JP4490682B2 - Synthetic phlogopite powder, process for producing the same, and cosmetics containing the powder - Google Patents

Description

  The present invention relates to a synthetic phlogopite powder, particularly a synthetic phlogopite powder that has a very low solubility in acid and has almost no elution of fluorine ions, and has a good feeling of use.

Currently, mica can be synthesized artificially. Synthetic mica containing OH, like the crystal structure of natural mica, needs to melt the raw material mixture under pressure. Fluorine mica, in which OH in natural mica crystals is replaced with fluorine, melts under normal pressure. Since they can be synthesized, most of the industrially synthesized mica is fluorine mica, and synthetic mica usually refers to such fluorine mica.
There is a melting method as a general production method of fluorine mica that is adopted industrially. In this method, an oxide such as SiO ₂ , Al ₂ O ₃ , MgO, and a fluorine compound such as K ₂ SiF ₆ , KF are used. Alternatively, carbonate or the like is used as a raw material, and these are mixed according to the composition of the intended synthetic mica, and this raw material mixture is melted at about 1400 to 1600 ° C. in an electric furnace. And after cooling the obtained melt and depositing a crystal | crystallization, it grind | pulverizes, classifies, etc. according to a use, It is set as a powder product.

Potassium phlogopite [theoretical formula: KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ ] has a structure in which OH of natural phlogopite [theoretical formula: KMg ₃ (AlSi ₃ O ₁₀ ) (OH) ₂ ] is replaced by fluorine. It has a synthetic fluorine phlogopite. Potassium phlogopite is not swellable like natural phlogopite, and does not contain impurities compared to natural phlogopite. Therefore, potassium phlogopite has been frequently used as a body pigment for cosmetics in recent years.
In general, when the interlayer ion is potassium ion, it is non-swellable to water, and when the interlayer ion is sodium ion or lithium ion, it is considered to be swellable to water. It is said that sodium phlogopite [theoretical formula: NaMg ₃ (AlSi ₃ O ₁₀ ) F ₂ ] in which potassium of phlogopite is replaced with sodium shows swelling properties.

However, sodium phlogopite has never been found in nature, and high-purity sodium phlogopite could not be obtained even by artificial synthesis.
That is, when a raw material mixture is melted in an electric furnace to synthesize sodium phlogopite as in the prior art, a swellable synthetic mica can be used even if a raw material is mixed in a proportion corresponding to the theoretical formula. Therefore, it is necessary to prepare an excess sodium fluoride as a raw material in the raw material mixture (Non-patent Document 1). Therefore, an impurity phase is contained in the product, and it has not been possible to obtain a powder having a desired swelling property and cation exchange ability. In addition, since excessive sodium fluoride is used, the raw material cost is increased, and further, the amount of fluorine ions eluted is significantly higher than that of ordinary swelling mica.

Fluorine ions are hardly eluted with non-swellable fluorine mica, whereas swellable fluorine mica swells in water and increases the interlayer distance, so that fluorine ions are easily eluted. In the cosmetics field, it is currently used that the elution amount of fluorine ions in a hot water elution test at 100 ° C. for 1 hour is 20 ppm or less in consideration of the safety of eluted fluorine ions and the effect on the quality of the composition. It is a standard. Fluorine ion elution amount of commercially available swellable fluorinated mica is as high as 100 to 10000 ppm. Therefore, swellable fluorinated mica has various organic compounds depending on its thickening gelling ability, emulsifying ability, or its cation exchange ability. In spite of having the ability to form a complex with inorganic compounds, inorganic swellable fluorine mica has not been put into practical use in the cosmetics field.
As a method for reducing the elution property of fluorine ions from fluorine mica, for example, heat treatment of fluorine mica at 600 to 1350 ° C. is known (Patent Document 1).
However, sodium phlogopite synthesized using a raw material mixture containing excess sodium fluoride as described above must satisfy the standard values of the severe dissolution test as described above even if heat treatment as described above is performed. I couldn't.

