JP6792353B2 - Water-in-oil emulsified composition - Google Patents

Description

The present invention relates to a water-in-oil emulsified composition having excellent stability and usability.

Poly (12-hydroxystearic acid) esters of polyhydric alcohols are known to be suitable for producing a fluid low-viscosity emulsified composition having excellent high-temperature and low-temperature stability (Non-Patent Document 1: FRAGRANCE JOURNAL September 1999). Poly (12-hydroxystearic acid) esters of polyhydric alcohols are light-feeling and non-greasy by themselves, so they are particularly oily and heavy-use emulsifying compositions for cosmetics that tend to be avoided. Widely used as an emulsifier for. Patent Document 1 (Patent No. 4146979) discloses a multi-layer emulsifier type skin external preparation containing a poly (12-hydroxystearic acid) ester of a polyhydric alcohol.
In general, in the water-in-oil emulsified composition, since the dispersed aqueous phase particles do not have an electric charge, coalescence cannot be prevented by electrostatic repulsion between the emulsified particles, and stabilization cannot be achieved. Therefore, for the problem of precipitation and separation in the emulsified composition, the outer phase (oil phase) is thickened with a thickener, or the interface is strengthened by using a plurality of emulsifiers in combination (the increase in viscosity is too small). Method such as (cannot be expected) is adopted.

As an example of blending a thickener, an oil containing 1 to 50% by mass of poly (12-hydroxystearic acid) ester and triacylglycerin, and a fructo-oligosaccharide fatty acid ester as a thickening gelling agent, and an oil containing water. A medium-water emulsified composition has been proposed (Patent Document 2: Japanese Patent No. 4676634). However, this emulsified composition has problems in usability such as a sticky feeling.
In addition, water-in-oil emulsified cosmetics in which a poly (12-hydroxystearic acid) ester of a polyhydric alcohol is used in combination with a phospholipid as a different type of emulsifier and glyceryl as an oil-based gelling agent (behenic acid / eicosandioic acid) Fees have been proposed (Patent Document 3: Japanese Patent No. 5527356). This emulsified cosmetic has some improvements in usability, but it does not have sufficient skin familiarity and firmness as a cosmetic. Moreover, its stability at high temperatures is unknown.
In addition, a water-in-oil emulsified cosmetic containing an oily component, a poly (12-hydroxystearic acid) ester of a polyhydric alcohol, a specific silicone oil, and an organically modified clay mineral which is an oily gelling agent has also been proposed. (Patent Document 4: Japanese Patent No. 3933505). It is stated that this emulsified cosmetic was stable at 50 ° C. However, nothing is described about oil removal in the cream dosage form, and the feeling of use is not sufficient.
Further, in Non-Patent Document 1 shown above, when the polyhydric alcohol poly (12-hydroxystearic acid) ester is excessively blended and the volume ratio of the internal aqueous phase is increased (90%), water in oil It has been described that the viscosity of the mold emulsified composition increases. However, the water-in-oil emulsified composition with a high internal water phase has a unique splash feeling (the feeling that the internal water phase pops out at the time of application) and does not give a feeling of naturally blending into the skin, and is excellent in usability. It's hard to say.

Among the water-in-oil emulsified compositions, cream-type cosmetics and external preparations are sold by filling them in tube containers and jar containers. However, the cream formulation having a high viscosity often entrains air when the emulsified composition is filled in a tube container or a jar container, and voids are generated inside. When the cream dosage form with such voids is stored at a high temperature or for a long period of time, the oil contained in the oil phase separates and accumulates in the voids (hereinafter referred to as "oil removal"). May occur. This oil release is due to the instability of the structure and composition constituting the oil phase, unlike the emulsion stability. Degreasing generated in the voids is easily recognized as a defective product and poses a problem in design quality.

