KR102506722B1 - Water-in-oil-in-water type multiple emulsion for cosmetic composition with low viscosity - Google Patents

Abstract

It relates to a low-viscosity water-in-oil-in-water multi-emulsion cosmetic composition, and the cosmetic composition according to one aspect forms lamellar liquid crystals of a thin film structure on the surface of emulsion droplets, thereby providing excellent formulation stability without using higher alcohol, low viscosity and feeling of use This has an excellent effect.

Description

Water-in-oil-in-water type multiple emulsion for cosmetic composition with low viscosity}

The present invention relates to a low-viscosity water-in-oil-in-water (W/O/W) multi-emulsion cosmetic composition.

In general, multiple emulsions are systems composed of smaller, phase-different emulsions within an emulsion. Water-in-oil-in-water cosmetic, one of multiple emulsions, is composed of W/O droplets in which oil-phase droplets are dispersed within oil-phase emulsion droplets, dispersed in the outermost water phase (W2). W / O / W multi-emulsion is easy to coalesce between droplets or separate phases because droplets are larger and not uniform in size than simple emulsified emulsions. In addition, if the energy balance and osmotic pressure between the aqueous phase and the outermost phase are not balanced, the innermost and outermost phases may be united and eventually converted into an O/W emulsion.

In order to solve these unstable elements, the viscosity of the emulsion was increased by forming liquid crystals of several films using higher alcohols and glucoside-based surfactants. However, this has a fatal disadvantage that the film feeling felt after the initial moisture feeling of the W / O / W may be uncomfortable by causing a stiff feeling peculiar to the higher alcohol-based liquid crystal emulsion (Korean Patent Publication No. 10-2016-0116877). Although it is possible to prepare water-in-oil-in-water emulsions without higher alcohol, the phase may become unstable within a few hours due to the very low viscosity. Even if the low viscosity is solved by increasing the content of the water-soluble thickener, the unique feeling of the thickener negatively affects the feeling of use.

As another example of stabilizing the W/O/W emulsion, a W/O/W having a hard core-shell structure may be prepared by introducing a polymer such as polyethylene glycol-diacrylate into the innermost phase. However, when applied to a cosmetic formulation, the polymerized hard innermost phase may escape from the skin surface without being absorbed into the skin, resulting in a negative feeling of use and skin irritation. Alternatively, when W/O/W of a core-shell structure in which W1, the innermost layer, is composed of a single droplet and formed into a very thin film structure is manufactured, the stability is improved, but the low oil content causes a feeling of use that is too light. .

Ultimately, in order to maximize the technical characteristics of the water-in-oil-in-water emulsion and overcome the disadvantages of the above cases, it is required to develop a formulation with a natural film feeling of W1/O oil while maintaining the initial moisture feeling of O/W2.

One aspect is a first aqueous phase comprising a polyol; An oil phase part containing two or more polyglyceryl surfactants; It is to provide a water-in-oil-in-water (W1/O/W2) multi-emulsion cosmetic composition having a lamellar liquid crystal structure including a second aqueous phase portion containing a hydrophilic surfactant and a polyol.

Another aspect is a first aqueous phase comprising a polyol; An oil phase part containing two or more polyglyceryl surfactants; It is to provide a water-in-oil-in-water (W1/O/W2) multi-emulsion composition for external application for skin having a lamellar liquid crystal structure, including a second water phase portion containing a hydrophilic surfactant and a polyol.

One aspect is a first aqueous phase comprising a polyol; An oil phase part containing two or more polyglyceryl surfactants; It provides a water-in-oil-in-water (W1/O/W2) multi-emulsion cosmetic composition having a lamellar liquid crystal structure including a second aqueous phase portion containing a hydrophilic surfactant and a polyol.

The polyglyceryl-based surfactant is a lipophilic surfactant, and may be a polyglyceryl-based surfactant having a hydrophilic-lipophile balance (HLB) value of less than 7, for example, 2 to 6. In one embodiment, the two or more polyglyceryl surfactants may include a low molecular weight polyglyceryl surfactant and a high molecular weight polyglyceryl surfactant. The term “molecular weight” may mean average molecular weight.

Specifically, the low molecular weight polyglyceryl surfactant may have a molecular weight of 1,500 g/mol or less. In one embodiment, the low molecular weight polyglyceryl-based surfactant is polyglyceryl-4 isostearate, polyglyceryl-2 isostearate, polyglyceryl-2 diisostearate, polyglyceryl-5 hexa It may be at least one selected from the group consisting of stearate, polyglyceryl-10 heptaoleate, polyglyceryl-10 pentastearate, and polyglyceryl-10 decastearate, for example, polyglyceryl-2 iso stearate (HLB 4.7, molecular weight 450 g/mol), polyglyceryl-2 diisostearate (HLB 5.5, molecular weight 699.1 g/mol).

In addition, the high molecular weight polyglyceryl-based surfactant may have a molecular weight greater than 1,500 g/mol and less than 10,000 g/mol. In one embodiment, the high molecular weight polyglyceryl-based surfactant is polyglyceryl-6 polyhydroxystearate, polyglyceryl-10 polyhydroxystearate, polyglyceryl-3 polyricinoleate, polyglyceryl-3 It may be at least one selected from the group consisting of reel-4 polyricinoleate, polyglyceryl-5 polyricinoleate, polyglyceryl-6 polyricinoleate, and polyglyceryl-10 polyricinoleate, for example For example, it may be polyglyceryl-6 polyricinoleate (HLB 3.3, molecular weight 4250 g/mol) or polyglyceryl-3 polyricinoleate (HLB 4.0, molecular weight 3950 g/mol), even if they have the same chemical structure. Depending on the number of moles of fatty acids to be polymerized, specific HLB values and molecular weights may be different.

