JPH043253B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a water-in-oil type (hereinafter referred to as W/O type) emulsifying composition useful as cosmetics and pharmaceuticals, and more specifically, the present invention relates to a water-in-oil type (hereinafter referred to as W/O type) emulsion composition that is useful as cosmetics and pharmaceuticals. It can be used in a wide range of applications, the powder can be incorporated into either the internal or external aqueous phase, and the resulting emulsified composition has excellent temperature stability and usability. The present invention relates to an O-type emulsion composition. [Prior art] Conventionally, in order to obtain a W/O type emulsion composition, a lipophilic surfactant with an HLB value of 1 to 12, such as a polyhydric alcohol fatty acid ester-based active agent such as glycerin fatty acid ester or sorbitan fatty acid ester, is used as an emulsifier. Add about 0.4 to 5.0 g of the active agent to the oil phase, heat and dissolve at about 70 to 80°C, then add the water phase heated to the same temperature and stir with a homomixer etc. A W/O emulsion composition (hereinafter referred to as W/O emulsion) was obtained. [Problems to be Solved by the Invention] However, the W/O type emulsion thus obtained is an oil-in-water type (hereinafter referred to as O/W type).
Compared to emulsions, it has the disadvantage that it is difficult to obtain a system with excellent temperature stability and usability. For example, regarding temperature stability, at low temperatures the continuous oil phase tends to separate due to agglomeration of water droplets;
Furthermore, at high temperatures, the particle size increases due to the coalescence of water droplets.
Phenomena such as oil phase separation, where the oil settles to the lower layer and the upper layer consists only of the oil phase, are likely to occur. On the other hand, in terms of usability, since the external phase is oil, it has advantages in the fields of cosmetics and pharmaceuticals, such as protecting the skin and imparting flexibility, but on the other hand, it is sticky and has a high skin-occluding ability when used. One way to improve temperature stability is to increase the viscosity by blending a large amount of wax into the oil phase.This method improves low temperature stability, but during high temperature storage, the blended wax The oil phase separation caused by the coalescence of water droplets could not be sufficiently improved due to the softening and melting of the water droplets, resulting in new problems regarding usability such as spread. As a method to improve such problems in usability, it is preferable to incorporate polar oils with ester bonds, etc., which are often used in O/W emulsion systems, but the conventional W/O emulsifiers It has been difficult to produce a W/O type emulsion with excellent stability using a system containing a polar oil. As a result of intensive research to improve the shortcomings of the prior art, the present inventors discovered that by treating water-swellable clay minerals with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant. A W/O emulsion obtained by blending powder, oil, and water using the resulting organically modified clay mineral as an emulsifier can be emulsified even with a relatively small amount of emulsifier, and is viscous even when a polar oil is blended. Highly sexual,
The inventors have also discovered that it is possible to produce a W/O type emulsion with excellent usability such as low temperature stability and low stickiness, and have completed the present invention based on this knowledge. [Means for Solving the Problems] That is, the present invention provides an organically modified clay mineral obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant. The present invention provides a water-in-oil emulsion composition comprising powder, oil, and water. The configuration of the present invention will be described below. The water-swellable clay mineral used in the present invention is a type of colloidal hydrous aluminum silicate having a three-layer structure, and