JP4624333B2 - Mica-based composite material and method for producing the same - Google Patents

Description

  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.

  In fields where special design properties are required, such as cosmetics and paints, not only specific colors are required for powders such as pigments, but there are many changes in color tone or interference color depending on glitter or viewing angle. There is an increasing demand for powders having a color flip-flop effect. In order to satisfy these requirements, the mica-based composite material whose surface of mica has been coated with titanium dioxide or iron oxide or the mica-based composite material is further combined with ultramarine, bitumen, carmine, cobalt oxide, zirconium oxide, aluminum oxide. A material coated with one or more of 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.

However, since the conventional mica-based composite material has a particle diameter of 0.08 mm (80 μm) or less even when the particle diameter is large, the coated surface is considered to be almost uniform, and the interference color that is brilliantly shining is obtained. It was a mica-based composite material that could not exhibit strong luster and pleochroic flip-flop effect and had poor design.
On the other hand, JP-A-6-93205 discloses that a mica surface having a particle diameter of 0.1 to 5 mm is coated with 0.1 to 15% by weight of one or more metal oxide fine particles with respect to the mica and not oriented. A decorative pigment is disclosed that can exhibit a brilliant feeling when viewed from any angle.

However, this pigment does not have to be oriented so that it can exhibit a radiant sensation from any angle. Therefore, it is necessary to make the nuclei mica into a thick cubic shape, and the pleochroic flip-flop effect is not exhibited at all. It was.
JP-A-6-93205

  The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a mica-based composite material that is excellent in glitter and can exhibit a polychromatic flip-flop effect.

As a result of intensive studies by the present inventors in order to achieve the above object, excellent glitter and pleochroic flip-flops are obtained by coating flaky large particle mica with metal oxide or metal hydroxide. The present invention has been completed.
That is, in the method for producing a mica-based composite material according to the present invention, the average plate diameter of particles obtained by wet crushing in water is 0.1 mm or more and less than 0.5 mm, and the average thickness of the particles is 0.2. On the surface of the large particle size flaky synthetic mica of ~ 2 μm,

Forming a coating layer composed of one or more of metal oxide and / or metal hydroxide to form a mica-based composite material ;
In the case where the metal oxide contains titanium dioxide, the titanium dioxide is rutile type and / or anatase type, which is a method for producing a mica-based composite material having glitter and polychromatic flip-flop properties.

Further, in the material according to the present invention, the metal in the metal oxide or metal hydroxide is a group consisting of titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth, tungsten, tin. It is suitable that it is 1 type selected from 2 or more types.
Further, in the material according to the present invention, the coating amount of one or more of the metal oxide or metal hydroxide is preferably 0.1 to 50% by weight with respect to the large particle size flaky mica. It is.
In addition, the production method according to the present invention is characterized in that a large particle size flaky mica is coated with one or more metal oxides and / or metal hydroxides and then fired at 200 to 1200 ° C. .

According to the mica-based composite material according to the present invention, the large particle size flaky mica is coated with the metal oxide and / or metal hydroxide. It can be demonstrated.
In addition, according to the method for producing a mica-based composite material according to the present invention, a large particle size flaky mica is coated with a metal oxide or a metal hydroxide, and then fired. The flip-flop effect can be exhibited more remarkably.

Hereinafter, preferred embodiments of the present invention will be described.
The large particle size flaky mica preferably used in the present invention may be natural mica or synthetic mica, but since natural mica contains impurities, the particles of the large particle flaky mica are transparent. The characteristics are slightly reduced. In this respect, synthetic mica having less impurities and high transparency and whiteness is preferable. When natural mica is used, it is preferably washed with an aqueous solution of hydrochloric acid or nitric acid in order to increase transparency.
An example of the production process of large particle size flaky mica is shown below.