The basic composition of the water-in-oil emulsified cream is an oil, an emulsifier, an oil-based gelling agent, and water. In cosmetics, the oily gelling agent is added not only for the purpose of increasing the viscosity of the composition but also for improving the usability. In locally used cosmetics such as eye cream, usability such as "tension", "skin familiarity", and "thickness" is an important design item. The combination of oil-based gelling agent, emulsifier, and oil agent becomes complicated in order to realize the feeling of use.
When the compatibility of each of these components is not good, the above oil release occurs. Further, in the oil phase, various oil agents are present together with the oil-based gelling agent. At this time, if the oil agent is held in the network of the network structure formed by the oily gelling agent, the composition is stable and no quality problem occurs. However, when the oil-based gelling agent particles and molecules attract each other due to high temperature or long-term storage, the network of the network structure is disturbed, and when the network is closely spaced, the oil agent cannot be retained in the network of the network structure. .. Then, the oil agent that cannot be retained is pushed out of the network structure of the oil phase, and "oil separation" occurs. Therefore, in terms of quality design, it has the basic feeling of use of cosmetics, such as "smoothness" and "non-stickiness", while also providing "tension", "familiarity with the skin", and "thickness". In order to achieve this, if multiple different oil phase components such as oil-based gelling agents, silicones and hydrocarbon oils are combined to achieve a complex usability, the balance in the oil phase will be lost and "oil separation" will easily occur. Become. In particular, the favorable usability and suppression of "oil separation" required for the water-in-oil emulsified cream formulation for topical use have been difficult issues for cosmetic prescription design engineers.
Prior arts for solving such oil separation include, for example, Patent Document 5 (Japanese Patent Laid-Open No. 2007-153812) and Patent Document 6 (Japanese Patent Laid-Open No. 2013-107827).

Japanese Patent No. 4146979 Japanese Patent No. 4676634 Japanese Patent No. 5527356 Japanese Patent No. 3993505 JP-A-2007-153812 Japanese Unexamined Patent Publication No. 2013-107827

FRAGRANCE JOURNAL September 1999, pp. 83-86

The applicant has been continuing to develop a water-in-oil emulsified composition having excellent usability and stability by using a poly (12-hydroxystearic acid) ester of a polyhydric alcohol. In particular, the present inventor has a favorable basic feeling of use such as "smoothness of spread" and "non-stickiness" as a cosmetic for topical use such as cream for eyes, and further as a cream for eyes. We are conducting research and development of a water-in-oil cream type emulsification composition that has the essential feelings of use, such as "tension", "familiarity with the skin", and "thickness". In this process, the present inventor invented a container filled with a water-in-oil emulsified composition in which a poly (12-hydroxystearic acid) ester of a polyhydric alcohol, a lecithin, a gelling agent, and a highly polymerized silicone were combined. The present invention has been completed by finding that a cosmetic having excellent storage stability and usability does not cause oil separation even if voids are formed in the above.
That is, the present invention has high emulsification stability, is excellent in basic usability as a cosmetic, and also has "tension", "skin familiarity", and "thickness" in oil that does not cause oil release. An object of the present invention is to provide an aqueous emulsified composition.

The main configurations of the present invention are as follows.
(1) A water- in- oil emulsified composition containing (A) to (E) , characterized in that the viscosity measured by a B-type viscometer at 25 ° C. is 20000 to 50000 mP · s. Aqueous emulsified composition.
(A) Lipophilic surfactant (B) Lecithin 0.3 to 1% by mass
(C) Oil-based gelling agent (D) Highly polymerized silicone , dimethylsiloxane having a kinematic viscosity of 20 mm ² / s as measured by the capillary method , mixed and dispersed at a ratio of 20% by mass by the rotation method. When measuring the viscosity, the highly polymerized silicone (E) oil agent (2) (A) lipophilic surfactant showing 40,000 to 50,000 mPa · s is a poly (12-hydroxystearic acid) ester of a polyhydric alcohol (1). The water-in-oil emulsion composition according to the above.
(3) The water-in-oil emulsified composition according to (1) or (2) , wherein the oil-based gelling agent is an organically modified clay mineral.
(4) The water-in-oil emulsified composition according to any one of (1) to (3), wherein the organically modified clay mineral is dimethyl distearyl ammonium hectorite.
(5) The water-in-oil emulsified composition according to any one of (1) to (4), which further contains (C) an inulin fatty acid ester and / or a dextrin fatty acid ester as an oily gelling agent.
(6) (E) The oil agent contains one or more from the group consisting of silicone oil and volatile silicone oil, and one or more from the group consisting of ester oil, oil and fat, and hydrocarbon oil (1) to (5). The water-in-oil emulsified composition according to any one of.
(7) The water-in-oil emulsified composition according to any one of (1) to (6) , which is a cream for eyes.