Water-in-oil-in-water emulsions are inherently thermodynamically unstable systems due to the coalescence between the aqueous solution of the innermost phase and the aqueous solution of the outermost phase. To solve this problem, higher alcohol may be added to the oil phase, but in this case, the viscosity may increase and a stiff feeling peculiar to higher alcohol may appear. In addition, the use of a higher alcohol in a water-in-oil-in-water multi-emulsion having a higher water content than an oil-in-water emulsion has a side effect that precipitation may occur due to compatibility problems between oils. In one embodiment, the cosmetic composition containing at least one polyglyceryl-based surfactant of low molecular weight and at least one of each of high molecular weight polyglyceryl-based surfactant forms a stable water-in-oil-in-water emulsion with a clear curvature. Confirmed. However, in the case of a cosmetic composition containing one or more low molecular weight polyglyceryl surfactants, the formulation is very unstable, and the W1 phase in the water-in-oil-in-water droplet is mostly combined with W2, and the high molecular weight polyglyceryl surfactant In the case of a cosmetic composition containing one or two or more, it was confirmed that the viscosity increased explosively and became a water-in-oil emulsion. That is, the water-in-oil-in-water multi-emulsion cosmetic composition according to one aspect is polyglyceride without using a higher alcohol-based surfactant added to the oil phase to solve the problem caused by the union between the aqueous solution of the innermost phase and the aqueous solution of the outermost phase. Formulation stability can be realized by the formation of thin liquid crystals on the surface of emulsion droplets by two or more surfactants of the reel series, and thus, a water-in-oil-in-water multi-emulsion with low viscosity and improved feeling of use can be implemented. In one embodiment, the water-in-oil-in-water multi-emulsion cosmetic composition containing two or more polyglyceryl-based surfactants may not contain a higher alcohol. The “not including” means “not substantially including”, and “substantially” here means that up to 3.0% by weight or less of the total weight of the first water phase part and the oil phase part may be included. In addition, this may mean that the higher alcohol is included in an amount level at which the composition maintains a low viscosity. For example, the “free” or “substantially free” amount may be less than or equal to 3%, 2%, 1%, or 0.9% by weight. The cosmetic composition of the present invention may not contain any higher alcohol. The composition may exhibit improved feeling of use while having low viscosity as it does not substantially contain higher alcohol. The higher alcohol may be, for example, one selected from the group consisting of myristyl alcohol, cetyl alcohol, cetearyl alcohol, arachidyl alcohol, and behenyl alcohol.

The term "viscosity" is a measure of the resistance of a fluid when it changes shape or the property of sticking parts to keep from falling, a value measured for 1 minute at 30 rpm with a Brookfield DV2TLV equipped with an LV 64 spindle. It is defined as low if it is less than 8,000 cPs. Therefore, the cosmetic composition according to one aspect may be a low-viscosity emulsion composition having a viscosity of 2,000 cPs to 8,000 cPs. For example, the composition may have a viscosity of 2,000 cPs to 8,000 cPs, 2500 cPs to 8,000 cPs, 3,000 cPs to 8,000 cPs, 4,000 cPs to 8,000 cPs, 3,500 cPs to 6,500 cPs, 06,500 cPs or cPs0. may be

In one embodiment, the lamellar liquid crystal structure may be formed in the form of a thin film on the surfaces of droplets of the W1/O interface and the O/W2 interface. The liquid crystal structure of the term “thin film form” may refer to a liquid crystal structure in which a thin film band surrounds the liquid droplet at each interface, unlike the Maltese cross pattern seen in a polarizing microscope image of a conventionally known liquid crystal emulsion.

In one embodiment, the two or more polyglyceryl surfactants are present in an amount of 0.5 to 6.0% by weight, for example, 0.5 to 5.5% by weight, based on the total weight of the first aqueous phase part and the oil phase part, that is, the total weight of the oil-in-water emulsion. to 5.0 wt%, 0.5 to 4.5 wt%, 0.5 to 4.0 wt%, 0.5 to 3.5 wt%, 0.5 to 2.0 wt%, 1.0 to 6.0 wt%, 1.0 to 5.5 wt%, 1.0 to 5.0 wt%, 1.0 to 4.5 wt% 1.0 to 4.0 wt%, 1.0 to 3.5 wt%, 1.0 to 2.0 wt%, 1.5 to 6.0 wt%, 1.5 to 5.5 wt%, 1.5 to 5.0 wt%, 1.5 to 4.5 wt%, 1.5 to 4.0 wt% , 1.5 to 3.5% by weight, may be included in 1.5 to 2.0% by weight. When the two or more polyglyceryl-based surfactants are less than 0.5% by weight, the viscosity of the emulsion is too low and the formulation becomes unstable, and when it exceeds 6.0% by weight, the viscosity becomes too high and the feeling of use becomes stiff .

In one embodiment, the low molecular weight polyglyceryl surfactant is 0.1 to 5.0% by weight, for example, 0.1 to 4.5% by weight, based on the total weight of the first aqueous phase part and the oil phase part, that is, the total weight of the oil-in-water emulsion. 0.1 to 4.0% by weight, 0.1 to 3.5% by weight, 0.5 to 5.0% by weight, 0.5 to 4.5% by weight, 0.5 to 4.0% by weight, 0.5 to 3.5% by weight, 1.0 to 5.0% by weight, 1.0 to 4.5% by weight, 1.0 to 4.0 wt%, 1.0 to 3.5 wt% may be included. When the low molecular weight polyglyceryl-based surfactant is less than the above range, emulsion droplets may not be dispersed small and densely, resulting in unstable formulation, and when it exceeds the above range, a problem of stiff feeling may occur. The high molecular weight surfactant may be included in an amount of 0.1 to 2.0% by weight, for example, 0.1 to 1.5% by weight, 0.5 to 2.0% by weight, 0.5 to 1.5% by weight, 1.0 to 2.0% by weight, or 1.0 to 1.5% by weight. . When the high molecular weight polyglyceryl surfactant is less than the above range, the viscosity of the emulsion is too low and the formulation becomes unstable, and when it exceeds the above range, the viscosity of the formulation becomes too high and long-term stability becomes unstable. can In one embodiment, the low molecular weight and high molecular weight polyglyceryl surfactants may be mixed in a weight ratio of 1:10 to 10:1. For example, 1:10 to 10:1, 1:9 to 9:1, 1:7 to 7:1, 1:6 to 6:1, 2:7 to 7:2, 1:3 to 3: It may be mixed in a weight ratio of 1, 1:2 to 2:1, or 1:1. At this time, when the mixing ratio of the low-molecular-weight and high-molecular-weight polyglycerin-based surfactant is less than the above range, the formulation stability of the emulsion formulation is not maintained and is unstable, resulting in phase separation of the oil phase and the water phase. If the viscosity increases, the feeling of use may be unpleasant.