  In the Japanese Patent Application No. 2003-304868, when the raw material mixture is melted in a high frequency induction furnace, the raw material is mixed in a proportion corresponding to the theoretical composition of sodium phlogopite without adding excess sodium fluoride. Using this mixture, it was reported that sodium phlogopite containing almost no impurities was obtained. Since this sodium phlogopite powder has high purity, the cation exchange capacity (CEC) is very high, and the elution amount of fluorine ions is also very low as compared with the conventional electric furnace melting method. Further, if the sodium phlogopite powder is subjected to the baking treatment of Patent Document 1 described above, it is possible to obtain a powder having a fluorine ion elution amount of 20 ppm or less in a severe elution test of cosmetic safety standards. The sodium phlogopite powder was very excellent in that it had a soft, moist and very good feel that was not found in potassium phlogopite.

However, in this sodium phlogopite powder, the acid-soluble matter amount in the acid-soluble matter test was very high at 30 to 40%, and there was a problem in acid resistance.
Regarding mica, in addition to the elution amount of fluorine, the acid solubility is low due to concern about the quality, and specifically, the acid-soluble matter amount in the acid-soluble matter test is 2.0% or less. It is defined by cosmetic safety standards. Therefore, in practical application in the cosmetics field, it is also important to satisfy the standard value of this acid-soluble matter test. Some potassium phlogopite meets these criteria, but lacks the soft and moist feel of sodium phlogopite.

Fluorine micas p.123-141, Chapter 16 Water-swellable fluorinated mica and montmorillonite, author: Haskiel R. Shell & Kenneth H. Ivey, publisher: US Dept. of the Interior, Bureau of Mines, publication year: 1969 Year. Japanese Patent Publication No.7-115858

  The present invention has been made in view of the above-mentioned problems of the background art, and its purpose is that the elution of fluorine ions and the solubility in acid are very low, the touch is soft, and the moisture is very good. It is to provide a synthetic phlogopite powder that feels good.

  As a result of intensive studies by the present inventors in order to solve the above problems, the synthetic sodium phlogopite powder melt-synthesized in a high-frequency induction furnace is brought into contact with a monovalent cation Y having an ion radius of 1.20 mm or more. It was found that a phlogopite powder having high acid resistance and almost no elution of fluorine ions can be obtained by replacing a part of sodium ions of sodium phlogopite with cation Y. It was also found that the phlogopite powder feels inferior to the synthetic sodium phlogopite powder before contact with the cation solution and has a soft and moist feel, thus completing the present invention. It was.

That is, the synthetic mica powder of the present invention, 5 to 50 mol% of sodium synthetic sodium phlogopite in the powder are replaced by an ion radius 1.20Å least one divalent cation Y, acid solubles The acid-soluble substance amount in the test is 2.0% or less, and the fluorine elution amount in a hot water elution test at 100 ° C. for 1 hour is 20 ppm or less .
In the synthetic phlogopite powder of the present invention, Y is preferably at least one selected from the group consisting of potassium (K), ammonium (NH ₄ ), silver (Ag), rubidium (Rb), and cesium (Cs). It is.

The manufacturing method of a synthetic phlogopite powder to the present invention, a synthetic sodium phlogopite powder, is contacted with an ionic radius 1.20Å least one divalent cation Y, sodium synthetic sodium phlogopite in the powder Of these, 5 to 50 mol% is substituted with a monovalent cation Y having an ionic radius of 1.20Å or more .
In the method of the present invention, it is preferable that the synthetic sodium phlogopite powder obtained by melting by high frequency induction heating is subjected to contact treatment with the monovalent cation Y and further heat treated at 600 to 1350 ° C. is there.
In the method of the present invention, it is preferable that the synthetic sodium phlogopite powder obtained by melting by high-frequency induction heating is heat-treated at 600 to 1350 ° C. and then contacted with the monovalent cation Y. It is.
Moreover, the cosmetic according to the present invention is characterized in that the synthetic phlogopite powder described above is blended.

  The synthetic phlogopite powder of the present invention has an acid-soluble substance amount of 2.0% or less in a cosmetic safety standard acid-soluble substance test and a fluorine ion elution amount of 20 ppm or less in a hot water elution test. Since the feeling of use is soft and moist, and is very good, it is particularly suitable as a cosmetic raw material.

