JPS6139349B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a colored porous powder obtained by coloring a newly created porous powder, and specifically, strength, heat resistance, light resistance, fragrance retention, moisture retention, dispersibility, and air permeability. The present invention relates to a colored porous powder that has excellent filling properties and tactile properties and is suitable for various cosmetic base materials, paint base materials, synthetic resins, and colorants for ceramics. Powders conventionally used as carriers for pigments have complex crystal growth processes, so they often already have defects when the structure is formed by crystallization, especially in natural minerals. Due to randomness of atomic arrangement, dropout of atoms, lack of homogeneity within the crystal, etc., crystals exhibit a structure consisting of a discontinuous collection of blocks, and there are almost no crystals that have an ideal arrangement. Powders made of such natural minerals have elasticity, specific heat, specific gravity, transparency, hardness, electromagnetic properties, malleability, heat resistance, cleavability,
It has unique characteristics such as flexibility, and has various properties depending on its crystal structure, density, and crystal shape. For example, minerals that are scaly and have a three-layer structure have weak bonds between layers and are fully cleaved, giving them a slippery feel and being highly elastic. The lack of this is one of the causes of manufacturing problems. In addition, only a small portion of powders with a two-layer structure have excellent cleavage properties, and since the crystals are amorphous, close-packed packing is required due to the flexibility of the powder and the denseness of the crystal shape. It is difficult to obtain a structure, poor in filling properties, and at the same time, it is not possible to obtain a material that is satisfactory in terms of sliding feel. On the other hand, natural minerals contain water and impurities, and there are some sensitive minerals that are affected by the production conditions and non-sensitive minerals that are not affected.
Water in the crystal structure includes free water, attached water, adsorbed water,
Although there is bound water, free water, attached water, and adsorbed water are easily desorbed, attached, or adsorbed depending on external conditions. In particular, when bound water is desorbed, the crystal structure changes. As can be understood from the above, most natural minerals inherently have low moisture retention properties. Viewed from a structural perspective, natural minerals are proven to have the disadvantage of having poor retention of moisture and fragrance, and the smell of fragrance weakens over a short period of time. In addition, most natural minerals have a one-, two-, or three-layer structure, but since they are not porous, they have poor breathability, and when mixed into cosmetics and applied to the skin. It tends to inhibit the skin's ability to breathe, causing stress on the skin. The present invention solves the conventional problems as mentioned above,
This provides a colored porous powder with excellent physical properties. That is, in the colored porous powder according to the present invention, a polyvalent metal hydroxide is impregnated and deposited on the surface of the porous powder, or a thin film of amorphous silicic acid is further fixed thereon. , and the porous powder is a coating material consisting of fine powder of one or more types of anhydrous silicic acid compound, aluminosilicate compound, magnesium silicate compound, and mica, and a metal carbonate compound, an anhydrous powder containing volatile components other than water. It is fixed to the surface of an inner core material made of fine powder of one or more types of aluminosilicate compounds, volatile substances, and combustible substances, or is formed by removing or shrinking the inner core material. It is characterized by To explain the details of the present invention in detail below, first of all, preferred specific examples of natural minerals constituting the porous powder coating material are as shown in the table below, and those having an average particle size of about 1 to 50μ One type or a mixture of two or more types are used.

【table】

[Manufacturing method 1]

The porous powder is uniformly stirred and dispersed in purified water at room temperature to a concentration of 0.1 to 50% by weight, and if necessary, the pH is adjusted to an acidic range of about 2 to 7 with an inorganic acid such as sulfuric acid, nitric acid, or hydrochloric acid. 0.1 in purified water at 80℃
~50% by weight of a water-soluble polyvalent metal salt dissolved in the porous powder and the polyvalent metal salt in a ratio of 1:0.01~
Add at a ratio of 1:1 and stir uniformly so that the pH is in the acidic range of 2 to 6. Next, an alkali such as ammonia water, sodium hydroxide, potassium hydroxide, or an aqueous solution of the alkali and the inorganic acid is gradually added while stirring to make the pH range from 7.5 to 14 to form a porous powder. Polyvalent metal hydroxides are impregnated and deposited on the surface of the body. Thereafter, the powder is sufficiently washed with water until the pH is in the neutral range of 6.5 to 7.5, and air dried or hot air dried at 40 to 100°C to obtain a colored porous powder. Further, if necessary, the oxidation color of the polyvalent metal hydroxide can be changed by firing the obtained colored porous powder at 300 to 1500°C for about 1 to 24 hours. The firing atmosphere may be in an oxidizing state, reducing state, or inert state,
By selecting the atmosphere, it is possible to stabilize the color tone and expand the color tone range. The colored state of the colored porous powder before and after firing is as follows.

