JP4293864B2 - Synthetic sodium phlogopite powder, process for producing the same, and cosmetics containing the powder - Google Patents

Description

  The present invention relates to a synthetic sodium phlogopite powder, and in particular, to a synthetic sodium phlogopite powder having a high cation exchange capacity, almost no elution of fluorine ions, soft on the skin, and exhibiting a moist use feeling. .

  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 with F. 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 K, it is considered to be non-swelling with respect to water, and when the interlayer ion is Na or Li, it is considered that the interlayer ion is swellable with respect to water. Sodium phlogopite [theoretical formula: NaMg ₃ (AlSi ₃ O ₁₀ ) F ₂ ] in which K is replaced with Na is said to exhibit swelling properties.

However, sodium phlogopite has not yet 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 and an attempt is made to synthesize Na 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. The swellable fluorine mica has a very high fluorine ion elution amount of 100 to 10000 ppm. Therefore, the swellable fluorine 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 can't.

Fluorine micas p.123-141, Chapter 16 Water-swellable fluoromica 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 prior art, and provides a Na phlogopite powder that contains almost no impurities, has high cation exchange ability and swelling property, and has almost no elution of fluorine ions. For the purpose.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research. As a result, when the raw material mixture is melted in a high-frequency induction furnace, the theoretical composition of sodium phlogopite is used without adding excessive sodium fluoride. It was found that sodium phlogopite containing almost no impurities can be obtained using a mixture mixed at a ratio corresponding to. This sodium phlogopite powder has a high purity, so the cation exchange capacity (CEC) is very high, and the elution amount of fluorine ions is very low compared to the conventional electric furnace melting method. It was. Furthermore, it has been found that 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 the severe elution test of the cosmetic safety standard. The present inventors have also found that the sodium phlogopite powder is soft and has a moist feel, thereby completing the present invention.

That is, the synthetic sodium phlogopite powder of the present invention has a cation exchange capacity (CEC) of 50 meq / 100 g or more, and the amount of fluorine ions eluted in a hot water dissolution test at 100 ° C. for 1 hour was used in the test. It is 1000 ppm or less with respect to body mass.
In the powder of the present invention, the fluorine ion elution amount is preferably 20 ppm or less with respect to the mass of the powder used in the test.
In the method for producing a synthetic sodium phlogopite powder according to the present invention, the ratio of Na, Mg, Al, Si, and F is 95 to 105 mol% with respect to the theoretical composition of the synthetic sodium phlogopite. In addition, a raw material mixture in which oxides, carbonates or fluorides of Na, Mg, Al, and Si are mixed is melted by high frequency induction heating.

Moreover, it is suitable that a raw material mixture consists of sodium silicofluoride, sodium carbonate, magnesium oxide, aluminum oxide, and silicon dioxide.

Further, in the above manufacturing method, Ri preferably der be heat treated obtained further 600-1350 ° C. The synthesis of sodium phlogopite powder was, furthermore, synthetic sodium phlogopite powder after heat treatment, cation exchange capacity (CEC) is preferably 50 meq / 100 g or more, and the fluorine ion elution amount in a hot water elution test at 100 ° C. for 1 hour is preferably 20 ppm or less based on the mass of the powder used in the test.
The cosmetic according to the present invention contains the synthetic sodium phlogopite powder.

  Since the sodium phlogopite powder of the present invention contains almost no impurities, it has a high cation exchange capacity and exhibits excellent swelling properties. Therefore, it can be used for thickeners, emulsifiers, composite host compounds, and other known swellable synthetic mica applications. In particular, the sodium phlogopite powder of the present invention has a soft and moist feel. It is particularly suitable as a raw material for cosmetics because it has a very good feeling of use and does not contain coloring elements like natural mica, and the fluoride ion elution amount in a severe elution test of cosmetic safety standards can be 20 ppm or less. It is.

  Further, according to the production method of the present invention, the raw material powder is mixed in a proportion corresponding to the theoretical composition of sodium phlogopite, and this raw material mixture is melted by high frequency induction heating, so that it contains almost no impurities and is cation exchange. It is possible to efficiently synthesize sodium phlogopite powder with high capacity and swelling property. Moreover, if the powder obtained in this way is further heat-treated, the amount of fluorine ions eluted can be reduced to the level of non-swelling fluorine mica.

First, the manufacturing method of the sodium phlogopite of this invention is demonstrated.
The sodium phlogopite of the present invention is melted by high frequency induction heating. Melting can be carried out in the atmosphere at normal pressure. 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 a 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 classified according to necessity after dry and / or wet pulverization in the same manner as in a conventionally known process to obtain a mica powder.

