TW201336519A - High internal aqueous phase water-in-oil type emulsion composition - Google Patents

Abstract

The present invention provides a water-in-oil type emulsion composition containing an aqueous component of 70 to 98 mass%, and the internal aqueous phase having an average emulsion particle diameter of 10 to 100 μ m, the composition providing an excellent temporal stability and an excellent moisturizing effect without sticky feeling, and providing a felling of water running over (=phase inversion) when applied. The water-in-oil type emulsion composition contains the following components (A) to (E): (A) 3, 7, 11, 15-tetramethyl-1, 2, 3-hexadecane triol, (B) diglyceryl diisostearate, (C) polyoxyethylene/methyl polysiloxane copolymer, (D) an aqueous component, (E) an oily component. Relative to the whole composition, the mass of aqueous component of component (D) is 70 to 98 mass%, the average emulsion particle diameter of the internal aqueous phase is 10 to 100 μ m; and relative to the whole composition, the total mass of the component (A), (B), and (C) is 0.07 to 0.9 mass%.

Description

Water-type emulsified composition in high internal water phase oil

The present application claims priority from Japanese Patent Application No. 2012-55449, filed on Mar.

The present invention relates to an aqueous emulsified composition in oil. More specifically, it is an improvement of the temporal stability of the water-type emulsified composition in the oil having a high internal phase emulsified particle size.

It is an important function expected by the emulsified composition for skin care to keep the skin moisturized and moisturized. Among the emulsified compositions, the water-based emulsified composition containing the aqueous component as the external phase (continuous phase) imparts an excellent effect on the skin's tenderness, but does not easily exhibit moisturizing sensation. On the other hand, the oil-based emulsified composition of the oil having the oil component as the external phase (continuous phase) is excellent in moisturizing the skin, but has a problem that it tends to cause a sticky feeling and is less likely to be noticeable.

The above-mentioned tackiness of the water-based emulsified composition in oil is widely attempted to be eliminated by increasing the ratio of the aqueous component of the internal phase (= internal water ratio). The problem with this method is due to the increase in internal water. The emulsification system becomes unstable, and when the internal water is 70% by mass or more, the emulsion stability is drastically lowered. Accordingly, in the prior art, a water-based emulsified composition of a high internal aqueous phase oil having good stability has been produced by working on the types of surfactants and emulsifiers.

Patent Document 1 combines a polyether-modified silicone oil with a specific polyether-modified polyfluorene oxide or a sucrose fatty acid ester having an HLB of 4 or less, and emulsifies to prepare a high internal aqueous phase oil having good stability. Water-type emulsified composition. However, since the polyether silicone exhibits a function as a polymer surfactant, a sticky feeling is caused by the entanglement of the polymer chain.

Further, Patent Document 2 produces a high internal aqueous phase and has good stability by using a dimethylpolyoxyalkylene polyoxyethylene copolymer containing 5 to 30% by weight of polyoxyethylene in one molecule as an emulsifier. An aqueous emulsified composition of oil. However, the maintenance of its stability requires the formulation of sugars and/or inorganic salts and polyols, so there is a problem that the raw materials are limited.

Further, Patent Document 3 produces a water-based emulsified cosmetic material having high stability in a high internal phase oil by using a dimethyl polyoxyalkylene polyoxyalkylene copolymer and a fatty acid dextrin ester in an emulsifier. . However, in the composition, the chain polyoxyxene oil needs to account for 30% by mass or more of the oil phase.

Further, Patent Document 4 is a combination of monooleic acid glyceride and 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (common name is phytantriol) As an emulsifier, a water-type emulsified composition of high internal phase oil having high stability is produced. However, when the monoolein contains impurities (glycerin fatty acid diester and/or fat) When the ratio of the acid triglyceride is 25 mass or more, the stability is lowered.

Moreover, Patent Document 5 discloses a water-type emulsified composition of a high internal aqueous phase oil containing glyceryl isostearate and 3,7,11,15-tetramethyl-1,2,3-hexadecanol triol. Things. However, the composition needs to contain 30% by mass of isoparaffin having a carbon number of 20 or less in the oil component, and the amount of monoisostearic acid glycerin mixed in the aforementioned glyceryl isostearate is also limited.

As described above, the water-based emulsified composition of the conventional high internal phase oil has a problem of improving the emulsion stability and remains sticky (Patent Document 1), and is reacted by the surfactant and the emulsifier. Those who are affected by the by-products (Patent Documents 4 and 5) are limited by the type and amount of oil content (Patent Documents 1, 3, and 5), or those who need to add other components (Patent Document 2); People are satisfied. Further, even if the stickiness is lowered, the high water tenderness such as the oily emulsified composition in the water is not exhibited.

Here, an attempt is made to rapidly disintegrate the emulsified particles at the time of coating so that the water of the internal phase is released to the skin, and even if the water-based emulsified composition in the oil is used, the water which is overflowing is remarkable. Tenderness. Since this feeling of use is caused by the phase shift of the water in the oil to the oil type in the water, it is called a sense of phase change (or a feeling of overflow of water).

