JP2018104305A - External preparation and method for producing external preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external preparation having an excellent moisture transpiration suppression effect and to provide a method for producing an external preparation.SOLUTION: There is provided an external preparation which comprises a hydrating oil agent, water and a closed endoplasmic reticulum formed by an amphiphilic substance or polycondensation polymer particles having a hydroxyl group, wherein the concentration of the hydrating oil agent is more than 0.015 mass% and a part of the hydrating oil agent is dispersed in an oil gel in a lyotropic spherical liquid crystal state. There is provided a method for producing an external preparation, which comprises a step of dispersing an O/W type emulsified liquid obtained by emulsifying and dispersing a hydrating oil agent in a water phase with an emulsifier composed of a closed endoplasmic reticulum formed by an amphiphilic substance in a water phase or polycondensation polymer particles having a hydroxyl group in an oil gel as a continuous phase, wherein at least a part of the hydrating oil agent forms a lyotropic spherical liquid crystal and the blending amount of the hydrating oil agent is 0.015 mass% or more relative to the external preparation.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an external preparation for skin or hair and a method for producing the external preparation.

  Conventionally, oil is used as an external preparation applied to skin and hair for the purpose of moisturizing.

  In particular, oil gel cosmetics (see, for example, Patent Documents 1 to 3) have been used as external preparations applied to the skin and hair since they are excellent in applicability and usability.

Japanese Patent Laid-Open No. 2006-69383 JP 2010-260795 A JP 2010-260795 A

  However, conventional oil gels such as those described in Patent Documents 1 to 3 are still not sufficiently effective in suppressing moisture transpiration and have room for improvement.

  This invention is made | formed in view of the above situation, and aims at providing the manufacturing method of the external preparation and the external preparation excellent in the moisture transpiration suppression effect.

  The present inventors have found that a high moisture transpiration suppressing effect can be obtained by dispersing lyotropic spherical liquid crystals in an oil gel, and have completed the present invention. Specifically, the present invention provides the following.

(1) including polycondensation polymer particles having closed vesicles or hydroxyl groups formed by a water-containing oil, water, and an amphiphile;
An external preparation characterized in that the concentration of the hydrated oil is greater than 0.015% by mass and at least a part of the hydrated oil is dispersed in an oil gel as a continuous phase in a lyotropic spherical liquid crystal state.

(2) A method for producing an external preparation,
An O / W emulsion obtained by emulsifying and dispersing a water-containing oil in an aqueous phase with an emulsifier composed of closed endoplasmic reticulum formed by an amphiphilic substance in an aqueous phase or polycondensation polymer particles having a hydroxyl group, as a continuous phase A step of dispersing in an oil gel of
At least a portion of the hydrated oil forms a lyotropic spherical liquid crystal;
The amount of the hydrated oil is 0.015% by mass or more based on the external preparation.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the external preparation and the external preparation excellent in the moisture transpiration suppression effect can be provided.

About the emulsion of the reference example 1, it is the image image | photographed with the microscope, respectively (a) before the storage in 40 degreeC, (b) 7 days after the storage start in 40 degreeC. (A) Example 1, (b) Example 2, (c) Example 3, (d) Example 4, (e) Example 5, (f) Example 6, (g) Comparative Example 2 It is the image observed with the microscope about the external preparation. It is a graph of the TEWL change rate before and after application | coating when the TEWL recovery test after tape stripping was done about the external preparation of Example 2 and Comparative Example 2. FIG. It is a graph which shows the weight change rate (moisture residual rate) of a sample when the moisture transpiration suppression test by a cup method is done about the external preparation of Examples 1-6 and Comparative Examples 2 and 3. FIG. It is a graph which shows the weight change rate (moisture residual rate) of a sample when the moisture transpiration suppression test by a cup method is done about the external preparation of Example 2 and Comparative Examples 2 and 4. FIG. It is a graph which shows the weight change rate (moisture residual rate) of a sample when the moisture transpiration suppression test by a cup method is done about the external preparation of Example 6, 7 and the comparative example 3. FIG. It is a graph which shows the weight change rate (moisture residual rate) of a sample when the moisture transpiration suppression test by a cup method is done about the external preparation of Example 6, 8 and the comparative example 3. FIG. It is a graph which shows the weight change rate (water residual rate) of a sample when the moisture transpiration suppression test by a cup method is done about the external preparation of Example 9 and Comparative Example 5. FIG. It is a graph which shows the weight change rate (moisture residual rate) of a sample when the moisture transpiration suppression test by a cup method is done about the external preparation of Example 2, 10, 11 and the comparative example 2. FIG. It is a graph which shows the weight change rate (water residual rate) of the sample when the moisture transpiration suppression test by the cup method is done about the external preparation of Example 2, the hyaluronic acid aqueous solution of Reference Example 2, and the external preparation of Comparative Example 2. .

  Hereinafter, although embodiment of this invention is described, this invention is not limited to these.

<External preparation>
The external preparation of the present invention comprises polycondensation polymer particles having closed vesicles or hydroxyl groups formed by a water-containing oil agent, water, and an amphiphile, and the water-holding oil agent concentration is more than 0.015% by mass. At least a portion is dispersed in an oil gel as a continuous phase in a lyotropic spherical liquid crystal state. Thereby, an external preparation has a favorable moisture evaporation suppression effect. Moreover, the external preparation of this invention has favorable adhesiveness to skin, it is hard to stick, and adhesiveness is favorable. In addition, the external preparation of the present invention has a good film feeling because of its good hardness and adhesion, and further has excellent gloss durability, wrinkle improvement effect, moist feeling, ease of conformation, and plump feeling. High moisturizing effect. In the present invention, the reason for the effect of suppressing moisture transpiration is presumed as follows.

