JPH10316882A - Mica-based composite material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a mica-based composite material developing multi-colored flip-flop effect, having excellent glittering property, designability, light-resistance, heat-resistance and stability and useful for coating material, cosmetic, etc., by providing a specific flaky mica having large diameter and a specific coating layer. SOLUTION: This composite material is provided with (A) a large-diameter flaky mica having a plate diameter of 0.1-2 mm and a thickness of 0.2-2 μm and (B) a coating layer formed on the surface of the mica and composed of one or more kinds of oxide and/or hydroxide of titanium, iron, zinc, zirconium, etc. The amount of the coating layer is preferably 0.1-50 wt.% based on the large-diameter flaky mica. The mica-based composite material can be produced by coating a large-diameter flaky mica with one or more kinds of metal oxide and/or metal hydroxide and baking at 200-1200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a mica-based composite material and a method for producing the same, and more particularly to a mica-based composite material having excellent optical properties.

[0002]

2. Description of the Related Art In fields where special design is required, such as cosmetics or paints, not only powders such as pigments are required to have a specific color, but also color tone or interference color depending on glitter or viewing angle. Such as changing multicolor flip
Demand for powder having a flop effect and the like is increasing. In order to satisfy these requirements, conventionally, mica-based composite materials in which the surface of mica is coated with titanium dioxide or iron oxide, or mica-based blue, navy blue, carmine, cobalt oxide, zirconium oxide, and aluminum oxide A material coated with one or two or more of a material, silicon oxide, lithium oxide, nickel oxide and the like is known. Since these mica-based composite materials have various interference colors as pearlescent pigments, they have been widely used as pigments for cosmetics, paints, plastics, and the like.

[0003]

However, the conventional mica-based composite material has a particle size of 0.0
Since the thickness is 8 mm (80 μm) or less, the coated surface is perceived as being substantially uniform, and cannot exhibit a strong brilliant interference color and a multicolor flip-flop effect. It was a weak mica-based composite material. On the other hand, JP-A-6-93205 discloses that the particle size is 0.1 to
A decorative pigment is disclosed in which one or more metal oxide fine particles are coated on a mica surface of 5 mm in an amount of 0.1 to 15% by weight with respect to the mica, and can exhibit brilliant feeling from any angle without being oriented. I have.

However, this pigment needs to be formed in a thick cubic shape for the nucleus mica in order to exhibit a brilliant feeling from any angle without being oriented, and the polychromatic flip-flop effect is not exhibited at all. Was something. SUMMARY OF THE INVENTION 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 mica-based composite material which is excellent in glitter and can exhibit a polychromatic flip-flop effect.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, the present invention provides a method for coating a flaky large particle mica with a metal oxide or a metal hydroxide. The inventors have found that excellent glitter and polychromatic flip-flop effects can be obtained, and have completed the present invention.
That is, the mica-based composite material according to the present invention has a large diameter flaky mica having a particle diameter of 0.1 to 2 mm and a particle thickness of 0.2 to 2 μm;

[0006] A coating layer comprising one or more of metal oxides and / or metal hydroxides formed on the surface of the mica. In the material according to the present invention, the mica is preferably a synthetic mica.

In the material according to the present invention, the metal in the metal oxide or metal hydroxide is titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth,
It is preferable to use one or two or more selected from the group consisting of tungsten and tin. In the material according to the present invention, the coating amount of one or more of the metal oxides or metal hydroxides is preferably 0.1 to 50% by weight based on the large-diameter flaky mica. It is. Further, the production method according to the present invention is characterized in that after coating one or two or more kinds of metal oxides and / or metal hydroxides on the large-particle-size flaky mica, firing is performed at 200 to 1200 ° C. .

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. The large-grained flaky mica preferably used in the present invention may be natural mica or synthetic mica, but the natural mica contains impurities and thus the particles of the large-grained flaky mica are transparent. The properties are slightly reduced. In this respect, synthetic mica having a small amount of impurities and high transparency and whiteness is preferable. When using natural mica, it is preferable to wash with an aqueous solution of hydrochloric acid or nitric acid in order to increase the transparency. An example of the production process of a large particle size flaky mica is shown below.