  In order to obtain a large particle size flaky mica 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 was calcined in the atmosphere at 750 to 800 ° C. for about 2 hours. After cooling, in order to flake the mica, it was suspended in a dilute hydrochloric acid aqueous solution to form a slurry. After standing for a whole day and night, sodium carbonate was added thereto to open the layers, making it easy to cleave. Slip pulverization was performed in a wet state in a slurry state. Crushing is carried out for 12 hours, and water is added to this and passed through a 20-mesh sieve. The passed wet pulverized product was passed through a 200-mesh sieve, and the non-passed product was collected. Water was further added to this and passed through the 200-mesh sieve to allow fine particles to pass through. This process was repeated three times to sufficiently remove the fine particles. In addition, the non-passed matter remaining on the 20 mesh sieve was again wet crushed for 12 hours and treated in the same manner as described above. The pulverized natural mica after pulverization was filtered until the water content was about 30%. In order to further increase the whiteness, 1 L of a 0.2N nitric acid aqueous solution was added to 1 kg of crushed natural mica containing 30% water. To this was added 50 g of citric acid, and propeller stirring was performed for 1 day. After filtration and washing with water, it was dried at a low temperature of 80 ° C. or lower. The dried product was flocculated with a low-speed Henschel mixer to obtain 650 g of flake natural mica having a large particle size.

As an example of obtaining large particle size flaky mica from synthetic mica, an example using synthetic fluorine mica will be described. The chemical formula of the synthetic fluorine phlogopite is KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ . When producing a melt deposition method, for example, a SiO ₂ 1800 g, 510 g of _Al 2 _{O 3,} 690 g of K ₂ CO _3, MgF 2 and 630g weighed and thoroughly mixed in a V-blender. The mixture is heated to 1500 ° C. and brought into a molten state, and then cooled from the molten state to 1300 ° C. in order to obtain a flaky large particle size synthetic mica. The cooling rate at this time was 100 ° C./15 hours. Further, it was left at 1300 ° C. for 24 hours. Thereafter, it was allowed to cool at room temperature for 3 days. Thus, synthetic mica having good crystallinity was obtained, and this was coarsely pulverized to about 20 mm. This was crushed, sieved and dried in the same process as adding water to obtain flaky natural mica with a large particle size. The dried product was loosened to obtain 1000 g of a large particle size flaky synthetic fluorine phlogopite.

As described above, the large particle size flaky mica was produced by the 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 large particle size flaky mica obtained by the above-described production method as a nucleus, and the surface of the nuclei mica particle is one or more of metal oxide and / or metal hydroxide. It is covered. The metal of the metal oxide and / or metal hydroxide is selected from titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth, tungsten, and tin. And the coating amount by 1 type, or 2 or more types of a metal oxide and / or a metal hydroxide is 0.1 to 50 weight% with respect to a large particle size flaky mica. Furthermore, the large particle size flaky mica coated with one or more metal oxides and / or metal hydroxides is preferably fired at 200 to 1200 ° C., preferably 500 to 1100 ° C., to obtain a mica-based composite material. . 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 cannot provide high-colored and brilliant interference colors, has poor glitter, and is multicolored. The effect of the flip-flop effect is poor. On the other hand, if it exceeds 50% by weight, the thickness of the particle becomes 2 μm or more although it has coloring properties, the reflection on the side surface becomes strong, the brilliant interference color becomes weak, the glitter property, and the pleochroic property. The flip-flop effect is poor, and the design is lacking. Further, in the mica-based composite material coated with one or more metal oxides and / or metal hydroxides, the mica-based composite material obtained by firing at a temperature of less than 200 ° C. is less colored and moreover. The color flip-flop effect was very poor and the design was lacking. Furthermore, the mica-based composite material obtained by firing at a temperature exceeding 1200 ° C. from the coated state causes the coating to agglomerate and at the same time the agglomeration of the coated mica-based composite material, resulting in a brilliant interference color. Further, it is not preferable because it has poor glitter and poor polychromatic flip-flop effect and poor design.

