JP2006036981A - Surface-treated, non-swelling synthetic mica powdery material, method for producing the same and cosmetic blended with the powdery material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-swelling mica powdery material without having creaking or rough feeling, having a good sliding property and a very good use feeling. <P>SOLUTION: The surface-treated non-swelling synthetic mica powdery material is characterized by surface-treating a non-swelling synthetic mica powder material with an ammonium cationic surfactant, and having ≤0.25 dynamic frictional coefficient and ≥120° contact angle with water. After heat-treating the non-swelling synthetic mica powdery material at 600-1,350°C, the surface-treated material is obtained by bringing the material into contact with the ammonium cationic surfactant in an aqueous solvent. By heat-treating before the surface-treatment, the non-swelling synthetic mica powdery material having a very high water repellency and use feeling is obtained. By using the ammonium cationic surfactant and a higher fatty acid together, the water repellency and use feeling are further improved. It is suitable to use 0.1-5 mass% ammonium cationic surfactant and 0.1-5 mass% higher fatty acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a surface-treated non-swellable synthetic mica powder, and more particularly to improvement of water repellency and feeling of use.

In cosmetics, layered clay minerals such as mica, sericite, talc and kaolin are blended. Among these, natural mica is frequently used because it has good elongation, a slimy feeling, and good adhesion to the skin and extensibility. However, since natural mica contains a coloring element such as iron, the whiteness is low and dullness occurs due to the influence of sweat and sebum.
Synthetic mica such as synthetic phlogopite (potassium phlogopite) or potassium tetrasilicon mica is used as a solution to such problems of natural mica. Similar to natural mica, these synthetic mica are non-swelling and colorless and transparent, and have less iron element than natural mica, and therefore, the degree of dullness due to the effects of sweat and sebum is small.

However, with these layered silicate powders, a squeaky feeling (edge feeling) is felt when stretched on the skin, and there is a crisp feel. For this reason, it was not sufficient in terms of usability.
Conventionally, it is known to perform a surface treatment in order to improve the properties of the layered silicate powder. For example, silicon treatment or fluorine treatment is performed to improve water repellency. However, even with these surface treatments, the feeling of roughness cannot be improved.

Boron nitride is more slippery than natural mica and the like, and is one of the most excellent powders among cosmetic powders in terms of use feeling such as smoothness. However, boron nitride is very expensive.
Therefore, if it is possible to eliminate the squeaky feeling (edge feeling) and rough feeling of the layered silicate powder by a simple method, and improve the feeling of use by improving the smoothness, it is very useful. It is done.

In order to eliminate the squeaky feeling of pigments used in cosmetics and improve the familiarity and adhesion to the skin, raw powders such as titanium oxide, zinc oxide, calcium carbonate, mica and talc are used in organic solvents such as alcohol. A method is known in which the organic solvent is volatilized and treated after mixing with a cationic surfactant dissolved in (Patent Document 1).
However, in this treatment method, the treatment agent and the extender pigment are physically adsorbed, and the powder and the treatment agent are easily separated when washed with a treatment agent solubilizer such as alcohol. Therefore, even if the squeaky feeling can be temporarily eliminated and the adhesiveness can be improved, the treatment agent on the skin surface gradually becomes raw powder due to sweat, sebum, or alcohol components blended in cosmetics. The effect was not sufficient because it was easily released from the body.
In addition, when such a treated powder is used in cosmetics, the released cationic surfactant may penetrate into the stratum corneum of the skin, causing strong irritation to the skin or causing rough skin. There was a problem to actually use.
Also known is a method in which a pigment such as talc, mica, kaolin, titanium dioxide or the like is dispersed in a solvent such as water and a cationic surfactant is added for surface treatment (Patent Document 2).
However, this method has not been sufficiently effective.

On the other hand, in swellable layered silicates such as montmorillonite, organically modified clay minerals modified with quaternary ammonium cationic surfactants are used to thicken gels in organic solvents and emulsify water-in-oil emulsions. It is known to be effective for stabilization (Patent Document 3).
In swellable layered silicates, interlayer cations such as Na and Li are easily exchanged for other cations. The modification of the swellable layered silicate by the ammonium cation utilizes the property of the swellable layered silicate, and the interlayer becomes hydrophobic when the ammonium cation enters the layer. As a result, it is considered that the thickening gelling ability with respect to the organic solvent and the emulsion stabilization ability with the water-in-oil emulsion are exhibited.