In order to obtain flaky mica having a large particle size from natural mica, first, the mined raw ore mica is roughly pulverized with a crusher to obtain an irregular coarse powder of about 20 mm. This is 750
Calcination was performed at 800 ° C. for about 2 hours in the air. After cooling, the mica was suspended in a dilute aqueous hydrochloric acid solution to form a slurry in order to make the mica thin. After standing all day and night, sodium carbonate was added to this to open the layers and facilitate cleavage. The slurry was disintegrated in a slip in a wet manner. Crushing is carried out for 12 hours, water is added thereto and the mixture is passed through a 20-mesh sieve. The wet pulverized product that passed through was passed through a 200-mesh sieve, and the unpenetrated material was recovered. Water was further added to the wet-crushed material and passed through a 200-mesh sieve to pass fine particles. Repeat this process three times,
Fine particles were sufficiently removed. The unpenetrated material remaining on the 20-mesh sieve was subjected to wet pulverization again for 12 hours, and processed in the same process as described above. The natural mica collected after crushing and sieving was collected and filtered until the water content became about 30%. Cracked natural mica 1 containing 30% water to further increase whiteness
1 L of a 0.2 N nitric acid aqueous solution was added to Kg. To this was added 50 g of citric acid, and the mixture was stirred with a propeller for one day. After filtration and washing with water, drying was performed at a low temperature of 80 ° C. or less. The dried product was deagglomerated with a low-speed Henschel mixer to obtain 650 g of flaky natural mica having a large particle diameter.

As an example of obtaining a large particle size flaky mica from a synthetic mica, an example using synthetic fluorine mica will be described. The chemical formula of synthetic fluorophlogopite is KMg ₃ (AlSi ₃ O ₁₀ ) F
₂ In the case of manufacturing by a melt deposition method, for example, 1800 g of SiO ₂ , 510 g of Al ₂ O ₃ , and 690 g of K ₂ CO ₃
g, and 630 g of MgF ₂ were weighed and sufficiently mixed with a V-type blender. After the mixture is heated to 1500 ° C. to be in a molten state, the mixture is cooled from the molten state to 1300 ° C. in order to obtain a flaky large-diameter synthetic mica. The cooling rate at this time was 100 ° C./15 hours. 24 hours at 1300 ° C
Left for hours. Then, it was allowed to cool to room temperature for 3 days. In this way, synthetic mica having good crystallinity was obtained and coarsely pulverized to about 20 mm. Water is added to this and crushed in the same process as obtaining large particle size flaky natural mica,
Sieved and dried. The dried product was loosened to obtain 1000 g of flaky synthetic fluorophlogopite having a large particle diameter.

As described above, the flaky mica having a large particle diameter was produced by a sieve classification method, and the thickness of the particles was obtained by observing with a scanning electron microscope. The mica-based composite material according to the present invention has a core of the large-diameter flaky mica obtained by the above-described production method, and the surface of the core mica particles is one or more of metal oxides and / or metal hydroxides. Coated. The metal of these metal oxides and / or metal hydroxides is selected from titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth, tungsten and tin. And a metal oxide and / or
Alternatively, the coating amount of one or more metal hydroxides is 0.1 to 50% by weight based on the large particle size flaky mica.
Further, flaky mica having a large particle diameter coated with one or more metal oxides and / or metal hydroxides is 200 to 120.
It is preferable to obtain a mica-based composite material by firing at 0 ° C, preferably 500 to 1100 ° C. When the coating amount of the metal oxide and / or metal hydroxide is 0.1% by weight or less, the obtained mica-based composite material does not have high chromatic color and brilliant interference color, is poor in glitter, and is multicolored. The expression of the flip-flop effect is poor. On the other hand, when the content exceeds 50% by weight, the particles have a coloring property, but the thickness of the particles becomes 2 μm or more, so that the reflection on the side surface becomes strong, the interference color that shines glaringly becomes weak, and the brilliancy, and further the polychromaticity The flip-flop effect is poor, and the design is poor. Further, in a mica-based composite material coated with one or more of metal oxides and / or metal hydroxides, the mica-based composite material obtained by firing at a temperature of less than 200 ° C. has little coloring and has many colors. The color flip-flop effect was very poor and the design was poor. In addition, 1200 ° C
When the mica-based composite material obtained by firing at a temperature higher than the above, the coating is agglomerated and the coated mica-based composite material is also agglomerated at the same time. The expression of the color flip-flop effect is poor and the design is inferior, which is not preferable.