  Although the above-mentioned conventional oil gel has an effect of suppressing the transpiration of water from the skin and hair by covering the skin and hair, it can sufficiently suppress the transpiration from complex fine irregularities in the skin and hair. could not. In contrast, the oil gel of the present invention disperses the lyotropic spherical liquid crystal as a continuous phase in the oil gel, thereby improving the adhesion of the preparation to the skin and hair and maintaining the water flow of the liquid crystal structure in an equilibrium state. Depending on the nature, it is possible to obtain an effect of sufficiently suppressing the transpiration of water from complex fine irregularities in the skin and hair.

  The “external preparation” of the present invention refers to an external preparation for skin or hair.

  In the present invention, the lyotropic spherical liquid crystal is obtained by overlapping spherical layers of lamellar liquid crystal. In the lyotropic spherical liquid crystal, the shape of the internal phase (phase containing a water-containing oil agent) observed in the all-optical micrograph of the emulsion is substantially circular (a perfect circle, an ellipse, or a shape close to it), and a polarizing micrograph The black cross Nicole is identified in the corresponding internal phase (oil phase containing a water-containing oil agent). The lyotropic spherical liquid crystal is a conventionally known thermotropic liquid crystal spherulite (the black crossed Nicol in the polarization micrograph shows an internal phase (including a water-containing oil agent) in which the direction of the liquid crystal and the direction of irradiation of the polarized light have a predetermined relationship. Observed only in the oil phase), the probability is significantly different from that in the lyotropic spherical liquid crystal). Hereinafter, in the present invention, an oil phase containing a water-holding oil agent may be referred to as a “water-holding oil agent phase”, and an oil phase containing an oil gel (hereinafter also referred to as “oil-gel phase”). To distinguish.

  In the external preparation of the present invention, it is sufficient that at least a part of the hydrated oil agent is dispersed in the oil gel as the continuous phase in the lyotropic spherical liquid crystal state, and all the hydrated oil agents are not in the lyotropic spherical liquid crystal state. May be. Further, it is sufficient that at least a part of the lyotropic spherical liquid crystal is dispersed in the oil gel of the continuous phase, and not all the lyotropic spherical liquid crystals may be dispersed in the oil gel of the continuous phase. However, it may be a hydrated oil phase having a cross-sectional major axis of 1.0 μm or more in that the above effect can be sufficiently obtained. In addition, "cross-sectional major axis of 1.0 micrometer or more" here refers to the cross-sectional major axis of the hydrated oil agent phase in the visual field of an all-optical microscope. As will be described later, since the oil phase with an excessively small particle size cannot emit white light due to interference light under visible light, the proportion of the oil phase in the lyotropic spherical liquid crystal state in the population that does not include such an oil phase is better. It will reflect the performance of the external preparation with high accuracy.

  The external preparation in the present invention can be formed by first forming an O / W emulsion with a water-holding oil agent which is a lyotropic spherical liquid crystal and water, and dispersing the O / W emulsion in an oil gel.

  By increasing the particle size of the lyotropic spherical liquid crystal, the lyotropic spherical liquid crystal becomes fragile when applied, and the water hydrated oil agent tends to spread evenly on the application target, making it easy to sufficiently close fine irregularities on the skin and hair. It becomes easy to obtain a high moisture transpiration suppression effect. Therefore, the average particle diameter of the lyotropic spherical liquid crystal is preferably 1.0 μm or more, more preferably 3.0 μm or more, and most preferably 5.0 μm or more. As a result, a high moisture transpiration effect can be obtained, so that the above characteristics (particularly hardness, adhesion, coating feeling, gloss persistence, wrinkle improvement effect, moist feeling, ease of fitting, plump feeling, moisturizing effect, etc.) More improved. Further, from the viewpoint of balance between ease of production and the above effect, the average particle diameter of the lyotropic spherical liquid crystal is not particularly limited, but may be 20 μm or less, 15 μm or less, and 10 μm or less. The average particle diameter of the water hydrated oil phase is measured by a laser diffraction / scattering particle size distribution analyzer (SALD2100, Shimadzu Corporation) in a state where the viscosity of the external preparation is sufficiently low (diluted if necessary).

  Although the water-holding oil is not particularly limited, any oil-soluble substance that has one or more polar groups in the molecule and is liquid or pasty or solid at room temperature can be used. Regardless of the state, it is useful in that it can provide an effect of suppressing moisture transpiration. Examples of the water-holding oil include fatty acids such as isostearic acid, isopalmitic acid, oleic acid, palmitoleic acid, linoleic acid, ricinoleic acid, lanolin derivatives such as lanolin, lanolin alcohol, hydrogenated lanolin alcohol, cetanol, hexyldecanol, isostearyl. Alcohol, stearyl alcohol, octyldodecanol, oleyl alcohol, cetostearyl alcohol, behenyl alcohol, fatty alcohol esters and fatty acid oligomers derived from animal and vegetable oils such as cholesterol derivatives and phytosterol derivatives, octyldodecyl myristate Etc., and may be one or more of these. Examples of the cholesterol derivative and phytosterol derivative include macadamia nut oil fatty acid cholesteryl, macadamia nut oil fatty acid phytosteryl, lanolin fatty acid cholesteryl, and cholesteryl 12-hydroxystearate. Of these, higher alcohols are particularly preferred from the viewpoint of easily forming lyotropic spherical liquid crystals.