First, a method for producing the synthetic phlogopite powder of the present invention will be described.
The production of the synthetic phlogopite powder of the present invention is characterized in that the synthetic sodium phlogopite powder is brought into contact with a monovalent cation Y having an ion radius of 1.20Å or more. In this contact treatment, a part of sodium ions of sodium phlogopite is replaced with monovalent cation Y.
In the synthetic phlogopite powder of the present invention, it is preferable that the molar ratio of Na: Y is 95: 5 to 50:50. When the substitution rate of the cation Y is less than 5 mol%, the acid-soluble matter amount in the acid-soluble matter test does not become 2.0% or less, and the safety standard may not be satisfied. On the other hand, the upper limit of the substitution rate of the cation Y is at most about 50 mol% in the method of the present invention.

The contact treatment method using the monovalent cation Y is not particularly limited as long as the effect of the present invention is obtained. For example, the contact treatment method can be suitably performed by bringing the synthetic sodium phlogopite powder into contact with a solution containing the cation Y. . This treatment is possible in the atmosphere at normal pressure.
Specific examples of the monovalent cation Y include silver ion (Ag ⁺ ), potassium ion (K ⁺ ), ammonium ion (NH ₄ ⁺ ), rubidium ion (Rb ⁺ ), and cesium ion (Cs ⁺ ). , Preferably potassium ion (K ⁺ ) or ammonium ion (NH ₄ ⁺ ). In the present invention, the ionic radius is based on the values described in Shannon (1976) Acta Crystallogr., A32, 751.

The cation Y used for the contact treatment must have an ionic radius of 1.20 mm or more and a monovalent one. A monovalent or polyvalent cation having an ionic radius of less than 1.20Å [eg, lithium ion (Li ⁺ ), sodium ion (Na ⁺ ), calcium ion (Ca ²⁺ ), zinc ion (Zn ²⁺ ), aluminum ion ( Al ³⁺ )] or a solution containing a divalent cation [for example, barium ion (Ba ²⁺ )] having an ionic radius of 1.20 mm or more has an acid-soluble substance amount of 2 in the acid-soluble substance test method. Not less than 0.0%. In addition, when they are brought into contact with these cation solutions, the amount of elution of fluorine is increased, and the value may be much higher than 20 ppm.

The solution of the monovalent cation Y can be prepared by dissolving an inorganic or organic acid salt such as chloride, hydroxide, nitrate, sulfate, carbonate or acetate containing the cation Y in water. These salts and complex salts such as potassium ammonium sulfate can also be used.
The amount of the monovalent cation Y used is 9.0 × 10 ⁻⁵ mol or more, preferably 1.8 × 10 ⁻⁴ mol or more, more preferably 9.0 × 10 ⁴ g per 1 g of the raw material sodium phlogopite powder. ^-4 mol or more is used. As an example, when 9.0 × 10 ⁻⁵ mol of monovalent cation Y is brought into contact with 1 g of raw material mica powder, 15 g of mica powder is added to 300 g of 0.03 wt% potassium chloride aqueous solution. May be mixed and contacted.

The contact temperature may be appropriately set depending on the conditions such as the type and concentration of the cation Y solution, the particle size of the mica powder, and is usually 5 ° C to 100 ° C, preferably 10 ° C to 70 ° C, more preferably 25 ° C. It is 40 degreeC.
The contact time may be appropriately set depending on the conditions such as the type and concentration of the cation Y solution, the particle size of the mica powder, and is usually 10 minutes to 12 hours, preferably 30 minutes to 6 hours, more preferably 1 to 3 hours. The contact with the cation Y solution is more effective when the raw mica powder and the monovalent cation Y in the solution are uniformly contacted using a stirrer or the like. After such contact treatment, washing, drying, classification, etc. are performed as necessary to obtain a product powder.

The particle size of the synthetic phlogopite powder of the present invention is appropriately determined depending on the use, but is usually 1 to 60 μm and a thickness of 0.05 to 2 μm when blended with cosmetics.
The phlogopite powder of the present invention can be blended into a known cosmetic base material. For example, in addition to makeup cosmetics such as foundation, makeup base, blusher, mascara, lipstick, nail enamel, suntan Stop cosmetics, hair cosmetics, and the like can be mentioned. In particular, powder cosmetics such as powdery foundations, face powders, eye shadows, eyebrows and the like are suitable for sufficiently exhibiting softness and moist feeling.