Patent Documents 6 to 8 disclose a water-based emulsified cosmetic in a high internal aqueous phase oil produced by using a specific crosslinked polyether modified polyfluorene as a main emulsifier, which exhibits excellent phase inversion at the time of coating. sense.

However, the cross-linked polyether modified polyfluorene oxide is difficult to disperse, and it needs to be swelled in a low-viscosity polyoxyxene oil to be kneaded/ The cutting process is performed to form a three-dimensional structure in advance. Further, since the stability with time is insufficient (Patent Document 6), it is necessary to formulate an aqueous tackifier (carboxymethylcellulose salt) to stabilize the internal aqueous phase (Patent Document 7), or to be blended to exhibit a sense of phase change. Specific ester oil (Patent Document 8).

As described above, the appearance of the phase change sensation can solve the problem of the aforementioned feeling of use accompanying the water-based emulsified composition in the oil (strongly sticky, not watery), but in the prior art, pretreatment of the emulsifier Before the cumbersome steps are required, the type of oil that can be adjusted is limited.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-89356

[Patent Document 2] Japanese Patent No. 2654960

[Patent Document 3] Japanese Patent No. 2791677

[Patent Document 4] Japanese Patent No. 4681439

[Patent Document 5] Japanese Patent No. 4629799

[Patent Document 6] Japanese Patent No. 3782914

[Patent Document 7] Japanese Patent No. 4150280

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2001-2521

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2011-21007

As described above, the phase inversion feeling is a feeling of use which is manifested by rapidly disintegrating the emulsified particles by the physical pressure generated at the time of coating. Further, in the oil-based emulsified system, the internal water ratio is higher, and the emulsified particle diameter of the inner phase is larger, and aggregation and disintegration of the emulsified particles are more likely to occur. Therefore, the more It is a high internal aqueous phase and the larger the emulsified particle size, the more the phase change feeling can be obtained at the time of coating.

However, if the agglomeration or disintegration of the emulsified particles occurs before use, the aqueous phase is separated from the oil phase, and it cannot be used as a commercial product. Therefore, in the conventional oil-in-oil emulsified composition, when the internal water is increased, the emulsified particle diameter of the internal aqueous phase tends to be small (preferably 1 μm or less). Although there is also a report of a water-type emulsified composition in a high internal aqueous phase oil having an average emulsified particle diameter of 10 μm or more, the composition imparts high elasticity to the oil phase by formulating a hydrophobic powder (preferably an elastic material). It is not possible to show a sense of change (Patent Document 9).

Therefore, in the case of producing an oil-based emulsified composition which is excellent in the sense of phase change, it is required that the emulsified particles of the internal aqueous phase are easily aggregated/disintegrated (= low emulsion stability), but The emulsion stability is finely adjusted before use, in such a manner that aggregation/destruction does not occur (= high stability over time).

The present invention has been made in view of the above problems, and in particular, it is an object of the present invention to provide an oil-in-oil emulsified composition which is 70 to 98% by mass in terms of internal water, and has an emulsified particle diameter of 10 to 10 in the internal aqueous phase. The formulation/form of 100 μm, which tends to cause aggregation/destruction of emulsified particles in a general state, but has good stability over time, and the emulsified particles are easily damaged at the time of coating to exhibit a remarkable phase change feeling.

In response to the above problems, the present inventors have conducted intensive studies and found that by using 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, diiso. The diglyceryl stearate and the polyoxyethylene/methyl polyoxyl copolymer are used in combination as an emulsifier, even if the internal water is 70 to 98% by mass and the internal aqueous phase has an average emulsified particle size of 10 to At 100 μm, an oil-in-water emulsified composition having good stability over time can be produced. Therefore, the water-based emulsified composition of the oil has no stickiness, and exhibits excellent phase change feeling at the time of coating, and is also excellent in imparting moisturizing feeling and moisturizing effect, and has completed the present invention.

That is, the water-type emulsified composition of the oil of the present invention comprises the following components (A) to (E): (A) 3,7,11,15-tetramethyl-1,2,3-hexadecane Triol (B) diisostearic acid diglyceride (C) polyoxyethylene / methyl polyoxyalkylene copolymer (D) aqueous component (E) oily component, relative to the composition as a whole, component (A) to The total amount of (C) is 0.9% by mass or less; the mass of the component (D) is 70 to 98% by mass with respect to the entire composition; and the average emulsified particle diameter is 10 to 100 μm.

The water-type emulsified composition of the oil of the present invention has good stability over time and has no stickiness, and exhibits excellent phase change feeling (=water overflow feeling) at the time of coating, and imparts moisturizing effect and moisturizing effect. The aspect is also excellent.

Fig. 1 is a micrograph showing the emulsified particle diameter of the water-type emulsified composition (Example 12) in the oil of the present invention.

<constitutional component>

The water-type emulsified composition in the oil of the present invention is an essential constituent component (A) to (E). Each component is detailed below.

[ingredient A: 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (common name: phytantriol)]

3,7,11,15-Tetramethyl-1,2,3-hexadecanetriol is a surfactant known by the conventional name: phytantriol. For the commercial product, for example, "phytosanol" manufactured by DSM Nutrition Japan Co., Ltd. can be used.