〔Production method 〕

The porous powder is uniformly stirred and dispersed in purified water at room temperature to a concentration of 0.1 to 50% by weight, and if necessary, the pH is adjusted to an acidic range of about 2 to 7 with an inorganic acid such as sulfuric acid, nitric acid, or hydrochloric acid. 0.1 in purified water at 80℃
~50% by weight of a water-insoluble polyvalent metal salt dissolved in the porous powder and the polyvalent metal salt in a ratio of 1:0.01
Gradually add while stirring evenly so that the ratio is ~1:1. Next, an alkali such as ammonia water, sodium hydroxide, potassium hydroxide, or an aqueous solution of the alkali and the inorganic acid is gradually added while stirring to obtain a porous powder in the alkaline range of about 7.5 to 14. Polyvalent metal hydroxides are impregnated and deposited on the surface of the body. Then increase the pH to 6.5-7.5
Rinse thoroughly with water until neutral, then air dry or
Colored porous powder is obtained by drying with hot air at 40 to 100°C. The subsequent firing treatment and amorphous silicate thin film forming treatment are the same as in manufacturing method 1. [Production method] Porous powder is stirred and dispersed uniformly in purified water at room temperature to a concentration of 0.1 to 50% by weight, and this dispersion is mixed with inorganic acids such as sulfuric acid, nitric acid, and hydrochloric acid, and sodium hydroxide and potassium hydroxide. After adjusting the pH to a neutral range of 6.5 to 7.5 with an alkali such as ammonia, the ratio of porous powder and polyvalent metal salt is 1:0.01 to 1:
A solution of a polyvalent metal salt and a strong acid dissolved in water so as to have a concentration of 1 is gradually added at room temperature, and at the same time, air is introduced by vigorously stirring the reaction mixture or using a nozzle or the like. at a temperature of 0 to 50 °C, preferably 15 to 40 °C, to form oxyhydroxide in the presence of air as an oxidizing agent;
The pH is adjusted with the above alkali so as to maintain a certain amount within the range of 5 to 11, preferably 6 to 9.
As a result, the oxyhydroxide is impregnated and deposited on the surface of the porous powder particles. Thereafter, this is over-separated, thoroughly washed with water, and air-dried or dried with hot air at 40 to 100°C to obtain a colored porous powder. The subsequent firing treatment and amorphous silicate thin film forming treatment are the same as in manufacturing method 1. The colored porous powder according to the present invention produced by the above manufacturing method is not simply a porous powder with pigments attached to its surface, but an extremely thin porous fine powder impregnated with pigments. It consists of a wall membrane that behaves as a unit. Since the constituent components of the porous powder are inorganic substances, it has excellent heat resistance and light resistance, and especially when a thin film of amorphous silicate is firmly formed, the light resistance and chemical resistance can be further improved. It is possible. In addition, this colored porous powder has a light apparent specific gravity and is compatible with solvents, so it has non-sedimenting properties in a mixed system, behaves as a single body, has excellent dispersibility, and is superior to conventional powders. It provides a moist feel that powders do not have, and can provide a product that is smooth to the touch and has good adhesion. Furthermore, when filled into a container, it is easy to create a close-packed structure and has excellent packing properties. Furthermore, the porous powder according to the present invention has skin irritation,
It is completely non-toxic, and no abnormalities were observed after 24 or 72 hours in a patch test of 102 women with healthy skin. Such colored porous powder has a fragrance-retaining ability, and when it is incorporated into cosmetics, for example, it emits a fragrance for a long time, has an excellent cosmetic effect, and greatly improves filling properties. Furthermore, when blended into paints, etc., it can improve fluidity, heat resistance, light resistance, etc. Furthermore, when blended into synthetic resins as a filler, it is useful for reducing the weight of products. In addition, the porous powder constituting the present invention can freely adjust the particle size and the strength of the coating material layer by changing the ratio of the coating material and the inner core material when they are combined. It is something. Furthermore, the colored porous powder according to the present invention has a particle size of 1
It is about ~100μ. Next, production examples of the porous powder constituting the present invention and the colored porous powder according to the present invention will be shown. Production example 1 5 parts of biotite with a particle size of 3 to 8μ and 40 parts of sericite with a particle size of 2 to 5μ are mixed with 100 cps of dimethylsiloxane.
