JPS5949944B2 - colored porous powder - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a colored porous powder formed by depositing a thin film of a water-insoluble aluminum salt impregnated with a dye on the surface of a newly created porous powder. , has excellent light resistance, fragrance retention, moisture retention, dispersibility, air permeability, fillability, and tactility, and has a particle size of 1 to 1, suitable for coloring agents for various cosmetic bases, paint bases, synthetic resins, ceramics, etc. This relates to a colored porous powder of about 100μ.

Conventionally used powders often have defects when the structure is formed by crystallization due to the complicated crystal growth process. Especially in natural minerals, for example, the disorder of atomic arrangement, There are very few crystals that have a structure consisting of a discontinuous collection of blocks due to dropout of atoms, lack of homogeneity within the crystal, etc., and that have an ideal arrangement.

Powders made of natural minerals have the physical properties of ordinary powders, such as elasticity, specific heat, specific gravity, transparency, hardness, electromagnetic properties,
It has unique properties such as ductility, heat resistance, interosseousness, and flexibility, and it has various properties depending on its crystal structure, its density, and crystal shape. For example, minerals that are scaly and have a three-layer structure have weak bonds between layers and complete interosseous structures, giving a slippery feel and being highly elastic. This lack of quality is one of the causes of manufacturing problems. In addition, only a small portion of powders with a two-layer structure have excellent interosseous properties, and since the crystals are amorphous, close-packing is required due to the flexibility of the powder and the denseness of the crystal shape. It is not possible to obtain a material that is difficult to construct, has poor filling properties, and at the same time provides a satisfactory slippery 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 within a crystal structure includes free water, attached water, adsorbed water, and bound water. Free water, attached water, and adsorbed water are easily desorbed, attached, or adsorbed depending on external conditions, and especially When bound water is desorbed, it causes a change in the crystal structure. As can be understood from the above, most natural minerals inherently have low moisture retention properties. From a structural perspective, natural minerals contain water,
It has been proven that this product has the disadvantage that the fragrance retention property is low and the flavor gradient becomes weaker after a short period of time. In addition, most natural minerals have a one-, two-, or three-layer structure, but since they do not have porosity, they have poor breathability, so they cannot be mixed into cosmetics and applied to the skin. When exposed to sunlight, it tends to inhibit the skin's ability to breathe, causing stress on the skin.

The present invention solves the conventional problems as described above and provides a colored porous powder obtained by coloring a porous powder with excellent physical properties. That is, the colored porous powder according to the present invention is a coating material consisting of fine powder of one or more types of anhydrous silicic acid compound, alumina silicate compound, magosium silicate compound, and mica, and a metal carbonate compound, a volatile material other than water. Porous powder fixed to the surface of the inner core material consisting of fine powder of one or more types of anhydrous alumina silicate compound, volatile substance, and combustible substance, and a gel solution of aluminum hydroxide or aluminum salt. The first feature is that it consists of a thin film of a water-insoluble aluminum salt impregnated with a dye, which is obtained by the reaction between the powder and the dye sting, and which is deposited on the surface of the porous powder.

In addition, the second feature of the porous powder is that the inner core material is removed or shrunk to become hollow.

Hereinafter, the details of the present invention will be explained in detail. Firstly, it is preferable that the natural mineral constituting the coating material of the porous powder has a cation exchange capacity of 20 to 500 milliequivalents; Preferred specific examples are as shown in the following table, in which one or more types of particles having an average particle size of about 1 to 50 μm are used.

Next, the metal carbonate compounds that constitute the inner core material of the porous powder include magnesium carbonate, beryllium carbonate, calcium carbonate, ferric carbonate, barium carbonate, manganese carbonate,
Examples include lithium carbonate, cobalt carbonate, magnesium potassium hydrogen carbonate, strontium carbonate, lithium hydrogen carbonate, zinc carbonate, and chromium carbonate.Metal carbonate compounds that exist as natural minerals include dolomite, calcite, aralite, and strontianite. , Lyokudoite, Dokujiyudoite, etc.