  As for the external preparation of this invention, the compounding quantity of a water-holding oil agent is more than 0.015 mass% with respect to an external preparation. Since the lyotropic spherical liquid crystal based on the water-repellent oil gives the desired properties, it is preferable that the amount of the water-hydrate oil is sufficiently large. In the external preparation of the present invention, the solidification of the water hydrated oil is highly suppressed, so that the amount of the water hydrated oil can be sufficiently increased, and is 0.02% by mass or more, 0.03% with respect to the external preparation. Mass% or more, 0.04 mass% or more, 0.05 mass% or more, 0.06 mass% or more, 0.07 mass% or more, 0.08 mass% or more, 0.09 mass% or more, 0.1 mass% % Or more, 0.2 mass% or more, 0.3 mass% or more, 0.4 mass% or more, and 0.5 mass% or more are preferable. On the other hand, the upper limit of the amount of the hydrated oil is 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 5.0% by mass or less with respect to the external preparation. 0.0 mass% or less, 1.0 mass% or less, etc. may be sufficient. In addition, each compounding quantity in this invention is the content measured by the quantity which actually mix | blended or gas chromatography.

  The hydrated oil phase may contain an oil other than the hydrated oil depending on the performance required for the emulsion. However, in the present invention, since the solidification of the hydrated oil is suppressed as described above, it is necessary to use a liquid oil component (for example, mineral oil) as the hydrated oil phase in order to suppress the solidification of the hydrated oil. Absent.

  The water contained in the present invention is used when forming an O / W emulsion with a water-holding oil that is a lyotropic spherical liquid crystal. The water content is not particularly limited, but the content of the water hydrated oil phase or oil gel phase is relatively increased, a high moisture transpiration suppression effect can be obtained, and a high film feeling can be obtained by suppressing the hardness. Therefore, the content is preferably 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, and 1% by mass or less with respect to the external preparation. On the other hand, from the viewpoint of obtaining a moisturizing effect, for example, 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.5% by mass or more. preferable.

  The oil gel in the present invention refers to a gel-like oil (oil component) thickened with a lipophilic oil gelling agent, and can be prepared by adding an oil gelling agent to oil, for example. Examples of the oil used in the oil gel include liquid oils such as mineral oils (mineral oils), animal and vegetable oils, hydrocarbon oils, fatty acid esters, and waxes (natural waxes such as beeswax, candelilla wax, carnauba wax, lanolin). Semi-solid or solid oils such as esters, microcrystalline waxes, synthetic waxes such as paraffin wax).

  The oil content of the oil gel is not particularly limited, but is 40% by mass or more, 50% by mass or more, and 60% by mass with respect to the external preparation in that the amount of oil increases and the effect of suppressing water transpiration increases. As mentioned above, it is preferable that they are 70 mass% or more, 80 mass% or more, and 90 mass% or more. On the other hand, the upper limit of the oil content of the oil gel may be 98% by mass or less, 97% by mass or less, 96% by mass or less, 95% by mass or less, etc. with respect to the external preparation.

  The oil gelling agent refers to a substance that thickens oil. As the oil gelling agent, known ones can be used, for example, dextrin fatty acid ester, glycerin fatty acid ester, pullulan fatty acid ester, organic modified clay ore (organic modified clay obtained by treating quaternary ammonium with clay mineral such as montmorillonite. Mineral), fine particle silica and the like. Examples of the dextrin fatty acid ester include esters of dextrin and higher fatty acids having 8 to 22 carbon atoms, specifically, dextrin palmitate, dextrin ethylhexanoate, dextrin laurate, dextrin myristate, dextrin stearate, behenine Acid dextrin etc. are mentioned.

  The water-holding oil has a property of taking a liquid crystal structure, but when it comes into contact with water, it may solidify soon and not take a liquid crystal structure. However, in the present invention, the inclusion of particles of closed vesicles or polycondensation polymer in the oil gel suppresses solidification of the water-containing oil mixed with water at room temperature (specifically, 25 ° C.) and flows. The liquid crystal state is realized by realizing the state, and the hydrated oil agent is spherically emulsified by van der Waals force in the process, so that the lyotropic spherical liquid crystal can be formed. This effect is unique to three-phase emulsification with closed endoplasmic reticulum or polycondensation polymer particles and cannot be obtained with conventional surfactants. From this viewpoint, the external preparation of the present invention contains polycondensation polymer particles having closed vesicles and / or hydroxyl groups formed of an amphiphilic substance. The polycondensation polymer particles having closed vesicles or hydroxyl groups formed of amphiphiles are particles having hydrophilic surfaces, for example, intervening at the interface with the oil phase in the aqueous phase by van der Waals force. Thus, the emulsified state may be maintained. This state is confirmed by observing the emulsion with a transmission electron microscope (TEM) (for example, Japanese Patent No. 3855203). Incidentally, the emulsification mechanism by the closed condensation endoplasmic reticulum or the polycondensation polymer particles having a hydroxyl group is known as a three-phase emulsification mechanism, and the emulsification mechanism by the surfactant, that is, the hydrophilic part and the hydrophobic part are converted into an aqueous phase and an oil phase, respectively. And an emulsification mechanism that maintains the emulsified state by lowering the oil-water interface tension (see, for example, Japanese Patent No. 3855203).