The sodium phlogopite powder thus obtained has a very small amount of fluorine ion elution compared to the sodium phlogopite powder obtained by the conventional method, and can be 1000 ppm or less, further 800 ppm or less. However, when it is desired to further reduce the fluorine ion elution amount, it is preferable to further heat-treat the mica powder at 600 to 1350 ° C. according to the method described in Patent Document 1. By such heat treatment, 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 and drying are performed as necessary to obtain a product powder.

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.
One feature of the production method of the present invention is that raw materials mixed in a molar ratio equivalent to the theoretical composition of sodium phlogopite can be used. The mixing ratio of the raw materials is within an allowable range of about 95 to 105 mol% with respect to the amount of each raw material converted from the theoretical formula 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. Further, since an excess amount of sodium fluoride is used, the amount of elution of fluorine is much larger than that of the powder of the present invention, and even when the above heat treatment is performed, the amount of elution of fluorine ions 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 an electrode, and the entire raw material is uniformly heated and mixed to produce a uniform melt. This is considered to be a factor.
Since the sodium phlogopite powder obtained by the production method of the present invention is produced using a raw material mixture having a molar ratio equivalent to the theoretical formula composition without using excess sodium fluoride, impurities are hardly present. It is not contained and exhibits very high cation exchange capacity and swelling. In addition, fluorine ion elution is low. Furthermore, the sodium phlogopite powder of the present invention can impart softness and moist feeling when blended in cosmetics. In order to develop such a feeling of use, the CEC of the sodium phlogopite powder is preferably 50 meq / 100 g or more, more preferably 100 meq / 100 g or more.
Although it is not clear as a cause that such a feeling of use is exerted, the sodium phlogopite powder of the present invention has a cation exchange ability and swelling property. Well, it can be considered moist.

The particle size of the powder of the present invention is appropriately determined depending on the use, but is usually 1 to 60 μm and the thickness is 0.05 to 2 μm when blended with cosmetics.
The sodium phlogopite powder of the present invention can be blended in a known cosmetic base. However, when the softness and moist feeling are sufficiently exhibited, powder foundation, face powder, eye shadow, eyebrow, etc. The powder cosmetic is suitable. Further, it can be suitably used for water-based cosmetics, emulsified cosmetics, gel cosmetics and the like as thickeners and emulsifiers.

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 50% median diameter Using a laser diffraction method, LA-500 manufactured by Horiba Ltd. was used.

(2) Measurement of cation exchange capacity (CEC) 0.2 g of mica powder was added to 20 ml of distilled water, heated to 90 ° C., and 8 ml of 1/20 mol CaCl ₂ solution was added dropwise. After making the total volume 200 ml with distilled water, one buffer indicator (Code No. 1.08430.0500) manufactured by Merck and ammonia water were added to give a red color. To this red solution, 0.01M EDTA solution was added dropwise until the red color disappeared. CEC was calculated from the dripping amount using the following formula.
CEC = 80 × F _cacl2 −8 × F _EDTA × v (meq / 100g)
Where F _{cacl2 is} a factor of 1/20 mol CaCl ₂ solution, F _{EDTA is} a factor of 0.01M EDTA solution, and v is a titrated 0.01M EDTA solution amount (ml).

(3) Measurement of fluorine ion elution amount After adding 5 g of test powder to 100 ml of water and boiling at 100 ° C. for 1 hour, the anion in the water is only fluorine ions by ion chromatography separation, and electric conduction By measuring the degree, the fluorine ion elution amount relative to the test powder mass was calculated.

(4) Evaluation of softness and moist feeling Each of the items of softness and moist feeling when the test powder is applied on the skin by five specialist panels, the following 5-5 sensory evaluations went.
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

Synthesis of sodium phlogopite Production Example 1
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. The mica crystal was dry-pulverized to obtain a mica powder having a 50% median diameter of 50 μm. The amount of fluorine ions eluted from this mica powder was 634 ppm. CEC was also measured.
The mica powder having a 50% median diameter of 50 μm was further finely pulverized by wet grinding and classified to obtain a mica powder having a 50% median diameter of 12 μm. The mica powder was heat treated at 1000 ° C. for 4 hours, washed with water, dehydrated, dried and crushed to obtain the product of the present invention. About the obtained mica powder, the fluorine elution amount and CEC were measured, and the softness and moist feeling were evaluated.