Gradually add the mixture to 250 parts with stirring, stir at room temperature for 2 hours, take out, filter through a suction aspirator, bake at 850℃ for 1 hour, and quench to obtain a particle size of 5-14.
40 parts of cored porous powder of μ was obtained. Production example 2 15 parts of magnesium carbonate with a particle size of 2 to 8μ and a particle size of 1
45 parts of potassium feldspar with a diameter of ~3μ was dispersed in 1500ml of purified water, stirred with an agitator for 1 hour, taken out, filtered with an aspirator, and fired at 950°C for 18 hours to form a porous core with a particle size of 6~15μ. 55 parts of powder was obtained. Production Example 3 50 parts of the porous powder according to Production Example 2 was mixed with 5% hydrochloric acid.
The powder was immersed in 300 ml for 3 hours, taken out, filtered and dried using a suction aspirator to obtain 43 parts of hollow porous powder. Production example 4 10 parts of bentonite with a particle size of 0.3 to 1.0μ and a particle size of 3 to
Gradually add 10 parts of 7μ butylparaben to 500 parts of 100cps dimethylsiloxane with stirring, stir at room temperature for 30 minutes, take out, absorb with a suction aspirator, and heat in an electric furnace at 130°C at 20°C.
The temperature was raised to 0.degree. C. for 3 hours to sublimate the inner core material, butylparaben, and the mixture was further calcined at 900.degree. C. for 3 hours to obtain 8.5 parts of hollow porous powder with a particle size of 5 to 9 .mu.m. Production Example 5 40 parts of dimethylbenzene pinhole polymer with an average particle size of 5μ and 60 parts of kaolin with an average particle size of 2μ were put into a centrifugal rotary ball mill, mixed and ground for 15 hours, taken out, and heated at 50℃ for 1 hour to 700℃. The temperature was then raised at 800°C for 2 hours to burn off the dimethylbenzene pinhole polymer, which is the inner core material, and then fired at 1000°C for 5 hours and cooled to reduce the average particle size to 5μ.
56 parts of hollow porous powder were obtained. Example 6 Add particle size 3 to 15 parts of kaolionite with particle size 2 to 5μ
Disperse 15 parts of diatomaceous earth with a diameter of 5μ, 10 parts of calcium carbonate with a particle size of 8 to 10μ, and 10 parts of magnesium carbonate with a particle size of 5 to 9μ in 500ml of purified water, stir in an agitator for 1 hour, and then take it out and suction it with a suction aspirator. passed,
The mixture was fired at 1000° C. for 12 hours to obtain 40 parts of cored porous powder with a particle size of 9 to 18 μm. Production example 7 15 parts of bentonite with a particle size of 1 to 2μ and a particle size of 3 to 5
15 parts of μ muscovite and methyl paraben with a particle size of 5 to 7 μ
15 parts and 15 parts of starch with a particle size of 6 to 9μ in 200 ml of purified water.
After stirring in an agitator for 2 hours, it was suctioned through an aspirator and heated to room temperature in an electric furnace.
The temperature is raised to 300℃ in 4 hours to sublimate methylparaben, the inner core substance, and burn starch.
The mixture was further calcined at 1000°C for 8 hours to obtain 28 parts of hollow porous powder with a particle size of 7 to 15 μm. Production Example 8 A 5% by weight nickel nitrate solution was prepared by uniformly dispersing 100 parts of the porous powder according to Production Example 5 in 500 parts of purified water at 40°C and dissolving it in the purified water at 20°C.
After injecting 200 parts to adjust the pH to 3.1 and stirring for 10 minutes,
Gradually add _IN potassium hydroxide solution while stirring to adjust the pH to 9.2, and continue stirring for another 10 minutes to impregnate and deposit nickel hydroxide on the surface of the powder. Next, this powder was separated, thoroughly washed with water, and air-dried to obtain 98.5 parts of blue hollow porous powder. Production Example 9 500 parts of 98.5 parts of the blue hollow porous powder of Production Example 8
Calcinate at ℃ for 8 hours to obtain gray-green hollow porous powder 98.0
I got the department. Production Example 10 The mixed solution in which the nickel hydroxide of Production Example 8 is impregnated and deposited on the surface of the powder (before the powder is separated and dried) is adjusted to pH 8.3 with ammonia water and 25% by weight.
Add 50 parts of an aqueous solution of sodium disilicate and stir thoroughly to adjust the pH to approximately 11.3. Next, this mixture was heated and maintained at 75°C, and 125 parts of 5% sulfuric acid was added over 90 minutes to adjust the pH to 7.6.
After keeping at ℃, 50% sulfuric acid was gradually added to adjust the pH.
6.1. After that, separate the powder from the mixed liquid and repeat washing with water until all soluble salts are removed.