  The amphiphile that forms the closed endoplasmic reticulum is not particularly limited, but is a polyoxyethylene hydrogenated castor oil derivative represented by the following general formula 1, a dialkylammonium derivative represented by the general formula 2, or a trialkylammonium Derivatives, tetraalkylammonium derivatives, dialkenylammonium derivatives, trialkenylammonium derivatives, or derivatives of halogen salts of tetraalkenylammonium derivatives.

General formula 1

  In the formula, E, which is the average added mole number of ethylene oxide, is 3 to 100. If E is excessive, the type of good solvent that dissolves the amphiphilic substance is limited, and thus the degree of freedom in producing hydrophilic nanoparticles is narrowed. The upper limit of E is preferably 50, more preferably 40, and the lower limit of E is preferably 5.

General formula 2

In the formula, R 1 and R 2 are each independently an alkyl group or alkenyl group having 8 to 22 carbon atoms, R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is F, Cl, Br, I or CH ₃ COO.

  As the amphiphile, phospholipids, phospholipid derivatives, etc., in particular, those in which a hydrophobic group and a hydrophilic group are ester-bonded may be employed. Moreover, dilauroyl glutamic acid lysine Na is also preferable in terms of excellent stimulus relaxation properties.

  As the phospholipid, among the structures represented by the following general formula 3, DLPC (1,2-Dilauroyl-sn-glycero-3-phospho-rac-1-choline) having a carbon chain length of 12, DMPC (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-choline), DPPC with a carbon chain length of 16 (1,2-Dipalmitoyyl-sn-glycero-3-phospho-rac-1-choline) Can be adopted.

General formula 3

In addition, among the structures represented by the following general formula 4, DLPG (1,2-Diilauroyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH ₄ salt of carbon chain length 12 and carbon NaPG or NH4 salt of DMPG (1,2-Dimyristol-sn-glycero-3-phospho-1-rac-1-glycerol) having a chain length of 14, DPPG (1,2-Dipalmitoyyl-sn-glycero-) having a carbon chain length of 16 3-phospho-rac-1-glycerol) Na salt or NH ₄ salt may be employed.

Formula 4

  Furthermore, lecithin such as egg yolk lecithin, soybean lecithin, fractionated lecithin, lysolecithin or the like obtained by hydrogenation thereof may be employed as the phospholipid in the amphiphile. Of these, lysolecithin and fractionated lecithin are preferred.

  The polycondensation polymer having a hydroxyl group may be either a natural polymer or a synthetic polymer, and may be appropriately selected according to the use of the emulsifier. However, natural polymers are preferable from the viewpoint of safety and generally inexpensive, and sugar polymers described below are more preferable from the viewpoint of excellent emulsifying function. The particles include both single particles of the polycondensation polymer and those in which the single particles are connected, but do not include aggregates (having a network structure) before being formed into single particles.

  The sugar polymer is a polymer having a glucoside structure such as cellulose and starch. For example, those produced by microorganisms with some sugars among monosaccharides such as ribose, xylose, rhamnose, fucose, glucose, mannose, glucuronic acid, gluconic acid, xanthan gum, gum arabic, guar gum, caraya gum, carrageenan , Pectin, fucoidan, quinseed gum, tranto gum, locust bean gum, galactomannan, curdlan, gellan gum, fucogel, casein, gelatin, starch, collagen and other natural polymers, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, Hydroxymethylcellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, propylene glycol alginate, cellulose Crystals, starch-acrylic acid sodium graft polymer, hydrophobic hydroxypropylmethylcellulose, semi-synthetic polymers and the like, such as sulfonated cellulose derivatives such as stearoxy PG hydroxyethylcellulose sulfonic acid Na. In addition, examples of the polycondensation polymer having a hydroxyl group other than a sugar polymer include synthetic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, polyacrylate, and polyethylene oxide.

  The polycondensation polymer particles having closed vesicles and hydroxyl groups have an average particle diameter of about 8 nm to 800 nm before the formation of the emulsion, but an average particle diameter of 8 nm to 500 nm in the O / W emulsion structure (that is, when forming a lyotropic spherical liquid). Degree. In addition, the particle | grains of the polycondensation polymer which have the closed endoplasmic reticulum of an amphiphile and a hydroxyl group may contain only one, or both. When both are included, for example, separately emulsified emulsions may be mixed.

  The external preparation (aqueous phase, hydrated oil phase, or oil gel phase) in the present invention may contain any other component that can be used in the external preparation. For example, the external preparation of the present invention may contain components such as a preservative, a colorant, and a pH adjuster. Further, for example, the external preparation of the present invention may contain a surfactant, but it is preferable not to contain it. When the surfactant is included, the content of the surfactant is preferably 1.0% by mass or less, 0.1% by mass or less, and 0.01% by mass or less with respect to the external preparation.

  Moreover, even if the external preparation of this invention does not contain hyaluronic acid or its salt, the high moisture transpiration suppression effect can be acquired. In this respect, the external preparation of the present invention may have a low content of hyaluronic acid or a salt thereof. For example, the content of hyaluronic acid or a salt thereof is 1.0% by mass or less, 0.5% It may be not more than mass%, not more than 0.1 mass%, not more than 0.01 mass%, etc. Moreover, the external preparation of this invention does not need to contain hyaluronic acid or its salt.