The blending amount of 3,7,11,15-tetramethyl-1,2,3-hexadecanoltriol is preferably 0.01 to 0.4% by mass, and more preferably 0.1 to 0.4% by mass based on the entire composition. Good, 0.3% by mass is the best.

[ingredient B: glyceryl diisostearate]

Examples of the diisostearic acid glyceride used in the present invention include WOGEL-18DV (manufactured by Matsumoto Pharmaceutical Co., Ltd.) and the like.

The amount of the diisostearic acid glyceride is preferably 0.01 to 0.7% by mass, more preferably 0.2 to 0.6% by mass, and most preferably 0.4% by mass based on the total amount of the composition.

[Component C: Polyoxyethylene/methyl polyoxyalkylene copolymer]

Examples of the polyoxyethylene/methyl polyoxyalkylene copolymer used in the present invention include KF-6028 and KF6017P (all manufactured by Shin-Etsu Chemical Co., Ltd.).

Polyoxyethylene/methyl polyoxane relative to the composition as a whole The blending amount of the alkane copolymer is preferably 0.05 to 0.3% by mass, more preferably 0.05 to 0.3% by mass, and most preferably 0.1% by mass.

The above components (A) to (C) are preferably from 0.07 to 0.9% by mass or less, more preferably from 0.4 to 0.8% by mass, most preferably 0.7, based on the total amount of (A) to (C). Up to 0.8% by mass. In this case, when it is more than 0.9% by mass, a sticky feeling is generated, and when it is less than 0.07% by mass, it may be difficult to emulsify.

[ingredient D: aqueous component]

The (D) aqueous component of the present invention can be used as an aqueous component of cosmetics and pharmaceuticals, in addition to water, without impairing the stability of the emulsion. Examples of such an aqueous component include alcohols, water-soluble polymers, and humectants.

Examples of the alcohol include ethanol, propanol, isopropanol and the like.

Examples of the water-soluble polymer include plant-based polymers such as gum arabic, carrageenan, pectin, amaranth, alfalfa seeds, and starch; dextran, pullulan, and the like. Microbial polymers; starch-based polymers such as carboxymethyl starch and methyl hydroxypropyl starch; animal polymers such as collagen, casein, and gelatin; starches such as carboxymethyl starch and methyl hydroxypropyl starch Molecular acid; alginic acid polymer such as sodium alginate; ethylene polymer such as carboxyl vinyl polymer; polyoxyethylene polymer; polyoxyethylene polyoxypropyl propylene copolymer polymer; sodium polyacrylate, polypropylene strontium An acrylic polymer such as an amine; an inorganic water-soluble polymer such as bentonite, aluminum magnesium silicate, or Laponite.

Examples of the humectant include: 1,3-butanediol, polyethylene glycol Alcohol, propylene glycol, dipropylene glycol, glycerin, diglycerin, xylitol, maltitol, maltose, D-mannitol, glucose, fructose, sodium chondroitin, sodium hyaluronate, sodium lactate, glucosamine , cyclodextrin and so on.

In the oil-type emulsified composition of the oil of the present invention, the amount of the (D) aqueous component is from 70 to 98% by mass based on the entire composition. If it is less than 70% by mass, it is difficult to obtain an excellent phase change feeling, and if it exceeds 98% by mass, the stability with time is lowered, and phase separation easily occurs before use.

[ingredient E: oily ingredients]

As the (E) oil component of the present invention, an oily component which can be generally used for cosmetics and pharmaceuticals can be used without detracting from the stability of the emulsion.

Examples of the oily component in the form of a liquid include a chain polyoxyxane such as dimethylpolysiloxane, methylphenylpolysiloxane or methylhydrogenpolysiloxane; and octamethylcyclotetrazepine. A cyclic polyoxyxene oil such as octamethylcyclotetrasiloxane, decamethylcyclopentaoxane, decamethyltetraoxane or dodecamethylcyclohexaoxane.

Examples of the oily component of the solid form include solid oils such as cocoa butter, coconut oil, horse oil, hardened coconut oil, palm oil, tallow, sheep fat, hardened castor oil, and phytosterol hawaiian soybean oil fatty acid ester; paraffin wax (paraffin wax) (linear hydrocarbons), microcrystalline wax (branched saturated hydrocarbons), celesin wax, wood wax, montan wax, Fischer-Tropsch Wax and other hydrocarbons Class, beeswax, lanolin, carnauba wax, candelilla wax, rice bran wax Wax), Spermaceti wax, wax, brown carbon wax, Kapok wax, bayberry wax, shellac wax, sugar cane wax, isopropyl lanolate, laurel Acid hexyl ester, reduced lanolin, hard lanolin, POE lanolin ether, POE acetylated lanolin alcohol, POE cholesterol ether, lanolin acid polyethylene glycol, POE hydrogenated lanolin alcohol, etc.; Higher fatty acids such as acid, palmitic acid, stearic acid, and behenic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, and cetearyl alcohol.