In one embodiment, the hydrophilic surfactant may be a surfactant having an HLB value of 7 or more, for example, 7 to 20. In one embodiment, the hydrophilic surfactant is polysorbate 60, polysorbate 80, polysorbate 20, PEG-100 stearate/glyceryl stearate, PEG-30 glyceryl stearate, glyceryl stearate as late citrate, glyceryl oleate citrate, polyglyceryl-6 caprate, polyglyceryl-4 caprate, polyglyceryl-3 methylglucose distearate and methoxyPG-114/polyepsiloncaprolactone It may be one or more selected from the group consisting of

In one embodiment, the hydrophilic surfactant is 0.2 to 3.0% by weight, for example, 0.2 to 2.5% by weight, 0.2 to 2.0% by weight, 0.2 to 1.0% by weight, 0.2 to 0.5% by weight, based on the total weight of the composition, 0.3 to 3.0% by weight, 0.3 to 2.5% by weight, 0.3 to 2.0% by weight, 0.3 to 1.0% by weight, 0.3 to 0.5% by weight, or 0.3 to 0.45% by weight. When the hydrophilic surfactant is less than 0.2% by weight, round emulsion droplets are not formed and an elongated unstable water-in-oil-in-water type macroemulsion may be formed, and when the amount exceeds 3.0% by weight, a problem in that the feeling becomes stiff may occur.

In one embodiment, the first aqueous phase part and oil phase part 5 to 35% by weight, for example, 5 to 35% by weight, 10 to 35% by weight, 10 to 30% by weight, 20 to 35% by weight based on the total weight of the composition It may be included in weight%, 20 to 30% by weight. The first aqueous phase part and the oil phase part form a water-in-water (W1 / O) emulsion in a water-in-oil-in-water (W1 / O / W2) multi-emulsion cosmetic composition, the content of the first water phase part and the oil phase part, that is, in water If the content of the type emulsion is less than 5% by weight based on the total weight of the composition, a problem of not being able to realize the unique feeling of use of the water-in-oil-in-water type emulsion may occur, and if it exceeds 35% by weight. It can be converted to an oil-in-water emulsion rather than a water-in-oil-in-water emulsion.

In one embodiment, the polyol may be at least one selected from the group consisting of diglycerin, glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, methyl propanediol, and sorbitol. The polyol of the second aqueous phase forming the outermost phase of the water-in-oil-in-water emulsion may be included in an amount equal to that of the polyol of the first aqueous phase forming the innermost phase of the internal water-in-oil emulsion to balance the osmotic pressure. The polyol may be included in an amount of 3.0 to 40% by weight based on the total weight of the composition. For example, 3.0 to 40% by weight, 3.0 to 35% by weight, 3.0 to 30% by weight, 3.0 to 25% by weight, 3.0 to 20% by weight, 10 to 40% by weight, 10 to 30% by weight, 10 to 20% by weight %, 5.0 to 20% by weight, or 5.0 to 10% by weight. If the content of the polyol is less than the above range, not only is it not sufficient for skin moisturizing, but the temperature stability of the formulation is poor, and there is a problem in that the phases of the oil phase and the water phase are separated. If it exceeds the above range, it gives a sticky feeling when applied to the skin There is a problem that the feeling of use is unpleasant. That is, the polyol may be used to prevent phase separation due to freezing point depression as well as moisturizing effect.

In one embodiment, the cosmetic composition may further include a hydrocarbon-based oil, a vegetable oil, an oil gelling agent, and an oil thickener in the oil phase.

The hydrocarbon-based oil may be a paraffinic, olefinic, aliphatic, alicyclic, or aromatic hydrocarbon oil, and the like, for example, isododecane, paraffin, isoparaffin, squalane, squalene, polybutene, polydecene, polyisoprene, It may be at least one selected from the group consisting of hydrogenated polydecene, hydrogenated polyisobutene, hydrogenated poly (C6-14 olefin), and mineral oil.

The vegetable oil is from the group consisting of macadamia seed oil, meadowfoam seed oil, olive oil, apple seed oil, grape seed oil, sunflower seed oil, camellia oil, hazelnut oil, argan oil, rosehip fruit oil, avocado oil, and jojoba oil. There may be more than one selected.

The hydrocarbon-based oil and the vegetable oil are suitably within a weight ratio range of 1:99 to 99:1 depending on the formulation. can be combined.

Additionally, the oil phase part may include waxes having low melting points such as shea butter and hydrogenated vegetable oil, or silicone oils including dimethicone, cyclomethicone, alkylsiloxane, and cycloalkylsiloxane.

The oil gelling agent may be a polar oil depending on the formulation, and its types include disteadimonium hectorite, cetylethylhexanoate, isopropyl myristate, isopropylstearate, capphylic triglyceride, and octyl palmitate. , alkyl (14,16,18) 2-ethylhexanoate, octyldodecyl myristate, octyldodecanol, hexyllaurate and the like can be used. The oil gelling agent may be included in 5 to 20% by weight, for example, 5 to 15% by weight, 10 to 20% by weight, or 10 to 15% by weight based on the total weight of the first water phase part and the oil phase part.

The oil thickener is dextrin palmitate/ethylhexanoate, dextrin palmitate, dextrin myristate, dextrin palmitate/hexyldecanoate, stearoyl inulin, dibutyl ethylhexanoyl glutamide, dibutyl lauroyl It may contain glutamide and the like, 0.1 to 2.0% by weight, for example, 0.1 to 1.5% by weight, 0.1 to 1.0% by weight, 0.5 to 2.0% by weight, 0.5 to 2.0% by weight based on the total weight of the first aqueous phase part and the oil phase part to 1.5% by weight or 0.5 to 1.0% by weight.