However, organically modified clay minerals in which swellable layered silicates are modified with ammonium cations tend to have the same or lower use feeling as powders, and there is no elongation on the skin, and the texture is low. There is a feeling.
JP 2001-335410 A Japanese Examined Patent Publication No. 4-45483 JP-A-2-32015

  The present invention has been made in view of the above-mentioned problems of the prior art, and its purpose is that it does not have a squeaky or harsh feeling, is slippery, fits to the skin, and has a very good feeling of use and makeup. An object of the present invention is to provide a swellable synthetic mica powder and a method for producing the same.

  As a result of intensive studies by the present inventors in order to achieve the above object, after heat-treating the non-swellable synthetic mica powder at a high temperature, surface treatment with an ammonium cation surfactant in an aqueous solvent, when heat treatment is not performed, It was revealed that the water repellency was remarkably improved and the feeling of use was also improved. The ammonium cation bound to the powder does not desorb even when washed with hot water or alcohol, and has a very strong binding state. When surface treatment is performed using a higher fatty acid together with an ammonium cation surfactant. It was also found that the effect was further improved, and the present invention was completed.

That is, in the surface-treated non-swellable synthetic mica powder according to the present invention, the non-swellable synthetic mica powder is surface-treated with an ammonium cationic surfactant, the dynamic friction coefficient is 0.25 or less, and the contact angle with water is 120 °. It is the above.
It is preferable that the powder of the present invention is substantially free of free ammonium cationic surfactant.
Further, it is preferable that the non-swellable synthetic mica powder is further surface-treated with a higher fatty acid together with the ammonium cation surfactant, and further, the contact angle with water is preferably 130 ° or more.

In the method for producing a surface-treated non-swellable synthetic mica powder according to the present invention, the non-swellable synthetic mica powder is heat-treated at 600 to 1,350 ° C., and then contacted with an ammonium cationic surfactant in an aqueous solvent. It is characterized by surface treatment.
In the production method of the present invention, it is preferable that the ammonium cation is brought into contact with an aqueous solvent, followed by solid-liquid separation, and the resulting powder is washed with hot water and / or alcohol.
Moreover, it is suitable to use 0.1-5 mass% of ammonium cation surfactant with respect to non-swellable synthetic mica powder.
Further, after heat-treating the non-swellable synthetic mica powder at 600 to 1,350 ° C., it is preferable to carry out a surface treatment by contacting a higher fatty acid together with the ammonium cation in an aqueous solvent. It is preferable to use 0.1 to 5% by mass of higher fatty acid with respect to the synthetic synthetic mica powder.
The cosmetic according to the present invention is characterized by blending the surface-treated non-swellable synthetic mica powder described above.

  The surface-treated non-swellable synthetic mica powder according to the present invention can be obtained by heat-treating the non-swellable synthetic mica powder at a high temperature and then treating with an ammonium cationic surfactant in an aqueous solvent, It has high water repellency and a unique velvety feel that is slippery and creamy. Ammonium cations are firmly bonded to the non-swellable synthetic mica powder and are not easily detached even by hot water or alcohol, so that a treated powder substantially free of free ammonium cations can be obtained. Therefore, the powder of the present invention is excellent in stability and safety. Moreover, if it processes using a higher fatty acid with an ammonium cation, water repellency and a usability | use_condition can be improved further.

The non-swellable synthetic mica powder that is the raw material powder of the present invention is a synthetic mica that does not swell with water, and examples thereof include synthetic phlogopite, potassium tetrasilicon mica, and synthetic phlogopite iron. In the present invention, two or more of these may be used in combination.
In the present invention, it is necessary to heat-treat such a non-swellable synthetic mica powder at a high temperature before the surface treatment. When the surface treatment is performed without heat treatment, the water repellency is limited as compared with the raw material powder. On the other hand, when the surface treatment is performed after the heat treatment at a high temperature, the water repellency is higher than when the surface treatment is performed without the heat treatment, and for example, the contact angle with respect to water can be 120 ° or more. In addition, the feeling of use is very good as compared to the case without heat treatment, and there is no feeling of creaking or roughness on the skin, and the feeling of use is smooth and creamy.

  Even with the same non-swellable mica, the effect of heat treatment is not exhibited in the case of natural mica. When natural mica is surface-treated without heat treatment, there is still a limit to the improvement of the effect. When surface treatment is performed after heat treatment at a high temperature, the water repellency is higher than when surface treatment is performed without heat treatment. Is unpractical since the feeling of use becomes very poor.