In addition, as a polar oil, it can be formulated as follows: 2-ethylhexanoic acid, glyceryl triisostearate, isodecyl pivalate, tripropylene glycol trimethylacetate, N-lauroyl-L-glutamic acid 2 (phytosterol/2-octyldodecyl, tris-2-ethylhexanoic acid glycerol, tetraethyl 2-ethylhexanoate pentaerythritol, tetrakis(behenic acid/benzoic acid/ethylhexanoic acid) pentaerythritol ester, three ( Caprylic acid) glyceride, diisostearyl malate, Hawaiian soybean oil, polyglycerol-2 ester of triisostearic acid, ethylhexyl ethylhexanoate, ethylhexyl palmitate, cetyl octanoate, Hexyl laurate, isopropyl myristate, octyl palmitate, isocetyl stearate, isopropyl isostearate, octyl isopalmitate, isodecyl isostearate, 2-ethyl succinate Ester oil represented by hexyl hexyl ester, diethyl sebacate, etc.; and jojoba oil, meadowfoam seed oil, isostearic acid, and the like.

In addition, as a non-polar oil, it can be formulated, for example, liquid paraffin, squalane, squalene, paraffin, isoparaffin, heavy liquid isoparaffin, isododecane, isohexadecane, olefin oligomerization Hydrocarbon oil.

The blending amount of the (E) oily component in the water-type emulsified composition of the oil of the present invention is from 1.1 to 29.93 mass%, based on the entire composition. It is preferably from 7 to 20% by mass. When the blending amount of the oily component is less than 1.1% by mass, there is a case where the moisturizing feeling and the moisturizing effect are poor. Further, if it is more than 29.93% by mass, the result is a sticky feeling and a poor sense of phase change.

In the oil-type emulsified composition of the present invention, in addition to the above components (A) to (D), the oil can be used in oils such as general cosmetics or pharmaceuticals without damaging the effects of the present invention. The other components of the emulsified composition. Examples of such ingredients may be suitably formulated as needed: anti-UV agents, chelating agents, antioxidants, preservatives, tackifiers, perfumes, powders, coloring materials, crude drugs, and various other medicinal ingredients.

Examples of the anti-UV agent include a benzoic acid-based ultraviolet absorber such as an amino-based benzoic acid; an o-amine benzoic acid-based ultraviolet absorber such as methyl ortho-benzoate; and a salicylic acid-based ultraviolet absorber such as octyl salicylate; A cinnamic acid ultraviolet absorber such as isopropyl cinnamate or octyl p-methoxycinnamate; a UV absorber such as urocanic acid or ethyl urate; 2-hydroxy-4-methoxy A benzophenone-based ultraviolet absorber such as benzophenone or dihydroxybenzophenone; a UV absorber such as a benzotriazole-based ultraviolet absorber or 2-phenylbenzimidazole-5-sulfonic acid.

Further, examples of the chelating agent include edetate sodium and sodium metaphosphate.

Examples of the antioxidant include ascorbic acid, α-tocopherol, dibutylhydroxytoluene, and butylhydroxyanisole.

Further, examples of the preservative include benzoic acid, salicylic acid, p-hydroxybenzoic acid ester (methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, butyl paraben), and sorbic acid (sorbic). Acid), right P-chlorometacresol, hexachlorophenol, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, photoreceptor , phenoxyethanol and the like.

Further, the powder may, for example, be mica, talc, kaolin, sericite, muscovite, phlogopite, synthetic mica, red mica, sericite, lithium mica, synthetic mica, calcium carbonate, magnesium carbonate, phthalic anhydride (oxidation) Sil(silica), aluminum citrate, barium strontium citrate, calcium citrate, magnesium citrate, barium strontium citrate, alumina, barium sulfate, iron oxide, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine blue, Prussian blue , titanium oxide, zinc oxide, mica titanium (titanium coated with titanium oxide), fish scale foil, barium oxychloride, boron nitride, red 228, red 226, blue 404, polyethylene powder, poly Methyl methacrylate powder, polyamide resin powder (Nylon powder), cellulose powder, organopolysiloxane elastomer, aluminum powder, copper powder, and the like.

In addition, the medicinal ingredients can be formulated, for example, vitamin A oil, retinol, retinol palmitate, pyridoxine hydrochloride, benzyl nicotinic acid, nicotinamide , niacin dl-α-tocopherol, magnesium ascorbyl phosphate, vitamin D ₂ , dl-α-tocopherol, pantothenic acid, biotin and other vitamins; azulene, glycyrrhizin and other anti-inflammatory agents; bearberry Glycosides, 4-methoxysalicylic acid, tranexamic acid, ethyl vitamin C, magnesium ascorbyl phosphate, etc.; hormones such as estradiol; astringents such as zinc oxide and tannic acid; L-menthol, camphor (camphor) and other cooling agents; other lysozyme chloride, pyridoxine hydrochloride, sulfur and the like. In addition, various extracts can be formulated to express a wide variety of effects.

The above components are examples and are not limited to these. Further, the components may be appropriately combined depending on the desired form.