generally has the following general formula (X, Y) _2-3 (Si, Al) ₄ O ₁₀ (OH) ₂ Z _1/3・nH ₂ O However, X=Al, Fe〓, Mn〓, Cr〓 Y=Mg, Fe〓, Ni, Zn, Li Z=K, Na, Ca, specifically montmorillonite The montmorillonite group (commercially available products include Veegum, Kunipia, Laponite, etc.), natural or synthetic such as saponite and hectorite (in this case, the immediate (OH) group is substituted with fluorine), and sodium silicate. Synthetic mica known as tsukuma squid, sodium or lithium taeniolite (commercially available products include daimonite; manufactured by Topy Industries, Ltd., etc.). The quaternary ammonium salt type cationic surfactant used in the present invention has the following general formula: (In the formula, R ₁ is an alkyl group having 10 to 22 carbon atoms or a benzyl group, R ₂ is a methyl group or a carbon number 10 to 22
R ₃ and R ₄ are alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups, and X is a halogen atom or a methyl sulfate residue. ). For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aracyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride. , Arakyldimethylethylammonium chloride, Behenyldimethylethylammonium chloride, Myristyldiethylmethylammonium chloride, Cetyldiethylmethylammonium chloride, Stearyldiethylmethylammonium chloride, Arakyldiethylmethylammonium chloride, Behenyldiethylmethylammonium chloride, Benzyldimethylmyristylammonium chloride , benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride,
Benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, distearyldimethylammonium chloride, dibehenyldihydroxyethylammonium chloride, and corresponding bromides, as well as dipalmitylpropylethylammonimethyl sulfate, etc. can be given. In carrying out the present invention, one or more of these may be arbitrarily selected. The nonionic surfactant used in the present invention is
The HLB value (Note 1) is within the range of 2 to 16, and 3 to
12 is even more preferred. For example, addition of 2 to 30 moles of polyoxyethylene {hereinafter referred to as POE (2 to 30 moles)
30). }Oleyl ether, POE (2-35)
Stearyl ether, POE (2-20) lauryl ether, POE (1-20) alkyl phenyl ether, POE (6-18) behenyl ether, POE (5
~25) 2-decyl pentadecyl ether, POE
(3-30) 2-decyltetradecyl ether,
Ether type activators such as POE (8-16) 2-octyldecyl ether, and POE (4-60) hydrogenated castor oil, POE (3-14) fatty acid monoester,
POE (6-30) fatty acid diester, POE (5-20)
Ester-type active agents such as sorbitan fatty acid ester, POE (2-30) glyceryl monoisostearate, POE (10-60) glyceryl triisostearate, POE (7-50) hydrogenated castor oil monoisostearate, POE (12-60) Ethylene oxide-added surfactants such as ether ester type surfactants such as hydrogenated castor oil triisostearate, and decaglyceryl tetraoleate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, diglyceryl Examples include polyhydric alcohol fatty acid ester type surfactants such as polyglycerin fatty acid esters such as diisostearate, glycerin fatty acid esters such as glyceryl monostearate, glyceryl monoisostearate, and glyceryl monooleate. Among these, polyglycerin fatty acid esters higher than diglycerin such as decaglyceryl tetraoleate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, diglyceryl diisostearate, POE (2-12) oleyl ether,
POE (3~12) stearyl ether, POE (2~
10) Lauryl ether, POE (2-10) nonyl phenyl ether, POE (6-15) behenyl ether, POE (5-20) 2-decyl pentadecyl ether, POE (5-17) 2-decyl tetradecyl ether , POE-added ether type activators such as POE (8-16) 2-octyldecyl ether, and
POE addition ester type activators such as POE (10-20) hydrogenated castor oil, POE (5-14) oleic acid monoester, POE (6-20) oleic acid diester, POE (5-10) sorbitan oleate,
Particularly preferred are ethylene oxide-added nonionic surfactants such as POE-added ether ester type surfactants such as POE (3-15) glyceryl monoisostearate and POE (10-40) glyceryl triisostearate. In carrying out the present invention, one or more of these nonionic surfactants may be arbitrarily selected and used. (Note 1) The HLB value of a nonionic activator is calculated using the Kawakami formula below. HLB=7+11.7・logM _w /M _p (Here, M _w represents the molecular weight of the hydrophilic group, and M _p represents the molecular weight of the lipophilic group, respectively.) The organically modified clay minerals used in the present invention are, for example,