  The mica-based composite material of the present invention has a large particle size flaky mica surface, preferably titanium, iron, zinc, zirconium, cobalt, nickel, lithium, sodium, silicon, aluminum, bismuth, tungsten, tin metal oxide, and Although it is a thing coat | covered with 1 type, or 2 or more types of a metal hydroxide, various methods are employable in order to obtain this. As its production method, there is a vacuum deposition coating method, but a soluble inorganic salt such as that disclosed in Japanese Patent Publication No. 43-25644, for example, an aqueous solution of chloride, sulfate, nitrate, carbonate, hydroxide, etc. The large particle size flaky mica-based composite material is hydrolyzed in the presence of the diameter flaky mica and the metal oxide and / or metal hydroxide is precipitated on the surface of the large particle size flaky mica and then heated. can get.

The large particle size flaky mica-based composite material of the present invention is a highly designed mica-based composite material that exhibits a high chromatic glitter and a strong brilliant interference color and a polychromatic flip-flop effect.
In addition, it has excellent stability such as light resistance and heat resistance, and is useful as a powder, colored pearl luster material for paints, cosmetics, plastics, inks, paints, ornaments, household goods, textiles, ceramics, etc. It is expected as a highly functional material.

Hereinafter, based on an Example, this invention is demonstrated in detail. The present invention is not limited to these examples.
Example 1
Large particle size flaky natural mica 100 g (average particle size of about 0.5 mm, average particle thickness of about 1 μm was added to 1 liter of ion-exchanged water and stirred well with a propeller to disperse uniformly. After adding 102 ml of titanyl sulfate aqueous solution with a concentration of 40% by weight and heating with stirring, it was boiled for 3 hours. As a result of analyzing the obtained large particle size flaky natural mica by X-ray diffraction and a scanning electron microscope, a large particle size coated with titanium dioxide anatase type was obtained. The coating amount of titanium dioxide was determined by fluorescent X-ray analysis, and as a result, the coating amount of titanium dioxide was 14% by weight.
Next, comparison results between various powders and the powders described in Example 1 are shown.

(Table 1)
────────────────────────────────────
Test example
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 dice mica based composite material----○
────────────────────────────────────
Evaluation item Glittering △ ◎ × × ○
Flip flop ○ ◎ × × ×
────────────────────────────────────
Pearl agent: average 50μm diameter, thickness 0.2μm
Large-diameter flaky (synthetic gold) mica-based composite material: Average 1 mm diameter Thickness 1 μm
Large diameter silica, large diameter spherical resin (styrene) powder: average 1 mm diameter large particle size dice mica: average particle size about 0.5 mm average particle thickness about 200 μm
Titanium dioxide coverage 10%

<Result>
As is clear from Table 1 above, in the case of a commonly used pearl agent (Test Example 1), although a slight sparkle is exhibited, it is still not sufficient. However, in the case of a large particle size flaky mica diameter composite material (Test Example 2), the flip-flop property exhibiting a far more brilliant brightness and a different color tone depending on the viewing direction is observed, which is superior to the case of using a pearl agent. Demonstrate its design.

In addition, when a powder having a diameter close to that of a large particle size flaky mica-based composite material is used (Test Examples 3 and 4), the glittering shine is not exhibited, and, of course, the flip-flop property is also observed. Was not.
On the other hand, the large dice mica-based composite material (Test Example 5) is sparkling and exhibits a certain degree of brightness, and has a glittering feeling regardless of the viewing direction, but in particular, no polychromatic flip-flop effect is observed. It was.