In one embodiment, the cosmetic composition is salt in the first aqueous phase; A salt and a thickening agent may be further included in the second aqueous phase.

The salt is a component that controls the freezing point, and may be, for example, sodium chloride (NaCl), magnesium sulfate (MgSO4), potassium chloride (KCl), calcium chloride (CaCl2), or a combination thereof. Water-in-oil-in-water emulsions under low-viscosity conditions are thermodynamically very vulnerable to temperature stability, so they may contain salts as freezing point regulators and polyols used as humectants.

The thickener may be at least one selected from the group consisting of xanthan gum, carbomer, hydroxypropyl starch phosphate, sodium magnesium silicate, hydroxyethyl cellulose, and hydroxyethyl acrylate/sodium acryloyl dimethyl taurate copolymer. there is.

The water-in-oil-in-water cosmetic composition can be used for skin, mucous membranes, scalp or hair, and is not particularly limited. For example, basic cosmetics such as softening lotion, nutrient lotion, cream, pack, gel, patch, lipstick, and makeup base , color cosmetics such as foundation, shampoo, rinse, body cleanser, toothpaste, mouthwash, etc., hair tonics, gels, mousses, etc., hair products such as hair growth agents, hair dyes, and the like.

The cosmetic composition may include additional ingredients commonly used in cosmetics, such as thickeners, dispersants, fragrances, fillers, preservatives, preservatives, neutralizers, sweeteners, vitamins, free-radical scavengers, metal ion sequestering agents, functional ingredients and these It may further include any conventional cosmetic ingredient which may be selected from mixtures of One skilled in the art may select any additional ingredients and/or amounts thereof such that the beneficial properties of the compositions according to the present disclosure are not adversely affected or substantially unaffected by the anticipated addition.

Another aspect is a first aqueous phase comprising a polyol; An oil phase part containing two or more polyglyceryl surfactants; A water-in-oil-in-water (W1/O/W2) multi-emulsion composition for external application for skin having a lamellar liquid crystal structure comprising a second water phase portion containing a hydrophilic surfactant and a polyol. The external skin preparation may be a composition for transdermal delivery of a drug (physiologically active substance). Details of the composition for external application for skin are as described above.

The external skin preparation may be a cream, gel, ointment, skin emulsifier, skin suspension, transdermal delivery patch, drug-containing bandage, lotion, or a combination thereof. The external skin preparation is a component commonly used in external skin preparations such as pharmaceuticals, for example, water-based components, oil-based components, powder components, alcohols, moisturizers, thickeners, ultraviolet absorbers, whitening agents, preservatives, antioxidants, surfactants, fragrances, and colorants. , various skin nutrients, or a combination thereof and may be suitably blended as needed. The external skin preparations include metal sequestering agents such as disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, and gluconic acid, caffeine, tannin, bellapamil, licorice extract, glabridin, and calin. Hot-water extracts of fruits, various herbal medicines, tocopherol acetate, glycyrrhizic acid, tranexamic acid and its derivatives or salts and other drugs, vitamin C, magnesium ascorbate phosphate, ascorbic acid glucoside, arbutin, kojic acid, glucose, fructose, Sugars, such as trehalose, etc. can also be mix|blended suitably.

Another aspect provides a method for preparing a water-in-oil-in-water (W1/O/W2) multi-emulsion cosmetic composition having a lamellar liquid crystal structure. The method comprises the steps of preparing an oil phase part by mixing two or more surfactants having different molecular weights and dissolving them by heating at a temperature of 75 to 95 °C; preparing a W1/O type emulsion by adding a first water phase part containing a polyol to the oil phase part; and emulsifying by adding the W1/O emulsion to the second aqueous phase part W2. In the above method, the surfactant, the first water phase part, the oil phase part, and the second water phase part are as described above. The W1/O emulsion has a lamellar liquid crystal structure, and when preparing a water-in-oil-in-water liquid crystal emulsion, the liquid crystal present at the W1/O interface may be adsorbed to another O/W2 interface to stabilize the interface. The emulsification rate and time may be flexibly adjusted according to the size of emulsion droplets to be produced.

The cosmetic composition according to one aspect forms lamellar liquid crystals of a thin film structure on the surface of emulsion droplets, thereby providing excellent formulation stability without the use of higher alcohol, low viscosity and excellent usability.

1A to 1D are optical microscope images immediately after preparation of emulsions of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 3, respectively.
2A and 2B are optical microscope and polarization microscope images immediately after preparing the emulsion of Comparative Example 4, respectively; 2C and 2D are optical microscope and polarization microscope images immediately after preparing the emulsion of Comparative Example 5, respectively; 2E and 2F are optical microscope and polarization microscope images immediately after preparing the emulsion of Comparative Example 6, respectively; 2G and 2H are optical microscope and polarization microscope images immediately after preparing the emulsion of Comparative Example 7, respectively.
Figure 3 is an optical microscope image of the emulsion according to the type of emulsifier and the emulsification speed when preparing the water-in-oil-in-water type low-viscosity liquid crystal emulsions of Examples 3 and 4, Figures 3A to 3C are disper during the preparation of Example 3, respectively When emulsified for 1 minute at 1000 rpm with a mixer, when emulsified for 1 minute at 2500 rpm with a homo mixer, when emulsified for 3 minutes at 5000 rpm with a homo mixer, Figure 3D shows Example 4 at 5000 rpm with a homo mixer for 3 minutes when it is emulsified.
4A and 4B are optical microscope images and polarized light microscope images of the water-in-water low-viscosity liquid crystal emulsion of Example 3, respectively.
5 is a result confirming the presence of lamellar peaks in the water-in-water type low-viscosity liquid crystal emulsion of Example 3 through small angle X-ray scattering.
6A and 6B are cryo-SEM analysis images and enlarged images near the center of the water-in-oil-in-water low-viscosity liquid crystal emulsion of Example 3, respectively.
7A and 7B are optical microscopy images of Example 4 immediately after 1 month of stability at 50 ° C and 5 times of F / T stability, respectively.
8 is a viscosity measurement graph according to F / T storage conditions of Examples 3 to 5.
9 is a viscosity measurement graph according to 50 ° C. storage conditions of Examples 3 to 5.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are intended to illustrate the present invention by way of example, and the scope of the present invention is not limited to these examples.