  The external preparation of the present invention is an O / W type in which a water-containing oil is emulsified and dispersed in an aqueous phase by an emulsifier composed of closed vesicles formed by an amphiphilic substance in an aqueous phase or polycondensation polymer particles having a hydroxyl group. Including a step of dispersing the emulsified liquid in an oil gel as a continuous phase, wherein at least part of the hydrated oil agent forms a lyotropic spherical liquid crystal, and the blending amount of the hydrated oil agent is 0.015% by mass or more based on the external preparation By the method which is, the above-mentioned external preparation can be manufactured. More specifically, for example, a closed layer formed of an amphiphilic substance is formed by dispersing a layered body of a bilayer film of an amphiphilic substance in water or by making a polycondensation polymer having a hydroxyl group into water into single particles. By mixing the emulsifier dispersion containing particles of the vesicles or polycondensation polymer, the emulsifier dispersion, and the oil containing the water hydrated oil at a temperature equal to or higher than the melting point of the water hydrated oil, O / W It is produced by a method having a step of forming an emulsion and a step of dispersing an O / W emulsion in an oil gel.

  By sufficiently forming closed vesicles or polycondensation polymer particles, a hydrated oil phase in a lyotropic spherical liquid crystal state having a sufficient particle size can be obtained. As such a method, the above-mentioned amphiphilic substance and / or polycondensation polymer having a hydroxyl group is added to a dispersion medium (that is, water) and stirred for a long time. After the particles are dissolved in a good solvent, the solution is mixed with water (for example, see JP-A-2006-241424). Thereby, the above-mentioned moisture evaporation suppression effect improves more. Specifically, the above step is preferably performed until the particles of the closed vesicles or the polycondensation polymer in the emulsifier dispersion exhibit an average particle diameter of 8 nm or more and 800 nm or less.

  Single particles of polycondensation polymer are prepared by dispersing granules containing a conjugate of polycondensation polymer particles in water, preparing a dispersion, then swelling the granules, and further reversing the hydrogen bonds derived from the granules under reversible conditions. The product is relaxed by generating a relaxed product in which the higher order structure of the conjugate is relaxed, and after a while, hydrogen bonds in the conjugate are broken and the polycondensation polymer particles are separated into water. It is preferable. If this process is not performed, it is difficult to sufficiently obtain polycondensation polymer particles (single particles to several single particles).

  In the step of forming the O / W emulsion, the blending amount of the liquid oil component contained in the hydrated oil phase is preferably less than 10% by mass with respect to the O / W emulsion. Thereby, inhibition of lyotropic spherical liquid crystal formation by a liquid oil component is suppressed. When a large amount of the liquid oil component is required, it is preferable to separately prepare an emulsion of the liquid oil component and mix it with the emulsion of the present invention.

  In the step of forming the O / W emulsion, it is preferable that the amount of the water-containing oil agent is more than 1% by mass with respect to the O / W emulsion. Thereby, the high moisture evaporation suppression effect of a lyotropic spherical liquid crystal substance can be improved more.

  Moreover, after forming the O / W emulsion, it is preferable to gradually cool the emulsion so as not to inhibit the liquid crystal formation of the internal phase (an oil phase containing a water-containing oil agent). Although it does not specifically limit, What is necessary is just to cool at the speed | rate about 30-120 degreeC per hour.

  Although the external preparation of this invention is applied to skin or hair, it can be used as cosmetics applied to skin or hair, for example. The cosmetic in the present invention means a concept including quasi-drugs (medicinal cosmetics) in addition to so-called cosmetics. Specific forms of cosmetics are not particularly limited, but skin cosmetics such as creams, oil serums, facial cleansers, cleansings, lip preparations (lipsticks, lipstick bases), hair treatments, styling agents, permanent colors It may be a product (so-called miscellaneous goods) that is not subject to the Pharmaceutical Affairs Law and has a dosage form similar to that of hair cosmetics such as pre- and post-treatment agents and cosmetics. Among these, the external preparation of the present invention is used as a lip preparation because it is excellent in adhesion, adhesion, non-stickiness, moist feeling and its long-lasting effect, coating feeling, gloss persistence, wrinkle improving effect, and moisturizing effect. It is preferable. Moreover, since the external preparation of this invention is excellent in a moisturizing effect, it is preferable to be used as a formulation (for example, eye preparation, nail preparation) that requires moisturizing properties. The external preparation of the present invention may appropriately contain other components depending on the intended use.

<Confirmation of stability of lyotropic spherical liquid crystal>
(Reference Example 1)
A dispersion of sulfonated cellulose derivative particles was prepared. 1,2-Pendanediol and 1,3-butylene glycol were added, the dispersion was heated to 80 ° C., warm water was added, hydrogenated rapeseed oil alcohol at 80 ° C. was added, and 6000 rpm, 80 ° C., The mixture was stirred for 10 minutes for emulsification. Thereafter, the mixture was allowed to cool for 15 minutes and further cooled to 35 ° C. to prepare an emulsion having lyotropic spherical liquid crystals. In addition, the compounding ratio of each component is as shown in Table 1.