<Manufacturing method>

As a method for producing the water-based emulsified composition of the oil of the present invention, first, oil phase components (components (A) to (C), (E), and other hydrophobic components) and water phase components (component (D) are respectively And other hydrophilic components) are heated and mixed, and adjusted to a uniform mixture in advance. Next, by using a stirring and mixing device, the mixture of the aqueous phase components is gradually added to the mixture of the oil phase components to be emulsified (=emulsification step) while stirring the mixture of the oil phase components. The water-type emulsified composition in the oil of the present invention is obtained.

The emulsified particle size of the aqueous emulsified composition in the oil of the present invention can be controlled by various methods, and the most common and suitable method is a method of controlling by the stirring conditions of the aforementioned emulsification step. In general, the larger the number of rotations of the agitation mixing device used in the emulsification step, and the longer the agitation time, the greater the load caused by shear/impact/cavitation, so that the load is formed. The emulsified particles are miniaturized. Therefore, the emulsified particle diameter of the water-type emulsified composition in the oil of the present invention can be adjusted by the purpose of adjusting the type of the stirring and mixing device, the number of rotations of the stirring and mixing device, and the stirring time of the stirring time. Particle size range.

Examples of the stirring and mixing device used for the agitation and mixing include a homodisperser, a homomixer, a homogenizer, and a microfluidizer. A high-speed emulsification device such as a microfluidizer; a dispersion mixer having a serrated agitating blade; and an impeller-type agitating device including a rotating piece. The oil-in-water emulsified composition of the specific emulsified particle diameter of the present invention can be produced by using any of the aforementioned agitating and mixing devices, and it is particularly preferable to use a high-speed emulsification device represented by a homodispersing machine.

Further, in the examples of the present invention, the mixture was stirred for 30 to 180 seconds by using a homodisperser (manufactured by PRIMIX Corporation) at a number of revolutions of 3000 to 6000 rpm, and adjusted to be an aqueous emulsified oil having an average emulsified particle diameter of 10 to 20 μm. Composition.

<Emulsion particle size>

The emulsified particle diameter of the water-type emulsified composition in the oil of the present invention, that is, the water droplets dispersed in the oil phase, has a particle diameter of 10 to 100 μm, preferably 10 to 30 μm, and most preferably 20 μm. If the emulsified particle diameter is less than 10 μm, there is a case where an excellent phase change feeling cannot be obtained. Further, when the emulsified particle diameter exceeds 100 μm, the chronological stability of the emulsified composition becomes low, and it may be unsuitable as a product.

In addition, the term "emulsified particle size" used in the present invention means an average value of the emulsified particle diameter calculated from the measured value by measuring the particle diameter of about 100 emulsified particles arbitrarily selected in the micrograph of the emulsified composition.

The water-type emulsified composition of the oil of the present invention can be widely applied to cosmetics, pharmaceuticals, and guasi-drugs, and is particularly suitable for use in cosmetics. Examples of the application of the cosmetic material include a cosmetic liquid, an emulsion, a cream, a base makeup, an eye shadow, an eyeliner, a mascara, and the like, and other application examples include Such as skin external ointment.

Such articles may be made according to conventional methods, but the invention is not limited to such articles.

(Example)

The invention will be more specifically described by the following examples, but the invention is not limited thereto. In addition, if the amount of blending is not specified, it means mass%.

<Assessment Benchmark>

The composition prepared in the examples was evaluated for stability over time and feeling of use according to the following criteria.

Time stability

After the oil-in-oil emulsified composition was allowed to stand at 0 ° C or at 25 ° C for 4 weeks, the stability was visually evaluated according to the following criteria.

◎: None of the oil droplets/separation was confirmed

○: Confirmed oil drop

△: Confirmation of separation

×: Confirmation of separation within 30 minutes after manufacture

Sense of change

Regarding the sense of phase change at the time of application (=water overflow feeling), 10 professional panelists were asked to apply the sample to the face, and the feeling of use was evaluated according to the following criteria.

◎: More than 9 reviewers answered that there was a sense of change during coating.

○: The 7 or more and less than 9 reviewers answered that there was a sense of change in the direction of coating.

△: 5 or more and less than 7 reviewers answered that there was a sense of change during coating.

×: The reviewer who did not reach 5 responded that there was a sense of change in the direction of coating.

No sticky feeling

Regarding the lack of stickiness during use, 10 professional panelists were asked to apply the sample to the face and evaluate the feeling of use according to the following criteria.

◎: More than 9 reviewers answered that there was no sticky feeling during use.

○: 7 or more and less than 9 reviewers answered that there was no sticky feeling during use.

△: The reviewer with more than 5 panelists and less than 7 respondents answered that there was no sticky feeling during use.

×: The tester who did not reach 5 responded that there was no stickiness in use.

Moisturizing

For the moisturizing feeling of the skin in use, 10 professional reviewers were asked to apply the sample to the face and evaluate the use according to the following criteria.

◎: More than 9 reviewers will use the skin to moisturize the skin.

○: 7 or more testers who have not reached 9 will answer the skin and moisturize the skin during use.