Preparation Examples 1 to 8. Preparation of W1/O type liquid crystal emulsion

In order to prepare a water-in-oil-in-water liquid crystal emulsion, Preparation Examples 1 to 8 of a water-in-oil liquid crystal emulsion were first prepared with the components and composition ratios shown in [Table 1] below.

Specifically, surfactant, emulsion stabilizer, hydrocarbon oil, vegetable oil, oil gelling agent, oil thickener, and skin conditioning agent among the oily components of A were measured and evenly dispersed at 80 ° C. for 10 minutes with an agi-mixer. Subsequently, the aqueous phase component of B was weighed, and the purified water heated to 80 ° C. and the remaining components were evenly stirred. While slowly adding the aqueous phase component of B to A, the mixture was stirred for 10 minutes at 500 rpm with a disper mixer. It was then emulsified for 3 minutes at 7000 rpm. After emulsification, when the temperature of the emulsion solution was 40 ° C., water correction and preservatives were added, followed by emulsification at 7000 rpm for 1 minute. Unless otherwise stated herein, component content is in weight percent.

ingredient Preparation Example 1 Preparation Example 2 Preparation Example 3 Production Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 A: Paid interface
activator Polyglyceryl-2 isostearate 3.1 3.1 3.1 3.1 6 3 Polyglyceryl-2 diisostearate 3 Polyglyceryl-6 Polyricinoleate 1.4 1.4 1.4 1.4 3 1.5 Polyglyceryl-3 Polyricinoleate 1.5 emulsion stabilizer behenyl alcohol 0.9 hydrocarbon oil squalane 15 15 15 15 15 15 15 15 isododecane 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 oil
gelling agent Disteadymonium hectorite 13.5 13.5 13.5 13.5 13.5 13.5 13.5 13.5 oil
thickener Dextrin Palmitate One One One One One One One One skin conditioning agent Mango Seed Butter 2 candelilla wax 2 2 vegetable oil jojoba oil 4 4 4 4 4 4 4 4 sunflower seed oil 4 4 4 4 4 4 4 4 B: award menstruum Purified water Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount moisturizer dipropylene glycol 4 4 4 4 4 4 4 4 glycerin One One One One One One One One 1,3 Butylene Glycol 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 bulking agent magnesium
sulfate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 antiseptic Ethylhexylglycerin 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 caprylyl glycol 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Examples 1 to 5. Preparation of W1/O/W2 type liquid crystal emulsion cosmetic composition

A water-in-oil-in-water type liquid crystal emulsion cosmetic composition was prepared by adding the W1/O type liquid crystal emulsion prepared in Preparation Examples 1 to 4 to another aqueous phase W2 with the components and contents shown in Table 2 below.

Specifically, the aqueous phase component of B was measured. The thickener was added last and evenly dispersed for 5 minutes with an agi-mixer. Subsequently, the W/O emulsion of A was added and stirred for 5 minutes at 500 rpm with a disper mixer. It was then emulsified for 1 minute at 5000 rpm.

ingredient Example 1 Example 2 Example 3 Example 4 Example 5 A: W/O emulsion Preparation Example 1 Free from conditioning agents and behenyl alcohol 10 20 30 30 Preparation Example 2 Contains conditioning agent Production Example 4 Contains behenyl alcohol 30 B: award menstruum Purified water Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount moisturizer dipropylene glycol 4 4 4 4 4 glycerin One One One One One 1,3 Butylene Glycol 2.5 2.5 2.5 2.5 2.5 bulking agent magnesium
sulfate 0.5 0.5 0.5 0.5 0.5 Surfactants polysorbate 60 0.45 0.45 0.45 0.45 0.45 thickener Hydroxyethyl Acrylate/Sodium Acryloyl Dimethyl Taurate Copolymer 0.5 0.5 0.5 0.5 0.25 antiseptic Ethylhexylglycerin 0.1 0.1 0.1 0.1 0.1 caprylyl glycol 0.3 0.3 0.3 0.3 0.3

Comparative Examples 1 to 7. Preparation of W1/O/W2 type liquid crystal emulsion cosmetic composition

The W1 / O type liquid crystal emulsion prepared in Preparation Examples 1 to 8 was added to another aqueous phase W2 with the components and contents shown in [Table 3], but in the same manner as in Examples 1 to 5. A water-in-oil liquid crystal emulsion cosmetic composition was prepared.

ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 A: W/O emulsion Preparation Example 1 Free from conditioning agents and behenyl alcohol 30 40 Preparation Example 2 Contains conditioning agent 30 Preparation Example 4 Contains behenyl alcohol Preparation Example 5 1 type with a molecular weight of 1500 g/mol or less 30 Preparation Example 6 2 types of molecular weight less than 1500 g/mol 30 Preparation Example 7 1 type with a molecular weight of 10000 g/mol or less 30 Preparation Example 8 2 types of molecular weight less than 10000 g/mol 30 B: award menstruum Purified water Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount Appropriate amount moisturizer dipropylene glycol 4 4 4 4 4 4 4 glycerin One One One One One One One 1,3 Butylene Glycol 2.5 2.5 2.5 2.5 2.5 2.5 2.5 bulking agent magnesium
sulfate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Surfactants polysorbate 60 0.1 0.45 0.45 0.45 0.45 0.45 0.45 thickener Hydroxyethyl Acrylate/Sodium Acryloyl Dimethyl Taurate Copolymer 0.5 0.5 0.5 0.5 0.5 0.5 0.5 antiseptic Ethylhexylglycerin 0.1 0.1 0.1 0.1 0.1 0.1 0.1 caprylyl glycol 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Experimental Example 1: Evaluation of stability of monodisperse water-in-oil-in-water emulsion

In order to evaluate the stability of the water-in-oil-in-water emulsions prepared in Example 3 and Comparative Examples 1 to 7, optical microscope images immediately after preparation of each emulsion were analyzed.