The surface-treated non-swellable synthetic mica powder of the present invention has a very high water repellency and a low coefficient of dynamic friction. If both the water repellency and the coefficient of dynamic friction are high, or if both are low, a good feeling of use cannot be obtained, and these are considered to contribute to an excellent feeling of use. The water repellency is preferably 120 ° or more, more preferably 130 ° or more as a contact angle with respect to water, and the coefficient of dynamic friction is preferably 0.25 or less, more preferably 0.22 or less.
Thus, it has not been reported so far that water repellency and feeling of use can be remarkably improved by heat-treating the non-swellable synthetic mica powder before the surface treatment. It was issued.

If the temperature of the heat treatment before the surface treatment is too low, a sufficient effect cannot be obtained, and if it is too high, the non-swellable synthetic mica powder may be decomposed. Therefore, the heat treatment temperature is 600 to 1,350 ° C, preferably 700 to 1,200 ° C.
The heat treatment time can be appropriately determined depending on the treatment temperature and the like, and is usually about 10 minutes to 10 hours. However, when heat treatment is performed at 1,000 ° C., about 20 to 2 hours is sufficiently effective.
The heat treatment method can be performed by a known method such as an external heating furnace, an internal heating furnace, a rotary kiln or the like.
The heat treatment atmosphere is sufficient in the air, but an oxidizing atmosphere, a reducing atmosphere, an inert gas atmosphere, an ammonia gas atmosphere, a vacuum, and the like can also be selected.

  The particle size of the non-swellable synthetic mica powder that is the raw powder is not particularly limited, but the larger the aspect ratio, the lower the dynamic friction coefficient, the better the slip, and the creamy feeling is noticeable. The aspect ratio is usually 25 or more, preferably 40 or more, particularly preferably 60 or more.

  As the ammonium cationic surfactant used as the surface treatment agent in the present invention, a known one can be used, but it is necessary to have at least one long-chain hydrocarbon group having 8 or more carbon atoms. If the hydrocarbon group has 7 or less carbon atoms, the effects of the present invention cannot be obtained sufficiently. Moreover, even if the total number of carbon atoms of the ammonium cationic surfactant is 8 or more, the effect of the present invention cannot be sufficiently obtained with an ammonium cationic surfactant having no long chain having 8 or more carbon atoms.

As the long chain hydrocarbon group, an aliphatic hydrocarbon group is preferred. Examples thereof include an alkyl group having 8 to 28 carbon atoms and an alkenyl group having 8 to 28 carbon atoms. In the present invention, it is more preferable to have a long-chain hydrocarbon group having 10 or more carbon atoms. The hydrocarbon group may have a branched or cyclic structure in addition to a straight chain, but in any case, the straight chain portion preferably has 8 or more carbon atoms. In the present invention, the alkenyl group can have at least one carbon double bond at any position.
In addition to the long-chain hydrocarbon group, the ammonium cation may have an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group, a methylbenzyl group, or an ethylbenzyl group. Good.

（式(I)中、Ｒ_１〜Ｒ_４はそれぞれ次の基（Ａ）又は基（Ｂ）であり、Ｒ_１〜Ｒ_３のうち１〜３個は基（Ａ）である。
基（Ａ）：炭素数８〜２８のアルキル基及びアルケニル基から選ばれる基。
基（Ｂ）：炭素数１〜３のアルキル基、炭素数１〜３のヒドロキシアルキル基、ベンジル基、メチルベンジル基、及びエチルベンジル基から選ばれる基。） Examples of the ammonium cation include a quaternary ammonium cation represented by the following general formula (I), a tertiary ammonium cation represented by the following general formula (II), and a secondary ammonium cation represented by the following general formula (III). Is mentioned.

(In formula (I), R < ₁ > -R < ₄ > is the following group (A) or group (B), respectively, 1-3 are groups (A) among R < ₁ > -R < ₃ >.
Group (A): a group selected from an alkyl group having 8 to 28 carbon atoms and an alkenyl group.
Group (B): a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group, a methylbenzyl group, and an ethylbenzyl group. )

（式(II)中、Ｒ_１〜Ｒ_３はそれぞれ次の基（Ａ）又は基（Ｂ）であり、Ｒ_１〜Ｒ_３のうち１〜３個は基（Ａ）である。
基（Ａ）：炭素数８〜２８のアルキル基及びアルケニル基から選ばれる基。
基（Ｂ）：炭素数１〜３のアルキル基、炭素数１〜３のヒドロキシアルキル基、ベンジル基、メチルベンジル基、及びエチルベンジル基から選ばれる基。
Ｒ_４は水素原子である。）