△: 5 or more and less than 7 reviewers answered that they will moisturize the skin during use.

×: The reviewer who has not reached 5 will answer the skin and moisturize the skin.

Moisturizing effect

For the moisturizing effect of the skin in use, 10 professional reviewers were asked to apply the sample to the face and evaluate the use according to the following criteria.

◎: More than 9 reviewers answered that they had a moisturizing effect during use.

○: 7 or more and less than 9 reviewers answered that there was a moisturizing effect during use.

△: 5 or more and less than 7 reviewers answered that there was a moisturizing effect during use.

×: The reviewer who did not reach 5 responded that there was a moisturizing effect during use.

Further, the examples use the following articles.

*1: Syncelane4 (manufactured by Nikko Chemicals Co., Ltd.)

*2: NIKKOL CIO (manufactured by Nikko Chemicals Co., Ltd.)

*3: RA-G-308 (made by Nippon Seika Co., Ltd.)

*4: PE-MC wax (manufactured by Nikko-rica Co., Ltd.)

*5: KF-96L-1.5cs (manufactured by Shin-Etsu Chemical Co., Ltd.)

*6: KF-96L-2cs (manufactured by Shin-Etsu Chemical Co., Ltd.)

*7: Phytantriol (made by DSM Nutrition Japan Co., Ltd.)

*8: San soft O-30S (made by Sun Chemical Co., Ltd.)

*9: WOGEL-18DV (made by Matsumoto Pharmaceutical Co., Ltd.)

*10: KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)

*11: KF-6017P (manufactured by Shin-Etsu Chemical Co., Ltd.)

*12: KSG-18A (manufactured by Shin-Etsu Chemical Co., Ltd.)

*13: a mixture of poly(oxyethylene/oxypropylene) methyl polyoxyalkylene copolymer (50%) and light mobile isoparaffin (50%)

*14: ABIL EM90 (manufactured by Degussa)

<Measurement of emulsified particle size>

In order to make it easy to discriminate the outline of each emulsified particle, the emulsified composition was diluted with cetyl 2-ethylhexanoate (manufactured by Nikko Chemicals Co., Ltd.), and a photograph was taken using a microscope (BX51, manufactured by OLYMPUS Co., Ltd.). Fig. 1 is a view showing a part of a photograph taken in Example 12 (emulsified particle diameter = 15 μm). About 100 emulsified particles were arbitrarily selected from the photographs obtained in this manner, and the particle diameter was measured, and the average value was calculated.

[Test Example 1]

The water-type emulsified composition in the high internal aqueous phase oil was prepared according to the conditions shown in Table 1, and the stability over time and the feeling of use were evaluated.

Formulation of (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) glyceryl diisostearate, and (C) polyoxyethylene/methyl poly The alkane copolymer is used as a surfactant, and comprises (D) an aqueous component and (E) a component of an oil component (Examples 1 to 5), which is excellent in stability over time and has no stickiness. It has a remarkable sense of phase change and is also excellent in moisturizing and moisturizing effects on the skin. On the other hand, in the compositions of Comparative Examples 1 to 3 in which one of the surfactants (A) to (C) was lacking, a stable emulsification system could not be formed and phase separation occurred. Further, the composition of Comparative Example 4 (= the component (D) was removed from the composition of Example 1) containing no (D) aqueous component, or the composition of Comparative Example 5 containing no (E) oil component ( = The component (E) was removed from the composition of Example 1, and the volume was adjusted by the purified water, and the emulsion system was not formed (Comparative Examples 4 and 5).

Therefore, if (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) glyceryl diisostearate, and (C) polyoxyethylene/ The methyl polyoxyalkylene copolymer is combined and the emulsification of the (D) aqueous component and the (E) oily component is excellent in stability over time and phase change, and has no stickiness, and further, it is clear that moisturizing effect can be produced. And an oil-based emulsified composition that is excellent in moisturizing the skin.

As described above, 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (ingredient (A) of the present invention) and triolein are used as an emulsifier in water. In the emulsified composition, when the ratio of the fatty acid diglyceride and/or the fatty acid triglyceride contained in the glycerol monooleate is 25% or more, the stability is poor (Patent Document 4). However, even in the composition of Example 1 of the present invention, the blend contains 55 mass% of diolein and trioleate. The glycerol monooleate of the acid glyceride also did not impair its stability (Example 4).

Further, a dimethylpolyoxyalkylene polyoxyethylene copolymer containing 5 to 30% by weight of polyoxyethylene in one molecule is used as a composition of an emulsifier, and a saccharide and/or an inorganic salt is not lacking in order to maintain emulsion stability. The formulation of the class and the polyol (Patent Document 2), and even if the polyol was removed from the composition of Example 2 of the present invention, no effect was observed on the stability (Example 5).

Further, the compositions of the present invention (Examples 1 to 6) and the patent documents 6 to 8 are the same as the crosslinked polyether modified polyfluorene (methylphenyl polyoxyalkylene crosslinked methylbenzene). a polyoxyalkylene; comprising diphenylmethoxy phenyl polytrimethyl decane (about 84% by mass) and (polydimethyl methoxy oxane / phenyl vinyl polydimethyl decane) The composition of Comparative Example 6 produced by using a dimethicone/phenyl vinyl dimethicone crosspolymer (about 16% by mass) as an emulsifier was compared, and it was understood that the stability of the composition of the present invention was equivalent. High, in addition, the sense of phase change is also better.