(Stability confirmation)
One drop of the spherical lamella preparation was dropped on the glass plate of Reference Example 1 and stored in a constant temperature bath at 40 ° C. The lyotropic spherical liquid crystal was confirmed with a microscope before storage and after 7 days from storage. The result is shown in FIG. As shown in FIG. 1, it was found that the lyotropic spherical liquid crystal was stably maintained even after 7 days at 40 ° C.

<Examples 1 to 6, Comparative Example 1>
The external preparations of Examples 1 to 6 and Comparative Example 1 were prepared with the formulations shown in Table 2 below. Specifically, first, a dispersion of sulfonated cellulose derivative particles was prepared. 1,2-Pendanediol and 1,3-butylene glycol were added, the dispersion was heated to 80 ° C., warm water was added, hydrogenated rapeseed oil alcohol at 80 ° C. was added, and 6000 rpm, 80 ° C., The mixture was stirred for 10 minutes for emulsification. Thereafter, the mixture was allowed to cool for 15 minutes and further cooled to 35 ° C. to prepare an emulsion having lyotropic spherical liquid crystals. On the other hand, dextrin palmitate is added to mineral oil, heated to 100 ° C or higher to confirm dissolution of dextrin palmitate, and then allowed to cool to prepare an oil gel, followed by mixing the emulsion and oil gel External preparations of Examples 1 to 6 and Comparative Example 1 were prepared.

<Comparative example 2>
The external preparation of Comparative Example 2 was prepared with the formulation shown in Table 2 below. Specifically, dextrin palmitate is added to mineral oil, heated to 100 ° C. or higher to confirm dissolution of dextrin palmitate, and then allowed to cool to prepare an oil gel, 1,2-pendanediol, 1,3-butylene glycol and the oil gel were mixed to prepare an external preparation of Comparative Example 2.

<Comparative Example 3>
The external preparation of Comparative Example 3 was prepared with the formulation shown in Table 2 below. Specifically, dextrin palmitate is added to mineral oil, heated to 100 ° C. or higher to confirm dissolution of dextrin palmitate, and then allowed to cool to prepare an oil gel. It was.

<Confirmation of lyotropic spherical liquid crystal>
About the external preparation of Examples 1-6, it was observed with the microscope whether the lyotropic spherical liquid crystal was formed. The result is shown in FIG. 2, (a) is Example 1, (b) is Example 2, (c) is Example 3, (d) is Example 4, (e) is Example 5, and (f) is Example. 6 and (g) show images of Comparative Example 1, respectively. As shown in FIG. 2, although the lyotropic spherical liquid crystal was not formed in Comparative Example 1 with a small amount of the water-holding oil, Examples 1 to 6 in which the amount of the water-containing oil was more than 0.015% by mass. It was confirmed that lyotropic spherical liquid crystals were formed in all of the external preparations.

<TEWL recovery test after tape stripping>
A TEWL recovery test after tape stripping was performed on five subjects in their 20s to 40s using the external preparations of Example 2 and Comparative Example 2. Specifically, first, the inside of the subject's left forearm was washed with soap bubble soap, and was applied 7 times with a cellophane tape having a width of 1.8 cm and a length of 3 cm. Thereafter, the stratum corneum moisture transpiration (tevameter) was measured before application of the peeled portion. Thereafter, about 1 rice grain was applied to each of the external preparations of Example 2 and Comparative Example 2, and the stratum corneum moisture transpiration (tevameter) was measured 15 minutes after the application. The result is shown in FIG.

  As shown in FIG. 3, when the TEWL average value before use is 1, the external preparation of Example 2 has a lower TEWL value than the external preparation of Comparative Example 2 that does not have lyotropic spherical liquid crystals. From the fact that the rate of change was large, it was found that the improvement effect of TEWL of Example 2 was large.

<Moisture transpiration suppression test 1 by cup method>
Using the external preparations of Examples 1 to 6 and Comparative Examples 2 and 3, a moisture transpiration suppression test by the cup method was performed. First, 50 g of water was put in a glass bottle, a nonwoven fabric was placed thereon, and 0.5 g of each external preparation was applied on the nonwoven fabric. After incubating at 60 ° C. for 96 hours, the weight of the sample (water remaining in the glass bottle) was measured, and the water residual rate was evaluated when the sample weight before incubation was taken as 100% (n = 3). Moreover, the nonwoven fabric which has not apply | coated nothing was prepared as control, and the moisture residual rate of this was also evaluated (control example 1). The result is shown in FIG. In addition, it means that the transpiration of the water | moisture content in a glass bottle was suppressed, so that a moisture residual rate is high.

  As shown in FIG. 4, all of the external preparations of Examples 1 to 6 having lyotropic spherical liquid crystals have a higher water residual ratio than the external preparations of Comparative Examples 2 and 3 having no lyotropic spherical liquid crystals, that is, moisture. It was found that transpiration was suppressed.

<Comparative example 4>
The external preparation of Comparative Example 4 was prepared with the formulation shown in Table 3 below. Specifically, first, a dispersion of sulfonated cellulose derivative particles was prepared. To this dispersion, octyldodecyl myristate, 1,2-pentanediol, and 1,3-butylene glycol were added, and the mixture was stirred with a homomixer at 6000 rpm, 80 ° C. for 10 minutes. An emulsion without was prepared. On the other hand, dextrin palmitate is added to mineral oil, heated to 100 ° C or higher to confirm dissolution of dextrin palmitate, and then allowed to cool to prepare an oil gel, and the emulsion and the oil gel are mixed. Four external preparations were prepared.

