JP2006124319A - Surfactant free emulsified composition for skin and surfactant free skin cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a surfactant free emulsified composition for skin excellent in emulsion stability, safety to the skin and usability, and skin care preparations for external use such as a skin care medicine for external use, a skin cosmetic, and the like, comprising the emulsified composition for skin. <P>SOLUTION: The emulsified composition for skin contains an oil component, a glycyrrhizinic acid salt, a humectant and water and substantially no material having ≤500 μN/cm surface tension in a 1 wt.% aqueous solution. Or, the composition contains the oil component, the glycyrrhizinic acid salt, the humectant and water and, if needed, a material selected from the group consisting of colorants, flavors, pigments, antiseptics, antioxidants, UV protective agents, clay minerals, buffers for pH, ethanol and organic thickeners. In the composition, the sum total concentration of the above components is ≥99.5 wt.%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention does not contain a surfactant that is generally applied as an emulsifier in skin external preparations, skin external preparations including skin cosmetics, etc., and has excellent emulsification stability, skin safety, and usability. The present invention relates to an active agent-free emulsified composition for skin and an external preparation for skin comprising the emulsified composition for skin.

  In recent years, it has been attracting attention that the number of people with sensitive skin has increased. The causes include external stimuli such as low temperature and dryness due to climate, physical stimuli, chemical stimuli, stress, Internal factors due to eating habits, etc. are considered.

  To make skin preparations for sensitive skin, it is necessary to select raw materials with high skin safety (oils, moisturizers, emulsifiers, preservatives, drugs, fragrances, coloring agents, pH buffering agents, etc.). Of particular importance is the selection of the emulsifier used to maintain emulsion stability.

  As emulsifiers, ionic surfactants, amphoteric surfactants, nonionic surfactants and polymer surfactants have been generally used.

  In general, ionic surfactants and amphoteric surfactants have low skin safety. In addition, it is known that nonionic surfactants have higher skin safety than ionic surfactants and amphoteric surfactants. However, nonionic surfactants also have skin safety depending on their molecular weight and molecular structure. It is a well-known fact that sex is greatly affected.

  Among the nonionic surfactants, those having particularly high skin safety include glycerin, diglycerin, polyglycerin, sorbitol, sorbitan, which have a branched alkyl group having 14 or more carbon atoms as a hydrophobic group. Derivatives such as sugar esters and hydrophilic groups include POE (polyoxyethylene) alkyl derivatives having 20 or more oxyethylene repeating units in one molecule, polyoxyethylene hydrogenated castor oil, phytosterols, cholesterol derivatives and the like. As long as it is a surfactant, it is impossible to completely suppress irritation to the skin.

  As a formulation technology that does not use a so-called surfactant, development of a W / O (water-in-oil) type skin cosmetic that uses a water-soluble polymer and a clay mineral in combination as an emulsifier (for example, Patent Document 1, 2). However, due to the characteristic of W / O type, it has a large occlusion property, but it is seldom preferred in terms of usability because it makes it feel oily.

  Examples of the polymer surfactant include those using carboxyvinyl polymer (for example, Hibiswako 105, manufactured by Wako Pure Chemical Industries, Ltd.) as an emulsifier, and PEMULEN emulsification using an acrylic acid-alkyl methacrylate copolymer as an emulsifier. Development of skin cosmetics by the law (see, for example, Patent Document 3) has also been carried out, but the emulsified particles are immediately destroyed at the time of application, so that the feeling of use may be unsatisfactory.

In addition, development of fat emulsions and skin cosmetics using animal and plant lipids having a function as a surfactant (see, for example, Patent Document 4) has been carried out. There is a frustrating problem, and a satisfactory product has not been developed.
JP-A-11-188253 (Claims) JP 2002-253949 A (Claims) JP 09-255529 A (Claims) JP 2001-151624 A (Claims) Booklet “Dipotassium glycyrrhizinate”, Maruzen Pharmaceutical Co., Ltd., March 1994

  The present invention solves the above-mentioned problems, does not contain a surfactant, and is a surfactant-free emulsion composition for skin that is excellent in emulsion stability, skin safety, and usability, and the emulsion composition for skin An object of the present invention is to provide an external preparation for skin, such as a pharmaceutical preparation for external use of skin and skin cosmetics. Still other objects and advantages of the present invention will become apparent from the following description.

  According to one aspect of the present invention, a surfactant-free skin containing oil, glycyrrhizinate, a humectant, and water, and containing substantially no substance having a surface tension of 500 μN / cm or less in a 1 wt% aqueous solution. An emulsified composition is provided.