Further, the compositions of Patent Documents 1, 3, and 6 to 8 must be formulated with a polyoxygenated oil, but the composition of Example 6 of the present invention can obtain excellent stability over time and feeling of use even without containing polyoxygenated oil. .

Therefore, the present invention does not require a cumbersome pretreatment step for the emulsifier, and even if the oil type is not limited, it is possible to achieve an excellent excellent phase transition feeling and good temporal stability.

[Test Example 2]

Secondly, review the impact of internal water on the stability and use of time.

A composition comprising all of the components (A) to (E) of the present invention and having an internal water ratio of 70 to 97.9% by mass (Examples 7 to 10) exhibits the entire effects of the present invention (good stability over time, no hair) Sticky, excellent moisturizing effect / moisturizing / phase change). In particular, it was confirmed that the composition of Example 10 is an extremely high internal water phase even if the internal water is 97.9%, and its stability over time at both high temperature (50 ° C) and constant temperature (0 ° C). Still good.

On the other hand, in the composition (comparative example 7) in which the internal water was 49% by mass, the stability over time was good, but the stickiness was not lowered, and the phase change feeling was deteriorated.

Therefore, the water-type emulsified composition in the oil of the present invention is preferably in the range of from 70 to 98% by mass, more preferably from 80 to 95% by mass, most preferably from 85 to 90% by mass, based on the internal water.

[Test Example 3]

As described above, in the water-based emulsification system in the high internal phase oil, the larger the emulsified particle diameter of the inner phase, the more excellent the phase change sensation, and the lower the stability over time. Here, the internal water phase of the emulsified composition of the present invention was fixed to a state of a high internal water phase of about 86% by mass, and the influence of the emulsified particle diameter of the internal phase on the stability over time and the sense of phase change was examined.

Formulation of (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) glyceryl diisostearate, and (C) polyoxyethylene/methyl poly As a composition of a surfactant, a siloxane has a good stability over time in the range of 1 to 100 μm (Comparative Examples 8, 9, and Examples 11 to 14), wherein the phase change is also The superior one is an emulsion of a composition having an particle diameter of 10 to 100 μm (Examples 11 to 14). Therefore, it is understood that the water-type emulsified composition in the high internal phase oil of the present invention has an emulsified particle diameter of 10 to 100 μm, preferably 10 to 30 μm, and most preferably 20 μm by the internal phase, and can be achieved well. The stability of time and the significant sense of phase change.

In contrast, poly(oxyethylene/oxypropylene) methyl polyoxyalkylene or cetyl dimethicone copolyol (C) is substituted with a general lipophilic surfactant. In any one or all of the surfactants of (C), even if the emulsified particle diameter is from 1 to 100 μm, the stability with time and the sense of phase change are not good. Results (Comparative Examples 10 to 15). The composition having an average emulsified particle diameter of 1 μm (Comparative Example 10) and 3 μm (Comparative Example 11) had good stability with time, but did not give a phase change feeling; 10 μm (Comparative Example 12), 15 μm ( In the composition of Comparative Example 13), although the phase change feeling was obtained, the stability with time was poor. Further, the compositions of 30 μm (Comparative Example 14) and 100 μm (Comparative Example 15) failed to form an emulsification system and phase separation occurred.

As described above, in the conventional high-grade aqueous phase oil, the water-based emulsion system has an emulsified particle diameter of 10 μm or more, that is, aggregation or disintegration of the emulsified particles is likely to occur, and the tendency of the emulsified particle size is more remarkable. In contrast, the water-type emulsification in the high internal aqueous phase oil produced by the components (A) to (C) of the present invention is used. As a result, in terms of the temporal stability of the system, those having an emulsified particle diameter of 10 to 30 μm are more excellent than those having an emulsified particle diameter of 1 to 3 μm.

Therefore, it is clear that (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) glyceryl diisostearate, and (C) polyoxyethylene/ The combination of the methyl polyoxyalkylene copolymers is very suitable for the stabilization of emulsified particles having a low curvature of the interface film (specifically, emulsified particles having a particle diameter of 10 to 100 μm).

[Test Example 4]

Next, the amount of the components (A) to (C) is reviewed.

The total of (A) to (C) was 0.45 mass% (Example 15), 0.75 mass% (Example 16), 0.8 mass% (Example 17), and 0.85 mass% (Example 18). In other words, the results are excellent in stability and phase change, and there is no stickiness. In addition, it is also excellent in moisturizing and moisturizing effects. On the other hand, it was confirmed that the composition (Comparative Example 16) in which the total of (A) to (C) was 0.95% by mass had a low phase transition feeling. Therefore, in the case of producing a water-type emulsified composition in a high internal aqueous phase oil which is excellent in the sense of phase change and has no stickiness, the total amount of the blending amounts of (A) to (C) is 0.07 as a whole with respect to the entire composition. It is preferably 0.9% by mass, more preferably 0.4% to 0.8% by mass, most preferably 0.7% to 0.8% by mass.