The composition of the present invention has high emulsification stability, excellent basic usability as a cosmetic, and also has "tension", "skin familiarity", and "thickness", and further causes oil release. No, it becomes a water-in-oil emulsified composition. Further, the composition of the present invention does not separate in a cycle test (twice a 12-hour cycle) at −20 ° C. and room temperature (25 ° C.), and even when stored for a long period of time (stored at 50 ° C. for 1 month), oil is released into the voids. Is a composition that does not cause Further, since oil separation does not occur in the voids, the tube container can be filled and provided in which there is a risk of voids being generated. Furthermore, the water-in-oil emulsified composition obtained by the constitution of the present invention is "smooth in oil" and is for eyes such as "no stickiness", "tension", "familiarity with skin", and "thickness". Since the feeling of use required for cream is excellent, it is particularly excellent as a cosmetic used locally such as around the eyes.

The present invention relates to a water-in-oil emulsified composition containing (A) a lipophilic surfactant, (B) lecithin, (C) an oil-based gelling agent, (D) a highly polymerized silicone, and (E) an oil agent. Is.
The components of the present invention will be described below.

Essential Ingredients [(A): Lipophilic Surfactant]
The composition of the present invention is a water-in-oil emulsified composition and is required to contain a lipophilic surfactant. As the lipophilic surfactant, it is preferable to use a poly (12-hydroxystearic acid) ester of a polyhydric alcohol from the viewpoint of usability.
The poly (12-hydroxystearic acid) ester of the polyhydric alcohol used in the present invention is prepared by reacting a polyhydric alcohol such as polyethylene glycol with a halogenating agent such as thionyl chloride in the presence of an alkali. It can be obtained by reacting the prepared acid chloride.
As the polyvalent alcohol, propylene glycol, butanediol, pentandiol, (poly) glycerin, (poly) propylene glycol, polyethylene glycol and the like can be preferably exemplified. Among them, polyethylene glycol is particularly preferable. The polyethylene glycol in this case preferably has an average molecular weight of 400 to 6000. On the other hand, the poly (12-hydroxystearic acid) serving as a hydrophobic group preferably has an average molecular weight of 1000 to 3000.
The di (12-hydroxystearic acid) ester of polyethylene glycol is preferably one whose INCI name is listed as PEG-30 dipolyhydroxystearic acid, and commercially available products include Aracel P-135 manufactured by Unichema and Crowder Japan. There is Sysrol DPHS manufactured by Co., Ltd.
When a poly (12-hydroxystearic acid) ester of a polyhydric alcohol is blended, the blending amount is preferably 0.1 to 5% by mass, particularly preferably 1 to 5% by mass. If it is less than 0.1% by mass, emulsification may be insufficient. If it exceeds 5% by mass, it may give a sticky feeling.

[(B): Lecithin]
As the lecithin used in the present invention, natural phospholipids such as egg yolk lecithin and soybean lecithin, hydrogenated soybean lecithin in which unsaturated carbon chains in lecithin are converted into saturated bonds by hydrogenation, hydrogenated egg yolk lecithin and the like can be used. These hydrogenated substances are collectively referred to as hydrogenated lecithin (hydrogenated lecithin) in the present specification. In the present invention, it is preferable to use hydrogenated lecithin. In the present invention, lecithin is preferably blended in an amount of 0.1 to 1% by mass.