It was dried at a temperature of 112 parts of green hollow porous powder in which a thin film of amorphous silicic acid was fixedly formed on the surface of the porous powder impregnated with a polyvalent metal salt. Production Example 11 112 parts of the green hollow porous powder of Production Example 10 was heated at 500°C.
The mixture was fired for 8 hours to obtain 110 parts of a gray-green hollow porous powder. Production Example 12 40 parts of the porous powder from Production Example 6 was uniformly stirred and dispersed in 300 parts of purified water, and the pH was adjusted to 3.5 with dilute sulfuric acid.
Chromium sulfate, which has been dissolved in sulfuric acid at 20° C., is gradually added with uniform stirring. Next, add iron hydroxide aqueous solution gradually while stirring to adjust the pH.
11.3, and a polyvalent metal salt is impregnated and deposited on the surface of the porous powder. Thereafter, it was thoroughly washed with water until the pH reached 7.2 and dried with hot air at 50°C to obtain 39.5 parts of a gray-green porous powder. Production Example 13 39.5 parts of the gray-green porous powder of Production Example 12 was heated to 750°C.
The mixture was fired for 10 minutes to obtain 39 parts of green hollow porous powder. Production Example 14 Add ammonia water to the mixed solution in which the iron hydroxide of Production Example 12 is impregnated and deposited on the surface of the powder (before the powder is separated and dried) to adjust the pH to 8.7, and make 31.5% by weight.
Add 30 parts of an aqueous sodium orthosilicate solution and stir thoroughly to adjust the pH to 11.4. Next, mix this mixture at 80℃
The mixture is heated and maintained at 200°C, diluted sulfuric acid (5%) is added to adjust the pH to 7.8, and after further holding at 80°C for 50 minutes, 5% sulfuric acid is gradually added to adjust the pH to 6.5. After that, the powder is separated from the mixed solution, washed repeatedly with water until all soluble salts are removed, and dried at 80°C. A thin film of amorphous silica is coated on the surface of the porous powder impregnated with polyvalent metal salts. 61 parts of yellowish brown porous powder was obtained. Production Example 15 61 parts of the tan porous powder of Production Example 14 was heated at 850℃.
After firing for 12 hours, 60 parts of reddish-purple porous powder was obtained. Production Example 16 100 parts of the porous powder from Production Example 6 was uniformly dispersed in 400 parts of purified water, and concentrated ammonia water and dilute sulfuric acid were added to this dispersion to adjust the pH to 7.3, and ferric sulfate was added to this dispersion. A solution of 60 parts dissolved in 300 parts of concentrated sulfuric acid (97%) and 500 parts of water was gradually added while stirring, and the mixture was vigorously stirred with a stirrer for 20 minutes to incorporate air. Next, use concentrated ammonia water (25
%) was gradually added to adjust the pH to 7.3 and maintain it to impregnate and deposit ferric sulfate into the porous powder.Then, the powder was separated, thoroughly washed with water, and air-dried to form a yellow-orange porous powder. Obtained 110 copies. Production Example 17 110 parts of the yellow-orange porous powder of Production Example 16 was heated to 1000°C.
The mixture was fired for 9 hours to obtain 108.5 parts of black porous powder. Production Example 18 Add ammonia water to the mixed solution in which ferric sulfate from Production Example 16 is impregnated and deposited on the surface of the powder (separate the powder, before drying) to adjust the pH to 9.0, and then adjust the pH to 28.4.
Add 50 parts of sodium silicate containing % silicic acid, pH 11.0
Mix thoroughly until evenly dispersed. This mixture was heated to 80°C, 5% sulfuric acid was gradually added for 2 hours to make the pH 7.7, and the mixture was further kept at 80°C for 1 hour until 50% sulfuric acid was added.
Sulfuric acid was added to adjust the pH to 6.1, and the powder was separated, washed with water until no soluble salts were present, and dried with hot air at 80°C to obtain 113 parts of a yellow cored porous powder. Production Example 19 110 parts of the yellow-orange porous powder of Production Example 16 was fired at 650°C for 5 hours to obtain 108.5 parts of black porous powder. Here, the results of a sensory test of fragrance retention conducted by 10 perfumers are shown. All samples were pressed powder containing 65% by weight of porous powder and flavored with 0.6% by weight of lemon, and samples A-1, A-2, and A-
3 and A-4 used the colored porous powders according to Production Examples 8, 10, 12, and 14, respectively, and sample B used a normal natural mineral fine powder (talc). In the following table, ± represents the volatilization strength, - means no, and + means yes.

