 7. The Ti according to claim 1, wherein
When the hue of the appearance color of the Ti—Co—Al based composite oxide-coated mica is represented by the Hunter's Lab value, the value of a is −31.13 to 11. .35, b is -29.46-3
1.22. A mica coated with a Ti—Co—Al-based composite oxide, wherein the value of L is in the range of 30.82 to 88.23. 8. The Ti according to claim 1, wherein
-A coated body, characterized in that a composition containing mica coated with a Co-Al-based composite oxide is applied to a substrate. 9. The coated body according to claim 8, wherein the T
A coated body characterized in that the color tone of the substrate coated with the composition containing the i-Co-Al-based composite oxide-coated mica is in a gray scale range of white to black. 10. The coated body according to claim 8, wherein the color tone of the base material coated with the composition containing the composite oxide-coated mica is blue. 11. The coated body according to claim 8, wherein the Ti-Co-A applied on a base material.
A coated body, characterized in that the thickness of the composition containing the 1-type composite oxide-coated mica is 5 μm or more.