JPH0462775B2 - - 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. Temperature stability of emulsified compositions that can be widely used and obtained by blending mucopolysaccharides,
The present invention relates to a water-in-oil emulsion composition that is characterized by extremely excellent usability. [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 constant temperature, 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. It was discovered that the emulsion is an excellent W/O type emulsion having high viscosity, good temperature stability, and smooth usability, and based on this knowledge, the present invention was 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. The present invention provides a water-in-oil emulsion composition comprising one or more mucopolysaccharides, 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) ₂₃ (Si, Al) ₄ O ₁₀ (OH) ₂ Z. nH ₂ O However, X=Al, Fe, Mn, Cr Y=Mg, Fe, Ni, Zn, Li Z=K, Na, Ca, specifically, natural or Synthesis {In this case, the (OH) group in the formula is substituted with fluorine} of the montmorillonite group (commercially available products include Veegum, Krypia, Laponite, etc.) and the names of sodium silicate squid and sodium or lithium taeniolite. Synthetic mica (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 or hydroxyalkyl groups having 1 to 3 carbon atoms, 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, Benzyldimethylmyrisammonium chloride , benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzyldimethylethylcetylammonium chloride, benzyldimethylethylstearylammonium chloride, distearyldimethylammonium chloride, dibehenylhydroxyethylammonium chloride, and the corresponding bromides. Further examples include dipalmitylpropylethylammonium methyl sulfate. In carrying out the present invention, one or more of these may be arbitrarily selected. Nonionic surfactant used in the present invention
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) uralyl ether, POE (1-20) alkyl phenyl ether, POE (6-18) behenyl ether, POE (5
~25) 2-decyl pentacyl ether, POE (3
~30) 2-decyltetradecyl ether, POE
(8-16) Ether-type activators such as 2-octyldecyl ether, and POE (4-20) hydrogenated castor oil, POE (3-14) fatty acid monoester, POE
(6-30) fatty acid diester, POE (5-20) ester type activator such as sorbitan fatty acid ester,
Furthermore, POE (2-30) glyceryl monoisostearate, POE (10-60) glyceryl triisostearate, POE (7-50) hydrogenated castor oil monoisostearate, POE (12-60) hydrogenated castor oil triiso Ethylene oxide-added surfactants such as ether ester type surfactants such as stearate, and polyglycerin fatty acid esters such as decaglyceryl tetraoleate, hexaglyceryl triisostearate, tetraglyceryl diisostearate, and diglyceryl diisostearate. , glyceryl fatty acid esters such as glyceryl monostearate, glyceryl monoisostearate, and glyceryl monooleate, and polyhydric alcohol fatty acid ester type surfactants. Among these, polyglycerin fatty acid esters higher than triglycerin such as decaglyceryl tetraoleate, hexaglyceryl triisostearate, and tetraglyceryl 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-decylpentadecyl ether, POE(5-17) 2-decyltetradecyl ether, POE(8-16) 2-octyldecyl POE-added ether type activator such as ether,
and POE (10-20) hydrogenated castor oil, POE (5-20)
14) POE addition ester type activators such as oleic acid monoester, POE(6-20) oleic acid diester, POE(5-10) sorbitan oleate, POE(3-15) glyceryl monoisostearate, POE( 10-40) Ethylene oxide-added nonionic surfactants such as POE-added ether ester type surfactants such as glyceryl triisostearate are particularly preferred. In the present invention, one or more kinds of nonionic surfactants are arbitrarily selected and used from among these nonionic surfactants. (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 advance. 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 ( 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 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 in the W/O emulsion of the present invention is 0.25 to 5% by weight.
0.5 to 3% by weight is preferred. 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. Acidic mucopolysaccharides such as are preferred, and among them, hyaluronic acid and its salts are particularly preferred. The blending amount of these mucopolysaccharides is about 0.001 to 5% by weight in the W/O emulsion, and 0.005 to 5% by weight.