Examples of anhydrous alumina-silicic acid compounds containing volatile components other than water include kakunaiite, biotite, yellow dumolychealite, and zuniite, which lose their volatile components when heated and easily transform into mullite. Minerals that shrink in volume and expand when heated are undesirable, such as nacre, kokuryoku, and pine, and should not be used. In addition, the volatile substances preferably have a dry average particle size of 1 to 50μ, including menthol, gunfur, methylparaben, ethylparaben, propylparaben, butylparaben, naphthalene, sulfur zorpic acid, dehydroacetic acid, benzoic acid, salicylic acid, and cinnamic acid. Examples of combustible substances include nylon, polystyrene, Teflon, polyethylene, polypropylene, polyolefin, Delrin, distylbenzene pinhole polymer, benzoguanamine powder, and other synthetic resins; Examples include copolymers, starch, carbon, and sulfur, and these are preferably spheres or porous spheres. When producing the porous powder applied to the present invention, the weight ratio of the coating material and the inner core material is about 8:2 to 1:9, and the mixture is preferably kept at room temperature in an aqueous system. 700～
When stirred under a reduced pressure of about 760 mmHg, an adsorbed ion layer is formed on the surface of the inner core material, and the negatively charged minerals that are the coating material are attracted to these layers, causing the coating material to adhere and coagulate on the surface of the inner core material. Cored porous powder with an average particle size of about 1 to 50 μm is produced.

The porous powder applied to the present invention can also be produced using an inert solvent instead of in an aqueous system. In this case, the weight ratio of the coating material and the inner core material is 8:2 to 2:8, and the weight ratio of the coating material and the inner core material to the inert solvent is preferably 9:1 to 6:4. is 8.3:1.7. Examples of inert solvents include silicone oil, polybran, and polyoxyethylene tall oil derivatives. The coating material and the inner core material are added to these inert solvents at room temperature, preferably under reduced pressure of about 700 to 76,011 Hg. When vigorously stirred, the coating material and the inner core material are surrounded by the inert solvent and are physically united, and when they are sucked out, a cored porous powder is obtained. Next, the powder produced as described above was heated to 50 to 1500°C in an oxidizing atmosphere.
When fired for about 1 to 24 hours, the fine powder particles constituting the coating material are firmly bound to each other and also to the inner core material, resulting in a powder that does not easily shatter.

If the inner core material is composed of a volatilized material, it will be volatilized during firing to become a hollow porous powder. If the inner core core material is composed of a metal carbonate compound, after firing, it is washed with an acid solution such as hydrochloric acid, nitric acid, or sulfuric acid at a concentration of 1 to 20% by weight to elute the inner core core material and create a hollow This is a porous powder. If the inner core material is made of a combustible material, especially a synthetic resin, the coating material and the inner core material may be mixed in a ratio of 7:3 to 3:7 in an agitating pulverizer of a centrifugal ball mill for 1 to 24 hours. Time-frictional mixing is performed to grind only the coating material and further refine it, and at the same time, the inner core material is charged by friction, and the fine coating material is deposited on the surface of the inner core material as single particles or aggregates. Make it adhere.

Next, this cored porous powder is taken out and heated in an oxidizing gas stream at a temperature of 150 to 1600°C under normal pressure.
As the inner core material burns, the fine powder particles constituting the coating material firmly bind to each other and become a hollow, porous powder that does not easily shatter. Furthermore, if the inner core material is composed of anhydrous alumina silicate compound containing volatile components other than water, the volume can be contracted by performing the firing treatment and acid treatment as described above to form a semi-hollow material. It becomes a porous powder.
In addition, when the inner core material is composed of two or more types of fine powder,
Removal or shrinkage is performed by appropriately combining the above treatments. According to electron microscopic observation (omitted) of the cored porous powder and hollow porous powder obtained as described above, the fine coating material of natural minerals has a spherical shape with a particle size of about 1 to 50 μm. They form an aggregate that is attached to each other in a similar shape, and each coating has voids of various sizes, and these voids, or these voids and the voids in the inner core, have the ability to absorb and dissipate liquids and gases. It turned out to be excellent.

