JPS5949945B2 - colored porous powder - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a colored porous powder made by bonding pigments to a newly created porous powder, specifically strength, heat resistance, light resistance, fragrance retention, and moisture retention properties. , relating to colored porous powders with a particle size of about 1 to 100μ that have excellent dispersibility, air permeability, fillability, and tactility, and are suitable as colorants for various cosmetic bases, paint bases, synthetic resins, ceramics, etc. It is.

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 are fully developed, giving a slippery feel and being highly elastic. This lack is one of the causes of manufacturing problems. In addition, only a small number of powders with a two-layer structure have excellent arm-opening properties; It is difficult to form a filling structure, the filling properties are poor, and at the same time, it is impossible to obtain a material that provides a satisfactory slippery feel. On the other hand, natural minerals contain moisture and impurities, and there are sensitive minerals that are affected by the production conditions and non-sensitive minerals that are not affected. There are three types of water in a crystal structure: free water, attached water, and bound water. Free water, attached water, and adsorbed water are easily desorbed, attached, or adsorbed depending on external conditions, and bound water in particular is easily desorbed. This causes a change in the crystal structure. As can be understood from the above, most natural minerals inherently have low moisture retention properties. Viewed from a structural standpoint, natural minerals are proven to have the disadvantage of having poor moisture and aroma retention, and the flavor gradient becoming weaker over 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, magnesium silicate compound, and micas, and a metal carbonate compound, volatile material other than water. The pigments are ionized to the porous powder that is fixed to the surface of the inner core material, which is one or more types of anhydrous alumina silicate compound, volatile substance, and combustible substance. The first feature is that the pigments are bound to the porous powder by an ion exchange reaction, and the pigments are further bound to the porous powder using polyvalent metal ions as a medium. The second characteristic is that

Furthermore, a third feature is that the pigments are bonded to the porous powder from which the inner core material has been removed or shrunk by an ion exchange reaction, and the pigments are bonded to the porous powder by an ion exchange reaction. Furthermore, the fourth feature is that pigments are bound to this porous powder using polyvalent metal ions as a medium. The details of the present invention will be specifically explained below.
First of all, as the natural mineral constituting the porous powder coating material, it is preferable to have a cation exchange capacity of 20 to 500 milliequivalents, and the preferred specific examples are as shown in the table below. One type or a mixture of two or more types of particles having a 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, chromium carbonate, etc. Metal carbonate compounds that exist as natural minerals include dolomite, calcite,
Examples include araleite, strontianite, lyokudite, and dokujiudite.

Examples of anhydrous alumina-silicic acid compounds containing volatile components other than water include kakunaiite, biotite, kodama, dumolychealite, and zunite. These lose their volatile components by heating and easily turn into mullite. It is a mineral that undergoes translocation and shrinks in volume.
Pearlite, blackstone, pinestone, etc., which expand when heated, are undesirable and should not be used. The volatile substances preferably have an average particle size of 1 to 50 μm, including menthol, gunfur, methylparaben, ethylparaben, propylparaben, butylparaben, naphthalene, sulfur zorpic acid, dehydroacetic acid, benzoic acid, salicylic acid, and cinnamic acid. , parachlorobenzoic acid, paraoxybenzoic acid, etc.Further combustible substances include synthetic resins such as nylon, polystyrene, Teflon, polyethylene, polypropylene, polyolefin, Delrin, distylbenzene pinhole polymer, benzokeanamine powder, etc. Examples include copolymers of, starch, carbon, sulfur, etc. 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. 70
When stirred under a reduced pressure of about 0 to 76011 Hg, 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 aggregate on the surface of the inner core material. A cored porous powder with an average particle size of about 1 to 50 μm is produced.

Moreover, 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. The ratio is 8.3:1.7. Inert solvents include silicone oil, polybran,
Examples include polyoxyethylene tall oil derivatives, and when the coating material and the inner core core material are added to these inert solvents and stirred vigorously at room temperature under reduced pressure, preferably about 700 to 76,011 Hg, the coating material and the inner core are separated. The core material is surrounded by an inert solvent and physically unified, and when they are filtered by suction, a cored porous powder is obtained. Next, the powder prepared as described above was heated to 50 to 150 ml in an oxidizing gas stream.
When fired at about 0°C for about 1 to 24 hours, the fine powder particles that make up the coating material are firmly bound to each other, and at the same time, the inner core material is also firmly bound to each other, resulting in a powder that does not easily shatter. .