The mica-based composite material of the present invention has a large particle size flaky mica surface, preferably a metal of titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth, tungsten, tin. It is coated with one or more of oxides and / or metal hydroxides, and various methods can be employed to obtain it. As a production method, there is a vacuum deposition coating method, but an aqueous solution of a soluble inorganic salt such as chloride, sulfate, nitrate, carbonate, hydroxide or the like as disclosed in JP-B-43-25644 is used. Large-grained flaky mica-based composite material is obtained by a method of hydrolyzing in the presence of large-grained flaky mica, depositing a metal oxide and / or metal hydroxide on the surface of the large-grained flaky mica, and then heating. can get.

The large particle size flaky mica-based composite material of the present invention comprises:
It is a highly designable mica-based composite material that exhibits a high brilliancy and a multicolor flip-flop effect of high-color glaring and brilliant interference colors. In addition, it has excellent stability such as light resistance and heat resistance, and is useful as powders such as paints, cosmetics, plastics, inks, paints, decorations, sundries, textiles, ceramics, and colored pearl luster materials. It is expected as a material with high properties.

[0014]

The present invention will be described below in more detail with reference to examples. Note that the present invention is not limited to these examples. Example 1 Large particle size flaky natural mica 100 g (average particle size about 0.5 mm,
An average particle pressure of about 1 μm was added to 1 liter of ion-exchanged water, sufficiently stirred with a propeller, and uniformly dispersed. To the resulting dispersion was added 102 ml of a 40% by weight aqueous solution of titanyl sulfate, and the mixture was heated with stirring and boiled for 3 hours. After cooling, the mixture was filtered, washed with water, and dried at 100 ° C. After drying, it was baked at 700 ° C. for 2 hours and allowed to cool to obtain 112 g of a silver-colored large-particle-size flaky natural mica. The obtained large-grained flaky natural mica was analyzed by X-ray diffraction and scanning electron microscope. As a result, it was found to be a large-grained flaky natural mica composite material coated with anatase type titanium dioxide. The coating amount of titanium dioxide was determined by fluorescent X-ray analysis. As a result, the coating amount of titanium dioxide was 14% by weight.
Met. Next, comparison results between various powders and the powder described in Example 1 are shown.

[0015]

[Table 1] {Example of test 1 2 3 4 5} ────────────────────────────────── Pearl agent ○ − − − − Large particle size flaky mica-based composite material − ○ − − − (Example 1) Large particle size silica − − ○ − − Large particle size spherical resin powder − − − ○ − Large particle size mica composite material − − − − ○ ────── ────────────────────────────── Evaluation item Glittering △ × × × ○ Flip-flop property ○ ◎ × × × × ────────────────────────────────── Pearl agent: average 50μm diameter, thickness 0.2μm, large diameter flake ( Synthetic gold) mica-based composite material: average 1 mm diameter, 1 μm thickness, large diameter silica, Large-diameter spherical resin (styrene) powder: average 1 mm diameter Large-diameter dice mica: average particle diameter about 0.5 mm average particle diameter about 200 μm Titanium dioxide coating amount 10%

<Results> As is clear from Table 1 above, in the case of a pearl agent which is usually used (Test Example 1), although it shows a slightly glittering shine, it is still insufficient. However, in the case of the large-grained flaky mica-diameter composite material of the present invention (Test Example 2), it was observed that the glitter was much more brilliant and the flip-flop property of exhibiting a different color tone depending on the viewing direction than in the case of using the pearl agent. It has excellent design.

In the case where a powder having a diameter similar to that of the large particle size flaky mica-based composite material is used as other powders (Test Examples 3 and 4)
Did not exhibit any sparkle and, of course, no flip-flop properties were observed. On the other hand, the large-grained mica-based composite material (Test Example 5) is brilliant, exhibits a certain degree of brilliance, and has a brilliance irrespective of the viewing direction, but in particular, no polychromatic flip-flop effect is observed. Was.