The surface layer forms a high-strength film due to permanent shrinkage of the coating material and partial conversion to crystalline material. Secondly,
First, the dyes impregnated into the thin film of water-insoluble aluminum salt include acid dyes, natural dyes, and basic dyes.The acid dyes include Red No. 2, Red No. 3, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1, Blue No. 2, Red No. 227, Red No. 203-1, Red No. 203-2, Red No. 232, Orange No. 205, Orange No. 207, Yellow No. 202-1, Yellow 20
2-2, Yellow No. 203, Green No. 201, Green No. 204,
Blue No. 205, Brown No. 201, Red No. 401, Red No. 40
No. 5, Red No. 503, Red No. 504, Red No. 506, Orange No. 402, Yellow No. 402, Yellow No. 403-1, Yellow 4
No. 06, yellow No. 407, etc. are exemplified, and natural pigments include brassillin, calsamine, hixin, norbixin, crocin, β-carotene, cabsanthin, safflower aerobic acid, carcinone, shisonine, delphinidin, cacao pigment, carminic acid, and katsukine. Examples include acid, chlorophyll, betanin, glucumin, caramel, monascolpurine, etc., and basic dyes such as auramine, Basic Yellow 1, Prilliant Yellow 14, Basic Orange 2, Basic Orange 14, and Basic Orange 22. , Basic Cred 12, Prilliant Cred 1
4, Basic 14, Basic 18, Basic 34, Basic 37, Crystal Violet 3, Crystal Violet 7, Crystal Violet 10) Crystal Violet 14,
Examples include Basic Bull 1, Basic Bull 15, Basic Bull 21, and Basic Green 4.

In the present invention, one or a mixture of two or more of these is used. Next, examples of aluminum salts constituting the water-insoluble aluminum salt include potassium aluminum sulfate, sodium aluminum sulfate, aluminum chloride, aluminum acetate, aluminum nitrate, and sodium aluminate.

Next, the outline of the method for producing colored porous powder of the present invention will be explained.

[Method 1]

1 part by weight of dry aluminum hydroxide gel (hereinafter abbreviated as DHAG) is suspended in 3 to 1000 parts by weight of water to give 40 to 7 parts by weight.
Warm to 0°C, gradually add 1 to 5 parts by weight of concentrated hydrochloric acid (36%), stir at 40 to 70°C for 15 to 60 minutes, and PHO. 5
~ 3.5 aluminum hydroxide gel solution.

To this gel solution, 0.1 to 50 parts by weight of porous powders applied to the present invention, such as those made in Production Examples 1 to 5 described below, are added and stirred until uniform, and then 0.001 to 0.0 parts of the dye is added. .2
A dye solution prepared by completely dissolving 5 parts by weight in deionized water is gradually added to precipitate the dye-impregnated insoluble aluminum salt on the surface of the porous powder, adjusting the pH to 3-8 if necessary. Then, the liquid temperature was further raised to 50 to 80°C, stirred while keeping it warm for 1 to 3 hours to mature the precipitate, and after cooling and standing overnight, the precipitate was separated in a furnace, washed with water, dehydrated with acetone, and air-dried. The desired colored porous powder is obtained. The precipitate is DHAG
The smaller the ratio of powder to powder, the easier it is to filter, and the lumped powder is brittle and easier to crush, and its gloss increases. 〔Method
1 weight of porous powder in 0.01 to 2.5 parts by weight of an aqueous solution of 0.1 mol of an aluminum salt such as ryorium aluminum sulfate, sodium aluminum sulfate, aluminum chloride, aluminum acetate, aluminum nitrate, sodium aluminate, etc. of the porous powder, and further add deionized water as appropriate so that the porous powder is uniformly suspended in the water.

After stirring this thoroughly, add an acidic detergent of 0.001 to 0.
Gradually add an alkaline dye solution prepared by dissolving 25 parts by weight in a warm alkaline solution such as 1N sodium carbonate, caustic soda, or aqueous ammonia. The amount of alkaline solution at this time is from the same amount to twice the specified amount of the aluminum salt used previously. The mixture is stirred and mixed and the pH is adjusted to 4 to 9 to gel the aluminum salt aqueous solution and precipitate the dye-impregnated insoluble aluminum salt on the surface of the porous powder. When the reaction is completed with sufficient precipitation, the gel solution is heated to 90%
The precipitate was aged at 60-80°C for 30 minutes to 3 hours, and after cooling overnight, the precipitate was filtered, washed with water, dehydrated with acetone, and air-dried to obtain the desired colored porous powder. It's something you get. The properties of the colored porous powder obtained are similar to those obtained by method I. [Method] Add 0.001 to 0.25 parts by weight of the dye. One part by weight of the porous powder is added to an alkaline dye solution prepared by dissolving it in a heated alkaline solution as shown in the method of IN, and is stirred to uniformly disperse it.