(In Formula (II), R < ₁ > -R < ₃ > is the following group (A) or group (B), respectively, 1-3 are groups (A) among R < ₁ > -R < ₃ >.
Group (A): a group selected from an alkyl group having 8 to 28 carbon atoms and an alkenyl group.
Group (B): a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group, a methylbenzyl group, and an ethylbenzyl group.
R ₄ is a hydrogen atom. )

（式(III)中、Ｒ_１及びＲ_２はそれぞれ次の基（Ａ）又は基（Ｂ）であり、Ｒ_１〜Ｒ_２のうち１〜２個は基（Ａ）である。
基（Ａ）：炭素数８〜２８のアルキル基及びアルケニル基から選ばれる基。
基（Ｂ）：炭素数１〜３のアルキル基、炭素数１〜３のヒドロキシアルキル基、ベンジル基、メチルベンジル基、及びエチルベンジル基から選ばれる基。
Ｒ_３及びＲ_４は水素原子である。）

(In formula (III), _{R 1} and _{R 2} are each following group (A) or group _(B), 1 to 2 amino of R 1 to R ₂ is a group (A).
Group (A): a group selected from an alkyl group having 8 to 28 carbon atoms and an alkenyl group.
Group (B): a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group, a methylbenzyl group, and an ethylbenzyl group.
R ₃ and R ₄ are hydrogen atoms. )

In the general formula _(I), respectively R 1 to R ₄ is a group _{(A) [alkyl} group _{C 8-28,} a group selected from alkenyl _{C 8-28],} or a group (B) _{[C 1 -3} alkyl group, C _1-3 hydroxyalkyl group, benzyl group, methylbenzyl group, ethylbenzyl group], and _{1 to} 3 of R _{1 to} R ₄ are groups (A) is there.

When only R _{1 is the} group (A), for example, dodecyltrimethylammonium, myristyltrimethylammonium, stearyltrimethylammonium, behenyltrimethylammonium, octacosyltrimethylammonium, cetyldimethylethylammonium, stearyldimethylethylammonium, myristyldiethylmethylammonium , Cetylbenzyldimethylammonium, stearylbenzyldimethylammonium, stearylbenzylethylmethylammonium, stearyldimethylhydroxypropylammonium, behenylbenzyldihydroxyethylammonium, dicetylbenzylmethylammonium, stearyldihydroxypropylmethylammonium, lauryl (ethylbenzyl) dimethylammonium And ammonium cations.

Moreover, when R < ₁ > and R < ₂ > is group (A), distearyl dimethyl ammonium, didecyl dimethyl ammonium, isostearyl lauryl dimethyl ammonium etc. are mentioned, for example.
Moreover, when R < ₁ > -R < ₃ > is group (A), a trilauryl methyl ammonium, a trioctyl methyl ammonium, etc. are mentioned, for example.

In the tertiary ammonium cation represented by the general formula (II), R _{1 to} R ₃ are each the group (A) or the group (B), and _{1 to 3} of R _{1 to} R ₃ are groups (A ). R ₄ is a hydrogen atom.
When only R _{1 is the} group (A), for example, tertiary ammonium cations such as stearyldimethylammonium, myristyldimethylammonium, lauryldimethylammonium, cocoylbis (2-hydroxyethyl) ammonium and the like can be mentioned.

Moreover, when R < ₁ > and R < ₂ > is group (A), distearyl methyl ammonium, dimyristyl methyl ammonium, dilauryl methyl ammonium, distearyl benzyl ammonium, etc. are mentioned, for example.
Moreover, when R < ₁ > -R < ₃ > is all group (A), a trimyristyl ammonium, a trilauryl ammonium, etc. are mentioned, for example.

In the secondary ammonium cation represented by the general formula (III), R _{1 to} R ₂ are each the group (A) or the group (B), and _{1 to} 2 of R _{1 to} R ₃ are groups (A ). R ₃ and R ₄ are hydrogen atoms.
When only R _{1 is the} group (A), for example, secondary ammonium cations such as cocoyl (2-hydroxyethyl) ammonium, stearylmethylammonium, stearylbenzylammonium and the like can be mentioned.
When R ₁ and R ₂ are the group (A), for example, distearyl ammonium and the like can be mentioned.

These ammonium cation salts can be suitably used as a surface treatment agent. Examples of the counter ion X of the salt include halogens such as chlorine, bromine and iodine, and methyl sulfate residues. In the present invention, a quaternary ammonium cation or a tertiary ammonium cation is preferable.
When acid addition salt of tertiary ammonium cation or secondary ammonium cation is used as a modifying agent, it may be used after reacting the corresponding amine and acid HX in advance to form a salt, or added separately. May be. Even if no acid is used, only the amine can be used when the amine is protonated in water to become an ammonium cation.