  Next, the raw material synthetic sodium phlogopite powder that is contact-treated with the monovalent cation Y will be described. In the present invention, it is desirable to use sodium phlogopite powder melt-synthesized in a high-frequency induction furnace. In addition, although the amount of fluorine elution can be reduced to some extent only by the contact treatment with the cation Y, in order to make it 20 ppm or less, the heat treatment is performed at 600 to 1350 ° C. before or after the contact treatment with the cation Y. It is desirable. Specifically, sodium phlogopite mixed with raw materials in accordance with the theoretical composition of sodium phlogopite and heat-treated sodium phlogopite powder that was melt-synthesized in a high-frequency induction furnace, then contacted or melt-synthesized in a high-frequency induction furnace After the powder is contacted, heat treatment can be performed.

  The sodium phlogopite powder melt-synthesized using an electric furnace contains a large amount of impurities other than sodium phlogopite so that it can be brought into contact with a monovalent cation Y having an ionic radius of 1.20 mm or more. The acid-soluble matter amount in the acid-soluble matter test may not be 2.0% or less. In addition, the sodium phlogopite powder has a high fluorine elution amount, and even if heat treatment or contact treatment is performed, it may be difficult to make the fluorine elution amount 20 ppm or less. Furthermore, the sodium phlogopite powder synthesized in an electric furnace cannot provide a soft and moist feel unlike the sodium phlogopite powder synthesized in a high-frequency induction furnace.

Synthesis of synthetic sodium phlogopite by high frequency induction heating is as described in Japanese Patent Application No. 2003-304868. That is, the raw material mixture is melted at normal pressure in the atmosphere using a high frequency induction furnace. The specifications of the high-frequency induction furnace can be appropriately determined depending on the melting scale, and the melting conditions may be set so that the raw material mixture is uniformly melted. For example, when a carbon crucible is used as the heating element with a melting amount of 2.5 kg, melting is performed at a high frequency of 500 Hz to 10 kHz, preferably 1 kHz to 3 kHz, and a high frequency output of 15 kW to 100 kW, preferably 25 kW to 50 kW.
The melt heated and melted in the high frequency induction furnace is transferred to a mold made of iron, carbon, etc., cooled to room temperature, and crystallized to obtain a sodium phlogopite ore. The obtained ore is subjected to dry and / or wet pulverization in the same manner as conventionally known processes, and then classified as necessary to obtain mica powder.

The sodium phlogopite powder thus obtained has a very small amount of fluorine ion elution compared to the sodium phlogopite powder obtained in an electric furnace or the like, and can be 1000 ppm or less, further 800 ppm or less. Further, by performing a heat treatment at 600 to 1350 ° C. according to the method described in Patent Document 1, the elution amount of fluorine ions can be reduced to 20 ppm or less.
As the heat treatment apparatus, for example, a known heating apparatus such as an external heating furnace, an internal heating furnace, or a rotary kiln is used. The heat treatment atmosphere can be performed in an oxidizing atmosphere, a reducing atmosphere, an inert gas atmosphere, or an ammonia gas atmosphere under normal pressure to vacuum conditions. As heat processing temperature, it is 600-1350 degreeC, Preferably it is 700-1200 degreeC, More preferably, it is 900-1100 degreeC. The heating time may be appropriately set depending on each condition, but is usually 30 minutes to 10 hours. In addition, it is more effective to heat-treat the finely pulverized powder than the coarsely pulverized powder. After such heat treatment, washing, drying, or the like can be performed as necessary.

As a melting raw material, a known raw material powder used in a conventional melting method can be used. For example, a mixture obtained by converting silicon dioxide, magnesium oxide, aluminum oxide, sodium carbonate, sodium fluoride, sodium silicofluoride and the like so as to have a theoretical formula composition of sodium phlogopite can be used as the raw material mixture.
In the production method using high frequency induction heating, raw materials mixed so as to have a molar ratio equivalent to the theoretical composition of sodium phlogopite can be used. The mixing ratio of the raw materials can be varied as long as the effects of the present invention are not impaired, but is preferably about 95 to 105 mol% with respect to the amount of each raw material converted from the theoretical composition.