Next, the present inventors proceeded with studies on 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 diameter of about 0.1 mm)-○-----
(Average particle diameter of about 0.5 mm) − − ○ − − − −
(Average particle diameter of about 1.0 mm) − − − ○ − − −
(Average particle diameter of about 1.5 mm) − − − − ○ − −
(Average particle diameter of about 2.0 mm) − − − − − ○ −
(Average particle size of about 3.0 mm) − − − − − − ○
────────────────────────────────────
Evaluation item Glitter △ ○ ◎ ◎ ◎ ◎ ◎
Flip flop ○ ○ ◎ ◎ ◎ ◎ ◎
────────────────────────────────────

  From Table 2 above, the average particle diameter of mica is preferably 0.1 mm or more if design properties are taken into consideration, and particularly excellent brightness can be obtained at 0.5 mm or more. On the other hand, when it exceeds 2.0 mm, a rough feel is produced, and application to various uses tends to be poor. Accordingly, it is preferably 2.0 mm or less, particularly preferably 1.5 mm or less.

Examples 2-5
Using the same large particle size flaky natural mica as in Example 1, various composite materials were obtained in the same process except that the addition amount of titanyl sulfate was changed.
──────────────────────────────────── ――――
Example Large particle size Amount of titanyl sulfate Amount produced TiO ₂ color tone Titanium dioxide Flaky mica Cover amount ────────────────────────────── ────── ――――――
2 100g 138ml 120g Anatase Giragira and 18% by weight
Shined
Yellow interference color 3 100g 156ml 123g anatase glare and 20% by weight
Shined
Red interference color 4 100g 231ml 135g Anatase Gira Gira 27%
Shined
Blue interference color 5 100g 294ml 144g Anatase Giragira and 32wt%
Shined
Green interference color ──────────────────────────────────── ――――――

Examples 6-10
100 g of flaky synthetic mica having a large particle size was added to 1 L of ion-exchanged water and sufficiently stirred with a propeller to be uniformly dispersed. To the obtained dispersion was added 20 ml of a dilute hydrochloric acid solution containing 3.5 g of tin chloride, and an aqueous sodium hydroxide solution was added thereto to adjust the pH to 1.8. The pH adjusted dispersion was heated to 80 ° C. with stirring. While maintaining this state, the mixture was stirred for 1 hour. Further, a caustic soda aqueous solution and a 2 molar titanium tetrachloride aqueous solution were added to the heated stirring dispersion while maintaining the pH at 1.8. After the addition of the aqueous titanium tetrachloride solution, the mixture was aged by heating for 2 hours. After standing to cool, it was washed with filtered water and dried at 120 ° C. After drying, it was calcined at 900 ° C. for 2 hours. The obtained large particle size 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 Amount of titanyl sulfate Amount produced TiO ₂ color tone Titanium dioxide Flaky mica Cover amount ────────────────────────────── ────── ――――――
6 100g 105ml 114g Rutile and 14% by weight
Shiny silver color 7 100g 140ml 120g Rutile Giragira and 18% by weight
Shined
Yellow interference color 8 100g 160ml 123g Rutile Giragira and 20% by weight
Shined
Red interference color 9 100g 230ml 135g Rutile Giragira and 27% by weight
Shined
Blue interference color 10 100g 295ml 145g Rutile Giragira and 32% by weight
Shined
Green interference color ──────────────────────────────────── ――――――