  According to another aspect of the present invention, oil, glycyrrhizinate, humectant, water and optionally colorants, fragrances, pigments, preservatives, antioxidants, UV protection agents, clay minerals, pH An emulsified composition for skin containing a substance selected from the group consisting of a buffer, ethanol and an organic thickener, the oil in the emulsified composition for skin, glycyrrhizinate, humectant, water and necessary Depending on the total concentration of substances selected from the group consisting of colorants, fragrances, pigments, preservatives, antioxidants, UV protection agents, clay minerals, pH buffering agents, ethanol and organic thickeners. A surfactant-free emulsified composition for skin that is 99.5% by weight or more is provided.

  According to these aspects of the invention, a surfactant-free emulsified composition for skin that does not contain a so-called surfactant and is excellent in emulsion stability, skin safety, and usability can be realized.

  In any embodiment, the average particle size of the emulsified particles is in the range of 0.1 to 2.5 μm, the glycyrrhizic acid salt is contained in an amount of 0.01 to 3.0% by weight as glycyrrhizic acid, Is preferably selected from the group consisting of alkali metal salts, ammonium salts, amine salts, basic amino acid salts and mixtures thereof.

  According to another aspect of the present invention, there is provided a surfactant-free skin cosmetic comprising the above surfactant-free emulsion composition for skin.

  According to the embodiment of the present invention, it is possible to realize a surfactant-free external skin preparation that does not contain a so-called surfactant and is excellent in emulsification stability, skin safety, and usability.

  Such a surfactant-free skin cosmetic is preferable for sensitive skin.

  According to the present invention, a so-called surfactant-free emulsifying composition for skin that does not contain a so-called surfactant and is excellent in emulsification stability, skin safety, and usability, and a skin emulsifying composition for the skin. An external preparation for skin such as pharmaceuticals and skin cosmetics can be realized.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings, tables, examples and the like. In addition, these figures, tables, examples, etc., and explanations are only examples of the present invention, and do not limit the scope of the present invention. It goes without saying that other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.

  As a result of investigation, if glycyrrhizinate is used, it is suitable for use as a skin external preparation such as a skin external medicine or skin cosmetic, and is a surfactant-free skin excellent in emulsion stability, skin safety and usability. It has been found that an emulsion composition can be formed.

  Glycyrrhizinate has an anti-inflammatory action and an anti-allergic action, and is therefore mainly blended as a drug in skin external preparations including skin cosmetics (see Non-Patent Document 1, for example). Although it is known that this glycyrrhizinate also has some surface activity (see, for example, Non-Patent Document 1), a 0.72% by weight aqueous solution that is a solution of dipotassium glycyrrhizinate in CMC (critical micelle concentration) The surface tension at is as large as 556 μN / cm, which is not at a level generally recognized as a surfactant. Under such circumstances, there has been no research on emulsions using only glycyrrhizinate as an emulsifier, and it is unexpected that a skin emulsified composition suitable for use as a skin external preparation such as skin cosmetics can be obtained. It was the result.

  The emulsified composition for skin according to the present invention contains an oil, glycyrrhizinate, a humectant and water, and contains a surfactant-free material substantially free of a substance having a surface tension of 500 μN / cm or less in a 1 wt% aqueous solution. It is an emulsified composition for skin. It is sensitive because it has less anti-inflammatory and anti-allergic effects because it uses glycyrrhizinate, which is usually used as a drug, as an emulsifier instead of a surfactant. Even people with skin can use it with confidence.

  Glycyrrhizinate used as an emulsifier in the present invention is considered functionally similar to an ionic surfactant because of its structure, and in an environment where oil, humectant and water coexist according to the present invention. As long as an emulsion having emulsion particles with good uniformity is made, the emulsion stability is very good.

  In addition, the emulsion composition for skin according to the present invention does not immediately cause destruction of the emulsified particles even when applied on the skin, compared to an emulsion using a polymer surfactant belonging to a water-soluble polymer or the like. It is as good as conventional skin cosmetics because it does not have a sense of slimness or a slimy feeling peculiar to polymers.

  The emulsion composition for skin thus obtained is used as an external preparation for skin, such as skin cosmetics, in the form of final products such as creams, emulsions, essences, lotions, packs, ointments and the like. be able to.

  Regarding the emulsified composition for skin according to the present invention, an ionic surfactant, an amphoteric surfactant, a nonionic surfactant, and a polymeric surfactant may be used for substances having a surface tension of 500 μN / cm or less in a 1% by weight aqueous solution. Is included.

  Among the ionic surfactants, anionic surfactants include sodium cetyl sulfate, sodium lauryl sulfate, sodium POE tridecyl ether acetate, higher fatty acid sodium, and higher fatty acid potassium.

  Examples of the cationic surfactant among the ionic surfactants include POE stearamide, POE stearylpropylenediamine, and cetyltrimethylammonium chloride.

  Amphoteric surfactants include N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine sodium, N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine sodium lauryl sulfate, coconut oil fatty acid Mention may be made of amidopropyldimethylaminoacetic acid betaine.