Next, the present inventors have studied the particle size of mica.

[Table 2] ──────────────────────────────────── Test Example 6 7 8 9 10 11 12 ──────────────────────────────────── Mica (average particle size about 0.05mm) ○ − − − − − − (Average particle size about 0.1 mm) − ○ − − − − − (average particle size about 0.5 mm) − − ○ − − − − (average particle size about 1.0 mm) − − − ○ − − -(Average particle size about 1.5 mm)------(Average particle size about 2.0 mm)-------(Average particle size about 3.0 mm)-------─ ─────────────────────────────────── Evaluation item Glitter brilliance △ ○ ◎ ◎ ◎ ◎ ◎ Flip-flop property ○ ○ ◎ ◎ ◎ ◎ ◎ ───────────────── ──────────────────

From Table 2 above, the average particle size of mica is preferably at least 0.1 mm, particularly 0.5 mm, in consideration of design properties.
As described above, excellent brightness can be obtained. On the other hand, 2.0mm
When it exceeds, a rough touch is generated, and the application to various uses tends to be deteriorated. Therefore, it is preferably 2.0 mm or less, particularly preferably 1.5 mm or less.

Examples 2 to 5 Using the same large-grain flaky natural mica as in Example 1, various composite materials were obtained in the same steps except that the amount of titanyl sulfate added was changed. ──────────────────────────────────── Example Large particle size Titanyl sulfate amount Generated amount TiO ₂ color tone Titanium dioxide Flaky mica Coverage # 2 100g 138ml 120g Anatase 18% by weight brilliant yellow interference color 3 100g 156ml 123g anatase giraffea and 20% by weight brilliant red interference color 4 100g 231ml 135g anatase giraffea and 27% by weight brilliant blue interference color 5 100g 294ml kirara weight grease Green interference color ────────────────────────────────────

Examples 6 to 10 100 g of flaky synthetic mica having a large particle size was added to 1 L of ion-exchanged water, sufficiently stirred with a propeller, and uniformly dispersed. Dilute hydrochloric acid aqueous solution 2 containing 3.5 g of tin chloride in the obtained dispersion
0 ml was added, and an aqueous solution of sodium hydroxide was added thereto to adjust the pH to 1.
Adjusted to 8. The pH adjusted dispersion was heated with stirring to a temperature of 80 ° C. While maintaining this state, the mixture was stirred for 1 hour. Further, an aqueous solution of caustic soda and an aqueous solution of 2 molar titanium tetrachloride were added to the heated and stirred dispersion while maintaining the pH at 1.8. After adding the titanium tetrachloride aqueous solution, the mixture was heated and aged for 2 hours. After allowing to cool, it was washed with filtered water and dried at 120 ° C. After drying, firing was performed at 900 ° C. for 2 hours. The obtained large-grained flaky synthetic mica composite material was analyzed by X-ray diffraction and a scanning electron microscope in the same manner as in Example 1.

──────────────────────────────────── Example Large particle size Titanyl sulfate amount Generated amount TiO2 Color tone Titanium dioxide Flaky mica Coverage ６6 100g 105ml 114g rutile 100% 140ml 120g Rutile Kirara and 18% by weight Shining yellow interference color 8 100g 160ml 123g Rutile Kirara and 20% by weight Shining red interference color 9 100g 230ml 135g Rutile Kira and Kiriya Kira Blue interference color 10 100g 295ml 145g Rutile glowing and 32% by weight Shining green interference color ────────────────────────── ──────────

Example 11 100 g of flaky synthetic mica having a large particle diameter was added to 1 L of ion-exchanged water, and the mixture was sufficiently stirred with a propeller and uniformly dispersed. A 40% by weight aqueous solution of titanyl sulfate 6 was added to the obtained dispersion.
25 ml was added, and the mixture was heated with stirring and boiled for 6 hours.
After cooling, the mixture was filtered, washed with water, and dried at 100 ° C. 5 after drying
Baking was performed at 00 ° C. for 6 hours. After allowing to cool, 195 g of a mica-based composite material coated with titanium dioxide having a high interference color of green with high brightness was obtained. As a result of X-ray diffraction, titanium dioxide was anatase, and when observed with a scanning electron microscope, the particle surface was uniformly coated. The content of titanium dioxide determined by X-ray fluorescence analysis was 50% by weight.