A 0.1 molar aqueous solution of an aluminum salt as shown in the method below.
Gradually add 2.5 parts by weight of 01 to 2.5 parts by weight, stir and mix, and adjust the pH.
is adjusted to 4 to 7 to gel the aluminum salt aqueous solution and precipitate the dye-impregnated insoluble aluminum salt on the surface of the porous powder. The amount of alkaline solution is the same as in the method, the subsequent treatments are also the same as in method H, and the properties of the colored porous powder obtained are the same as in the method described above. The colored porous powder according to the present invention is not simply formed by precipitating a water-insoluble aluminum salt with a dye attached to the surface of the porous powder, but is formed by precipitating an extremely thin film of an insoluble aluminum salt impregnated with a dye. This thin film behaves as one with the porous powder.

Aluminum rake is heat resistant, light resistant, weather resistant,
It has excellent dispersibility, breathability, fragrance retention, moisture retention, filling properties, and texture, and the colored porous powder that forms during drying is brittle and easily pulverized, making it suitable for cosmetic ingredients, paints, etc. It is crushed by stirring and kneading it with ingredients, etc.
Therefore, no particular pulverization step is required. In addition, it is well dispersed in a medium and can be effectively applied as a pigment for cosmetics, paints, various decorations, etc. without causing segregation, color separation, color unevenness, or pigment sedimentation. Further, the vivid color tone of the dye is utilized, and by selecting the color tone of the dye, it is possible to obtain any color tone such as red, orange, green, purple, skin tone, and others. Furthermore, the colored porous powder according to the present invention has no skin irritation or toxicity, and is suitable for women with healthy skin.
In the patch test on the front part of the name, it was applied for 24 hours and 72 hours.
No abnormality was found in the evaluation after hours.

Cosmetics containing such colored porous powders are not only firm and smooth without putting a burden on the skin, but also have excellent adhesion, and have excellent fragrance retention and emit a fragrance for a long time. It not only has a cosmetic effect but also greatly improves filling properties. In addition, when blended into paints, etc., it can improve fluidity as well as heat resistance and light resistance, or when used as a filler in synthetic resins, it helps to reduce the weight of products due to its porosity. It is something. Furthermore, in the colored porous powder obtained by the present invention, the particle size and the strength of the coating material can be freely adjusted by changing the ratio of the coating material and the inner core material when they are combined. It is something that can be done.

Next, an example of manufacturing a porous powder applied to the present invention will be shown. [
Production Example 1] 5 parts of muscovite with a particle size of 3 to 8 μm and 40 parts of sericite with a particle size of 2 to 5 μm were gradually added to 250 parts of dimethylsiloxane at 100 cps with stirring, and the mixture was stirred at room temperature for 2 hours. Afterwards, it is taken out, passed through a suction aspirator, fired at 850°C for 1 hour, and rapidly cooled to form a cored porous powder 4 with a particle size of 5 to 14μ.
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Production example 2] Bentonite 1 with a particle size of 0.3 to 1.0μ
0 parts and 10 parts of butylparaben with a particle size of 3 to 7 μm to 100 parts.
It was gradually added to 500 parts of cps dimethylsiloxane with stirring, stirred for 30 minutes at room temperature, taken out, filtered with a suction aspirator, and heated to 1°C at 20°C in an electric furnace.
The temperature was raised to 30°C for 3 hours to sublimate the inner core material, butylparaben, and the mixture was further calcined at 900°C for 3 hours to obtain 85 parts of hollow porous powder with a particle size of 5 to 9μ. .

[Production Example 3] Distylbenzene pinhole polymer 40 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, and taken out.
℃ for 1 hour at a rate of 50℃, held at 800℃ for 2 hours to burn off the inner core material, distylbenzene pinhole polymer, and then calcined at 1000℃ for 5 hours and cooled. [Production Example 4] 15 parts of kaolionite with a particle size of 2 to 5 μ, 15 parts of diatomaceous earth with a particle size of 2 to 5 μ, and carbonic acid with a particle size of 8 to 10 μ 10 parts of calcium and 10 parts of magnesium carbonate with a particle size of 5 to 9μ are mixed with 5 parts of purified water.
00ml, stirred for 1 hour in an agitator, taken out, filtered with a suction aspirator, and heated to 1000°C for 1 hour.
After firing for 2 hours, 40 parts of cored porous powder with a particle size of 9 to 18 μm was obtained.