<Example 7>
The external preparation of Example 7 was prepared with the formulation shown in Table 3 below. Specifically, the external preparation of Example 7 was prepared by the same method as Example 1 except that the hydrogenated rapeseed oil alcohol was changed to stearyl alcohol and the blending ratio of each component was changed. The blending ratio of each component of Example 7 is as shown in Table 3.

<Example 8>
The external preparation of Example 8 was prepared with the formulation shown in Table 3 below. Specifically, the external preparation of Example 8 was prepared in the same manner as in Example 1 except that 1,2-pentanediol and 1,3 butylene glycol were not added and the blending ratio of each component was changed. did.

<Example 9>
The external preparation of Example 9 was prepared with the formulation shown in Table 3 below. Specifically, the external preparation of Example 9 was prepared in the same manner as in Example 1 except that microcrystalline wax was added and the blending ratio of each component was changed.

<Examples 10 and 11>
External preparations of Examples 10 and 11 were prepared with the formulations shown in Table 3 below. Specifically, external preparations of Examples 10 and 11 were prepared by the same method as Example 1 except that the blending ratio of each component was changed.

<Example 12>
The external preparation of Example 12 was prepared with the formulation shown in Table 3 below. Specifically, the external preparation of Example 12 was prepared in the same manner as in Example 7 except that the blending ratio of each component was changed. In addition, the external preparation of Example 12 is used in the test in the below-mentioned eye preparation.

<Comparative Example 5>
The external preparation of Comparative Example 5 was prepared with the formulation shown in Table 3 below. Specifically, the external preparation of Comparative Example 5 was prepared by the same method as Comparative Example 3 except that microcrystalline wax was added and the blending ratio of each component was changed.

<Reference Example 2>
The hyaluronic acid aqueous solution of Reference Example 2 was prepared with the formulation shown in Table 3 below. Specifically, water, mineral oil, dextrin palmitate and hyaluronic acid were blended in the proportions shown in Table 3 to prepare the hyaluronic acid aqueous solution of Reference Example 2.

<Moisture transpiration suppression test 2 by cup method>
Using the external preparations of Example 2 and Comparative Examples 2 and 4, a moisture transpiration suppression test by the cup method was performed. First, 150 g of water was put in a glass bottle, a nonwoven fabric was placed thereon, and 1 g of each external preparation was applied on the nonwoven fabric. After incubating at 60 ° C. for 96 hours, the weight of the sample (water remaining in the glass bottle) was measured to evaluate the moisture remaining rate. The result is shown in FIG. As shown in FIG. 5, since the water transpiration suppression effect was recognized in Example 2 as compared with Comparative Example 4 having no lyotropic spherical liquid crystal even in the case of a three-phase emulsion, the lyotropic spherical liquid crystal was water transpiration. It was suggested that it contributed to suppression.

<Moisture transpiration suppression test 3 by cup method>
Using the external preparations of Examples 6 to 8 and Comparative Example 3, a moisture transpiration suppression test by the cup method was performed. First, 50 g of water was put in a glass bottle, a nonwoven fabric was placed thereon, and 0.5 g of each external preparation was applied on the nonwoven fabric. After incubating at 60 ° C. for 96 hours, the weight of the sample (water remaining in the glass bottle) was measured to evaluate the moisture remaining rate. The results are shown in FIGS.

  As shown in FIG. 6, in Example 7 using stearyl alcohol, which is a long-chain alcohol (higher alcohol) having a carbon number different from that of hydrogenated rapeseed oil alcohol in the lyotropic spherical liquid crystal, an effect of suppressing moisture transpiration was observed. . From this, it has been found that any hydrated oil agent that forms a lyotropic liquid crystal having a certain number of carbon atoms or more, and it is important to be a lyotropic spherical liquid crystal.

  As shown in FIG. 7, the moisture transpiration suppression effect was also observed in Example 8 which does not contain 1,2-pentanediol and 1,3-butylene glycol. From this, it was confirmed that even if there is no 1,2-pentanediol or 1,3-butylene glycol, the moisture evaporation suppression effect can be obtained by including the lyotropic spherical liquid crystal.

<Water transpiration suppression test 4 by cup method>
Using the external preparations of Examples 2 and 9 to 11 and Comparative Examples 3 and 5, a moisture transpiration suppression test by the cup method was performed. First, 50 g of water was put in a glass bottle, a nonwoven fabric was placed thereon, and 0.5 g of each external preparation was applied on the nonwoven fabric. After incubating at 60 ° C. for 96 hours, the weight of the sample (water remaining in the glass bottle) was measured to evaluate the moisture remaining rate. The results are shown in FIGS.

  As shown in FIG. 8, the moisture evaporation suppression effect was also observed in the hard balm-like Example 9 using microcrystalline wax for the outer phase. From this, it was found that even when the oil gel of the outer phase is balm, the effect of suppressing moisture transpiration can be obtained by including the lyotropic spherical liquid crystal.

  As shown in FIG. 9, in any of Examples 10 and 11, a moisture transpiration suppressing effect was observed. From this, it was found that moisture transpiration suppression effect can be obtained by including lyotropic spherical liquid crystal without depending on the amount of 1,2-pentanediol, 1,3-butylene glycol and the like.