In the surface treatment of the present invention, the heat-treated non-swellable synthetic mica powder is brought into contact with the above ammonium cation surfactant in an aqueous solvent.
Specifically, for example, a non-swellable synthetic mica powder is dispersed in water, and an ammonium cationic surfactant is added thereto, mixed and sufficiently bonded. Thereafter, solid-liquid separation is performed by filtration, centrifugation, and the like, and washing, drying, pulverization, and the like are appropriately combined to obtain the surface-treated non-swellable synthetic mica powder of the present invention.
It is preferable to wash after the solid-liquid separation. Washing can remove free processing agents and other impurities that are simply attached without binding. As such a cleaning liquid, water (particularly hot water of 50 ° C. or higher) or a lower alcohol having 1 to 3 carbon atoms (particularly ethanol) can be preferably used.

Although the modification treatment with the ammonium cation can be performed at room temperature, in order to perform the treatment quickly, it is preferable to heat the solution so that at least a part, preferably all, of the ammonium cation modifier is dissolved. The treatment time may be appropriately determined according to the type of raw material used, reaction conditions, and the like, but is usually 10 minutes to 24 hours.
The aqueous solvent used for the modification treatment is preferably water. A water-soluble solvent such as acetone or ethanol can be mixed with water as long as there is no particular problem, but the powder and the ammonium cation modifier may be mixed in an organic solvent as in a conventionally reported method. In the case where the solvent is removed by volatilization after the mixing, and the treated powder obtained is washed with alcohol, the ammonium cation agent is almost completely desorbed from the treated powder. Be careful not to cause

In the surface-treated powder of the present invention, for example, even when washed with alcohol, the ammonium cation agent bonded to the powder is hardly removed and remains bonded to the powder. There is no decline. This indicates that the binding state of the ammonium cation is different from the treated powder obtained by treating in an organic solvent. And only when treated in an aqueous medium as in the present invention, the ammonium cation is firmly and stably bound to the surface of the non-swelled layered silicate powder, and the effect can be maintained for a long time. Is.
Therefore, one of the features of the product of the present invention is that the ammonium cation bound to the powder is not removed by alcohol washing, and this is clearly distinguished from the above-described conventional process powder.

The amount of the ammonium cation modifier used in the surface treatment may be appropriately determined so as to be the above binding amount, but is usually 0.1 to 5% by mass, preferably 0.5 to 0.5% with respect to the raw material powder. What is necessary is just to use 2 mass%.
In the surface treatment, when a higher fatty acid is used together with an ammonium cation, water repellency and feeling of use can be further improved. Examples of higher fatty acids include saturated or unsaturated fatty acids having 12 to 22 carbon atoms that are usually used in cosmetics and the like. Examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid.
The amount of the higher fatty acid used is usually 0.1 to 5% by mass, preferably 0.5 to 2% by mass, based on the raw material powder.
The higher fatty acid may be treated at the same time as the ammonium cation or separately, and the order thereof is not particularly limited, but it is easy to treat at the same time.
The surface-treated non-swellable synthetic mica powder of the present invention can be further subjected to a known surface treatment as long as the effects of the present invention are not impaired.

  The surface-treated non-swelling synthetic mica powder of the present invention has no squeaky (edge) feeling when stretched on the skin, has a good elongation, is very slippery and has a creamy feeling, and is absorbed into the skin. Familiarize to stick. It is a unique feeling like velvet. The dynamic coefficient of friction of the organically modified non-swellable layered silicate powder of the present invention is much lower than that of the raw powder, and the water repellency is particularly improved. The unique feeling of use of the powder of the present invention is presumed to be associated with a decrease in the dynamic friction coefficient and water repellency. In the powder of the present invention, the dynamic friction coefficient is preferably 0.25 or less, more preferably 0.22 or less. In the powder of the present invention, the contact angle with water is preferably 120 ° or more, and more preferably 130 ° or more.

  The organically modified non-swellable layered silicate powder of the present invention can be used in various applications where the conventional non-swellable layered silicate powder has been used. It can be suitably used for an external preparation. In particular, makeup cosmetics such as foundation, white powder, sunscreen, concealer, body powder, antiperspirant, face powder, blusher, eye shadow, eyebrow, etc. are suitable. The dosage form is not limited, but powder cosmetics and solid cosmetics are particularly suitable.

In addition, the skin external preparation of this invention can be mix | blended with the component which can be normally mix | blended with cosmetics and a pharmaceutical in the range which does not impair the effect of this invention.
Hereinafter, although this invention is demonstrated using a specific example, this invention is not limited to these. Unless otherwise specified, the amount is shown in mass%. The test method used in the present invention is as follows.