Example 12 100 g of flaky synthetic mica having a large particle size was added to 500 ml of ion-exchanged water.
And the mixture was sufficiently stirred with a propeller and uniformly dispersed. 0.1 g of ferric chloride and 0.1 g of urea were added to the obtained dispersion.
2 g was added and sufficiently stirred to dissolve. After dissolution, the mixture was heated with stirring and aged at a temperature of 80 ° C. or higher for 4 hours. After cooling, the mixture was filtered, washed with water, and dried at 100 ° C. 20 after drying
The mixture was fired at 0 ° C. for 2 hours at low temperature to obtain 98 g of a mica-based composite material coated with iron oxide having a pale orange appearance. Although no change was observed in the X-ray diffraction results, the result of X-ray fluorescence analysis revealed that iron was contained at 0.1% by weight.
Moreover, as a result of observation by a scanning electron microscope, it was found that the surface of the large-size flaky particles was coated.

Example 13 40 g of the titanium dioxide-coated large particle size flaky synthetic mica composite material obtained in Example 7 was added to 700 ml of ion-exchanged water, sufficiently stirred with a propeller, and uniformly dispersed. 4.5 g of ferric ammonium oxalate and 1.0 g of urea were added to the resulting dispersion.
g was weighed, 100 ml of ion-exchanged water was added thereto, and the mixture was stirred with a propeller until dissolved. This aqueous solution was added to a dispersion in which the titanium dioxide-coated large-particle-size flaky synthetic mica composite material was uniformly dispersed, heated to 80 ° C. with stirring, and continued heating and stirring for 4 hours. After 4 hours, the dispersion was allowed to cool, filtered, washed with water, and dried at 100 ° C. for 7 hours. After drying, the mixture was allowed to cool to obtain 41 g of a composite material having a high interference color, orange color, and a yellow interference color. Further, this was fired at 900 ° C. for 4 hours. After standing to cool, 40 g of a composite material having a bright and highly saturated yellow interference color of brilliant yellow was obtained. X-ray diffraction of the obtained composite material confirmed synthetic mica and rutile of titanium dioxide, and pseudoplatelet ilmenite (Fe ₂ TiO ₅ ) which is a compound of iron and titanium dioxide. According to the scanning electron microscope observation, the particles (approximately 0.08 μm) are slightly scattered on the particle surface, and the ultrafine particles of 0.02 μm are scattered under the particles. Was uniformly coated. Thus, the composite material according to the present example is a large-grained flaky synthetic mica composite material coated with titanium dioxide and pseudo-ilmenite, and the amount of iron is fluorescent X
The result of linear analysis was 0.7% by weight.

Example 14 To 40 g of the titanium dioxide-coated large particle size flaky natural mica composite material obtained in Example 4, 700 ml of ion-exchanged water was added, sufficiently stirred with a propeller, and uniformly dispersed. To this dispersion was added a solution prepared by dissolving 16 g of cobalt chloride hexahydrate in 150 ml of ion-exchanged water. Then, the dispersion was heated to 50 ° C., and a 1 molar aqueous solution of caustic soda was added at a dropping rate of 100 ml / min while stirring, and when the pH reached 9.0, the dropping of the caustic soda was stopped and the mixture was aged for 2 hours. Was. After completion of aging, the mixture was allowed to cool, washed with filtered water, and dried at 100 ° C. for 5 hours.
The dried powder was fired at 900 ° C. for 4 hours. The cooled composite material exhibited 43 g of a highly brilliant composite material in which the appearance color was green, and the interference color shining brightly was reddish blue.
X-ray diffraction of this material confirmed mica and titanium dioxide, and cobalt titanate generated from titanium dioxide and cobalt oxide. Further, from observation with a scanning electron microscope, granular particles of 0.5 μm were scattered on the surface of the large-sized flaky particles, and ultrafine particles of 0.02 μm were observed under the particles. Further, it was confirmed from the fluorescent X-ray analysis that 4% by weight of cobalt was coated. Then, the composite material was uniformly applied to a double-sided pressure-sensitive adhesive tape, stuck on a black and white opacity test paper, and measured at different colorimetric angles. As a result, 4
When the color was measured in the direction of 0 ° with respect to the incidence of 5 °, green was strongly reflected. When the color was measured in the direction of 30 ° close to the specular reflection direction, the reddish blue reflection was strongly observed. In other words, the large-grained flaky natural mica composite material coated with and baked with a metal oxide of cobalt and titanium has a strong brilliancy in which the appearance color is green and glittering,
In addition, a flip-flop effect exhibiting dichroism was exhibited. It was a mica-based composite material with excellent design properties.