[Production Example 5] 15 parts of bentonite with a particle size of 1 to 2μ, 15 parts of muscovite with a particle size of 3 to 5μ, 15 parts of methylparaben with a particle size of 5 to 7μ, and 15 parts of starch with a particle size of 6 to 9μ are mixed with purified water. 20
After stirring for 2 hours in an agitator and passing through a suction aspirator, it was heated to 30°C from room temperature in an electric furnace.
The temperature is raised to 0℃ in 4 hours to sublimate the inner core substance methylparaben and burn the starch, and then further heated to 1000℃.
The powder was fired for 8 hours to obtain 28 parts of hollow porous powder with a particle size of 7 to 15 microns.

Further, examples of the present invention will be shown below.

[Example 1] DHAG5O9 was suspended in purified water 5007!11, 50d of concentrated hydrochloric acid was gradually added, stirred at 40°C for 1 hour, and P
Let it be an aluminum hydroxide gel of H3O.

The porous powder 3509 prepared in Production Example 1 was heated in 4% hydrochloric acid for 30 minutes, washed with purified water, dried, added to the gel solution, stirred and mixed until uniform, and then red 5
No. 04 0.5f! A dye solution prepared by dissolving the powder in 100 ml of deionized water was gradually added, kept at 50°C, and stirred for 1 hour to deposit a thin film of insoluble aluminum salt impregnated with red No. 405 on the surface of the porous powder. do.

Thereafter, the mixture was left to cool overnight to remove the precipitate, washed with water, and air-dried to obtain red porous powder 3879. [Example 2] Porous powder 1009 prepared according to Production Example 4 was heated with 3% sulfuric acid at 60°C for 30 minutes, washed with water, dried, and added to 100 ml of a 0.1 M sodium aluminum sulfate aqueous solution and thoroughly stirred. Stir to obtain a uniform dispersion.

An alkaline dye solution prepared by dissolving carminic acid 109 in 1 mol of caustic soda solution 601 heated to 40°C was gradually added to the above dispersion and mixed with stirring, the pH was adjusted to 6.0, and the mixture was turned into a gel. A thin film of insoluble aluminum salt impregnated with carminic acid is deposited on the surface of the porous powder. After that, the temperature of the gel solution was raised to 90°C, and then to 70-80°C for 1
After the mixture was left to cool overnight, the precipitate was separated, washed with water, and air-dried to obtain a purple porous powder 1589.

[Example 3] Porous powder 1000f made according to Production Example 5! 3%
Heat to 60°C for 30 minutes with sulfuric acid, wash with water, dry, and add 2.59% of laccaic acid and 30% of a 0.5M sodium carbonate solution.
Add 0.09 to deionized water 10009 and stir thoroughly to make a uniform dispersion. To this, 0.1 mol potassium aluminum sulfate solution 5001 was gradually added with stirring and the pH was adjusted to 6.0 and mixed. The liquid is gelled to deposit a thin film of insoluble aluminum salt impregnated with laccaic acid on the surface of the porous powder.

Claims (1)

[Scope of Claims] 1 (a) A coating material consisting of fine powder of one or more types of anhydrous silicic acid compound, alumina silicate compound, magnesium silicate compound, and mica, containing a metal carbonate compound and a volatile component other than water. Porous powder fixed to the surface of an inner core material consisting of fine powder of one or more types of anhydrous alumina silicate compound, a volatile substance, and a combustible substance, and (b) a gel solution of aluminum hydroxide or aluminum salt. A colored porous powder comprising a thin film of a water-insoluble aluminum salt impregnated with a dye and precipitated on the surface of the porous powder obtained by a reaction between the porous powder and a dye. 2 (a) A coating material consisting of fine powder of one or more types of anhydrous silicic acid compound, alumina silicate compound, magnesium silicate compound, and mica is coated with a metal carbonate compound, an anhydrous alumina silicate compound containing volatile components other than water, and volatilization. (b) a hollow porous powder that is fixed to the surface of an inner core material made of fine powder of one or more types of combustible substances and combustible substances, and from which the inner core material has been removed or shrunk; 1. A colored porous powder comprising a thin film of a water-insoluble aluminum salt impregnated with a dye obtained by the reaction of a gel solution of aluminum or an aluminum salt with a dye and deposited on the surface of the porous powder.