Example 11
100 g of flaky synthetic mica having a large particle size was added to 1 L of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, 625 ml of an aqueous titanyl sulfate solution having a concentration of 40% by weight was added and heated with stirring to boil for 6 hours. After standing to cool, it was washed with filtered water and dried at 100 ° C. After drying, it was calcined at 500 ° C. for 6 hours. The mixture was allowed to cool to obtain 195 g of a mica-based composite material coated with titanium dioxide having a high-saturation green interference color that was glittering. As a result of X-ray diffraction, titanium dioxide was anatase, and the particle surface was uniformly coated when observed with a scanning electron microscope. Further, the result of quantitative determination of titanium dioxide by fluorescent X-ray 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 sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, 0.1 g of ferric chloride and 0.2 g of urea were 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 standing to cool, it was washed with filtered water and dried at 100 ° C. After drying, it was calcined at 200 ° C. for 2 hours, and 98 g of a mica-based composite material coated with iron oxide having a pale orange appearance was obtained. As a result of X-ray diffraction, no change was observed in the diffraction line, but as a result of fluorescent X-ray analysis, it was quantified to contain 0.1% by weight of iron. Moreover, as a result of observation with a scanning electron microscope, it was found that the surface of the large-sized 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 and sufficiently stirred with a propeller to uniformly disperse . 4.5 g of ferric ammonium oxalate and 1.0 g of urea were weighed, and 100 ml of ion-exchanged water was added thereto and 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 heated and stirred for 4 hours. After 4 hours, the dispersion was allowed to cool, washed with filtered 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 chroma and a yellow interference color that was orange and brilliant. Further, this was baked at 900 ° C. for 4 hours. After allowing to cool, 40 g of a composite material having a bright, highly saturated yellow, glittering yellow interference color was obtained. From the X-ray diffraction of the obtained composite material, synthetic mica, rutile titanium dioxide, and pseudo-plate titanite (Fe ₂ TiO ₅ ), which is a compound of iron and titanium dioxide, were confirmed. Further, according to observation with a scanning electron microscope, granular particles (approximately 0.08 μm) having slightly larger particles are scattered on the particle surface, and 0.02 μm ultrafine particle particles are scattered under the entire particle surface. Was uniformly coated. From this, the composite material according to this example is a large particle size flaky synthetic mica composite material coated with titanium dioxide and pseudo-plate titanite, and the amount of iron is 0.7% by weight as a result of fluorescent X-ray analysis. there were.

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 exchange water was added and sufficiently stirred with a propeller to uniformly disperse. A solution prepared by dissolving 16 g of cobalt chloride hexahydrate in 150 ml of ion-exchanged water was added to this dispersion. Next, the dispersion is heated to 50 ° C., and a 1 molar aqueous caustic soda solution is added at a dropping rate of 100 ml per minute while stirring to stop the dripping of caustic soda from aging for 2 hours. It was. After 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 composite material that had been allowed to cool was obtained with 43 g of a highly brilliant composite material having a green appearance color and a brilliant interference color of reddish blue. From the result of X-ray diffraction of this material, mica and titanium dioxide and cobalt titanate produced from titanium dioxide and cobalt oxide were confirmed. Further, from observation with a scanning electron microscope, 0.5 μm granular particles were scattered on the surface of large flaky particles, and 0.02 μm ultrafine particles were observed below the particles. Furthermore, it was confirmed from the fluorescent X-ray analysis that 4% by weight of cobalt was coated. And this composite material was uniformly apply | coated to the double-sided adhesive tape, and it affixed on the concealment rate test paper which consists of white and black, and changed the colorimetric angle, and measured the color. As a result, when the color was measured in the 0 ° direction with respect to 45 ° incidence, green was strongly reflected, and when the color was measured at 30 ° close to the regular reflection direction, reddish blue reflection was strongly observed. In other words, the large particle size flaky natural mica composite material coated with cobalt and titanium metal oxide and fired is a flip-flop effect that exhibits a brilliant, brilliant, brilliant appearance with a green appearance color. Expressed. It was a mica-based composite material with excellent design.