[(C): Oil-based gelling agent]
Examples of the oily gelling agent used in the present invention include organically modified clay minerals, dextrin fatty acid esters, inulin fatty acid esters, fine particle silica, and hydrogenated castor oil. Among them, it is preferable to blend an organically modified clay mineral. When dextrin fatty acid ester and inulin fatty acid ester are used in combination with organically modified viscous minerals, "thickness", "smoothness", "non-stickiness", "familiarity with the skin", and "tension" Is preferable because it improves. Organically modified clay minerals are clay minerals modified with a quaternary ammonium salt-type cationic surfactant. For example, organically modified bentonite, organically modified hectorite and the like can be used. More specifically, dimethyl distearyl ammonium hectorite, dimethyl alkyl ammonium hectorite, benzyl dimethyl stearyl ammonium hectorite, distearyl dimethyl ammonium chloride-treated aluminum magnesium silicate and the like can be mentioned. In the present invention, a premixed product containing an organically modified clay mineral may be used as the organically modified viscosity mineral. For example, distearyldimonium hectorite 12.5% by mass, PEG-10 dimethicone 37.5% by mass, cyclopentasiloxane 49.95% by mass, tocopherol 0.05, such as Nicomrus WO manufactured by Nippon Surfartant Industry Co., Ltd. A composition consisting of% by mass can be exemplified. The composition of the present invention preferably contains 0.05 to 2% by mass, more preferably 0.1 to 1% by mass, as an organically modified clay mineral.
Further, in the present invention, it is preferable to further blend either or both of inulin fatty acid ester and dextrin fatty acid ester in addition to the organically modified clay mineral. When the inulin fatty acid ester and / or the dextrin fatty acid ester is further added to the composition, the feeling of use such as "smoothness of spread" and "thickness" that is felt at the time of application becomes more excellent. As the inulin fatty acid ester, inulin stearate can be exemplified. Inulin stearate is inulin with stearic acid ester-bonded. As a commercially available product, Leopard ISL2 manufactured by Chiba Flour Milling Co., Ltd. can be exemplified. Further, as the dextrin fatty acid ester, dextrin palmitate can be exemplified. Dextrin palmitate is an ester bond of dextrin and palmitic acid. As a commercially available product, Leopard KL manufactured by Chiba Flour Milling Co., Ltd. can be exemplified. The blending amount of the inulin fatty acid ester and / or the dextrin fatty acid ester may be appropriately set, but by blending 0.1 to 1% by mass in the total amount, "smoothness", "thickness", and "thickness", " It is preferable because it improves the feeling of use of "non-sticky feeling", "familiarity with skin", and "tension feeling".

[(D): Highly polymerized silicone]
The highly polymerized silicone used in the present invention has a viscosity of 40,000 to 50,000 mPa · s by the rotation method when the highly polymerized silicone is dispersed in dimethylpolysiloxane having a kinematic viscosity of 20 mm ² / s by the capillary method at a concentration of 20% by mass. Refers to a silicone having the following characteristics. The degree of polymerization of this highly polymerized silicone is about 8000 when calculated from the weight average molecular weight based on the gel permeation chromatography method.
In the present invention, it is preferable to blend the highly polymerized silicone so as to contain 0.1 to 0.5% by mass, more preferably 0.2 to 0.4% by mass, per composition. Highly polymerized silicones having such properties are commercially available as composite products, and these can be used. As such a commercially available product, for example, MK-15H manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned. MK-15H is a mixture of highly polymerized methylpolysiloxane having a degree of polymerization of 8000 and low-viscosity methylpolysiloxane having a viscosity of 20 mm ² / s as measured by the capillary method at a ratio of 2: 8. When this MK-15H is used, it is preferably blended in an amount of 0.5 to 2.5% by mass, more preferably 1 to 2% by mass, per composition.
The MK-15H containing this highly polymerized silicone has a viscosity of 45,000 mPa · s when measured at 25 ° C. using a B-type viscometer.
By blending such a highly polymerized silicone together with the poly (12-hydroxystearic acid) ester and lecithin of the polyhydric alcohol, the water-in-oil emulsified composition of the present invention can have a "smoothness". The composition has an excellent feeling of use such as "thickness" and an effect of suppressing oil separation.
The viscosity of highly polymerized silicone when highly polymerized silicone was dispersed in dimethylpolysiloxane with kinematic viscosity of 20 mm ² / s by the capillary method at a concentration of 20% by mass was 40,000 mPa at 25 ° C. as measured by a B-type viscometer. If it is less than s or more than 50,000 mPa · s, oil separation occurs in the voids, which is not preferable.