Here, if the inner core material is composed of a volatile material, it will volatilize during firing and 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 with a concentration of about 1 to 20% by weight to elute the inner core core material and form hollow pores. It is made into a 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 flow at a temperature of 150 to 1,600 degrees Celsius under normal pressure.The inner core material burns and the fine powder particles that make up the coating material burn. are strongly bound together to form a hollow porous powder that cannot be easily crushed. Furthermore, if the inner core material is composed of an anhydrous alumina silicate compound containing a volatile component other than water, the volume can be contracted by performing the combustion treatment and acid treatment as described above to form a semi-hollow porous material. It becomes powder. In addition, when the inner core material is composed of two or more kinds of fine powders, the above-mentioned treatments are appropriately combined to remove or shrink the material. According to electron microscopic observation (omitted) of the cored porous powder and hollow porous powder obtained as described above, the natural minerals that are the fine coating material are spherical with a particle size of about 1 to 50 μm. It is an aggregate that is stuck together in a shape close to an elliptical sphere, and each coating has voids of various sizes, and liquids and gases are absorbed by these voids, or by these voids and the voids in the inner core. It was found that the dissipation ability was excellent.

The surface layer forms a high-strength film due to permanent shrinkage of the coating material and partial conversion to crystals. Second, the pigments applicable to the present invention include acid dyes, natural pigments,
Basic dyes include acidic dyes such as 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, and Red 203. −
No. 2, Red No. 232, Orange No. 205, Orange No. 207, Yellow No. 202-1, Yellow No. 202-2, Yellow No. 203, Green No. 201, Green No. 204, Blue No. 205, Brown 201
Examples include Red No. 401, Red No. 405, Red No. 503, Red No. 504, Red No. 506, Orange No. 402, Yellow No. 402, Yellow No. 403-1, Yellow No. 406, Yellow No. 407, etc., and natural pigments. As Brassillin, Calsamine,
Examples include hixin, norbixin, crocin, β-carotene, cabsanthin, safflower aerobic acid, carcinone, shisonin, delphinidium, cacao pigment, carminic acid, cutcaic acid, chlorophyll, petanine, glucumin/caramel, and monas erpurin. Basic dyes include auramine, Basic Yellow 1, Brilliant Yellow 14, Basic Yellow 2, Basic Orange 14, Basic Orange 22, Basic Cred 12, Brilliant Red 14, Basic Cred 14, Basic Cred 18, Basic Cred 34,
Basic Cred 37, Crystal Violet 3, Crystal Violet 7, Crystal Violet 10
) Crystal Violet 14, Basic Blue 1,
Examples include the basic bullion 5, the basic bullion 21, and the basic barrel 4.

In the present invention, one or a mixture of two or more of these is used. Next, water-soluble polyvalent metal compounds that create polyvalent metal ions include transition element magnesium, calcium, barium, zinc, tin, iron, zirconium, antimony, molybdenum, strontium, aluminum, and other nitrates, sulfates, and chlorides. Among these, nitrates, sulfates, etc. of calcium, aluminum, barium, zirconium, etc., which have a large adsorption capacity,
Chlorides and the like are preferred.

Next, to explain the gist of the method for producing colored porous powder of the present invention, for example, porous powder 10 produced in Production Examples 1 to 7 described below.
Disperse 0 part in 200-500 parts of purified water, adjust the pH to 2-7.5 with a buffer solution, and gradually add 50-100 parts of a dye aqueous solution containing 0.1-1 part of the dye to this with stirring. After stirring at 10 to 50°C for 10 minutes to 2 hours, the porous powder and the pigments are allowed to undergo an ion exchange reaction and bond together by being left to stand for 1 to 12 hours. The clear liquid is decanted until it becomes transparent, filtered, and air-dried or dried at 40 to 80°C to produce a colored porous powder. However, instead of decantation, a centrifuge is used to make the supernatant liquid clear. Treat until dry and air dry or 40-80℃
It is dried to form a colored porous powder.