1A to 1D are optical microscope images immediately after emulsion preparation of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 3, respectively.

As a result, as shown in FIG. 1A, it was confirmed that Comparative Example 1 did not form round emulsion droplets due to an insufficient amount of hydrophilic surfactant, but formed an elongated unstable water-in-oil-in-water macroemulsion. In addition, as shown in FIG. 1B, Comparative Example 2 confirmed that the multi-emulsion system contained a large amount of highly polar oil, resulting in instability due to a weakened water-oil interface. In addition, as shown in FIG. 1C, Comparative Example 3 confirmed that as the content of the oil-in-water emulsion exceeded 35%, it was converted to an oil-in-water emulsion rather than a water-in-oil-in-water emulsion. It was determined that electrical conductivity did not pass. On the other hand, as shown in FIG. 1D, it was confirmed that Example 3 formed a stable water-in-oil emulsion with a clear curvature.

This means that several conditions must be premised in order to prepare a water-in-oil-in-water emulsion with a clear curvature. That is, a certain level of hydrophilic surfactant (HLB 7 or higher) must be contained at a level where the droplet core (W1) is united with the external phase (W2) and is not destroyed, and butter or wax that can be precipitated at the interface content should be minimized. In addition, the osmotic pressure must be balanced by making the content of polyols present in the core and outer layer the same.

2A and 2B are optical microscope and polarization microscope images immediately after preparing the emulsion of Comparative Example 4, respectively; 2C and 2D are optical microscope and polarization microscope images immediately after preparing the emulsion of Comparative Example 5, respectively; 2E and 2F are optical microscope and polarization microscope images immediately after preparing the emulsion of Comparative Example 6, respectively; 2G and 2H are optical microscope and polarization microscope images immediately after preparing the emulsion of Comparative Example 7, respectively.

As a result, as shown in FIGS. 2A and 2C, in Comparative Examples 4 to 5 containing one or two polyglyceryl surfactants having a molecular weight of 1,500 g/mol or less, the formulations were very unstable and contained in water-in-oil-in-water type droplets. It was confirmed that most of the W1 phase was united with W2. In addition, as shown in Figures 2E and 2G, in the case of Comparative Examples 6 to 7 containing one or two polyglyceryl surfactants having a molecular weight of 10,000 g / mol or less, the viscosity increased explosively, resulting in a transition to a water-in-oil type emulsion. As a result of measuring the electrical conductivity, it was confirmed that the current does not flow. However, it was confirmed that the water-in-oil-in-water type droplets were connected in a thin and long continuous phase over a large range in the optical microscope. However, as shown in FIGS. 2B, 2D, 2F, and 2H, one or two polyglyceryl surfactants having a molecular weight of 1,500 g/mol or less, and polyglyceryl surfactant 1 having a molecular weight of 10,000 g/mol or less In the case of Comparative Examples 4 to 7 using one or two species, it was confirmed that stable water-in-oil-in-water emulsions could not be prepared, and liquid crystals were also formed at a very insignificant level.

This means that at least one polyglyceryl-based surfactant having a molecular weight of 10000 g/mol or less and at least one polyglyceryl-based surfactant having a molecular weight of 1500 g/mol or less must be included to form a stable water-in-oil-in-water emulsion. That is, polyglyceryl surfactants of 10000 g/mol or less serve as the main surfactant and are the main factors determining the viscosity of the emulsion, and polyglyceryl surfactants of 1500 g/mol or less are located between these surfactant molecules. A stable water-in-oil-in-water type emulsion can be prepared.

Experimental Example 2. Evaluation of water-in-oil-in-water emulsion morphology according to emulsification conditions

Figure 3 is an optical microscope image of the emulsion according to the type of emulsifier and the emulsification rate when preparing the water-in-oil-in-water type low-viscosity liquid crystal emulsions of Examples 3 and 4, Figures 3A to 3C are disper during the preparation of Example 3, respectively When emulsified for 1 minute at 1000 rpm with a mixer, when emulsified for 1 minute at 2500 rpm with a homo mixer, when emulsified for 3 minutes at 5000 rpm with a homo mixer, FIG. in case of emulsification.

As a result, as shown in FIG. 3A, when stirring for 1 minute at 1000 rpm with a disper mixer in the preparation of Example 3, it was confirmed that a relatively large water-in-oil-in-water emulsion was formed. When the emulsification speed is adjusted according to the purpose, for example, as shown in FIG. 3B, when emulsified for 1 minute at 2500 rpm with a homo mixer, an average water-in-oil-in-water emulsion of 30 to 40 μm is prepared, and as shown in FIG. 3C, the When the emulsion was additionally emulsified at 5000 rpm for 1 minute or more with a homo mixer, it was confirmed that a small and dense water-in-oil-in-water emulsion with an average size of 20 μm or less could be prepared. In addition, as shown in Figure 3D, Example 4 contains 0.9% by weight of fatty alcohol under the same emulsification conditions, so that although the curvature is not perfectly spherical, it is possible to prepare a water-in-oil-in-water emulsion that is stable and has an increased feeling of use. Confirmed.

Experimental Example 3: Confirmation of liquid crystal and structural analysis

In order to identify that the polyglyceryl surfactant stabilizes the entire emulsion system by forming liquid crystals while stabilizing each interface, the water-in-water emulsion of Example 3 was photographed and analyzed with a polarizing microscope.

4A and 4B are optical microscope images and polarization microscope images of the water-in-water low-viscosity liquid crystal emulsion of Example 3, respectively.

As a result, as shown in FIG. 4A, it was confirmed that a stable water-in-oil-in-water low-viscosity liquid crystal emulsion was prepared. In addition, as shown in FIG. 4B, it was confirmed that the liquid crystal structure was adsorbed to the W1/O and O/W2 interfaces, and liquid crystal was formed on both the outermost and inner surfaces. However, in Example 3, it was confirmed that a thin film band, not the Maltese cross pattern seen in a polarizing microscope image of a previously known liquid crystal emulsion, surrounds the oil droplet and also surrounds the core droplet (W2) therein.