[(E): Oil agent]
Examples of the oil agent that can be used in the present invention include ester oils, fats and oils, hydrocarbon oils, silicone oils, and volatile silicone oils. It is preferably a liquid oil or a paste-like oil.
Examples of the ester oil include cetyl ethylhexanoate, 1,3-butylene glycol diisononanoic acid, 1,3-butylene glycol di2-ethylhexanoic acid, dipropylene glycol diisononanoate, and dipropylene glycol di2-ethylhexanoate. Isononyl isononanoate, glyceryl tri2-ethylhexanoate, glyceryl tricaprate, glyceryl triisostearate, neopentyl glycol dicaprate, ethylhexyl palmitate, isostearyl neopentate, methyl-β-alanine myristoyl (phytosteryl / decyltetradecyl), etc. Can be mentioned.
Examples of fats and oils include liquid fats and oils such as camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, wheat germ oil, cocoa fat, coconut oil, palm oil, palm. Examples include nuclear oil.
Examples of the hydrocarbon oil include liquid paraffin, squalene, squalane and the like.
Examples of the silicon oil include dimethylpolysiloxane and methylphenylpolysiloxane. Examples of the volatile silicone oil include decamethylcyclopentasiloxane and cyclopentasiloxane. The composition containing the highly polymerized silicone may be blended in place of these.
In particular, pentaerythrityl tetraethylhexanoate, squalane, isostearyl isostearate, ethylhexyl palmitate, methylphenylpolysiloxane, methylpolysiloxane, cyclopentasiloxane, olive oil, jojoba oil, myristylmethyl-β-alanine (phytosteryl / decyltetradecyl). ) In combination is preferable from the viewpoint of usability. The blending amount of the oil agent in the present invention is not particularly limited, but is preferably 20 to 50% by mass with respect to the composition. In addition, in order to achieve good spreadability (“smoothness of spread”) and “feeling of familiarity with the skin”, 40 to 60 oils selected from the group consisting of silicone oil and volatile silicone oil are selected based on the total amount of oil. It is preferable to mix so as to have a mass%. Since ester oils, fats and oils, and hydrocarbon oils can give a moist feel, it is preferable to mix them in an amount of 60 to 40% by mass with respect to the total amount of the oil agent.

The viscosity of the water-in-oil emulsified composition of the present invention was No. 1 after storage at room temperature (25 ° C.) for 1 week. When measuring using a B-type viscometer equipped with 4 rotors under the conditions of a measurement temperature of 25 ° C., a rotor rotation speed of 6 rpm, and 30 seconds after the start of measurement, it is preferably in the range of 20000 to 50000 mPa · s. This viscosity is in a preferable range as the viscosity of the cream filled in the tube container so that the contents do not flow down even if the bottle filled in the 6K bottle (standard bottle) is tilted.

[Arbitrary component]
In the water-in-oil emulsified composition of the present invention, components usually used in cosmetics, for example, nonionic surfactants and anionic surfactants, are used as optional components as long as the effects of the present invention are not impaired. Agents, cationic surfactants, amphoteric surfactants, oils, moisturizers such as polyhydric alcohols, antioxidants, UV absorbers, salts, pH regulators, preservatives, ascorbic acid derivatives, antibacterial agents, chelating agents , Colorants, fragrances, etc. can be blended. In addition, beauty ingredients such as ceramide and plant extract can be blended.