  Nonionic surfactants include POE sorbitan fatty acid ester, POE sorbite fatty acid ester, POE alkyl ether, POE alkyl ester, polyglycerin fatty acid ester, POE glycerin fatty acid ester, and POE-POP (polyoxypropylene) alkyl ether. it can.

  Examples of the polymer surfactant include an alkyl acrylate-alkyl methacrylate copolymer.

  Among the above surfactants, those having a surface tension of 500 μN / cm or less in a 1% by weight aqueous solution are substantially not present in the emulsion composition for skin according to the present invention. “Substantially not present” means that the lower limit cannot be measured with a measuring instrument of 0.1% by weight. Here, the “surface tension in a 1% by weight aqueous solution” can be measured according to the ring method.

  The above is described from the viewpoint of the emulsified composition for skin without using a so-called surfactant, but from the viewpoint of the emulsified composition for skin containing oil, glycyrrhizinate, humectant and water. When viewed, oil, glycyrrhizinate, humectant, water and, if necessary, colorants, fragrances, pigments, preservatives, antioxidants, UV protection agents, clay minerals, pH buffering agents, ethanol and An emulsified composition for skin containing a substance selected from the group consisting of organic thickeners, wherein oil, glycyrrhizinate, humectant, water and optionally present in the emulsified composition for skin The total concentration of substances selected from the group consisting of colorants, fragrances, pigments, preservatives, antioxidants, UV protection agents, clay minerals, pH buffering agents, ethanol and organic thickeners is 99.5% by weight Less than In dermatological emulsion composition is, emulsion stability, skin safety, may serve as dermatological emulsion composition excellent in usability was found. In this case, a so-called surfactant can be contained up to a maximum of 0.5% by weight, but from the viewpoint of skin safety and usability, a smaller content is generally preferred. Specifically, the total concentration is more preferably 99.7% by weight or more. In the present invention, “surfactant-free” includes a case where such a surfactant is present in a very small amount, and does not necessarily mean that it does not contain any surfactant. Absent.

  The glycyrrhizinate that can be used in the emulsion composition for skin according to the present invention is obtained by neutralizing glycyrrhizic acid, which is a glycoside obtained from licorice, with various bases, but has three carboxy groups. It is possible to make a tri-salt from one. Mono- and di-salts are preferred from the viewpoint of emulsification. The emulsifiability is slightly different depending on the type of counter ion, but the emulsification stability is hardly changed.

  As the glycyrrhizinate, those selected from the group consisting of alkali metal salts, ammonium salts, amine salts, basic amino acid salts and mixtures thereof are preferable because of their availability. One molecule may contain a plurality of types of bases. FIG. 1 shows a structural example of dipotassium glycyrrhizinate. In addition, the glycyrrhizic acid salt which concerns on this invention may contain the glycyrrhizic acid which is not converted into a salt.

  There is no restriction | limiting in particular as oil which can be used for the emulsion composition for skin which concerns on this invention, It can select suitably from all the oils which can also be used for skin external preparations including a skin external preparation and skin cosmetics. Multiple oils may be used.

  Examples of oils with good skin safety include silicone oil (trade names Silicon DC246 and Silicone KF56 manufactured by Shin-Etsu Chemical Co., Ltd.), squalane, medium and high viscosity liquid paraffin, synthetic liquid paraffin (trade name NIKKOL Synthelan manufactured by Nikko Chemicals Co., Ltd.). 4), vegetable oils such as jojoba oil, macadamian nut oil, refined olive oil, hazelnut oil, avocato oil, tetra (2-ethylhexanoic acid) pentaerythritol, tri (2-ethylhexanoic acid) trimethylolpropane, triisostearic acid tri Examples thereof include synthetic ester oils such as methylolpropane.

  The fluidity of the oil according to the present invention is preferably liquid at 50 ° C. in view of stability of mixing and dispersion, but purified petrolatum (for example, Nikko Rica is more suitable than combining oils with high fluidity). Vaseline P-200 manufactured by the company, higher fatty acids, higher alcohols (eg, cetyl alcohol, stearyl alcohol, cetostearyl alcohol, behenyl alcohol) semi-solid, solid oil (ie, fat), the compatibility of the entire oil phase In view of the above, it is generally better in terms of usability to mix and blend.

  In addition, when used for a low-viscosity skin cosmetic such as a skin lotion type, an oil component having a large specific gravity is preferable from the viewpoint of preventing the emulsified particles from floating. For example, silicone KF56 (manufactured by Shin-Etsu Chemical Co., Ltd., specific gravity at 25 ° C. is 0.990 to 1.005), tetra (2-ethylhexanoic acid) pentaerythritol (manufactured by Nikko Chemical Co., Ltd., specific gravity at 30 ° C. is 0.955) 0.965).

  The humectant used in the present invention may be used in combination of one or more of the following humectants.