In addition, after ion exchange reaction between the porous powder and the pigments, a 0.1 to 10% by weight polyvalent metal salt aqueous solution of 50 to 500% is added.
After stirring for 20 minutes to 12 hours, the powder is treated as described above to obtain a colored porous powder. The colored porous powder according to the present invention is not simply a porous powder with pigments attached to its surface, but is composed of an extremely thin porous fine-walled membrane impregnated with pigments, which are integrally formed. It behaves as follows. and,
Since the constituent components of the porous powder are inorganic substances, it has excellent heat resistance and light resistance, and especially when treated with a polyvalent metal salt, the light resistance can be further improved. In addition, the colored porous powder according to the present invention has a light apparent specific gravity and has affinity with solvents, and therefore has non-sedimenting properties in a mixed system, behaves as a single body, and has excellent dispersibility. At the same time, it provides a moist feel that conventional powders do not have, and can provide a product that is smooth to the touch and has good adhesion.

In addition, when filling a container, it is easy to create a close-packed structure.
It also has excellent packing properties. Furthermore, the colored porous powder according to the present invention has no skin irritation or toxicity;
In a patch test on the anterior bound areas of 102 women with healthy skin, no abnormalities were observed after 24 and 72 hours.

Cosmetic products containing such colored porous powders are not only moisturizing and smooth without putting any burden on the skin, but also have excellent adhesion, and also have fragrance-retaining power 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 can help reduce the weight of products due to its porosity. It is. In addition, in the porous powder obtained by the present invention, the particle size and the strength of the coating material layer can be freely adjusted by changing the ratio of the coating material and the inner core material when they are combined. I can do it.

Next, an example of manufacturing a porous powder applied to the present invention will be shown.

[Production Example 1] 5 parts of biotite 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. It was then taken out, filtered with a suction aspirator, and incubated at 850°C for 1
The mixture was fired for a time and then rapidly cooled to obtain 40 parts of cored porous powder with a particle size of 5 to 14 μm.

[Production Example 2] 15 parts of magnesium carbonate with a particle size of 2 to 8μ and 45 parts of potassium feldspar with a particle size of 1 to 3μ are mixed with 1500W of purified water.
The powder was dispersed in L1, stirred with an agitator for 1 hour, taken out, filtered with suction using a suction aspirator, and calcined at 950°C for 18 hours to obtain 55 parts of cored porous powder with a particle size of 6 to 15 μm.

[Production Example 3] 50 parts of the porous powder according to Production Example 2 was added to 300 ml of 5% hydrochloric acid.
1 for 3 hours, taken out, filtered by suction using a suction aspirator, and dried to obtain a hollow porous powder.

[Manufacturing Example 4] 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 at room temperature for 30 minutes, taken out, filtered with suction using a suction aspirator, and heated to 1.5% at 20°C in an electric furnace.
The temperature was raised to 30°C for 3 hours to sublimate the inner core substance, butylparaben, and the mixture was further calcined at 900°C for 3 hours to obtain 8.5 parts of hollow porous powder with a particle size of 5 to 9μ. .

[Production Example 5] Distylbenzene pinhole polymer 40 with an average particle size of 5μ
and 60 parts of kaolin with an average particle size of 2μ were placed in a centrifugal rotating ball mill, mixed and ground for 15 hours, taken out, and heated to 700°C.
The temperature was raised at a rate of 50°C for 1 hour until 100°C, then held at 800°C for 2 hours to burn off the distylbenzene pinhole polymer, which is the inner core material, and then fired at 1000°C for 5 hours and cooled. 56 parts of hollow porous powder with an average particle size of 5 μm was obtained.

[Production Example 6] 15 parts of kaolionite with a particle size of 2 to 5μ, 15 parts of diatomaceous earth with a particle size of 3 to 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 are mixed with purified water. 5
00Tn1, stirred in an agitator for 1 hour, taken out, filtered with suction using a suction aspirator, and stirred at 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 7] 15 parts of pentonite 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 in an agitator for 2 hours, it was filtered using a suction aspirator, and heated to 300°C from room temperature in an electric furnace.
The temperature was raised in 4 hours to sublimate the inner core material methylparaben and burn the starch, and then further heated to 1000℃ for 8 hours.
After firing for a period of time, 28 parts of hollow porous powder with a particle size of 7 to 15 μm was obtained.