  When melting using an electric furnace or the like instead of a high-frequency induction furnace, even if a raw material mixture having a molar ratio equivalent to the theoretical composition of sodium phlogopite is used, only powder that is not swellable or swellable is obtained. I can't. If excess sodium fluoride is blended in the raw material, a swellable powder can be obtained even when melted in an electric furnace. However, in that case, impurities other than sodium phlogopite are generated. Moreover, since an excessive amount of sodium fluoride is used, the fluorine elution amount is very large, and even when the above heat treatment is performed, the fluorine ion elution amount is about 8000 ppm or more.

The reason why high-purity sodium phlogopite can be obtained by high-frequency induction heating is not fully understood, but high-frequency induction heating does not require electrodes, and the entire raw material is rapidly heated and mixed to produce a uniform melt. This is considered to be a factor.
Sodium phlogopite powder obtained by high-frequency induction heating is produced using a raw material mixture having a molar ratio equivalent to the theoretical formula composition without using excess sodium fluoride, so it contains almost no impurities, Exhibits very high cation exchange capacity and swelling. In addition, fluorine ion elution is low. Furthermore, when blended with cosmetics, softness and moist feeling can be imparted. The CEC of such sodium phlogopite powder is preferably 50 meq / 100 g or more, more preferably 100 meq / 100 g or more.

Hereinafter, the present invention will be further described with specific examples, but the present invention is not limited thereto. The test method used in the present invention is as follows.
(1) Measurement of Cation Exchange Capacity (CEC) 0.2 g of test powder is added to 20 ml of water, heated to 90 ° C., 8 ml of 1 / 20M CaCl ₂ solution is dropped, and water is added to make a total volume of 200 ml. One buffer indicator (code No. 1.08430.0500) and ammonia water were added and colored red. A 0.01 M EDTA solution was dropped into this red solution, and CEC was calculated from the amount of EDTA until the red color disappeared using the following equation.
CEC = 80 × F _{CaCl 2} −8 × F _EDTA × v (meq / 100 g)
Where F _CaCl2 : 1/20 M CaCl ₂ factor, F _EDTA : 0.01 M EDTA solution factor, v: titrated EDTA solution amount (ml).

(2) Measurement of fluorine ion elution amount In accordance with cosmetic safety standards, 5 g of test powder is added to 100 ml of water, boiled at 100 ° C. for 1 hour, and then anion in water is removed by ion chromatography separation. The amount of fluorine ions eluted with respect to the test powder mass was calculated by measuring the electrical conductivity with only ions.
(3) Measurement of acid-soluble matter In accordance with cosmetic safety standards, add 20 ml of 23.6 vol% dilute hydrochloric acid to 1 g of the test powder, heat it with stirring for 15 minutes at 50 ° C, and then add water to make exactly 50 ml. And filtered. Excluding the first 15 ml of filtrate, 25 ml of the next filtrate is accurately taken, evaporated to dryness on a water bath, ignited to constant weight, cooled in a desiccator, and then weighed to determine the mass of the test powder. The amount of acid-soluble matter was calculated.

(4) Analysis of Na and contact cation Y 0.1 g of a sample was weighed into a platinum crucible, and 5 ml of perchloric acid and 10 ml of hydrofluoric acid were added and heated on an electric heater. The white smoke of perchloric acid was sufficiently diffused and cooled, the test substance was transferred to a beaker with water, and 2 ml of hydrochloric acid was added and dissolved by heating. After standing to cool, it was transferred to a Teflon container for quantification and analyzed with an ICP emission spectrophotometer.
(5) Evaluation of touch It was evaluated whether there was a difference in softness and moist feeling with respect to each powder before and after contact with the cation solution by 20 expert panels. When the number of people who evaluated that there was no difference was 15 or more, there was no significant difference in feel.
(6) Measurement of 50% median diameter Using LA-500 manufactured by HORIBA, Ltd., measurement was performed by a laser diffraction method.