  As the humectant, propylene glycol, dipropylene glycol, hexylene glycol, pentylene glycol, polyglycerin, 1,3-butylene glycol, glycerin, diglycerin, sorbitol, low-polymerization polyethylene glycol such as polyethylene glycol-300, Polyethylene glycol-400, polyethylene glycol-600), glycoside trehalose (for example, Hayashibara, trade name Torunare), oligosaccharide, maltitol (for example, Hayashibara, trade name Mabit), polyethylene methylglycoside (for example, Nippon Oil & Fats, For example, the product name Macbiobride).

  Furthermore, the surfactant-free emulsified composition for skin of the present invention comprises a colorant, a fragrance, a pigment, an antiseptic, an antioxidant, an ultraviolet protective agent, a clay mineral, a pH buffer, ethanol, an organic system, if necessary. A thickener, a drug, and the like can be appropriately blended within a range not departing from the spirit of the present invention.

  Ethanol is added to adjust the specific gravity, impart a refreshing feeling, and impart an antiseptic effect. Since the organic thickener can prevent the emulsified particles from being lifted, it can be suitably used for an emulsion or the like. When the emulsified composition for skin according to the present invention is used as a skin external preparation such as a skin external medicine or skin cosmetic, the drug is used according to the specific purpose. Furthermore, sodium hexametaphosphate which is a chelating agent or a metal sealing agent can be added for the purpose of preventing a decrease in viscosity.

  In this way, for example, final products such as creams, emulsions, essences, lotions, packs, ointments and the like can be appropriately produced.

  As a coloring agent, safflower yellow, safflower red, methyl hesperidin, cyanocobalamin, β-carotene, carrot oil, agar extract (agar extract), as a preservative, a mixture of phenoxyethanol and glycerin fatty acid ester (for example, trade name Nicogard DL (Nikko) Chemical Co., Ltd.)), tocopherol, vitamin C, and L-cysteine as antioxidants, and as a UV protection agent, particulate zinc oxide (trade name Z-COTE) manufactured by Nikko Chemical Co., Ltd., Silica-coated titanium oxide (trade name Maxlite TS-04), silica-coated zinc oxide (trade name Maxlite ZS-032), vitamin E (tocopherol acetate, vitamin E acetate), stearyl glycyrrhetic acid, glyceryl retinoic acid as drugs Allantoin As organic thickeners, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, xanthan gum (for example, Dainippon Pharmaceutical Co., Ltd., trade name Celtrol), polyvinyl alcohol, high polymerization degree polyethylene glycol (molecular weight 2000 or more), Polyaspartic acid polymer, atelocollagen, hyaluronic acid, hyaluronic acid salt (for example, sodium salt), as clay mineral, bentonite (trade name Kunipia G-4, manufactured by Kunimine Kogyo Co., Ltd.), colloidal aluminum silicate magnesium (trade name Bea gum HV, Vanderbilt) and pH buffering agents include citric acid / trisodium citrate, lactic acid / sodium lactate, basic amino acids (for example, l-arginine) and the like.

  Regarding the composition of the emulsion composition for skin according to the present invention, it is preferable to contain 0.01 to 3.0% by weight of glycyrrhizinate as glycyrrhizic acid. More preferably, it is in the range of 0.05 to 0.5% by weight. If the blending amount of glycyrrhizinate is less than 0.01% by weight as glycyrrhizic acid, the emulsifying power may be insufficient and the emulsion stability may be deteriorated. It is not preferable because it becomes sticky in terms of usability. The above “amount of glycyrrhizinate as glycyrrhizic acid” means a value measured as the amount of glycyrrhizic acid present in the composition regardless of whether or not glycyrrhizic acid is present as a salt in the composition.

  In the case of a low-viscosity emulsion composition called so-called shabu-shabu type, the oil content is 1 to 10% by weight, and glycyrrhizinate is glycyrrhizic acid and 0.01 to 3.0% by weight in relation to other components. Further, 5 to 50% by weight of a humectant and 94 to 40% by weight of water can be contained. In the case of a milky skin emulsion composition such as milk lotion, the oil content is 3 to 40% by weight, the glycyrrhizinate is 0.01 to 3.0% by weight as glycyrrhizic acid, and the humectant is 5 to 40%. % By weight and 92 to 20% by weight of water can be included. In these cases, the total amount of oil, glycyrrhizinate, humectant and water does not exceed 100% by weight.

  It should be noted that the skin external preparations such as skin external medicines and skin cosmetics using the emulsified composition for skin according to the present invention preferably have various viscosities according to the purpose of use. In the emulsified composition for skin, such a request can be met by appropriately selecting the amount ratio of oil, glycyrrhizinate, humectant and water.