In order to confirm the macroscopic structure of the liquid crystal of a different form from the conventional one seen in a polarizing microscope, the liquid crystal structure immediately after preparation of the liquid crystal emulsion of Example 3 and after 8 weeks of storage at 50 ° C. was analyzed by small angle X-ray scattering. analyzed using

Specifically, it was conducted at room temperature using a light source with 3 GeV energy, and the light coming from the In-Vacuum Undulator 20 (IVU20, length: 1 m, period: 20 mm) of the PLS II storage ring was a mirror coated with rhodium. and is monochromated by Si (111) Double Crystal Monochromator (DCM) to produce a beam with a wavelength of 0.734 Å. The distance between the sample and the detector was 4 m, and the scattering vector (q = ) was 0.3 nm-1 < q < 6.85 nm-1. 2θ is the scattering angle, λ is the X-ray wavelength value, and the scattering angle was tested with silver behenate. Each sample was leveled in a semicircular direction, loaded between polyamide films, and measured for about 30 s.

5 is a result confirming the existence of lamellar peaks in the water-in-water type low-viscosity liquid crystal emulsion of Example 3 through small angle X-ray scattering. As a result, as shown in FIG. 5, the prepared liquid crystal emulsion had an x-axis value of q value immediately after preparation of 0.127 Å-1, 0.254 Å-1, and 0.381 Å-1 at a ratio of 1: 2: 3, Bragg According to the spacing ratio, when the ratio of small-angle X-ray scattering peaks was 1: 2: 3, it was found that the water-in-water type low-viscosity liquid crystal emulsion prepared in Example 3 had a lamellar structure because it had a lamellar structure. By substituting the first peak value, q1, into the equation d = 2π/q, the interlayer distance of the lamellar can be obtained. The q values of the F/T (freeze-thaw) stability 5-time emulsion were 0.126 Å-1, 0.252 Å-1, and 0.378 Å-1, with a ratio of 1:2:3, the same as immediately after preparation, and an interlayer distance of 4.984 nm has been shown to have

Therefore, it was found that even if a liquid crystal structure in the form of a thin film, as in Example 3, rather than the Maltese cross pattern on a polarizing microscope possessed by conventional liquid crystal emulsions, can be said to be a liquid crystal. Through this, it was proved that the water-in-water low-viscosity liquid crystal emulsion prepared with two or more polyglyceryl-based surfactants maintained a lamellar structure even under extreme conditions.

Experimental Example 4: Water-in-oil-in-water liquid crystal emulsion core structure analysis

A cryo-SEM (Cryogenic Scanning Electron Microscopy) analysis was performed to elucidate the structure of the multi-emulsion more clearly.

Specifically, after fixing the water-in-oil-in-water liquid crystal emulsion using a quick freezing method in a cryogenic state, the cross section was cut using an ion beam and observed. 6A and 6B are cryo-SEM analysis images and enlarged images near the center of the water-in-oil-in-water type low-viscosity liquid crystal emulsion of Example 3, respectively.

As a result, as shown in FIGS. 6A and 6B , it was confirmed that the core aqueous solution droplet W1 was present inside the oil droplet.

Experimental Example 5: Evaluation of long-term stability

To evaluate long-term storage stability, stability tests were conducted under two severe conditions.

5-1. Long term stability with temperature

In order to evaluate the long-term stability according to the temperature, Example 4 was stored at a high temperature (50 ° C.) for 8 weeks to confirm phase separation. In addition, Example 4 was stored alternately at low temperature (-20 ° C) and high temperature (50 ° C) for 24 hours, respectively, and a freeze-thaw (hereinafter referred to as F / T) test was performed. When stored for 24 hours at -20 ℃ and 24 hours at 50 ℃, it is marked as F/T once. After a total of 5 F/Ts, changes over time were observed.

7A and 7B are optical microscopy images of Example 4 immediately after 1 month of stability at 50 ° C and 5 times of F / T stability, respectively.

As a result, as shown in FIG. 7A, when Example 4 was stored at 50 ° C. for 8 weeks, the appearance was clean, and it was confirmed that the water-in-water emulsion form was well maintained when observed with an optical microscope. In addition, as shown in FIG. 7B, as a result of F / T stability a total of 5 times, the appearance was clean, and a small amount of coalescence occurred between particles when observed with an optical microscope, but the water-in-oil-in-water emulsion form was well maintained. Confirmed did

5-2. Long-term stability according to viscosity

In order to evaluate the long-term stability according to the viscosity, the viscosity of Examples 3 to 5 was measured for 1 minute at 30 rpm by installing an LV 64 spindle with a Brookfield DV2TLV.

8 is a viscosity measurement graph according to F / T storage conditions of Examples 3 to 5. 9 is a graph of viscosity measurement according to storage conditions of 50 ° C. in Examples 3 to 5.

As a result, as shown in FIG. 8, the viscosity of Examples 3 to 5 gradually increased with time under the F/T condition, but remained stable. In Example 4, the viscosity increased relatively as a small amount of fatty alcohol was contained, but the stable state was maintained. In addition, as shown in FIG. 9, the viscosity of Examples 3 to 5 gradually decreased with time at 50 ° C., but was apparently stable. In addition, as shown in FIGS. 8 and 9, it was confirmed that the viscosity of Examples 3 to 5 was low, ranging from 2,000 cPs to 8,000 cPs.

On the other hand, in Example 4, the driving force for maintaining stability even when a small amount of higher alcohol is contained is considered to be that the polyglyceryl surfactant-based thin liquid crystal is properly adsorbed and stabilized at each interface of the water-in-oil-in-water emulsion.