A water-swellable clay mineral, a quaternary ammonium salt type cationic surfactant, and a nonionic surfactant are dispersed and stirred in a low-boiling point solvent such as water, acetone, or a lower alcohol, or the water-swellable clay mineral is dispersed and stirred in a low-boiling point solvent such as water, acetone, or a lower alcohol. A cationically modified clay mineral is obtained by treating the mineral and a quaternary ammonium salt type cationic surfactant in a low boiling point solvent, followed by treatment with a nonionic surfactant and then removing the low boiling point solvent. You can get it. As the quaternary ammonium salt type cationic surfactant and the nonionic surfactant enter between the layers, the interlayer spacing of the water-swellable clay mineral widens, so the long-plane spacing is measured using X-ray diffraction. By doing so, it is possible to confirm whether or not the quaternary ammonium salt type cationic surfactant and the nonionic surfactant are adsorbed. In addition, if the obtained organically modified clay mineral is subjected to Soxhlet extraction using chloroform, ether, etc., the surfactant between the layers will be washed away, so the extract can be analyzed by gas chromatography, thermal decomposition temperature measurement, or thermal decomposition measurement ( The presence of a surfactant can be confirmed by conducting a DTA-TG measurement) or the like. The content of the quaternary ammonium salt type cationic surfactant in the W/O type emulsifier composition of the present invention is 60 to 140 milliequivalents (hereinafter abbreviated as meq) per 100 g of water-swellable clay mineral. is preferred. The content of the nonionic surfactant in the organically modified clay mineral is preferably 5 to 200 g, more preferably 15 to 170 g, per 100 g of the water-swellable clay mineral. The amount of the organically modified clay mineral blended into the W/O emulsion according to the present invention is about 0.25 to 5% by weight, preferably 0.5 to 3% by weight. The powder used in the present invention can be any of the common powders normally used in cosmetics, etc. For example, extender pigments such as talc, kaolin, calcium carbonate, magnesium carbonate, magnesium silicate, silica anhydride, titanium oxide, titanium oxide, etc. White pigments such as zinc, inorganic coloring pigments such as red iron oxide, yellow iron oxide, black iron oxide, chromium hydroxide, and black iron oxide, organic dyes such as tar pigments and safflower pigments, pearl pigments such as fish scale foil, titanium mica, and mica; Examples include metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, and zinc palmitate, and organic powders such as starch, nylon, and polyethylene. The blending amount of these powders in the W/O emulsion is approximately 0.05 to 30% by weight, preferably 0.1 to 25% by weight. The oil used in the present invention can be any of the common oils used in cosmetics, pharmaceuticals, etc., and can be used in a wide range from polar oils to non-polar oils. Examples of oils include hydrocarbon oils such as liquid paraffin, squalane, isoparaffin, and branched light paraffin, ester oils such as isopropyl myristate, cetyl isooctanoate, and glyceryl trioctanoate, decamethylpentasiloxane, dimethylpolysiloxane,
Examples include silicone oils such as methylphenylpolysiloxane. Further, waxes such as vaseline, microcrystalline wax, Larinon, and beeswax can also be incorporated within the range that does not impair the effects of the present invention. The blending amount of these oils in the W/O emulsion is about 5 to 90% by weight, preferably 10 to 80% by weight. The W/O emulsion of the present invention may contain humectants, thickeners, preservatives, antioxidants, sequestering agents, etc., as necessary, within a range that does not impair the effects of the present invention.