Example 15 In the same process as in Example 14, 2.5 g of lithium carbonate was mixed with 20 g of a composite material obtained by coating a titanium compound coated with a large particle size flaky natural mica composite material with a cobalt compound.
Fired for hours. After cooling, 22 g of a shining and shiny material having a highly saturated blue-green appearance was obtained. From the X-ray diffraction results of this material, it was determined that the material consisted of mica and titanium dioxide, and lithium cobalt titanate produced from titanium dioxide, cobalt oxide and lithium oxide. Also, from observation with a scanning electron microscope, 1 μm
, And 0.02 μm ultra-fine particles uniformly covered the whole surface underneath. Further, it was confirmed from the fluorescent X-ray analysis that 2.5% by weight of lithium was coated. The composite material was uniformly applied to a double-sided pressure-sensitive adhesive tape, applied to a black and white opacity test paper, and measured at different colorimetric angles. As a result, 0 for 45 ° incidence
When the color was measured in the 青 direction, the blue-green color was strongly reflected, and when the color was measured at 30 ° close to the specular reflection direction, a strong reddish blue reflection was observed. That is, a large particle size flaky natural mica composite material coated with a metal oxide of titanium, cobalt and lithium, and fired, has a strong blue-green brilliant appearance with high chroma, and a bluish green color. A flip-flop effect exhibiting dichroism and exhibiting a reddish blue interference color was developed.
The material according to the present example was a mica-based composite material having excellent design properties.

Example 16 40 g of the titanium dioxide-coated large particle size flaky synthetic mica composite material obtained in Example 10 was added to 700 ml of ion-exchanged water, sufficiently stirred with a propeller and uniformly dispersed. To the resulting dispersion, 10 g of nickel sulfate and 1 g of urea were dissolved in 100 ml of ion-exchanged water, and an aqueous solution was added. The mixture was boiled with stirring and aged for 4 hours. Allow to cool after aging, filter and wash with water
Dried at 00 ° C. The obtained material was a glistening material having a gray appearance color, and 42 g was obtained. Material 2 obtained
0 g was mixed with 3 g of sodium carbonate, and calcined at 1200 ° C. for 2 hours. After standing to cool, 21 g of a material having a bluish-green interference color with a strong glare and brilliant color having a highly saturated yellow appearance color was obtained. From the results of X-ray diffraction of the obtained material, it was confirmed that synthetic mica and titanium dioxide, and sodium nickel tetanet which is a compound of sodium, nickel and titanate were slight. In addition, a state in which the surface of the large-diameter flaky particles was molten was observed from a scanning electron microscope. Further, as a result of X-ray fluorescence analysis, sodium was 5.5% by weight and lithium was 7% by weight. In other words, this product is a large-grained flaky synthetic mica composite material in which synthetic mica is coated with titanium dioxide and sodium nickel titanate, has a highly saturated yellow appearance color, and has a bluish-green interference color with glare. A highly designable mica-based composite material having dichroism of yellow and interference colors.