<Moisture transpiration suppression test 5 by cup method>
Using the external preparation of Example 2, the aqueous hyaluronic acid solution of Reference Example 2, and the external preparation of Comparative Example 2, a moisture transpiration suppression test by the cup method was performed. First, 150 g of water was put in a glass bottle, a nonwoven fabric was placed thereon, and 1 g of each external preparation was applied on the nonwoven fabric. After incubating at 60 ° C. for 96 hours, the weight of the sample (water remaining in the glass bottle) was measured to evaluate the moisture remaining rate. The result is shown in FIG. As shown in FIG. 10, it was found that the lyotropic spherical liquid crystal by the three-phase emulsion has the same moisture transpiration inhibiting effect as that of hyaluronic acid.

<Sensory evaluation 1 as a lip preparation>
The sensory evaluation as a lip formulation of the external preparation of Example 2 and Comparative Example 2 was performed. Specifically, first, each external preparation was applied to the lips, and the items (1) to (10) in Table 4 were evaluated. Evaluation was evaluated with 1 to 7 points, and the higher the score, the higher the evaluation. Evaluation was performed by three women in their 20s to 30s. The average points are shown in Table 4 below.

  As shown in Table 4, in the overall evaluation, such as “no stickiness”, “moist feeling immediately after”, “persistence of moist feeling”, “compatibility with lipstick”, etc., Example 2 having lyotropic spherical liquid crystal However, the evaluation was superior to that of Comparative Example 2.

<Sensory evaluation as a preparation for the eye area>
Sensory evaluation as a preparation for the eye of the external preparation of Example 12 was performed. Specifically, first, an external preparation was applied to the eyes, and each item in Table 5 was evaluated. Evaluation was evaluated with 1 to 5 points, and the higher the score, the higher the evaluation. Evaluation was performed by three women in their 20s to 30s. The average score is shown in Table 5 below.

  As shown in Table 5, the overall evaluation was high, and it was found to have high moisture retention. From this, it was found that it is suitable for use as a moisturizing preparation such as eyes and nails.

<Evaluation as a base for lipstick>
The sensory evaluation as a base of the lipstick of the external preparation of Example 2 and Comparative Example 2 was performed. In addition to these, an external preparation (Comparative Example 6) having solid oil in the outer phase prepared in a ratio of 94.55% mineral oil, 0.15% microcrystalline wax and 5% dextrin palmitate was prepared. As for the lipstick, a sensory evaluation was performed as a foundation for lipstick.

  As a specific evaluation method, first, each preparation was applied to the inner side of the upper arm and left for 5 minutes. Thereafter, a stick lipstick was applied, and an external preparation for observation was applied to the eyes and observed to evaluate uniform adhesion to the skin. Evaluation was evaluated with 1 to 5 points, and the higher the score, the higher the evaluation. The evaluation results are shown in Table 6.

  As shown in Table 6, Example 2 having a lyotropic spherical liquid crystal had the highest uniform adhesion, indicating that it was suitable for a lipstick substrate.

<Example 12>
Except that the sulfonated cellulose derivative particles were replaced with lecithin, an external preparation of Example 12 was prepared in the same procedure as in Example 1 with the formulation shown in Table 7 below. In Table 7 below, the composition of Comparative Example 2 described above is also shown.

<Moisture transpiration suppression test 6 by cup method>
Using the external preparation of Example 12 and the external preparation of Comparative Example 2, a moisture transpiration suppression test by the cup method was performed. First, 50 g of water was put in a glass bottle, a nonwoven fabric was placed thereon, and 0.5 g of each external preparation was applied on the nonwoven fabric. After incubating at 60 ° C. for 96 hours, the weight of the sample (water remaining in the glass bottle) was measured to evaluate the moisture remaining rate. As a result, the residual moisture rate of Example 12 having lyotropic spherical liquid crystals was 89.39%, while the residual moisture rate of Comparative Example 2 was 85.97%. Thus, it was found that when lecithin is used as a closed endoplasmic reticulum, water transpiration can be similarly suppressed.

<Sensory evaluation 1 as a lip preparation>
The sensory evaluation as a lip preparation of the external preparation of Example 12 and Comparative Example 2 was performed. Specifically, each external preparation was first applied to the lips, and each item in Table 8 was evaluated. Evaluation was evaluated with 1 to 7 points, and the higher the score, the higher the evaluation. Evaluation was performed by three women in their 20s to 30s. The average points are shown in Table 8 below.

  As shown in Table 8, in the overall evaluation, Example 12 having lyotropic spherical liquid crystals was superior to Comparative Example 2 in evaluation. Thus, when lecithin was used as a closed endoplasmic reticulum, it turned out that it is suitable for a lip formulation similarly.

Claims (2)

Comprising polycondensation polymer particles having closed vesicles or hydroxyl groups formed by a water-holding oil, water, and an amphiphile;
An external preparation characterized in that the concentration of the hydrated oil is greater than 0.015% by mass and at least a part of the hydrated oil is dispersed in an oil gel as a continuous phase in a lyotropic spherical liquid crystal state. A method for producing an external preparation,
An O / W emulsion obtained by emulsifying and dispersing a water-containing oil in an aqueous phase with an emulsifier composed of closed endoplasmic reticulum formed by an amphiphilic substance in an aqueous phase or polycondensation polymer particles having a hydroxyl group, as a continuous phase A step of dispersing in an oil gel of
At least a portion of the hydrated oil forms a lyotropic spherical liquid crystal;
The amount of the hydrated oil is 0.015% by mass or more based on the external preparation.