Production of synthetic phlogopite powder Production Example 1
(1) Synthesis of sodium phlogopite powder:
A formulation consisting of 15.2% by weight sodium silicofluoride, 4.3% by weight sodium carbonate, 29.3% by weight magnesium oxide, 12.4% by weight aluminum oxide and 38.8% by weight silicon dioxide was thoroughly mixed. The ratio of Na, Mg, Al, Si, F in this mixture is the same as the molar ratio of the theoretical formula of sodium phlogopite.
Using this mixture, a high-frequency crucible induction furnace (power source: FTH-30-3M, furnace body: FBT-20) manufactured by Fuji Radio Industry Co., Ltd., a carbon crucible as a heating element, a high-frequency frequency of 3 kHz, and a high-frequency output of 30 kW Melted at conditions. Thereafter, the melt was taken out into a mold and cooled to obtain a synthetic sodium phlogopite crystal. This mica crystal was dry-pulverized to obtain a mica powder having a 50% median diameter of 50 μm. The mica powder had a fluorine ion elution amount of 634 ppm and a CEC of 140 meq / 100 g.
The mica powder was further pulverized by wet pulverization and classified to obtain a mica powder having a 50% median diameter of 12 μm. This mica powder was heat treated at 1000 ° C. for 4 hours, washed with water, dehydrated, dried and crushed to obtain a sodium phlogopite mica powder. This powder had a fluorine elution amount of 18 ppm and a CEC of 80 meq / 100 g, and was soft and moist with a very good feel.
(2) substituted by one divalent cations ^{(K +):}
15 g of the sodium phlogopite powder obtained in the above (1) was uniformly contacted with 300 ml of a 0.67 wt% aqueous potassium chloride solution at 25 ° C. for 1 hour. Thereafter, dehydration and drying were performed to obtain a desired powder.

Production Example 2
(1) Synthesis of sodium phlogopite powder:
Melting was performed in the same manner as in Production Example 1 (1), and then the melt was taken out into a mold and cooled to obtain a synthetic sodium phlogopite crystal. This mica crystal was dry pulverized, further wet pulverized and pulverized to obtain a sodium phlogopite powder having a 50% median diameter of 12 μm. This powder had a fluorine ion elution amount of 892 ppm and a CEC of 120 meq / 100 g, which was soft and moist and had a very good feel.
(2) substituted by one divalent cations ^{(K +):}
15 g of this sodium phlogopite powder was uniformly brought into contact with 300 ml of a 0.67 wt% potassium chloride aqueous solution at 25 ° C. for 1 hour, dehydrated and dried, and further subjected to heat treatment at 1000 ° C. for 4 hours. To obtain the desired powder.

Production Example 3
15 g of sodium phlogopite powder obtained in Production Example 1 (1) was uniformly contacted with 300 ml of 0.067 wt% aqueous potassium chloride solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.
Production Example 4
Using 15 g of the sodium phlogopite powder obtained in Production Example 1 (1), it was brought into contact uniformly with 300 ml of a 6.7 wt% aqueous potassium chloride solution at 70 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.

Production Example 5
Using 15 g of sodium phlogopite powder obtained in Production Example 1 (1), the mixture was uniformly contacted with 300 ml of 0.5 wt% aqueous potassium hydroxide solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.
Production Example 6
Using 15 g of the sodium phlogopite powder obtained in Production Example 1 (1), it was uniformly contacted with 300 ml of a 1.8 wt% silver nitrate aqueous solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.

Production Example 7
Using 15 g of the sodium phlogopite powder obtained in Production Example 1 (1), it was uniformly contacted with 300 ml of 0.58 wt% ammonium chloride aqueous solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.
Comparative Example 1
Using 15 g of the sodium phlogopite powder obtained in Production Example 1 (1), it was uniformly contacted with 300 ml of 0.006 wt% potassium chloride aqueous solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.

Comparative Example 2
Using 15 g of the sodium phlogopite powder obtained in Production Example 1 (1), the mixture was uniformly contacted with 300 ml of a 0.42 wt% sodium chloride aqueous solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.
Comparative Example 3
15 g of sodium phlogopite powder obtained in Production Example 1 (1) was used and uniformly contacted with 300 ml of 0.31 wt% lithium chloride aqueous solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.