(1) Sensory sensory evaluation The feel (squeaking, slipping, creamy feeling) when the sample was stretched on the skin with a finger was evaluated as follows.
◎ Very good ○ Good △ Slightly good × Bad

(2) Coefficient of dynamic friction A double-sided tape was applied to a slide glass, and a sample was applied thereto. A friction sensor (friction tester KES-SE: manufactured by Kato Tech Co., Ltd.) was slid five times on the sample surface, and the dynamic friction coefficient (MIU) was measured the fifth time.

(3) Contact angle (water repellency)
A double-sided tape was affixed to the slide glass, and a sample was applied thereto. Water was dropped on the sample surface, the contact angle of the water droplet was measured, and water repellency was evaluated.

Effect of heat treatment First, various non-swellable synthetic mica powders were treated with an ammonium cation surfactant. The same non-swelling synthetic mica powder was heat treated at 1000 ° C. for 1 hour, and the same treatment was performed.
Specifically, 100 g of synthetic phlogopite powder was dispersed in water to prepare a mica slurry having a solid content concentration of 10% by mass. Distearyldimethylammonium chloride was added to the mica slurry and stirred at 70 ° C. for 1 hour. After filtration, it was washed with water (70 ° C.), and the powder was collected and dried overnight at 110 ° C. to obtain a surface-treated powder.
The results are shown in Table 1.

(Table 1)
――――――――――――――――――――――――――――――――――――――――
Raw material powder Heat treatment Treatment agent Evaluation of treated powder Type Particle size Asper presence / absence Amount added Dynamic coefficient of friction Water repellency Feeling of use
(Μm) Kut ratio (mass% *)
――――――――――――――――――――――――――――――――――――――――
Synthetic phlogopite 1 3 25 Yes 2 0.23 130 ○
No 2 0.23 109 △
――――――――――――――――――――――――――――――――――――――――
Synthetic phlogopite 2 6 40 Yes 1 0.22 128 ○
No 1 0.20 109 △
――――――――――――――――――――――――――――――――――――――――
Synthetic phlogopite 3 12 58 Yes 1 0.21 125 ○
No 1 0.16 108 △
――――――――――――――――――――――――――――――――――――――――
Synthetic phlogopite 4 20 80 Yes 1 0.18 123 ○
No 1 0.18 105 △
――――――――――――――――――――――――――――――――――――――――
Synthetic phlogopite 5 40 100 Yes 0.5 0.16 124 ○
No 0.5 0.17 105 △
――――――――――――――――――――――――――――――――――――――――
Synthetic phlogopite 2 6 40 Yes-0.39 9 ×
(No surface treatment)
――――――――――――――――――――――――――――――――――――――――
* Amount added to raw powder

  As shown in Table 1, even when the surface treatment is performed without heat treatment, the water repellency and feeling of use can be improved. It can be seen that the feeling is improved and the usability is improved.

Table 2 shows the results when the addition amount of the ammonium cation treating agent is increased from 1% by mass to 5% by mass with respect to the synthetic phlogopite 2 (particle size 6 μm, aspect ratio 40).
As can be seen from Table 2, without heat treatment, even if the amount of the ammonium cation treatment agent is increased, the effect of improving the water repellency and the feeling of use is limited.
On the other hand, if heat treatment is performed before the surface treatment, water repellency and usability can be improved even with a small amount. In order to obtain an effect commensurate with the amount added, the amount of ammonium cation added is preferably 0.1 to 5% by mass, more preferably 0.5 to 2% by mass with respect to the raw material powder.

(Table 2)
――――――――――――――――――――――――――――――――――――――――
Ammonium cation treatment agent Heat treatment Presence of treated powder (mass%, raw powder) Dynamic friction coefficient Water repellency Feeling of use ――――――――――――――――――――――― ―――――――――――――――――
1% None 0.20 109 △
3% None 0.20 115 △
5% None 0.20 112 △
――――――――――――――――――――――――――――――――――――――――
0% Yes 0.39 9 ×
0.1% Yes 0.25 120 ○
1% Yes 0.22 128 ○
3% Yes 0.21 127 ○
――――――――――――――――――――――――――――――――――――――――

Table 3 shows the results of examining the effect of heat treatment on natural non-swellable synthetic mica powder in the same manner. The same treatment as in Table 1 was performed except that natural muscovite and natural sericite were used as the raw material powder. The addition amount of the ammonium cation surfactant was 1% by mass with respect to the raw material powder.
From Table 3, even in the case of natural mica, when the surface treatment is performed after the heat treatment, the water repellency is higher than when the surface treatment is performed without the heat treatment, but the use feeling tends to be inferior compared with the surface treatment without the heat treatment. was there. This is presumably because the dynamic friction coefficient was increased by the heat treatment.