  In preparing the emulsified composition for skin according to the present invention, sufficient emulsification treatment is important. The emulsification of the present invention requires a collision-mixing microfluidizer or Manton Gaurin that can give a strong shearing force. In order to improve the uniformity of the emulsified particles, for example, as the primary emulsification, In a composition comprising glycyrrhizinate, oil and water, stirring and mixing in an emulsification method (sometimes referred to as a conc-base emulsification method or a concentrated emulsification method) with a high concentration of glycyrrhizinate and oil Emulsion particles are prepared in advance by processing with a homomixer of the type, and further processed with a microfluidizer, etc., and by reducing the particle size, emulsions with good usability and emulsion stability (high concentration of glycyrrhizinate and Since it contains oil, it is referred to as “conc base emulsion” below. Water and various humectants, optionally, pH buffering agents, by adding other additives, can be manufactured dermatological emulsion composition excellent in emulsion stability.

  Furthermore, in the concentrated base emulsification method, if the amount of oil is reduced and emulsification is carried out with a large amount of glycyrrhizinate, weak stirring force such as a homomixer can be applied without applying strong stirring force such as a microfluidizer. However, it has been found that it is possible to produce emulsion particles with good uniformity and to obtain a stable emulsion. At that time, as described above, it is conceivable that the collision mixing method and the stirring mixing method are combined, or the mixing is performed only by the collision mixing method or only by the stirring mixing method.

  The amount of glycyrrhizinate varies depending on the amount of oil at the stage of producing a conc base microemulsion. When the oil content is increased (the ratio φ of the internal phase in the emulsified particles is increased), the viscosity is extremely increased at a stage where the emulsified particle size is reduced during high-pressure processing such as a microfluidizer. Weight% (φ = 0.6) is the limit. The glycyrrhizinate necessary for emulsifying 60% by weight of oil is 0.5 to 6.0% by weight as glycyrrhizic acid.

  Since the emulsification stability depends greatly on the size and uniformity of the emulsified particles, it is necessary to reduce the emulsified particle size. Specifically, the average particle diameter of the emulsified particles is preferably in the range of 0.1 to 2.5 μm. When it is larger than 2.5 μm, a tendency to separate into an aqueous phase and an oil phase tends to appear with time. An emulsified particle having an average particle size of less than 0.1 μm is difficult to produce, and even if it can be produced, it takes a long time and excessively increases the viscosity. The average particle size can be measured, for example, with a laser diffraction particle size analyzer. For this purpose, as described above, it is useful to adopt the collision mixing method, but in the composition according to the present invention, such a particle size can be obtained only by the stirring and mixing method if the conditions are selected. it can.

  Next, examples of the present invention will be described in detail. In the following examples and tables, “%” is by weight unless otherwise specified. The following evaluation method was adopted. The purified water was produced by a pure water production apparatus (SWAC) manufactured by Shimadzu Corporation.

・ Emulsified particle size (diameter)
By visual observation under an optical microscope. However, the average particle diameter (diameter) was determined using a laser diffraction particle size analyzer (SALD-700, manufactured by Shimadzu Corporation).

・ Emulsification stability test Predetermined test sample under constant temperature condition of 40 ° C, room temperature, 0 ° C, -5 ° C and cycle of 5-45 ° C twice / 24 hours (cycle test) Leave for a period of time, separation by coalescence of emulsified particles, bottom clear (separate two layers to make the lower layer appear clear) and oil up (separate two layers to see oil in the upper layer) ) Was observed. The symbol “◯” means that there was no bottom clear, no separation due to coalescence of emulsified particles, and no oil up.

・ Usage test A test sample was applied to the face for 2 weeks on subjects with sensitive skin selected by a questionnaire survey from the recruited general public. The application was performed every morning after washing the face, and was removed by washing with soap before going to bed. During the test period, the use of cosmetics other than point makeup such as lipstick was prohibited. The results of use were surveyed and related to the symptoms that the subjects studied in advance.

[Example 1]
(Manufacturing process of Conc Base Emulsion Formula A)
Components (1) to (5) in Table 1 were stirred and dissolved at room temperature to prepare an aqueous phase. On the other hand, components (6) to (8) are stirred and mixed to prepare an oil phase. While homomixing (8500 rpm), the oil phase is slowly added to the aqueous phase, and then component (9) is slowly added. A concentrated base emulsion having an emulsified particle size of 2.0 to 5.0 μm was obtained.

In order to further reduce the emulsified particle diameter of this emulsion, it is 0.2 to 0.00 by treating twice (1400 kg / cm ² ) with a microfluidizer (manufactured by Microfluidics International Corporation) at room temperature. A concentrated base microemulsion having a uniform emulsified particle size of 5 μm (average particle size of 0.31 μm) and good emulsification stability was obtained.

(Dilution process of Conc Base Emulsion Formula A)
This conc base microemulsion can be used as it is as a milk lotion with a lot of oil. However, in order to improve the usability, it is further diluted with the components shown in Table 2, and finally the surface activity shown in Table 3 is used. An agent-free milk lotion (fresh type) was obtained (pH: 5.87, viscosity: 2600 mPa). The average particle size was 0.31 μm.