Examples of the moisturizer include glycerin, diglycerin, 1,3-butylene glycol, dipropylene glycol, pentylene glycol and the like.
Examples of salts include sodium chloride, magnesium sulfate and the like.
Examples of the pH adjusting agent include citric acid, sodium citrate, phosphoric acid, sodium phosphate, potassium hydroxide and the like.
Examples of the preservative include phenoxyethanol and paraben.
Examples of the ascorbic acid derivative include L-ascorbic acid phosphate magnesium salt, L-ascorbic acid phosphate sodium salt, 2-O-α-D-glucopyranosyl-L-ascorbic acid and the like.
Examples of the ceramide include cetyl PG hydroxyethyl palmitide and cerebroside.

The water-in-oil emulsified composition of the present invention can be used as a cosmetic, a skin external preparation, a quasi-drug, or a pharmaceutical product. The dosage form is particularly preferably a creamy dosage form, and is suitable for locally used cosmetics and external preparations such as around the eyes.

The features and effects of the present invention will be described in more detail below with reference to Examples and Comparative Examples.
The water-in-oil emulsified composition (cream type) of Examples 1 to 6 with the composition of Table 1 and Comparative Examples 1 to 8 with the composition of Table 2 was prepared.
The compounding ingredients marked with * 1 to 4 in Tables 1 and 2 are as follows.
* 1: Nicomrus WO, manufactured by Nippon Surfartant Industry Co., Ltd .: distearyldimonium hectorite 12.5% by mass, tocopherol 0.05% by mass, PEG-10 dimethicone 37.5% by mass, cyclopentasiloxane 49.95% by mass %
* 2: MK-15H, manufactured by Shin-Etsu Chemical Industry Co., Ltd .: Highly polymerized methylpolysiloxane (degree of polymerization 8000) is converted to low-polymerized methylpolysiloxane (dimethylpolysiloxane with kinematic viscosity of 20 mm ² / s) at a concentration of 20% by mass. Dispersed dispersion (viscosity is 45,000 mPa · s)
* 3: BY11-040 manufactured by Toray Dow Corning Co., Ltd .: A dispersion of highly polymerized dimethylpolysiloxane (degree of polymerization 2800, viscosity 4 million mPa · s) dispersed in cyclopentasiloxane at a concentration of 15% (viscosity is 1500 mPa · s)
* 4: KF-96H-1 million mPa · s (manufactured by Shinetsu Chemical Industry Co., Ltd., degree of polymerization 2200) at a concentration of 20% by mass, low viscosity silicon (kinematic viscosity 20 mm ² / s when measured by capillary method) Dispersion dispersed in (corresponding) (viscosity is 1700 mPa · s)

(Preparation method)
The components (A) to (E) are heated to 90 ° C. and sufficiently stirred and mixed to prepare an oil phase. An aqueous phase component such as water or polyhydric alcohol is heated to 80 ° C. and sufficiently stirred and mixed to dissolve it to prepare an aqueous phase. While gradually adding the prepared aqueous phase to the oil phase, the mixture is emulsified by stirring at 6000 rpm for 2 minutes using a homomixer, and then cooled to room temperature with stirring to obtain a water-in-oil emulsified composition.

(Evaluation methods)
Measurements and sensory evaluations were performed on the following evaluation items.
<Viscosity>
The obtained water-in-oil emulsified composition was filled in a glass container having a diameter of about 4 cm, and stored in a heat insulating tank at 25 ° C. and 50 ° C. for 1 week, 2 weeks, and 1 month. After the number of storage days has elapsed, No. Using a B-type viscometer equipped with 4 rotors, the measurement was performed under the conditions of a measurement temperature of 25 ° C., a rotor rotation speed of 6 rpm, and 30 seconds after the start of measurement. Immediately before measuring the viscosity, the presence or absence of an oil separation layer (oil release) was confirmed on the surface of the emulsion. The evaluation of oil release was performed according to the following criteria of <confirmation of oil release into voids>.

