JPH0214098B2 - - 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. This invention relates to a water-in-oil emulsion composition that can be used in a wide range of applications and is characterized by the combination of an organic carboxylic acid salt and a mucopolysaccharide, resulting in extremely excellent temperature stability and usability of the resulting 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 the advantage of protecting the skin and imparting flexibility in the cosmetics and pharmaceutical fields, but has the disadvantage of being sticky and having 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 mucopolysaccharide, oil, and water using the obtained organically modified clay mineral as an emulsifier can be emulsified even with a relatively small amount of emulsifier, and can be emulsified even in systems containing polar oil. We found that it is an excellent W/O emulsion, with high viscosity, good temperature stability, and smooth usability, but we also added an alkali metal salt of an organic carboxylic acid or an organic amine salt. By doing this, we discovered that even when a relatively large amount of mucopolysaccharide is blended, the stability is further increased to an unexpected degree, and the moisturizing effect is enhanced without giving an undesirable feel such as stickiness. Based on this, the present invention has been completed. [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. , one or more mucopolysaccharides and their salts, one or more selected from the group consisting of alkali metal salts of organic carboxylic acids and organic amine salts, oil, and water in oil. The present invention provides a type emulsion composition. 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, Natural or synthetic materials such as saponite and hectorite (in this case, the (OH) group in the formula is substituted with fluorine), montmorillonite group (commercially available products include Veegum, Knipia, Laponite, etc.) and sodium silicic acid. Synthetic mica known as mica, 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 dipalmitylpropylethylammonium methylsulfate, 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 _O (Here, M _W represents the molecular weight of the hydrophilic group, and M _O 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 becomes widened, so the long-plane spacing can be measured by X-ray diffraction. By measuring, the presence or absence of adsorption of the quaternary ammonium salt type cationic surfactant and the nonionic surfactant can be confirmed. Furthermore, if this 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 amount measurement (DTA). -TG measurement) etc. to confirm the presence of surfactants. The content of the quaternary ammonium salt type cationic surfactant in the organically modified clay mineral according to the present invention is preferably 60 to 140 milliequivalents (hereinafter abbreviated as meq) per 100 g of the water-swellable clay mineral. . In addition, the content of nonionic surfactant in the organically modified clay mineral is 5 to 200 g per 100 g of water-swellable clay mineral.
is preferable, and more preferably 15 to 170 g. The amount of organically modified clay mineral blended into the W/O emulsion of the present invention is 0.25 to 5% by weight, preferably 0.5 to 3% by weight. The mucopolysaccharides used in the present invention are neutral mucopolysaccharides and acidic mucopolysaccharides commonly used in cosmetics, etc., such as hyaluronic acid, chondroitin sulfate A, chondroitin sulfate B, chondroitin sulfate C, heparan sulfate, heparin, and keratan sulfate. Preferred are acidic mucopolysaccharides such as hyaluronic acid,
Particularly preferred are chondroitin sulfates and their salts. The blending amount of these mucopolysaccharides is about 0.001 to 5% by weight in the W/O emulsion, and 0.005 to 3% by weight.
Weight percent is preferred. The organic carboxylic acids of the alkali metal salts or organic amine salts of organic carboxylic acids used in the present invention include glycolic acid, lactic acid, malic acid, tartaric acid,
Oxy acids such as citric acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, and fumaric acid, amino acids such as glutamic acid and aspartic acid, and others such as pyrrolidone carboxylic acid, edetacetic acid, benzoic acid, urocanic acid, formic acid, acetic acid,
Examples include propionic acid and sorbic acid. Among these, lactic acid, pyrrolidonecarboxylic acid, and glutamic acid are particularly preferred. Examples of the alkali metals or organic amines used to form salts with these organic carboxylic acids include sodium, potassium, aminomethylpropanol, monoethanolamine, diethanolamine, triethanolamine, and basic amino acids. These alkali metal salts or organic amine salts of organic carboxylic acids may be incorporated into the composition in the form of salts, but the corresponding acidic and basic substances are required to form the salts during composition production. It may be prepared by adding a stoichiometric amount. One or two types of alkali metal salts or organic amine salts of organic carboxylic acids used in the present invention are appropriately selected and blended. The blending amount is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, in the W/O emulsion. 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, lanolin, 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 amount of water used in the present invention is 95 to 10% by weight
90 to 20% by weight is preferred. In the present invention, other aqueous components can be blended into the water within a range that does not impair the effect. The W/O type emulsion of the present invention may contain oil-soluble and water-soluble substances, if necessary, within a range that does not impair the effects of the present invention. For example, NMF (Natural