  Specifically, after adding the component (3) to the component (2) in Table 2 and stirring and dissolving with a propeller stirring blade at room temperature, the components (4) to (7) are added, and the component (8) (9) to (12) were added to and dissolved by stirring. Finally, the conc. Base microemulsion A of component (1) was added, homomixing was performed (4000 rpm) so that the emulsion was uniform, and the oil content shown in Table 3 was 9.0% by weight, monoammonium glycyrrhizinate 0.2 A surfactant-free milk lotion (fresh type) containing% by weight was obtained.

実施例１のミルクロ−ション（さっぱりタイプ）についての乳化安定性試験結果を表４に、敏感肌の被験者を対象とした使用試験結果を表５、表６に、また、使用試験と同時に実施された使用性についてのアンケート調査結果を表７に示す。

The emulsion stability test results for the milk lotion (fresh type) of Example 1 are shown in Table 4, the use test results for subjects with sensitive skin are shown in Tables 5 and 6, and simultaneously with the use test. Table 7 shows the results of a questionnaire survey on usability.

乳化安定性試験の結果、４０℃、室温、０℃、−５℃およびサイクルテスト（５〜４５℃のサイクルを２回／２４時間の頻度で繰り返し実施）での乳化安定性は、６ヶ月後でも極めて安定であり、乳化粒子のボトムクリアも、乳化粒子同士の合一による分離も、オイルアップも見られず、全ての条件下で良好であった。

As a result of the emulsification stability test, the emulsification stability in 40 ° C., room temperature, 0 ° C., −5 ° C. and cycle test (5 to 45 ° C. cycle repeated at a frequency of 2 times / 24 hours) is 6 months later. However, it was extremely stable, and the bottom of the emulsified particles, separation by coalescence of the emulsified particles, and no oil-up were observed, which was good under all conditions.

  In the use test for subjects with sensitive skin, as a result of subject selection based on a preliminary questionnaire survey, responding with sensitive skin (including atopy skin) having symptoms (multiple answers) shown in the left column of Table 5 A test was conducted in which the milk lotion of Example 1 was actually used for 2 weeks. As a result, the results shown in the right column of Table 5 and Table 6 were obtained.

すなわち、ヒリヒリ感や肌にシミる感じを有する敏感肌の被験者や、皮膚の乾燥やカユミ等のアトピ−皮膚特有の症状を気にする超敏感肌を有する被験者を対象とした使用試験であったにもかかわらず、表６に示すごとくほとんど（９４％）の人が何ら症状を示さず使用できたこと、および実施例１のミルクロ−ションの使用中に症状が悪化した例がなかったことは、皮膚に対して非常に安全に使用できたことを示している。また、表５の左欄に示した症状別改善率がいずれも９０％以上と高かったことから、実施例１のミルクロ−ションはアトピ−皮膚のみならずアトピ−性皮膚炎の症状の緩和にも役立つものと考えられる。

In other words, it was a usage test for subjects with sensitive skin who feels tingling and tingling on the skin, and subjects with supersensitive skin who care about symptoms specific to atopic skin such as dry skin and kayumi. Nonetheless, as shown in Table 6, almost (94%) people were able to use without any symptoms, and there were no cases where the symptoms worsened while using the milk lotion of Example 1. This indicates that it can be used very safely against the skin. Moreover, since the improvement rate according to the symptom shown in the left column of Table 5 was as high as 90% or more, the milk lotion of Example 1 was effective for alleviating the symptoms of not only atopic skin but also atopic dermatitis. Is also considered useful.

  Regarding the usability of the milk lotion of Example 1, a questionnaire survey of 50 people was conducted at the same time. The results are shown in Table 7.

若干さっぱり感には欠けるものの、肌へのなじみ、しっとりさは好まれ、総合評価においても７０％の人がとてもよいと答えている。乳化剤としてグリチルリチン酸モノアンモニウムのみを使用した乳液にもかかわらず、使用感的には満足な結果が得られた。

Although it is slightly lacking in refreshing feeling, it is preferred to be familiar and moist with the skin, and 70% of the respondents answered that they are very good in the overall evaluation. Despite the emulsion using only monoammonium glycyrrhizinate as an emulsifier, satisfactory results were obtained in terms of usability.

[Example 2]
(Manufacturing process of Conc Base Emulsion Formula B)
Component (4) in Table 8 was added to components (1) to (3) and dissolved by stirring to prepare an aqueous phase. On the other hand, components (5) to (7) were stirred and mixed to prepare an oil phase. Next, the oil phase is slowly added to the aqueous phase while performing homomixer treatment (9,000 rpm), and then component (8) is added slowly to obtain a concentrated base emulsion B having an emulsified particle size of 2.0 to 5.0 μm. Obtained.