UV absorbers, drugs, dispersants, fragrances, etc. can be added. [Effects of the Invention] The W/O emulsion of the present invention requires only a small amount of organically modified clay mineral, about 0.25 to 5% by weight, and can be improved by controlling the amount or the ratio of the internal aqueous phase. It is possible to control the viscosity without adding large amounts of solidifying agents such as wax, and it is also possible to use highly polar oils, which were difficult to incorporate in the past, and can be used over a wide temperature range. It has excellent storage stability. In addition, depending on the amount and type of powder blended, the stickiness and skin occlusion ability during use may be further improved, and since it is a W/O type, it can be used as a cosmetic fan with water resistance and long lasting properties. It can have a function. The W/O type emulsion of the present invention, which has such great advantages, can be used in a wide range of fields such as cosmetics and pharmaceuticals by taking advantage of its characteristics. [Example] Next, in order to further understand the present invention, the present invention will be described in more detail by giving examples. The present invention is not limited thereby. In the examples, all parts and % are by weight. Example 1 100 g of Veegum (trade name of Vanderbilt, USA), a water-swellable clay mineral, was added to 500 ml of an aqueous solution of 45 g of benzyldimethylstearylammonium chloride (equivalent to about 100 meq) and 30 g of POE(6) lauryl ether dissolved at 50°C. Add and thoroughly disperse and mix with a disperser for about 30 minutes. Next, water was removed using a filter, and the mixture was dried for about a day and night to obtain the desired organically modified clay mineral. Benzyldimethylstearylammonium chloride {abbreviated as (A). } and POE(6) lauryl ether {abbreviated as (B). The presence or absence of adsorption of } can be determined by X-ray diffraction and
The determination was made by measuring the amount of thermal decomposition of the surfactant using the DTA-TG method and comparing it with that of a water-swellable clay mineral (veegum). The results are shown in Table 1.

[Table] Shows.
As is clear from Table 1, the organically modified clay mineral of Example 1 has a significantly wider interlayer spacing than the water-swellable clay mineral before treatment. As is clear from the results of DTA-TG measurement, it is clear that this is caused by the bond between benzyldimethylstearylammonium chloride and POE(6) lauryl ether. Example 2 POE (16) 2-octyldecyl ether {hereinafter
Abbreviated as (C). }20g of bentone-38, an organically modified clay mineral, was dissolved in 500ml of ethanol and 100g of montmorillonite was dissolved in 100meq of distearyldimethylammonium chloride (hereinafter abbreviated as (D)). } Thoroughly disperse and mix 100 g of organically modified clay mineral (trade name, manufactured by National Red Co., Ltd., USA) using a lab homogenizer. After removing ethanol with an evaporator, the mixture was dried at 50°C for about 1 day and night to obtain the desired organically modified clay mineral. As in Example 1, the presence or absence of surface modification was evaluated from X-ray diffraction and the amount of surfactant in the Soxhlet extract with chloroform. The results are shown in Table 2.

【table】

[Table] *Displayed in the same way as Table 1.
As is clear from Table 2, even when using an organically modified clay mineral (Bentone-38) that has been previously treated with the quaternary ammonium salt type cationic surfactant (D), the nonionic surfactant of (C) It was found that the interlayer spacing was further widened by treatment with the agent. Similar to Example 1, this is thought to be caused by the binding of the nonionic surfactant. The amount of the quaternary ammonium salt type cationic surfactant extracted by Soxhlet extraction is based on organically modified clay mineral (bentone) which has been organically modified by cation exchange reaction.
38) The amount of physically adsorbed quaternary ammonium salt type cationic surfactant in DTA-TG (chemically adsorbed cationic surfactant is not extracted).
Example 1 shows that the amount of all quaternary ammonium salt type cationic surfactants can be determined by the method.