Comparative Example 4
15 g of sodium phlogopite powder obtained in Production Example 1 (1) was used and uniformly contacted with 300 ml of 1.2 wt% aqueous calcium chloride solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.
Comparative Example 5
Using 15 g of the sodium phlogopite powder obtained in Production Example 1 (1), it was uniformly contacted with 300 ml of a 0.50 wt% zinc chloride aqueous solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.
Comparative Example 6
Using 15 g of the sodium phlogopite powder obtained in Production Example 1 (1), it was uniformly contacted with 300 ml of a 2.8% by weight barium acetate aqueous solution at 25 ° C. for 1 hour. Thereafter, the same treatment as in Production Example 1 (2) was carried out to obtain the intended powder.

Table 1 shows the CEC, fluorine elution amount, acid-soluble matter amount, and the molar ratio of sodium and contact cation Y in the powder obtained in each of the production examples and comparative examples. Table 2 shows the sensory evaluation results of the feeling of use.

As can be seen from Table 1, when a monovalent cation (K ⁺ , Ag ⁺ , or NH ₄ ⁺ ) of 1.20Å or more is used as the contact cation Y (Production Examples 1 to 7), it is soluble in acid. The amount of material could be reduced to 2.0% or less. Moreover, the amount of fluorine elution also tended to decrease, and all the powders satisfied the reference value of 20 ppm or less. Moreover, compared with the synthetic sodium phlogopite powder used as a raw material in the manufacture examples 1-7, all the powders obtained by processing with the cation Y tended to decrease CEC. As described above, the properties such as acid resistance, fluorine elution, and CEC were changed by the contact treatment with the cation Y. However, as shown in Table 2, no significant decrease was observed in the feeling of use. Similarly, it maintained a soft and moist feel.

On the other hand, in the case of a cation with an ionic radius of less than 1.20 な ど such as Na ⁺ , Li ⁺ , Ca ²⁺ , Zn ²⁺ (Comparative Examples 2 to 5), or even when the ionic radius of Ba ²⁺ is 1.20 Å or more In the case of a valent cation (Comparative Example 6), although the feeling of use was not changed by the contact treatment, the amount of acid-soluble substances did not decrease and the amount of fluorine elution tends to increase. Could not be satisfied.
Therefore, it is understood that in order to obtain a synthetic phlogopite powder having a low amount of acid-soluble matter and a small amount of fluorine elution, it is necessary to perform contact treatment with a monovalent cation having an ionic radius of 1.20 mm or more. The
In addition, as in Comparative Example 1, when the amount of monovalent cation having an ionic radius of 1.20Å or more is small, the substitution becomes insufficient, and as a result, the amount of acid-soluble matter should be 2.0% or less. There was something that could not be done. Also, there was almost no effect of reducing the fluorine elution amount. Therefore, in the synthetic sodium phlogopite powder of the present invention, the substitution rate of the cation Y with respect to the monovalent cation (the sum of Na and Y) in the powder is preferably 5 mol% or more.

Comparison with synthetic potassium phlogopite Comparative Example 7
A formulation consisting of 18.2% by weight potassium silicofluoride, 4.7% by weight potassium carbonate, 28.2% by weight magnesium oxide, 11.9% by weight aluminum oxide and 37.0% by weight silicon dioxide was thoroughly mixed. The ratio of K, Mg, Al, Si in this mixture is the same as the theoretical composition of potassium phlogopite.
The mixture was melted at 1450 ° C. in an electric furnace using an alumina crucible, and then cooled in the furnace to obtain a synthetic fluorine phlogopite. This mica crystal was dry-pulverized to obtain a mica powder having a 50% median diameter of 50 μm. The mica powder was further pulverized by wet pulverization and classified to obtain a mica powder having a 50% median diameter of 12 μm. This mica powder was heat treated at 1000 ° C. for 4 hours, washed with water, dehydrated, dried and crushed to obtain potassium phlogopite mica powder. This powder was a non-swellable powder having a fluorine elution amount of 16 ppm and a CEC of 0 meq / 100 g.