3% by weight is preferred. 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 W/O emulsion of the present invention may optionally contain Natural Moisturizing Factors present in the stratum corneum of the skin, within a range that does not impair the effects of the present invention.
Amino acids and their salts in (NMF), humectants, thickeners, preservatives, sequestering agents, ultraviolet absorbers, drugs, herbal medicines, dispersants, fragrances, etc. can be blended. Examples of the above amino acids include alanine, arginine hydrochloride, asparagine monohydrate, aspartic acid, citrulline, glutamic acid, glutamic acid hydrochloride, glutamine, glycine, histidine, histidine hydrochloride, hydroxyproline, isoleucine, leucine, lysine, and lysine hydrochloride. , ornithine hydrochloride, proline, phenylalanine, serine, threonine, tryptophan, tyrosine, valine, doper, α-aminobutyric acid, etc. These consist of L-form, D-form and DL-form. Among these, particularly preferred are glycine,
L-hydroxyproline, L-alanine, L-
Metals that form salts with proline and L-serine include sodium, potassium, lithium, calcium, and magnesium. [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 the usability is improved, but also the stability of the W/O emulsion is further 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, all parts and % are 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. Next, 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 treatment with 0.2 g of chloride 1.5 (4) Fragrance. Appropriate amount (5) Ethyl paraoxybenzoate 0.2 (6) L-serine 0.1 (7) Sodium hyaluronate 0.01 (8) Glycerin 10.0 (9) Water 59.69% Manufacturing method Mix and disperse (1) to (5) and add 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 was mixed with POE (14) dioleic acid ester 0.05 g and Decagryl tetraoleate
Organic modified clay mineral obtained by processing 0.05g 0.6g (5) Butyl parahydroxybenzoate 0.1 (6) Fragrance appropriate amount (7) Sodium hyaluronate 0.3 (8) Sodium chondroitin B sulfate 0.2 (9) Propylene glycol 5.0 (10) Water 61.8% Manufacturing method The desired night cream was obtained according to Example 1. Comparative Example 1 Comparative Example 1 was obtained in the same manner as in Example 2, except that sodium hyaluronate and sodium chondroitin sulfate B were removed from Example 2. Example 3 Nutritional cream (1) Squalane 20.0 (2) Cetyl isooctanoate 5.0 (3) Cyclic silicone 5.0 (4) 0.6 g of Veegum was treated with 0.2 g of benzyldimethylstearylammonium chloride and 0.2 g of POE(13) diisostearic acid organically modified clay mineral obtained by 1.0 (5) ethyl paraoxybenzoate 0.2 (6) fragrance appropriate amount (7) serine 0.1 (8) L-glycine 0.1 (9) sodium hyaluronate 0.1 (10) loofah extract 0.5 (11) ) Glycerin 15.0 (12) Maltitol 5.0 (13) Water 48.0% Manufacturing method A target nutritional cream was obtained according to Example 1. Comparative Example 2 Comparative Example 2 was obtained in the same manner as Example 3 except that sodium hyaluronate was removed. Table 1 shows the stability test results of Examples 2 and 3 and Comparative Examples 1 and 2, 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 2 weeks, and the results of the actual use test were evaluated based on the preference during use, using the following evaluation criteria. <Stability>◎; No separation observed ○; Almost no separation observed △; Separation of liquid phase (oil phase or water phase) occurred <Usability> A: Smooth and smooth B: Average C: Dislike

[Table] (1) Squalane 23.0 (2) Cyclic silicon 5.0 (3) Microcrystalline wax 2.0 (4) 0.5 g of bentone-38 was added to POE (14) dioleate 0.05 g and decalyl tetraoleate
Organically modified clay mineral obtained by processing with 0.05g 0.6 (5) Butyl parahydroxybenzoate 0.1 (6) Fragrance 0.1 (7) Titanium oxide 1.0 (8) Color pigment 0.1 (9) Heparin 0.05 (10) Dipropylene Glycol 5.0 (11) Water 63.05 Manufacturing method A target makeup base cream was obtained according to Example 1.

Claims (1)

[Scope of 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 one or more types of muco A water-in-oil emulsion composition containing a polysaccharide, an 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 a weight 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. Claim 1, wherein the mucopolysaccharide is 0.001 to 5% of hyaluronic acid and/or a salt thereof in the composition.
The water-in-oil emulsion composition described in 2.