Further, this emulsion was treated twice with a microfluidizer (1400 kg / cm ² ), whereby a concentrate having an oil content of 60% by weight and an emulsified particle size of 0.1 to 0.3 μm (average particle size of 0.23 μm) was obtained. Base microemulsion B was obtained.

(Dilution process of Conc Base Microemulsion B)
After the components (8) and (9) are stirred and dissolved in the component (11) of Table 9, the components (2) to (7) and (10) are sequentially added and mixed by stirring. Concent base microemulsion B was added and the propeller was sufficiently stirred. A surfactant-free lotion-like milk lotion (moisturizing) containing 6.0% by weight of oil and 0.5% by weight of dipotassium glycyrrhizinate shown in Table 10 Type)) was obtained (pH = 5.20).

  Although the emulsion particle size is as small as 0.1 to 0.3 μm (average particle size 0.23 μm), each temperature (40 ° C. for 6 months, room temperature, 0 ° C.) despite having almost no viscosity (for example, 50 cP or less). In the emulsification stability test at −5 ° C. and a cycle test (cycle of 5 to 45 ° C. repeated at a frequency of 2 times / 24 hours), as shown in Table 11, the bottom clear of the emulsified particles There was no separation due to coalescence between them, and there was no oil up.

  In addition, it is free from surfactants, and by reducing the water activity by adding a moisturizer, alcohol, etc., it can be made anti-bacterial just by adding more pear extract (which can also be used as a colorant) as a preservative. A lotion-like milk lotion (moist type) with good emulsification stability and good usability that can be used with peace of mind even for people with sensitive skin was obtained.

［実施例３］
（コンクベースマイクロエマルジョンＢの希釈工程）
表１２の成分（８）に成分（９）を撹拌溶解させた後、成分（１０）をダマにならないように均一に分散してからプロペラ撹拌を十分に行って溶解させ、更に成分（２）〜（７）、（１５）を順次加えて撹拌混合し水相を調製した。他方、成分（１１）に成分（１２）〜（１４）を添加して撹拌溶解した後に、前に調製した水相に添加し、撹拌中和を行った。次いで、成分（１）のコンクベースマイクロエマルジョンＢを添加してホモミキサ−処理（１／４馬力、４，０００ｒｐｍ）を行い、表１３に示すミルクローション（しっとりタイプ）を得た。平均粒子径は０．２３μｍであった。

[Example 3]
(Dilution process of Conc Base Microemulsion B)
After the component (9) is stirred and dissolved in the component (8) of Table 12, the component (10) is uniformly dispersed so as not to become lumpy and then sufficiently stirred with a propeller to dissolve, and further the component (2) To (7) and (15) were sequentially added and mixed by stirring to prepare an aqueous phase. On the other hand, components (12) to (14) were added to component (11) and dissolved by stirring, and then added to the previously prepared aqueous phase for neutralization by stirring. Subsequently, the conc. Base microemulsion B of component (1) was added and homomixing treatment (1/4 horsepower, 4,000 rpm) was performed to obtain a milk lotion (moist type) shown in Table 13. The average particle size was 0.23 μm.

実施例３のミルクローション（しっとりタイプ）の乳化安定性試験結果は、表１４に示すとおり、極めて安定であった。

As shown in Table 14, the emulsion stability test result of the milk lotion (moist type) of Example 3 was extremely stable.

［実施例４］
（コンクベースエマルジョン処方Ｃの製造工程）
表１５の成分（１）に（２）〜（５）を加えて撹拌溶解して水相を調製した。他方、成分（６）〜（８）を撹拌混合して油相の調製を行い、ホモミキサー処理（１／４馬力、９０００ ｒｐｍ）しながら油相を水相にゆっくり添加し乳化を行い、さらに成分（９）を加え、乳化粒子径が２．０〜５．０μｍのコンクベースエマルジョンを得た。

[Example 4]
(Manufacturing process of Conc Base Emulsion Formula C)
(2) to (5) were added to component (1) in Table 15 and dissolved by stirring to prepare an aqueous phase. On the other hand, the oil phase is prepared by stirring and mixing the components (6) to (8), and the oil phase is slowly added to the aqueous phase and emulsified with homomixer treatment (1/4 horsepower, 9000 rpm). Component (9) was added to obtain a concentrated base emulsion having an emulsified particle size of 2.0 to 5.0 μm.

Furthermore, high pressure treatment ((1060 kg / cm ² ), 3 times) with a microfluidizer was performed to obtain a concentrated base microemulsion C of emulsified particles having an emulsified particle size of 0.2 to 0.5 μm.