Example 17 Titanium dioxide-coated large-grain flaky natural mica 40 g obtained in Example 1 was added to 700 ml of ion-exchanged water, sufficiently stirred with a propeller and uniformly dispersed. In the obtained dispersion,
2.1 g of zirconium oxychloride in 50 ml of ion-exchanged water
Was added to the mixture, and the mixture was heated to boiling while stirring and aged for 3 hours. After aging, the mixture was allowed to cool and washed with filtered water. The material obtained after washing with water was added to 600 ml of ion-exchanged water, sufficiently stirred with a propeller and uniformly dispersed. A solution obtained by dissolving 28 g of aluminum sulfate and 2.3 g of urea in 100 ml of ion-exchanged water was added to the obtained dispersion. Heat with stirring. Aged at 80 ° C. for 4 hours. After aging, it was allowed to cool, washed with filtered water, and dried at 100 ° C. 20 obtained materials
Baking at 0 ° C. for 16 hours. After cooling, 42 g of a white shining material was obtained. 5 g of the obtained material is 50% by volume
Was added to 50 ml of an aqueous solution of ethanol, and the mixture was stirred with a propeller and uniformly dispersed. For comparison, the material obtained in Example 1 was dispersed in ethanol in the same manner as described above.
Each dispersion was irradiated with a 2.5 Kw Xe lamp for 30 hours. As a result, the material treated with zirconium oxychloride and aluminum sulfate glistened, but as a comparison, the material obtained in Example 1 had a gray-black appearance color and was changed to a glistening material. That is, the treated material was even more resistant to light.

From the X-ray diffraction of the obtained composite material, only anatase type of mica and titanium dioxide was confirmed. According to the scanning electron microscope, needle-like particles having a particle diameter of 0.5 μm and particles having a particle diameter of 0.1 μm or less were scattered on the surface of the large particles. Further, as a result of point analysis by EDX (energy dispersive X-ray analysis), the needle-like particles were composed of an aluminum compound, and the granular particles were composed of a zirconium compound. That is, the large particle size flaky mica composite material was coated with aluminum, a zirconium compound, and titanium dioxide. It was a shining material with strong light resistance. In addition, as a result of quantification, aluminum was 1% by weight, and zirconium was 0.8% by weight as a result of quantification.

Example 18 40 g of the titanium dioxide-coated large-grain flaky synthetic mica composite material obtained in Example 7 was added to 700 ml of ion-exchanged water, sufficiently stirred with a propeller and uniformly dispersed. To the obtained dispersion, 8 g of zinc chloride and 18 g of urea were added to and dissolved in 100 ml of a 0.1N aqueous hydrochloric acid solution, and this was added. The mixture was heated with stirring and aged at 80 ° C. for 4 hours. After aging, the mixture was allowed to cool, and filtered and washed with water. 600 ml of ion-exchanged water was added to the slurry, and the mixture was uniformly stirred with a propeller. An aqueous solution of caustic soda was added to the homogeneous dispersion to adjust the pH to 9, and the mixture was heated to 80 ° C. To this heated and stirred dispersion, 50 ml of an aqueous solution containing 2 g of water glass and a 1.0 N aqueous hydrochloric acid solution were simultaneously added dropwise. However, the pH was kept at 9 and the dropping rate of water glass was added at a rate of 10 ml per minute, and the mixture was aged for 2 hours after completion of the addition. Filtration after aging
It was washed with water and dried at 100 ° C. The dried material had a white glistening yellow interference color and 43 g were obtained.
From the obtained material, synthetic mica and rutile and zinc oxide of titanium dioxide were recognized by X-ray diffraction. Scanning electron microscopy observations revealed needle-like particles having a large particle surface of 0.5 μm and granular particles of 0.02 μm. Further, from the point analysis by EDX, the acicular shape was a zinc compound and 0.02 μm was a titanium compound. When the magnification of observation with a scanning electron microscope is increased to 100,000 times, the needle-like particles are finer 0.01 μm.
It was coated with the following particles, which were silicon compounds. From this, it was found that this material was a composite mica material in which flaky synthetic mica having a large particle diameter was coated with titanium dioxide, zinc oxide and a silicon compound. Furthermore, as a result of chemical analysis, zinc oxide was 10% by weight and silicon was 0.8% by weight.
% By weight.