<Emulsification stability>
Emulsification stability was evaluated by the cycle test shown below. The cycle test is a test for evaluating emulsion stability. Those that have separated in this test are judged to be "poor in emulsified state".
<< Cycle test >>
The obtained water-in-oil emulsified composition was filled in a glass container (6K bottle) having a diameter of about 4 cm, and low temperature (-20 ° C.) and room temperature were alternately repeated for 12 hours each, and this was repeated for 2 cycles. , The emulsified state was visually observed.
The evaluation was made in the following two stages.
〇: Not separated ×: Separated (water and aqueous phase components are separated)

<Confirmation of oil release>
The obtained water-in-oil emulsified composition is placed in a glass container (6K bottle) having a diameter of about 4 cm, and a narrow-mouthed piping bag (the tip of the plastic bag is cut off) is used to form a gap in the filling surface in contact with the glass. It was filled unevenly so that it could be observed, and the container was sealed tightly. This was stored in a heat insulating tank at 40 ° C. and 50 ° C. for one month, respectively, and the occurrence of oil separation into the voids formed in contact with the glass was visually observed. Oil removal is different from separation of emulsified compositions with separation of water. Further, the oil release may be observed on the surface of the composition filled in the 6K bottle, but since the oil spreads over the entire surface, if the amount is small, it may be overlooked by the visual appearance observation method. However, it can be confirmed by the test method in which the void is created. This test is an effective test as a method for confirming quality deterioration due to early oil release.
The visual evaluation criteria under each temperature condition were set to the following two stages.
〇: There is no oil release in the void
X: There is oil release in the voids. In this test, the surface was visually observed at the same time. The evaluation criteria in this case are as follows.
〇: There is no oil release on the surface
×: There is oil release on the surface

<Sensory evaluation>
Regarding the feeling of use, the following criteria were used for each evaluation item of "thickness", "smoothness of spread", "non-stickiness", "familiarity with the skin", and "tension" by two specialized sensory evaluators. Evaluated by. The evaluation results in the table were the same for both of them. The history of the sample was evaluated blindly by the sensory evaluator.

<< Thickness >>
◎: I feel very thick
〇: Feel the thickness
△: Feel a little thick
×: I do not feel the thickness

<< Smoothness of the stretch >>
◎: Very well stretched and feels smooth 〇: Feels stretched and smooth
△: Feels a little smooth
×: I do not feel the smoothness of the stretch

<< Non-sticky feeling >>
〇: I do not feel sticky
△: Feels a little sticky
×: Sticky

<< Skin familiarity >>
〇: Feel familiar with the skin
△: Feels a little familiar to the skin
×: Does not feel familiar to the skin

<< Tension >>
〇: Feel the tension
△: Feels a little firm
×: I do not feel the tension

(Evaluation results)
As shown in the lower part of Tables 1 and 2, the water-in-oil emulsified compositions of Examples 1 to 6 had no oil release in the voids even after visual confirmation after storage at a high temperature (50 ° C.) for 1 month. And all the evaluation items of usability ("smoothness", "non-stickiness", "thickness", "familiarity with the skin", "tension") are realized. I was able to confirm that. That is, it was found that the composition was stable and had all the feelings required for the eye cream.
On the other hand, the emulsified state of the compositions of Comparative Examples 1 to 5 was confirmed to be good in some Test Examples by the cycle test (Comparative Examples 1 and 2), but oil release to the voids was observed (Comparative Examples 1 and 2). Comparative Examples 1 to 4). In Comparative Example 5, although oil release did not occur, the usability was completely poor. In Comparative Examples 6 to 8, oil release occurred in all of them, and it was judged that the quality of the cream formulation to be filled in the tube container was unsuitable.
Focusing on the viscosity, in Example 4, oil separation did not occur even if the viscosity after storage at 50 ° C. decreased to 7,000 mPa · s, but in Comparative Example 6, the viscosity after storage at 50 ° C. was 38,900 mPa · s. The viscosity was more than 5 times higher than that of 4, but oil release was observed. That is, it was confirmed that the phenomenon of "oil removal" was not suppressed by the viscosity.
Further, when dimethyl distearyl ammonium hectorite was first selected as the oil-based gelling agent and further used in combination with dextrin palmitate or inulin stearate, "skin familiarity" and "tension" were excellent. Above all, it was confirmed that when inulin stearate was added in combination, the "thickness" and "smoothness" were also excellent.
The configuration of the present invention is that there is no "oil release" and all of the feeling of use ("feeling of smoothness", "feeling of non-stickiness", "feeling of thickness", "feeling of familiarity with the skin", "feeling of firmness"). It turned out that the item of can be realized.