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 dioxide-coated large particle size flaky natural mica composite material with a cobalt compound, and calcined at 950 ° C. for 8 hours. After standing to cool, 22 g of a brilliant and bright material having a blue-green appearance with high saturation was obtained. From the X-ray diffraction results of this material, it was determined that it consists 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 granular particles were scattered on the surface of the large flaky particles, and 0.02 μm ultrafine particles uniformly covered the entire surface under the particles. Furthermore, it was confirmed from the fluorescent X-ray analysis that 2.5% by weight of lithium was coated. Then, this composite material was uniformly applied to a double-sided adhesive tape and affixed to a white and black concealment rate test paper, and colorimetry was performed by changing the colorimetric angle. As a result, when the color was measured in the 0 ° direction with respect to 45 ° incidence, blue-green was strongly reflected, and when the color was measured at 30 ° close to the regular reflection direction, reddish blue reflection was strongly observed. In other words, the large particle size flaky natural mica composite material coated with a metal oxide of titanium, cobalt, and lithium and calcined with a bright blue-green color with a high appearance color and a brilliant glitter, A flip-flop effect exhibiting dichroism exhibiting a reddish blue interference color was developed. The material according to this 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 and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, 10 g of nickel sulfate and 1 g of urea were dissolved in 100 ml of ion exchange water, and an aqueous solution was added. The mixture was boiled with stirring and aged for 4 hours. After aging, it was allowed to cool, washed with filtered water and dried at 100 ° C. The obtained material was glaring with a gray appearance color, and 42 g was obtained. 20 g of the obtained material was mixed with 3 g of sodium carbonate and baked at 1200 ° C. for 2 hours. After standing to cool, 21 g of a material having a high-saturation yellow appearance color and having a brilliant and bright blue-green interference color was obtained. From the result of X-ray diffraction of the obtained material, it was confirmed that there was a slight amount of synthetic mica and titanium dioxide and sodium nickel tetanet which is a compound of sodium, nickel and titanate. In addition, a state where the surface of the large particle flaky particles was melted was observed from a scanning electron microscope. Furthermore, as a result of fluorescent X-ray analysis, sodium was 5.5% by weight and lithium was 7% by weight. In other words, this product is a large particle size flaky synthetic mica composite material in which synthetic mica is coated with titanium dioxide and sodium nickel titanate. It was a highly mica-based composite material having a dichroic property of yellow and interference color.

Example 17
40 g of the titanium dioxide-coated large particle size flaky natural mica obtained in Example 1 was added to 700 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. A solution obtained by dissolving 2.1 g of zirconium oxychloride in 50 ml of ion-exchanged water was added to the obtained dispersion, and the mixture was heated to boiling while stirring and aged for 3 hours. After aging, it 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 and sufficiently stirred with a propeller to uniformly disperse. 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. Heated with stirring. Aging was performed at 80 ° C. for 4 hours. After aging, the mixture was allowed to cool, washed with filtered water, and dried at 100 ° C. The resulting material was fired at 200 ° C. for 16 hours. After standing to cool, 42 g of white glittering material was obtained. 5 g of the obtained material was added to 50 ml of a 50% by volume ethanol aqueous solution and stirred with a propeller to uniformly disperse. 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 was shining brightly, but for comparison, the material obtained in Example 1 was changed to a material that had a gray-black appearance color and shining brightly. That is, the processed material was much more resistant to light.

  From the X-ray diffraction of the obtained composite material, only an anatase type of mica and titanium dioxide was confirmed. According to a 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. Furthermore, as a result of performing point analysis by EDX (energy dispersive X-ray analysis), the acicular 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 glittering material with strong light resistance. Moreover, aluminum was 1% by weight as a result of quantification, and zirconium was 0.8% by weight as a result of quantification.

Example 18
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 and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion liquid, 8 g of zinc chloride and 18 g of urea were added and dissolved in 100 ml of 0.1N hydrochloric acid aqueous solution, and this was added. The mixture was heated with stirring and aged at 80 ° C. for 4 hours. After aging, it was allowed to cool and washed with filtered water. To this slurry, 600 ml of ion-exchanged water was added and stirred uniformly with a propeller. A caustic soda aqueous solution was added to the uniform dispersion to adjust the pH to 9 and heated to 80 ° C. To this heated stirring dispersion, 50 ml of an aqueous solution containing 2 g of water glass and 1.0N aqueous hydrochloric acid were simultaneously added dropwise. However, pH 9 was maintained 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 the addition was completed. After aging, it was filtered, washed with water and dried at 100 ° C. The dried material had a white, glittery, yellow interference color, yielding 43 g. From the X-ray diffraction of the obtained material, synthetic mica, rutile titanium dioxide and zinc oxide were observed. Further, from observation with a scanning electron microscope, needle-like particles having a large particle surface of 0.5 μm and granular particles of 0.02 μm were observed. Further, from the point analysis by EDX, the needle shape was a zinc compound, and 0.02 μm was a titanium compound. When the observation magnification with a scanning electron microscope was increased to 100,000, the acicular particles were coated with finer particles of 0.01 μm or less, which were silicon compounds. This indicates that this material is a composite mica material in which large particle size flaky synthetic mica is 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.