Further, examples of the present invention will be shown below. [Example 1] Porous powder 1001 according to Production Example 5 was mixed with purified water 5 at 40°C.
00a, inject the buffer solution, stir for 10 minutes, and adjust the pH.
4. Adjust to O.

Next, 100 ml of a 2% by weight aqueous solution of Blue No. 1 dye was gradually added with stirring, and after stirring for 1 hour, the mixture was kept still and the process was repeated until the supernatant and filtrate became transparent. The precipitate was collected and air-dried. A blue porous powder of 99.49% was obtained. [Example 2] The porous powder 1009 according to Production Example 6 is dispersed in 500 ml of purified water at 20°C, and a buffer solution is poured into the dispersion, followed by stirring for 60 minutes to adjust the pH to 5.6.

Next, 200a of a 1% by weight calsamine aqueous solution was gradually added with stirring, and after stirring for 1 hour, 100Tn1 of a 2% by weight aluminum chloride aqueous solution was added, and after stirring for 30 minutes, the supernatant was removed. After repeating water washing and filtration until it became transparent, the precipitate was collected and dried in an oven at 40°C to obtain red porous powder 999. [Example 3]
Porous powder 1009 according to Production Example 5 was mixed with purified water 4 at 20°C.
Dispersed in 00WLI, 0.1N sodium citrate and 0
．． pH 6.4 with 1N sodium hydrogen phosphate buffer
Adjust to.

Next, 707IL1 of 0.1 (L) solution of Blue No. 1 was added, heated while stirring, continued stirring at 45°C for an additional 30 minutes, and then left standing at room temperature for one day and night.

Decantation and filtration of the sample after the ion exchange reaction were repeated until the supernatant liquid became transparent, and the filtered sample was air-dried to obtain a blue porous powder 969. [Example 4
] Porous powder 1009 according to Production Example 4 was mixed with purified water 3 at 20°C.
00111 and adjusted to pH 3.2 with a buffer of 0.1N succinic acid and 0.1N sodium dihydrogen phosphate.

Next, 300 a of 1':F6 solution of Green No. 3 was added and heated to 40° C. while stirring. After continuing stirring for another 1 hour, the mixture was allowed to stand at room temperature for 6 hours. Thereafter, decantation and filtration were repeated until the supernatant liquid became transparent, and the filtered sample was air-dried to obtain green porous powder 989. Also,
This green porous powder was added to a 5% solution of aluminum chloride, stirred for 30 minutes, allowed to stand, and the precipitate was collected and air-dried to obtain a dark green porous powder 989.

Claims (1)

[Scope of Claims] 1. A coating material consisting of a 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 and anhydrous alumina containing volatile components other than water. It is characterized in that pigments are bonded to porous powder fixed to the surface of an inner core material made of fine powder of one or more of silicic acid compounds, volatile substances, and combustible substances through an ion exchange reaction. colored porous powder. 2. 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 can be used as a metal carbonate compound, an anhydrous alumina silicate compound containing a volatile component other than water, or a volatile substance. , pigments are bonded to the porous powder fixed to the surface of the inner core material consisting of one or more fine powders of combustible substances through an ion exchange reaction, and furthermore, pigments are bonded to this porous powder in large quantities. A colored porous powder characterized by bonding with valent metal ions as a medium. 3. 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 volatile substances. , pigments are bonded to the porous powder by ion exchange reaction, which is fixed to the surface of the inner core material made of fine powder of one or more kinds of combustible substances, and from which the inner core material has been removed or shrunk. A colored porous powder characterized by: 4 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 a volatile component other than water, and a volatile substance. , the pigments are bonded to the porous powder by ion exchange reaction, which is fixed to the surface of the inner core material made of fine powder of one or more kinds of combustible substances, and from which the inner core material has been removed or shrunk; A colored porous powder characterized in that pigments are bonded to this porous powder using polyvalent metal ions as a medium.