As shown in Example 3 Example 4 Two parts of the organically modified clay mineral obtained in Example 2 are mixed and dispersed in 30 parts of liquid paraffin to form an oil phase in advance. Subsequently, 66 parts or 53 parts of water in which 2 parts or 15 parts of the blended powder had been previously dispersed was added at room temperature and thoroughly stirred and mixed with a disper to obtain W/O emulsions, which are referred to as Example 3 and Example 4, respectively. Comparative Example 1 Comparative Example 2 POE (3 molar adduct) sorbitan monooleate 3 parts, liquid paraffin 28 parts, microcrystalline wax 2 parts, blended powder 2 parts or 15 parts, water 65 parts
1 part or 52 parts were heated at 70°C and stirred and emulsified using a homomixer to obtain W/O emulsions, which are referred to as Comparative Example 1 and Comparative Example 2, respectively. Comparative Example 3 1 part of Bentone-38, 0.5 parts of glycerol isostearate, and 28.5 parts of liquid paraffin were mixed and stirred to form an oil phase in advance. To this was added 50 parts of water containing 20 parts of the blended powder, and the mixture was stirred and mixed with a disper to obtain a W/O type emulsion, which was designated as Comparative Example 3. Table 3 shows the system stability test results at 0°C, 25°C, and 50°C of the W/O emulsions obtained in Examples 3 and 4 and Comparative Examples 1, 2, and 3, and the actual use test results by a panel specializing in women's beauty. Shown below. The stability test was based on the appearance after being left for 2 weeks, and the practical use test was based on the preference during use, using the following evaluation criteria. <Stability>◎; No separation observed △; Separation of liquid phase (oil phase or aqueous phase) occurred ×; Significant separation of liquid phase was observed <Usability>A; Preferred B; Normal C ;dislike

[Table] As is clear from Table 3, the W/O emulsion of the present invention has excellent temperature stability even when the amount of organically modified clay mineral blended is small and even when adjusted at room temperature. Furthermore, it can be seen that it is also excellent in usability. Example 5 Foundation (1) Liquid paraffin 19.0% (2) Cetyl isooctanoate 10.0 (3) 0.6 g of Veegum was treated with 0.2 g of benzyldimethylstearylammonium chloride and 0.2 g of POE (13) diisostearate. Obtained organically modified clay mineral 1.0 (4) Flavor 0.2 (5) Methyl paraoxybenzoate 0.2 (6) Titanium oxide 15.0 (7) Kaolin 5.0 (8) Talc 3.0 (9) Color pigment 1.0 (10) Dispersant appropriate amount (11 ) Glycerin 3.0 (12) Water 42.6 Production method Prepare an oil phase in advance by mixing and dispersing (1) to (3) at room temperature. Disperse and mix (5) to (11) at 70℃, then gradually add to the oil phase using a disperser.
After sufficiently uniform mixing and stirring, (4) was added and further mixed to obtain the desired foundation. Example 6 Sunscreen cream (1) Liquid paraffin 27.0 (2) 2-ethylhexyl-p-dimethylaminobenzoate 3.0 (3) Obtained by treating 0.8 g of bentone-38 with 0.2 g of POE (10) glyceryl triisostearate. Organically modified clay mineral 1.0 (4) Ethyl parahydroxybenzoate 0.2 (5) Fragrance 0.1 (6) Fine particle titanium oxide Maximum particle size 0.1μ or less, average particle size 10-40μ 7.0 (7) Color pigment 0.5 (8) Dispersion Agent Appropriate amount (9) Propylene glycol 5.0 (10) Water 56.2 Manufacturing method According to Example 5, the desired sunscreen cream was obtained. Example 7 Makeup base cream (1) Squalane 23.0 (2) Cyclic silicone 5.0 (3) Microcrystalline wax 2.0 (4) 0.5 g of bentone-38 was mixed with POE (14) 0.05 g of dioleic acid ester and 0.05 g of decaglyceryl tetraoleate. Organically modified clay minerals treated with g.
0.6 (5) Butyl parahydroxybenzoate 0.1 (6) Fragrance 0.1 (7) Titanium oxide 1.0 (8) Color pigment 0.1 (9) Dipropylene glycol 5.0 (10) Water 63.1 Manufacturing method Target makeup according to Example 5 I got the base cream.

Claims (1)

[Claims] 1. An organically modified clay mineral obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant, and a powder;
A water-in-oil emulsion composition containing oil and water. 2 The content of quaternary ammonium salt type cationic surfactant is 60 to 100g per 100g of water-swellable clay mineral.
The water-in-oil emulsion composition according to claim 1, which has an amount of 140 milliequivalents. 3. The water-in-oil emulsion composition according to claim 1, wherein the content of the nonionic surfactant is 5 to 200 g per 100 g of water-swellable clay mineral. 4. The water-in-oil emulsion composition according to claim 1, wherein the powder accounts for 0.05 to 30% by weight of the composition.