For the synthetic phlogopite powder of Production Examples 1 and 2 and the potassium phlogopite powder of Comparative Example 7, each item of softness and moist feeling when the test powder was applied on the skin by five specialist panels Each was subjected to five-step sensory evaluation of the following 1-5.
1 ... bad 2 ... slightly bad 3 ... normal 4 ... slightly good 5 ... good The result was evaluated as follows as an average value of five-step evaluation of five people.
◎ ... 4.5-5.0
○ ... 3.5-4.4
□ ... 2.5-3.4
△ ... 1.5-2.4
× ... 1.0-1.4

表３のように、本発明の合成金雲母粉体は、カリウム金雲母粉体に比べて、柔らかさやしっとり感において優れた使用感を有することが理解される。

As shown in Table 3, it is understood that the synthetic phlogopite powder of the present invention has an excellent feeling of use in terms of softness and moistness compared to potassium phlogopite powder.

Formulation in cosmetics The synthetic phlogopite powder from the above production example was actually blended into cosmetics (powder foundation), and compared with the cosmetics blended with sodium phlogopite powder as the raw material, the evaluation was evaluated. went. The test prescription is as follows.
<Prescription>
(1) Test powder 55 parts (2) Titanium oxide 7 parts (3) White mica 3 parts (4) Talc 20 parts (5) Nylon powder 2 parts (6) Red iron oxide 0.5 parts (7) Yellow oxidation Iron 1 part (8) Black iron oxide 0.1 part (9) Silicone oil 1 part (10) 2-ethylhexyl palmitate 9 parts (11) Sorbitan sesquioleate 1 part (12) Preservative 0.3 part (13 ) Fragrance 0.1 parts

<Production method>
The above ingredients are mixed 1-8 in a Henschel mixer, molded after adding and mixing the ingredients 9 to 13 were heated and dissolved mixture to the mixture, it was triturated with a pulverizer, which dish in diameter 53mm at a pressure of 150 kg / cm ² And obtained a powdery foundation.
Table 3 shows the sensory evaluation results of the feeling of use when the powders of the respective production examples were blended in cosmetics with the above-mentioned formulation.

As shown in Table 4, the cosmetics containing Production Examples 1 to 7 in the present invention can provide a soft and moist feeling, and the cosmetics containing sodium phlogopite powder that is a raw material before the contact treatment. Compared to the charge, it was comparable.
As described above, the phlogopite powder of the present invention has a very low amount of acid-soluble matter and fluorine ion elution, and also maintains the feeling of use such as softness and moist feeling of the sodium phlogopite powder that is the starting material. is doing. Therefore, the phlogopite powder of the present invention can be used in various fields where conventional phlogopite powder is used, but is particularly useful as a cosmetic raw material.

Claims (6)

5 to 50 mol% of sodium synthetic sodium phlogopite in the powder are replaced by an ion radius 1.20Å least one divalent cation Y, acid solubles in the acid solubles test of 2.0% or less, A synthetic phlogopite powder having a fluorine elution amount of 20 ppm or less in a hot water elution test at 100 ° C. for 1 hour . The synthetic phlogopite powder according to claim 1, wherein Y is at least one selected from the group consisting of potassium (K), ammonium (NH ₄ ), silver (Ag), rubidium (Rb) and cesium (Cs). Synthetic phlogopite powder characterized by. Synthetic sodium phlogopite powder, ionic radius 1.20Å is contacted with more than one divalent cation Y, an ion radius 1.20Å or more monovalent 5 to 50 mol% of sodium synthetic sodium phlogopite in the powder 3. The method for producing a synthetic phlogopite powder according to claim 1 , wherein the cation Y is substituted . 4. The method according to claim 3 , wherein the synthetic sodium phlogopite powder obtained by melting by high frequency induction heating is contacted with the monovalent cation Y, and further heat treated at 600 to 1350 ° C. A method for producing a synthetic phlogopite powder characterized. 4. The method according to claim 3 , wherein the synthetic sodium phlogopite powder obtained by melting by high frequency induction heating is heat-treated at 600 to 1350 ° C. and then contacted with the monovalent cation Y. A method for producing a synthetic phlogopite powder. A cosmetic comprising the synthetic phlogopite powder according to claim 1 or 2 .