(Dilution process of Conc Base Microemulsion C)
After adding components (3) to (5) to component (2) in Table 16 and dissolving with stirring, components (6) to (7) are dissolved by propeller stirring, and further components (8) to (12) are added. The mixture was added and stirred. The component (13) was dissolved in the component (14) and added to the previously prepared aqueous phase for neutralization by stirring. Finally, the conc. Base microemulsion C of component (1) is added, homomixer processing (1/4 horsepower, 4,000 rpm) is performed, and the oil content is adjusted to pH = 7.0 shown in Table 17 with a viscosity of 3,900 mPa. A surfactant-free essence with good emulsion stability containing 2.5% by weight was obtained. The average particle size was 0.36 μm.

［実施例５］
（コンクベースエマルジョン処方Ｄの製造工程）
表１８の成分（１）に成分（２）〜（４）を５０℃に加熱溶解して水相を調製した。他方、成分（５）〜（１１）を６５〜７０℃で加熱溶解した後５０℃に温度調節し、ホモミキサー処理をしながらこれを前の水相にゆっくり添加し、更に５０℃に加熱した成分（１２）をゆっくり添加して乳化を行い、乳化粒子径が１〜４μｍのコンクベースエマルジョンＤを得た。

[Example 5]
(Manufacturing process of conc base emulsion formulation D)
Components (2) to (4) were heated and dissolved at 50 ° C. in component (1) of Table 18 to prepare an aqueous phase. On the other hand, the components (5) to (11) were dissolved by heating at 65 to 70 ° C., adjusted to 50 ° C., slowly added to the previous aqueous phase while being homomixed, and further heated to 50 ° C. The component (12) was slowly added to perform emulsification, and a concentrated base emulsion D having an emulsified particle size of 1 to 4 μm was obtained.

Further, the first microfluidizer treatment ((1400 kg / cm ² ) is performed at 50 ° C., the second and third microfluidizer treatment ((1400 kg / cm ² ) is performed at room temperature, and the emulsified particle size is 0.1. A conc base microemulsion D having a particle size of ˜0.2 μm (average particle size of 0.16 μm) was obtained.

(Dilution process of Conc Base Microemulsion D)
After component (6) is stirred and dissolved in component (7) in Table 19, components (4) to (5) are added and dissolved by propeller stirring which is a stirring and mixing method, and components (2) to (3) are further dissolved. Was mixed with stirring. Further, after adding components (9) to (11) to component (8) and stirring and dissolving them to the previously prepared liquid and neutralizing, the concentrated base microemulsion D of component (1) is added. In addition, a homomixer treatment (1/4 horsepower, 3,500 rpm) was performed, and a surfactant-free milk lotion containing 19.5% by weight of oil and 3.0% by weight of dipotassium glycyrrhizinate shown in Table 20 was obtained. Obtained (pH = 6.87, viscosity 4,100 mPa). The average particle size was 0.16 μm. This milk lotion is considered to function as a hand roughness improving agent having a high effect of improving hand roughness, excellent in emulsification stability, skin safety, and usability due to the component composition.

この手荒れ用ミルクローションの乳化安定性試験結果は、表２１に示すとおり、極めて安定であった。

The results of the emulsion stability test of this rough milk lotion were very stable as shown in Table 21.

It is a figure which shows one structural example of dipotassium glycyrrhizinate.

Claims (7)

Contains oil, glycyrrhizinate, humectant and water,
A surfactant-free emulsified composition for skin which does not substantially contain a substance having a surface tension of 500 μN / cm or less in a 1 wt% aqueous solution.   From oil, glycyrrhizinate, moisturizer, water and, if necessary, colorants, fragrances, pigments, preservatives, antioxidants, UV protection agents, clay minerals, pH buffering agents, ethanol and organic thickeners An emulsified composition for skin containing a substance selected from the group consisting of an oil, a glycyrrhizinate, a moisturizer, water, and a colorant and a fragrance, if necessary, in the emulsified composition for skin A total concentration of substances selected from the group consisting of pigments, preservatives, antioxidants, UV protection agents, clay minerals, pH buffering agents, ethanol and organic thickeners is 99.5% by weight or more An active agent-free emulsified composition for skin.   The surfactant-free emulsified composition for skin according to claim 1 or 2, wherein the average particle diameter of the emulsified particles is in the range of 0.1 to 2.5 µm.   The surfactant-free emulsified composition for skin according to any one of claims 1 to 3, comprising 0.01 to 3.0% by weight of the glycyrrhizinate as glycyrrhizic acid.   The surfactant-free surfactant according to any one of claims 1 to 4, wherein the glycyrrhizinate is selected from the group consisting of alkali metal salts, ammonium salts, amine salts, basic amino acid salts, and mixtures thereof. Emulsified composition for skin.   A surfactant-free skin cosmetic comprising the surfactant-free emulsified composition for skin according to any one of claims 1 to 5.   The surfactant-free skin cosmetic according to claim 6, which is for sensitive skin.

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