Comparative Example 1
A raw material mixture having the same composition as in Production Example 1 was placed in an alumina crucible, covered, melted in an electric furnace at 1450 ° C., and cooled in the furnace to obtain crystals. Thereafter, treatment and measurement were performed in the same manner as in Production Example 1.

Comparative Example 2
30.5% by weight of sodium fluoride was further added to the raw material mixture having the same composition as in Production Example 1 and mixed well. This mixture was put in an alumina crucible, covered, melted in an electric furnace at 1450 ° C., and cooled in the furnace to obtain crystals. Thereafter, treatment and measurement were performed in the same manner as in Production Example 1.

Comparative Example 3
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.
This mixture was placed in an alumina crucible, covered, melted in an electric furnace at 1450 ° C., and then cooled in the furnace to obtain synthetic fluorine phlogopite. Thereafter, treatment and measurement were performed in the same manner as in Production Example 1.

Comparative Example 4
A formulation consisting of 23.2% by weight sodium silicofluoride, 24.9% by weight magnesium oxide and 51.9% by weight silicon dioxide was thoroughly mixed. The ratio of Na, Mg, Si in this mixture is the same as the theoretical composition of Na-tetrasilicon mica.
This mixture was put in an alumina crucible, covered, melted in an electric furnace at 1450 ° C., and then cooled in the furnace to obtain synthetic Na-tetrasilicon mica. Thereafter, treatment and measurement were performed in the same manner as in Production Example 1.
Tables 1-2 show the CEC, fluorine elution amount, and feeling of use of the powders of Production Example 1 and Comparative Examples 1-4.

Table 1:
――――――――――――――――――――――――――――――――――
Test powder CEC (meq / 100g) F elution amount (ppm)
After dry grinding After 1000 ° C treatment After 1000 ° C treatment
50μm 12μm 12μm
――――――――――――――――――――――――――――――――――
Production Example 1 140 80 18
――――――――――――――――――――――――――――――――――
Comparative Example 1 41 1 162
Comparative Example 2 101 63 8220
Comparative Example 3 0 0 16
Comparative Example 4 100 0 350
――――――――――――――――――――――――――――――――――

Table 2:
――――――――――――――――――――――――――――――――――
Test powder Softness Moist ――――――――――――――――――――――――――――――――――
Production Example 1 ◎ ◎
――――――――――――――――――――――――――――――――――
Comparative Example 1
Comparative Example 2 × ×
Comparative Example 3
Comparative Example 4 ○ □
――――――――――――――――――――――――――――――――――

  As can be seen from Table 1, the powder obtained by the production method of the present invention (Production Example 1) had a very high cation exchange capacity of 140 meq / 100 g. Moreover, the elution amount of fluorine ions was 634 ppm, and it could be reduced to 20 ppm or less by performing a heat treatment at 1000 ° C. Even when heat-treated, it had a high cation exchange capacity of 80 meq / 100 g. And when this powder was applied on the skin, it was soft and moist and had a good feeling of use.

  On the other hand, when it manufactured with the electric furnace like the comparative example 1, the cation exchange capability of the obtained powder was low, and there was almost no cation exchange capability after baking at 1000 degreeC. In addition, the powder of Comparative Example 1 was not soft and moist when used. Moreover, even if it heat-processed at 1000 degreeC, the fluorine elution amount was as high as 162 ppm or more.

  Further, as in Comparative Example 2, when the sodium fluoride was excessively blended according to Non-Patent Document 1 and manufactured in an electric furnace, the obtained powder had a high cation exchange capacity, and 1000 The cation exchange capacity was exhibited even after heat treatment at ℃. However, in Comparative Example 2, the amount of elution of fluorine is as high as 8220 ppm even after the heat treatment at 1000 ° C., and the feeling of use is low due to low adhesion and extensibility to the skin. It was inappropriate as a raw material.

Comparative Example 3 is potassium phlogopite (fluorine phlogopite) known as non-swelling synthetic mica, and Comparative Example 4 is Na-tetrasilicon mica known as swelling synthetic mica [theoretical formula: NaMg2 _{. 5} (Si ₄ O ₁₀ ) F ₂ ] is produced by a conventional method.
Non-swelling potassium phlogopite has very little fluorine elution, but does not have cation exchange capacity and does not exhibit softness and moist feeling.