Contains ingredients commonly used in cosmetics and pharmaceuticals such as amino acids and their salts (Moisturizing Factor), humectants, thickeners, preservatives, sequestering agents, ultraviolet absorbers, drugs, herbal medicines, dispersants, fragrances, etc. be. [Effects of the invention] The W/O emulsion of the present invention requires only a small amount of organically modified clay mineral used as an emulsifier, 0.25 to 5% by weight, and it is possible to control the amount or the ratio of the internal aqueous phase. Therefore, it is possible to control the viscosity without incorporating 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 it has a wide temperature range. It has excellent storage stability over a long period of time. In addition, the formulation of mucopolysaccharides has good affinity for the skin because they are widely present in the connective tissue of mammals, and when cosmetics containing them are applied to the skin, the skin feels smooth and smooth. Not only is the usability improved, but in combination with the alkali metal salt of organic carboxylic acid or organic amine salt, the skin is kept moist and the stability of the W/O emulsion is also improved. 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. [Examples] Next, for further understanding of the present invention, the present invention will be described in more detail by giving Examples, but the present invention is not limited thereto. In the examples, parts and percentages are all percentages by weight. First, an example of preparing an organically modified clay mineral to be used as an emulsifier will be shown below. To 500 ml of an aqueous solution in which 45 g of benzyldimethylstearylammonium chloride (equivalent to about 100 meq) and 30 g of POE(6) lauryl ether were dissolved at 50°C, 100 g of Veegum (trade name of Vanderbilt Company, USA), a water-swellable clay mineral, was added. Thoroughly disperse and mix with a disperser for about 30 minutes. After removing water using a filter, the mixture is dried for about a day and night to obtain the desired organically modified clay mineral. Next, examples of the W/O type emulsion described so far will be shown. Example 1 Moisture cream (1) Squalane 20.0 (2) Cetyl isooctanoate 8.5 (3) 1.0 g of Veegum was mixed with 0.2 g of benzyldimethylammonium chloride, 0.1 g of distearyldimethylammonium chloride, and POE (10) glycerol triisostere. Organically modified clay mineral obtained by processing with 0.2g of rate 1.5 (4) Fragrance. Appropriate amount (5) Ethyl paraoxybenzoate 0.2 (6) Sodium lactate 1.0 (7) Sodium hyaluronate 0.01 (8) Glycerin 10.0 (9) Water 58.79% Manufacturing method Mix and disperse (1) to (5) and add in oil in advance. Prepare the phase. Next, a homogeneous solution of (6) to (9) was gradually added to the oil phase while stirring with a disperser to obtain the desired moisture cream. Example 2 Night cream (1) Squalane 30.0 (2) Lanolin 1.0 (3) Microcrystalline wax 1.0 (4) 0.5 g of Bentone 38 treated with 0.05 g of POE (14) dioleic acid ester and 0.05 g of decaglyceryl tetraoleate organically modified clay minerals obtained by
0.6 (5) Butyl parahydroxybenzoate 0.1 (6) Flavor appropriate amount (7) Sodium pyrrolidone carboxylate 4.0 (8) Sodium hyaluronate 0.3 (9) Sodium chondroitin B sulfate 0.2 (10) Propylene glycol 5.0 (11) Water 57.8 % Manufacturing method A target night cream was obtained according to Example 1. Comparative Example 1 A cream was prepared in the same manner as in Example 1 except that sodium lactate was removed. Comparative Example 2 A cream was prepared in the same manner as in Example 2 except that sodium pyrrolidone carboxylate was removed. Comparative Example 3 A cream was prepared in the same manner as in Example 1 except that sodium hyaluronate was removed. Comparative Example 4 Example 2 except that sodium hyaluronate and sodium chondroitin B sulfate were removed from Example 2.
A cream was prepared in the same manner. Table 1 shows the stability test results of Examples 1 and 2 and Comparative Examples 1 to 4, and the actual use test results by a female expert panel. The results of the stability test were evaluated based on the appearance after being left for one month, and the actual use test was evaluated based on the preference during use, using the following evaluation criteria. <Stability>〇; No separation observed △; Almost no separation observed ×; Separation of liquid phase (oil phase or aqueous phase) occurred <Usability> A: Smooth and non-sticky. Soft feel B; Smooth feel C; Moist feel

[Table] Example 3 Nutritional cream (1) Squalane 20.0 (2) Cetyl isooctanoate 5.0 (3) Cyclic silicone 5.0 (4) 0.6 g of Veegum, 0.2 g of benzyldimethylstearylammonium chloride and 0.2 g of POE (13) diisostearic acid Organically modified clay mineral obtained by processing with g 1.0 (5) Methyl paraoxybenzoate 0.2 (6) Flavor appropriate amount (7) Sodium glutamate 3.0 (8) Sodium hyaluronate 0.1 (9) Loofah extract 0.5 (10) Glycerin 15.0 (11) Maltitol 5.0 (12) Water 45.2% Manufacturing method A target nutritional cream was obtained according to Example 1. Example 4 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 mineral obtained by treatment with g.
0.6 (5) Butyl parahydroxybenzoate 0.1 (6) Fragrance 0.1 (7) Sodium edetacetate 0.7 (8) Titanium oxide 1.0 (9) Color pigment 0.1 (10) Heparin 0.05 (11) Dipropylene glycol 5.0 (12) Water 62.35 Manufacturing method A target makeup base cream was obtained according to Example 1.

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 mucopolysaccharides and their salts. A water-in-oil emulsion composition comprising one or more kinds, one or more kinds selected from the group consisting of alkali metal salts of organic carboxylic acids and organic amine salts, an oil component, and water. 2. The water-in-oil emulsion composition according to claim 1, wherein the mucopolysaccharide is hyaluronic acid or chondroitin sulfate. 3. The water-in-oil emulsion composition according to claim 1, wherein the organic carboxylic acid is lactic acid, pyrrolidone carboxylic acid, or glutamic acid. 4. The water-in-oil emulsion composition according to claim 1, wherein the content of the alkali metal salt or organic amine salt of an organic carboxylic acid is 0.1 to 10% by weight in the composition. 5 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 a weight of 140 milliequivalents. 6. 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. 7. The water-in-oil emulsion composition according to claim 1, wherein the content of mucopolysaccharides and their salts is 0.001 to 5% by weight in the composition.