Example 19
40 g of the titanium dioxide-coated large particle size flaky synthetic mica composite material obtained in Example 6 was added to 700 ml of ion-exchanged water and sufficiently stirred with a propeller to uniformly disperse. A solution obtained by dissolving 6 g of bismuth nitrate and 2 g of urea in 100 ml of ion-exchanged water was added to the obtained dispersion. The mixture was heated with stirring and aged at 80 ° C. for 4 hours. After aging, it was allowed to cool, washed with filtered water, and dried at 100 ° C. for 8 hours. After drying, it was calcined at 400 ° C. for 2 hours. After standing to cool, 44 g of yellow glittering material was obtained. X-ray diffraction of this material confirmed synthetic mica, titanium dioxide rutile and bismuth oxide. Further, granular particles having a large particle surface of 0.03 μm were scattered from a scanning electron microscope, and further, a slightly smaller granular particle of about 0.02 μm covered the entire surface. And it was found from the point analysis by EDX that the interspersed particles are bismuth and the underlying particles are titanium. Further, bismuth was 6% by weight from fluorescent X-ray analysis. From this, this material is a composite material with a large particle size flaky synthetic mica coated with bismuth oxide and titanium dioxide, which has a yellow appearance color and shines brightly.

Example 20
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 and sufficiently stirred with a propeller to uniformly disperse. To the obtained dispersion, an aqueous solution in which 5 g of tungsten oxychloride was dissolved in 100 ml of ion exchange water was added. The dispersion was heated to 80 ° C. with stirring, a 0.2N aqueous solution of caustic potash was added dropwise at a rate of 10 ml per minute, and the aqueous caustic potash solution was added dropwise until the pH of the liquid reached 9. The mixture was aged at pH 9 for 4 hours. After aging, it was allowed to cool, washed with filtered water, and dried at 100 ° C. The dried material was calcined at 500 ° C. for 2 hours. After standing to cool, 43 g of a material having a pale yellow glitter and a bright green interference color was obtained. X-ray diffraction of this material confirmed synthetic mica, titanium dioxide rutile and tungsten oxide. Further, from observation with a scanning electron microscope, it was found that irregular particles having a large particle surface of 0.3 μm were scattered, and below that, granular particles as small as 0.02 μm covered the entire surface. And the particle | grains scattered from the point analysis by EDX were tungsten, and the particle | grains under it were titanium. Moreover, tungsten was 5 weight% from the fluorescent X ray analysis. Therefore, this material is a large particle size flaky synthetic mica coated with tungsten oxide and titanium dioxide. It was a highly mica-based composite material with color and design

Claims (3)

The average plate diameter of particles obtained by wet crushing in water is 0.1 mm or more and less than 0.5 mm, and the surface of the large particle size flaky synthetic mica having an average particle thickness of 0.2 to 2 μm,
Forming a coating layer composed of one or more of metal oxide and / or metal hydroxide to form a mica-based composite material ;
Method for producing mica-based composite material having a characteristic that, luster and polychromatic flip-flop property that the titanium dioxide is rutile and / or anatase If the metal oxide comprises titanium dioxide. The roughly pulverized product of the synthetic mica was slurried in aqueous hydrochloric acid, after the addition of sodium carbonate to, mica-based composite according to claim 1, wherein the obtaining a large diameter thin-piece-like synthetic mica is wet-pulverized Material manufacturing method. The mica system according to claim 1 or 2, wherein the flaky synthetic mica having a large particle size is coated with one or more metal oxides and / or metal hydroxides and then fired at 200 to 1200 ° C. A method for producing a composite material.