(Table 3)
――――――――――――――――――――――――――――――――――――――――
Raw material powder Heat treatment Evaluation of treated powder Type Particle size Aspres dynamic coefficient of friction Water repellency Usability
(Μm) ct ratio ――――――――――――――――――――――――――――――――――――――――
Biotite 20 60 Yes 0.31 125
No 0.18 113 △
――――――――――――――――――――――――――――――――――――――――
Sericite 14 30 Yes 0.40 125
No 0.24 113 △
――――――――――――――――――――――――――――――――――――――――

Table 4 shows the effect of heat treatment conditions. The raw material powder was synthetic phlogopite 3 (particle size 12 μm, aspect ratio 58), and surface treatment was performed in the same manner as in Table 1 except that the treatment temperature and time were changed.
As shown in Table 4, if the heat treatment temperature is too low, the effect of improving water repellency and usability is not exhibited even if the treatment is performed for a long time. Further, when the heat treatment temperature is too high, the powder is decomposed (melted) even in a short time treatment. Accordingly, the heat treatment temperature is preferably 600 to 1,350 ° C, more preferably 700 to 1,200 ° C.
Further, even when the powder obtained by surface treatment after treatment at 1000 ° C. for 1 hour was washed with ethanol, the dynamic friction coefficient, water repellency and usability were not lowered.

(Table 4)
――――――――――――――――――――――――――――――――――――――――
Heat treatment Evaluation of treated powder Temperature (℃) Time Coefficient of dynamic friction Water repellency Feeling of use ――――――――――――――――――――――――――――――――― ―――――――
No heat treatment 0.16 108 △
500 1h 0.18 109 △
500 10h 0.18 109 △
700 1h 0.21 125 ○
1000 1h 0.21 125 ○
1200 1h 0.22 128 ○
1400 1h 0.30 120 Δ ～ ×
1400 10min 0.30 120 Δ ~ ×
――――――――――――――――――――――――――――――――――――――――

Surface treatment powders were prepared in the same manner as in Table 1 above, using distearyldimethylammonium chloride, higher fatty acids, or both as higher fatty acid effect treatment agents. The added amounts of distearyldimethylammonium chloride and higher fatty acid are 1% by mass with respect to the raw material powder, respectively, and the raw material powder is synthetic phlogopite 3 (particle size 12 μm, aspect ratio 58). The results are shown in Table 5.
As shown in Table 5, when an ammonium cationic surfactant and a higher fatty acid are used in combination, the water repellency and the feeling of use are enhanced compared to either the ammonium cationic surfactant alone or the higher fatty acid alone. It can be seen that a synergistic improvement effect is exhibited by the combined use of both.

(Table 5)
――――――――――――――――――――――――――――――――――――――――
Surface treatment agent Heat treatment Evaluation of treated powder Presence or absence of higher fatty acid ammonium Dynamic coefficient of friction Water repellency Feeling of use
Cation ――――――――――――――――――――――――――――――――――――――――
No Yes Yes 0.21 125 ○
Yes (stearic acid) Yes Yes 0.21 138 ◎
Yes (lauric acid) Yes Yes 0.21 137 ◎
――――――――――――――――――――――――――――――――――――――――
Yes (stearic acid) No Yes 0.22 25 △
Yes (lauric acid) No Yes 0.26 18 △
――――――――――――――――――――――――――――――――――――――――

Table 6 shows the results of examining the influence of the addition amount of higher fatty acids. A surface-treated powder was prepared in the same manner as in Table 5 except that the amount of higher fatty acid added was changed to 0.1 to 5% by mass with respect to the raw material powder. The higher fatty acid is stearic acid, and the amount of ammonium cationic surfactant added is 1% with respect to the raw material powder.
As can be seen from Table 6, in order to obtain an effect commensurate with the amount of the higher fatty acid added, 0.1 to 5% by mass, and further 0.5 to 2% by mass is preferable.