【table】

[Table] As is clear from these two tables, A according to the present invention
-1, A-2, A-3, A-4 are evaluated at room temperature, 40℃
It is understood that in all evaluations, the fragrance retention is much better than that of B.

Claims (1)

[Scope of Claims] 1. A colored porous powder in which a polyvalent metal hydroxide is impregnated and deposited on the surface of the porous powder; A coating material consisting of fine powder of one or more types of silicic acid compounds and micas is coated with one or more types of metal carbonate compounds, anhydrous aluminosilicate compounds containing volatile components other than water, volatile substances, and combustible substances. A colored porous powder, characterized in that it is configured by adhering to the surface of an inner core material made of fine powder. 2. A colored porous powder in which a polyvalent metal hydroxide is impregnated and deposited on the surface of the porous powder, and a thin film of amorphous silicic acid is further fixed thereon; the porous powder is anhydrous. A coating material consisting of a fine powder of one or more types of silicic acid compound, aluminosilicate compound, magnesium silicate compound, and mica can be used as a metal carbonate compound, an anhydrous aluminosilicate compound containing a volatile component other than water, a volatile substance, A colored porous powder characterized in that it is formed by adhering to the surface of an inner core material made of fine powder of one or more kinds of combustible substances. 3. A colored porous powder in which a polyvalent metal hydroxide is impregnated and deposited on the surface of the porous powder; the porous powder is an anhydrous silicic acid compound, an aluminosilicate compound, a magnesium silicate compound, or a mica. A coating material consisting of one or more fine powders of metal carbonate compounds, anhydrous aluminosilicate compounds containing volatile components other than water, volatile substances, and fine powders of one or more combustible substances. A colored porous powder characterized in that it is formed by adhering to the surface of an inner core material and removing or shrinking the inner core material. 4. A colored porous powder in which a polyvalent metal hydroxide is impregnated and deposited on the surface of the porous powder, and a thin film of amorphous silicic acid is further fixed thereon; the porous powder is anhydrous. A coating material consisting of a fine powder of one or more types of silicic acid compounds, alumino-silicate compounds, magnesium silicate compounds, and mica can be treated with metal carbonate compounds, anhydrous alumino-silicate compounds containing volatile components other than water, volatile substances, and combustion. 1. A colored porous powder, which is formed by adhering to the surface of an inner core material made of fine powder of one or more kinds of sexual substances, and removing or shrinking the inner core material.