The sum of (A) to (C) may be set to any value as long as the sum of (A), (B), and (C) is within the above range, but preferably (A) is 0.01 to 0.4% by mass. (B) is 0.01 to 0.7% by mass, (C) is 0.05 to 0.3% by mass; more preferably (A) is 0.1 to 0.4% by mass, (B) is 0.2 to 0.6% by mass, and (C) is 0.05. It is 0.3% by mass; preferably (A) is 0.3% by mass, (B) is 0.4% by mass, and (C) is 0.1% by mass.

[Test Example 5]

Table 5 shows the results of the review of the blending amount of the low-viscosity polysulfonated oil and the olefin oligomer in the composition of the present invention.

The low viscosity (dynamic viscosity at 25 ° C is 3 PCT (Centi Stokes; cs) or less) contained in the oil phase is 7.2% by mass (Example 19), 8.0% by mass (Example 20), or 14.8. In any of the compositions of % by mass (Example 21), the effects of the present invention (transfer phase feeling, non-stickiness, moisturizing feeling, and moisturizing effect) were excellent, and the stability over time was also good. Further, in any of the olefin oligomers contained in the oil phase, which are 0.5% by mass (Example 19), 18.5% by mass (Example 21), and 20.0% by mass (Example 20), excellent properties can be obtained. A sense of effect and good stability over time.

Therefore, the composition of the present invention is different from the water-type emulsified composition in a conventional type oil which is required to be blended with a polyoxygenated oil and a specific hydrocarbon oil (Patent Documents 1, 3, 5 to 8), even if the polyoxygenated oil is an oil phase. 10% by mass or less, and/or the olefin oligomer is 1% by mass or more of the oil phase, and does not impair the effect (transformation feeling, no stickiness, moisturizing feeling, and moisturizing effect) and stability over time. .

Further, from the above Table 5, the time stability of the composition of Example 20 was more excellent than that of the compositions of Examples 19 and 21. Therefore, it is considered that if the composition of the present invention contains a polypyroxene oil and an olefin oligomer having an kinetic viscosity of 3 PCT or less in the oil phase, and respectively, the polypyrene oil is less than 10 masses. % and 1% by mass or more (olefin oligomer), preferably 6 to 9% by mass (the polyoxyxane) and 15 to 20 masses (olefin oligomer), the stability over time is further improved .

Further, from the above Table 5, the time stability of the composition of Example 20 was obtained as compared with the compositions of Examples 19 and 21 over time. More excellent results. Therefore, it is considered that if the composition of the present invention contains a polypyroxene oil and an olefin oligomer having an kinetic viscosity of 3 PCT or less in the oil phase, and respectively, the polypyrene oil is less than 10 masses. % and 1% by mass or more (olefin oligomer), preferably 6 to 9% by mass (the polyoxyxane) and 15 to 20 masses (olefin oligomer), the stability over time is further improved .

The following is a typical example of the water-type emulsified composition in the oil of the present invention. Any of the following compositions exhibited good temporal stability, excellent phase change, and no stickiness, and also excellent moisturizing and moisturizing effects.

[Prescription Example 1: Cream] <prescription>

<Method>

In the above prescription, the oil phase components (1) to (9) are heated and mixed at 80 ° C, and the mixture of the aqueous phase components (10) to (14) (room temperature) is slowly added while stirring with a homodisperser. modulation.

[Prescription Example 2: Beauty Liquid] <prescription>

<Method>

In the above-mentioned prescription, the oil phase components (1) to (7) are mixed, and the mixture of the aqueous phase components (8) to (19) (room temperature) is gradually added while stirring with a homomixer to prepare a mixture.

[Prescription Example 3: Whitening Cream] <prescription>

<Method>

In the above-mentioned prescription, the oil phase components (1) to (9) are mixed, and the mixture of the aqueous phase components (10) to (20) (room temperature) is gradually added while stirring with a homodisperser to prepare a mixture.

[Prescription Example 4: Cream] <prescription>

<Method>

In the above prescription, the oil phase components (1) to (8) are heated and mixed at 80 ° C, and the mixture of the aqueous phase components (9) to (14) (room temperature) is slowly added while stirring with a homodisperser. modulation.

The micrograph of the emulsified particle size of the water-type emulsified composition in the oil of the present invention is not sufficient to represent the technical features of the present invention. Therefore, there is no designated representative map.

Claims (1)

An oil-in-oil emulsified composition comprising the following components (A) to (E): (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol ( B) diisostearic acid diglyceride (C) polyoxyethylene/methyl polyoxyalkylene copolymer (D) aqueous component (E) oily component; relative to the whole composition, component (D) aqueous component The mass is 70 to 98% by mass, the average emulsified particle diameter of the aqueous phase therein is 10 to 100 μm, and the total amount of the components (A), (B), and (C) is 0.07 to 0.9 mass with respect to the entire composition.