EXAMPLE 19 40 g of the titanium dioxide-coated large-grain flaky synthetic mica composite material obtained in Example 6 was added to 700 ml of ion-exchanged water, sufficiently stirred with a propeller and uniformly dispersed. 6 g of bismuth nitrate and 2 g of urea were added to the obtained dispersion,
A solution dissolved in 0 ml was added. Heat with stirring,
Aged at 80 ° C. for 4 hours. After aging, let cool, filter and wash with water,
Dry at 100 ° C. for 8 hours. After drying, it was baked at 400 ° C. for 2 hours. After cooling, 44g of shining yellow material
I got X-ray diffraction of this material confirmed synthetic mica and rutile and bismuth oxide of titanium dioxide. From the scanning electron microscope, it was found that the surface of large particles was scattered at 0.03 μm, and underneath the particles were slightly small particles of about 0.02 μm covering the entire surface. And point analysis by EDX revealed that the interspersed particles were bismuth and the particles below it were titanium. X-ray fluorescence analysis revealed that bismuth was 6% by weight. From this, this material is a composite material which is a large-grained flaky synthetic mica coated with bismuth oxide and titanium dioxide, has a yellow appearance color, and glitters.

Example 20 40 g of the titanium dioxide-coated large-grain flaky synthetic mica composite material obtained in Example 10 was added to 700 ml of ion-exchanged water, sufficiently stirred with a propeller and uniformly dispersed. An aqueous solution in which 5 g of tungsten oxychloride was dissolved in 100 ml of ion-exchanged water was added to the obtained dispersion. The dispersion was heated to 80 ° C. with stirring, and a 0.2N aqueous potassium hydroxide solution was added dropwise at a rate of 10 ml / min, and the aqueous potassium hydroxide solution was added dropwise until the pH of the liquid reached 9. Aged at pH 9 for 4 hours. After aging, the mixture was allowed to cool, washed with filtered water, and dried at 100 ° C. The dried material was fired at 500 ° C. for 2 hours. After standing to cool, 43 g of a material having a pale yellow glare and a bright green interference color was obtained. X-ray diffraction of this material confirmed synthetic mica, rutile of titanium dioxide and tungsten oxide. Scanning electron microscopy observation revealed that irregular particles having a large particle surface of 0.3 μm were scattered, and that small particles of as small as 0.02 μm covered the entire surface. And E
From the point analysis by DX, the particles interspersed were tungsten, and the particles below were titanium. In addition, fluorescent X
From line analysis, tungsten was 5% by weight. Therefore, this material is a large-grained flaky synthetic mica coated with tungsten oxide and titanium dioxide, has a glittering green color and a bright yellow interference color, and has a pale yellow and green interference color. It was a highly designable mica-based composite material with color properties.

[0034]

As described above, according to the mica-based composite material according to the present invention, a metal oxide and / or a metal hydroxide is coated on a large particle size flaky mica.
An excellent polychromatic flip-flop effect can be exhibited together with the glitter. Further, according to the method for producing a mica-based composite material according to the present invention, since a large-particle-size flaky mica is coated with a metal oxide or a metal hydroxide and then fired, the glittering and polychromatic properties are improved. The flip-flop effect can be more remarkably exhibited.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Masato Kuraya 1 Akemi-cho, Toyohashi-shi, Aichi Prefecture Topy Industries, Ltd. Toyohashi Plant

Claims (5)

[Claims] A large flaky mica having a particle diameter of 0.1 to 2 mm and a particle thickness of 0.2 to 2 μm, and a metal oxide and / or metal oxide formed on the mica surface. A mica-based composite material comprising: a coating layer made of one or more metal hydroxides. 2. The mica-based composite material according to claim 1, wherein the mica is a synthetic mica. 3. The material according to claim 1, wherein the metal in the metal oxide or metal hydroxide is titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth,
A mica-based composite material, which is one or more selected from the group consisting of tungsten and tin. 4. The material according to claim 1, wherein one or more of the metal oxides or metal hydroxides is coated in an amount of 0.1 to 0.5% with respect to the flaky mica having a large particle diameter. 1
50% by weight of the mica-based composite material. 5. A method for coating a large particle size flaky mica with one or two or more metal oxides and / or metal hydroxides.
A method for producing a mica-based composite material, characterized by firing at 0 to 1200 ° C.