  On the other hand, although the swellable Na-tetrasilicic mica has a cation exchange capacity, the fluorine elution amount does not fall below the standard value of the severe elution test even after heat treatment at 1000 ° C. It has disappeared. Moreover, although there was some softness and moist feeling, it was insufficient as compared with Production Example 1.

FIG. 1 is an X-ray diffraction pattern of the powders of Production Example 1, Comparative Example 1 and Comparative Example 2. In Production Example 1, a strong peak corresponding to (001) was observed at d = 9.7 mm, suggesting that sodium phlogopite was formed.
On the other hand, in Comparative Example 2, a peak corresponding to (001) was observed at d = 12.3 mm, but there were other peaks (arrows) indicating many impurities (expansion of interlayer distance). This is probably because the measured powder absorbed moisture and the layers were swollen). Therefore, the reason why the fluorine ion elution property and usability of Comparative Example 2 are significantly inferior to that of Production Example 1 is due to the fact that excessive sodium fluoride was used as a raw material and impurities were by-produced. Conceivable.
Further, in Comparative Example 1, the peak corresponding to (001) was very weak, and it was considered that almost no sodium phlogopite was generated even in view of its cation exchange ability and swelling property.

Blending into Cosmetics The powders of Production Example 1 or Comparative Examples 1 to 4 were actually blended into cosmetics (powder foundations) and the feeling of use was examined. The test prescription is as follows.

<Prescription>
(1) Test powder (12 μm after 1000 ° C. treatment) 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 iron oxide 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) antiseptic Agent 0.3 parts (13) Fragrance 0.1 parts

<Production method>
Ingredients 1-8 are mixed with a Henschel mixer, then ingredients 9-13, heated and dissolved and mixed in this mixture, are added and mixed, then pulverized with a pulverizer, and molded into a 53 mm diameter dish at a pressure of 150 kg / cm ^2. To obtain a powder foundation.

Table 3:
―――――――――――――――――――――――――――――――――――
Test powder Softness Moist feeling ―――――――――――――――――――――――――――――――――――
Production Example 1 ◎ ◎
―――――――――――――――――――――――――――――――――――
Comparative Example 1 □ △
Comparative Example 2
Comparative Example 3
Comparative Example 4 ○ □
―――――――――――――――――――――――――――――――――――

  As described above, the sodium phlogopite powder of the present invention has high cation exchange ability, low elution of fluorine ions, and gives softness and moist feeling when used in powder cosmetics. be able to. Accordingly, the sodium phlogopite powder of the present invention can be used in various fields where swellable viscosity minerals are conventionally used, but is particularly useful as a cosmetic raw material.

X-ray diffraction patterns of the powder obtained by the production method of the present invention (using a high frequency induction furnace) (Production Example 1) and the powder obtained by the conventional method (using an electric furnace) (Comparative Examples 1 and 2) FIG.

Claims (7)

  The cation exchange capacity (CEC) is 50 meq / 100 g or more, and the fluorine ion elution amount in a hot water elution test at 100 ° C. for 1 hour is 1000 ppm or less with respect to the mass of the powder used in the test. Synthetic sodium phlogopite powder.   2. The synthetic sodium phlogopite powder according to claim 1, wherein a fluorine ion elution amount in a hot water elution test at 100 ° C. for 1 hour is 20 ppm or less based on the mass of the powder used in the test. body. Na, Mg, Al, and Si oxides, carbonates, so that the ratio of Na, Mg, Al, Si, and F is 95 to 105 mol% with respect to the theoretical formula composition of synthetic sodium phlogopite Or the raw material mixture which mixed the fluoride is fuse | melted by high frequency induction heating, The manufacturing method of synthetic sodium phlogopite powder characterized by the above-mentioned. 4. A method for producing a synthetic sodium phlogopite powder according to claim 3, wherein the raw material mixture comprises sodium silicofluoride, sodium carbonate, magnesium oxide, aluminum oxide and silicon dioxide. According to claim 3 or 4 process according method of synthesizing sodium phlogopite powder, characterized in that a heat treatment at more 600-1350 ° C. The synthesis of sodium phlogopite powder obtained. 6. The production method according to claim 5, wherein the heat-treated synthetic sodium phlogopite powder has a cation exchange capacity (CEC) of 50 meq / 100 g or more, and a fluorine ion elution amount in a hot water elution test at 100 ° C. for 1 hour. Is a synthetic sodium phlogopite powder, characterized in that is 20 ppm or less based on the mass of the powder used in the test .   A cosmetic comprising the synthetic sodium phlogopite powder according to claim 1 or 2.

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