(Table 6)
――――――――――――――――――――――――――――――――――――――――
Stearic acid Heat treatment Presence or absence of evaluation of powder (mass%, raw material powder) Dynamic coefficient of friction Water repellency Feeling of use ――――――――――――――――――――――――― ―――――――――――――――
0 Yes 0.21 125 ○
0.1 Yes 0.21 130 ○ 〜 ◎
1 Yes 0.21 138 ◎
3 Yes 0.20 139 ◎
5 Yes 0.20 138 ◎
――――――――――――――――――――――――――――――――――――――――

Cosmetics Formulation Example 1 Powder Foundation (1) Sericite 30.0
(2) Surface-treated synthetic phlogopite (product of the present invention) 43.0
(3) Titanium oxide 10.0
(4) Bengala 2.0
(5) Yellow iron oxide 2.5
(6) Black iron oxide 0.1
(7) Perfluoropolyether 10.0
(8) Dimethylpolysiloxane 2.0
(9) Preservative 0.2
(10) Fragrance 0.2

Formulation Example 2 Amphibious Powder Foundation (1) Surface-treated synthetic phlogopite (product of the present invention) 40.0
(2) Titanium oxide 12.0
(3) Synthetic mica titanium 4.0
(4) Iron oxide (red, yellow, black) 4.0
(5) Zinc oxide 4.5
(6) Aluminum oxide 10.0
(7) Barium sulfate 5.0
(8) Polyethylene powder 1.0
(9) Dimethylpolysiloxane 4.0
(10) Lanolin 6.0
(11) Vaseline 1.0
(12) Liquid paraffin 1.0
(13) Isopropyl myristate 1.0
(14) Preservative 1.4
(15) Fragrance 0.1

Formulation Example 3 Loose Type Face Powder (1) Surface-treated synthetic phlogopite (product of the present invention) 98.8
(2) Bengala 0.1
(3) Liquid paraffin 1.0
(4) Fragrance 0.1

Formulation Example 4 Two-layer separation type liquid foundation After the oil phase was dissolved at room temperature, a pigment was added and dispersed with a disper. The aqueous phase was added with stirring and emulsified to produce a liquid foundation having the following composition.
(composition)
(1) Titanium oxide 6.0
(2) Surface-treated synthetic phlogopite (product of the present invention) 9.0
(3) Iron oxide (red, yellow, black) 1.2
(4) Octamethylcyclotetrasiloxane 20.0
(5) Dimethylpolysiloxane (6cs) 2.0
(6) Dimethylpolysiloxane / polyoxyalkylene copolymer 1.0
(7) Perfluoropolyether 10.0
(8) Glycerin 2.0
(9) Ethanol 15.0
(10) Purified water remaining amount (11) Perfume appropriate amount

The cosmetics of the above Formulation Examples 1 to 4 have significantly improved adhesion and smoothness compared to the case where the surface-treated synthetic phlogopite is blended with surface-treated synthetic phlogopite without heat treatment. The effect of preventing this was also high.

Claims (10)

  Surface-treated non-swellable synthetic mica powder, wherein the non-swellable synthetic mica powder is surface-treated with an ammonium cationic surfactant, has a dynamic friction coefficient of 0.25 or less, and a contact angle with water of 120 ° or more. .   The surface-treated non-swellable synthetic mica powder according to claim 1, which is substantially free of a free ammonium cationic surfactant.   3. The surface-treated non-swellable synthetic mica powder according to claim 1, wherein the non-swellable synthetic mica powder is further surface-treated with a higher fatty acid together with an ammonium cationic surfactant.   The surface-treated non-swellable synthetic mica powder according to claim 3, wherein a contact angle with water is 130 ° or more.   A surface-treated non-swellable synthetic mica powder, which is obtained by heat-treating a non-swellable synthetic mica powder at 600 to 1,350 ° C. and then bringing the surface into contact with an ammonium cationic surfactant in an aqueous solvent. Manufacturing method.   6. The surface treatment according to claim 5, wherein the ammonium cation is contacted in an aqueous solvent, followed by solid-liquid separation, and the obtained powder is washed with hot water and / or alcohol. Method for producing non-swellable synthetic mica powder.   The surface-treated non-swelling synthetic mica powder according to claim 5 or 6, wherein 0.1 to 5% by mass of an ammonium cationic surfactant is used with respect to the non-swelling synthetic mica powder. Manufacturing method.   In the manufacturing method in any one of Claims 5-7, after heat-processing non-swellable synthetic mica powder at 600-1350 degreeC, a higher fatty acid is contacted in an aqueous solvent with the said ammonium cation, and the surface A method for producing a surface-treated non-swellable synthetic mica powder, characterized by comprising:   The method for producing a surface-treated non-swellable synthetic mica powder according to claim 8, wherein 0.1 to 5% by mass of higher fatty acid is used with respect to the non-swellable synthetic mica powder. A cosmetic comprising the surface-treated non-swellable synthetic mica powder according to any one of claims 1 to 4.