Claims (21)

A first aqueous phase comprising a polyol; An oil phase part containing two or more polyglyceryl surfactants and an oil phase component; A water-in-oil-in-water (W1/O/W2) multi-emulsion cosmetic composition having a lamellar liquid crystal structure comprising a second aqueous phase containing a hydrophilic surfactant and a polyol,
The oil component is a water-in-oil-in-water (W1 / O / W2) multi-emulsion cosmetic composition having a lamellar liquid crystal structure comprising at least one selected from the group consisting of hydrocarbon-based oils, vegetable oils, oil gelling agents, and oil thickeners . The method according to claim 1, wherein the hydrocarbon-based oil is isododecane, paraffin, isoparaffin, squalane, squalene, polybutene, polydecene, polyisoprene, hydrogenated polydecene, hydrogenated polyisobutene, hydrogenated poly ( C6-14 olefin), and at least one selected from the group consisting of mineral oil cosmetic composition. The method according to claim 1, wherein the vegetable oil is macadamia seed oil, meadowfoam seed oil, olive oil, apple seed oil, grape seed oil, sunflower seed oil, camellia oil, hazelnut oil, argan oil, rosehip fruit oil, avocado oil, and jojoba oil. At least one cosmetic composition selected from the group consisting of oil. The method of claim 1, wherein the oil gelling agent is disteadimonium hectorite, cetylethylhexanoate, isopropyl myristate, isopropylstearate, capphylic triglyceride, octyl palmitate, alkyl (14,16,18) A cosmetic composition of at least one selected from the group consisting of 2-ethylhexanoate, octyldodecyl myristate, octyldodecanol, and hexyllaurate. The method according to claim 1, wherein the oil thickener is dextrin palmitate/ethylhexanoate, dextrin palmitate, dextrin myristate, dextrin palmitate/hexyldecanoate, stearoyl inulin, dibutyl ethylhexanoyl glutamide, And at least one cosmetic composition selected from the group consisting of dibutyl lauroyl glutamide. The method according to claim 1, wherein the first aqueous phase or the second aqueous phase further comprises one or more salts selected from the group consisting of sodium chloride (NaCl), magnesium sulfate (MgSO4), potassium chloride (KCl), and calcium chloride (CaCl2) Phosphorus cosmetic composition. The method according to claim 1, wherein the second aqueous phase is made of xanthan gum, carbomer, hydroxypropyl starch phosphate, sodium magnesium silicate, hydroxyethyl cellulose, and hydroxyethyl acrylate/sodium acryloyl dimethyl taurate copolymer. A cosmetic composition further comprising one or more thickeners selected from the group. The cosmetic composition according to claim 1, wherein the first aqueous phase part and the oil phase part are included in 5 to 35% by weight based on the total weight of the composition. The cosmetic composition according to claim 1, wherein the polyol is at least one selected from the group consisting of diglycerin, glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, methylpropanediol, and sorbitol. The cosmetic composition of claim 1, wherein the polyol is included in an amount of 3.0 to 40% by weight based on the total weight of the composition. The cosmetic composition of claim 1, wherein the two or more polyglyceryl-based surfactants are included in an amount of 0.5 to 6.0% by weight based on the total weight of the first aqueous phase part and the oil phase part. The method according to claim 1, wherein the two or more polyglyceryl surfactants include a low molecular weight polyglyceryl surfactant and a high molecular weight polyglyceryl surfactant,
The low molecular weight has a molecular weight of 1,500 g / mol or less, and the high molecular weight has a molecular weight of more than 1,500 g / mol and 10,000 g / mol or less, a cosmetic composition. The method according to claim 12, wherein the low molecular weight polyglyceryl-based surfactant is polyglyceryl-4 isostearate, polyglyceryl-2 isostearate, polyglyceryl-2 diisostearate, polyglyceryl-5 hexastearate At least one cosmetic composition selected from the group consisting of late, polyglyceryl-10 heptaoleate, polyglyceryl-10 pentastearate and polyglyceryl-10 decastearate. The method of claim 12, wherein the high molecular weight polyglyceryl-based surfactant is polyglyceryl-6 polyhydroxystearate, polyglyceryl-10 polyhydroxystearate, polyglyceryl-3 polyricinoleate, polyglyceryl A cosmetic composition comprising at least one selected from the group consisting of -4 polyricinoleate, polyglyceryl-5 polyricinoleate, polyglyceryl-6 polyricinoleate, and polyglyceryl-10 polyricinoleate. The cosmetic composition according to claim 12, wherein the low molecular weight polyglyceryl-based surfactant is included in an amount of 1 to 4.5% by weight based on the total weight of the first aqueous phase part and the oil phase part. The cosmetic composition according to claim 12, wherein the high molecular weight polyglyceryl-based surfactant is included in an amount of 0.1 to 2.0% by weight based on the total weight of the first water phase part and the oil phase part. The cosmetic composition according to claim 1, wherein the hydrophilic surfactant is included in an amount of 0.2 to 3.0% by weight based on the total weight of the composition. The method according to claim 1, wherein the hydrophilic surfactant is polysorbate 60, polysorbate 80, polysorbate 20, PEG-100 stearate/glyceryl stearate, PEG-30 glyceryl stearate, glyceryl stearate as citrate, glyceryl oleate citrate, polyglyceryl-6 caprate, polyglyceryl-4 caprate, polyglyceryl-3 methylglucose distearate, and methoxyPG-114/polyepsiloncaprolactone At least one cosmetic composition selected from the group consisting of. The cosmetic composition according to claim 1, wherein the composition has a viscosity of 2,000 cPs to 8,000 cPs. The cosmetic composition according to claim 1, wherein the lamellar liquid crystal structure is formed in the form of a thin film on the surface of droplets of the W1/O interface and the O/W2 interface. A first aqueous phase comprising a polyol; An oil phase part containing two or more polyglyceryl surfactants and an oil phase component; A water-in-oil-in-water (W1/O/W2) multi-emulsion composition for external application for skin having a lamellar liquid crystal structure comprising a second water phase portion containing a hydrophilic surfactant and a polyol,
The oily component is a water-in-oil-in-water (W1/O/W2) multi-emulsion skin external agent having a lamellar liquid crystal structure comprising at least one selected from the group consisting of hydrocarbon oils, vegetable oils, oil gelling agents, and oil thickeners composition.

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