Summarizing the above evaluations, the water-in-oil emulsified composition of the present invention has "smoothness of spread", "non-stickiness", "thickness", "familiarity with skin", and "tension". Since all of them can be realized and oil release does not occur even at high temperatures, it can be said that it is most suitable as a cream for eyes by filling it in a tube container.

The formulation, production method, and characteristics of the water-in-oil emulsified composition adopting the constitution of the present invention are shown below.
Prescription example 1 Formulation of high moisturizing cream
(Ingredients) (% by mass)
1. 1. Dipolyhydroxystearate PEG-30 2
2. 2. Hydrogenated lecithin 1
3. 3. Myristoylation methyl-β-alanine (phytosteryl / decyltetradecyl) 2
4. Olive oil 5
5. Jojoba oil 4
6. Glyceryl tri2-ethylhexanoate 3
7. Cyclopentasiloxane 5
8. Methylphenyl polysiloxane 5
9. (Dimethicone / Vinyl Dimethicone) Cross Polymer 1
10. Dimethyl distearyl ammonium hectorite 1
11. MK-15H (manufactured by Shin-Etsu Chemical Co., Ltd.) 2
12. Glycerin 5
13.1,2-Pentanediol 2
14. Phenoxyethanol 0.2
15. Sodium hyaluronate 0.1
16. Purified water residue

(Manufacturing method)
The oil phase (components 1 to 11) and the aqueous phase (components 12 to 16) were separately heated to 80 to 90 ° C. and sufficiently stirred to prepare the water phase and the oil phase. The obtained aqueous phase was added to the oil phase, and the mixture was emulsified by stirring at 6000 rpm for 2 minutes with a homomixer, and then cooled to room temperature with stirring to obtain a water-in-oil emulsified composition.

(Characteristic evaluation)
The viscosity, emulsion stability, oil release, and usability were evaluated in the same manner as above.
The highly moisturizing cream of Formulation Example 1 has an appropriate viscosity, has good emulsification stability, does not cause oil release, and has a feeling of use ("smoothness of spread", "non-stickiness", "thickness". It was excellent in "feeling", "feeling familiar to the skin", and "tightness"), and was excellent in storage stability.

Claims (7)

A water-in-oil emulsification composition containing (A) to (E), wherein the viscosity measured by a B-type viscometer at 25 ° C. is 20000 to 50,000 mP · s. Composition.
(A) Lipophilic surfactant (B) Lecithin 0.3 to 1% by mass
(C) Oil-based gelling agent (D) Highly polymerized silicone, mixed and dispersed in dimethylsiloxane having a kinematic viscosity of 20 mm ² / s as measured by the capillary method at a ratio of 20% by mass by the rotation method. Highly polymerized silicone showing 40,000 to 50,000 mPa · s when measuring viscosity 0.1-0.5% by mass
(E) Oil (A) The water-in-oil emulsified composition according to claim 1, wherein the lipophilic surfactant is a poly (12-hydroxystearic acid) ester of a polyhydric alcohol. (C) The water-in-oil emulsified composition according to claim 1 or 2, wherein the oil-based gelling agent is an organically modified clay mineral. The water-in-oil emulsified composition according to any one of claims 1 to 3, wherein the organically modified clay mineral is dimethyl distearyl ammonium hectorite. The water-in-oil emulsified composition according to any one of claims 1 to 4, further comprising (C) an inulin fatty acid ester and / or a dextrin fatty acid ester as an oily gelling agent. (E) The invention according to any one of claims 1 to 5, wherein the oil agent contains one or more from the group consisting of silicone oil and volatile silicone oil, and one or more from the group consisting of ester oil, oil and fat, and hydrocarbon oil. Water-in-oil emulsified composition. The water-in-oil emulsified composition according to any one of claims 1 to 6, which is a cream for eyes.