JP2013216649A - Water-in-oil emulsion composition having high internal water phase content - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-in-oil emulsion composition having good long-term stability and excellent moisturizing effect while being free from stickiness, and capable of giving a feeling of out-flowing water (a feeling of phase inversion) when applied, even though it includes 70-98 mass% of an aqueous component and has an average emulsion particle diameter of the internal water phase of 10-100 μm.SOLUTION: A water-in-oil emulsion composition includes following components (A)-(E): (A) 3,7,11,15-tetramethyl-1,2,3-hexadecane triol; (B) diglyceryl diisostearate; (C) a polyoxyethylene-methyl polysiloxane copolymer; (D) an aqueous component; and (E) an oily component. In the water-in-oil emulsion composition: the mass of the aqueous component (D) relative to the whole composition is 70-98 mass%; the average emulsion particle diameter of the internal water phase is 10-100 μm; and the total mass of the components (A), (B) and (C) relative to the whole composition is 0.07-0.9 mass%.

Description

  The present invention relates to a water-in-oil emulsion composition. More specifically, the present invention relates to improvement of the stability over time of a water-in-oil emulsion composition having a high inner aqueous phase and a large emulsion particle size.

  Keeping the skin moist and fresh is an important function expected for an emulsion composition for skin care. Among the emulsified compositions, an oil-in-water emulsified composition having an aqueous component as an outer phase (continuous phase) is excellent in the effect of imparting freshness to the skin, but is less likely to exhibit a moist feeling. On the other hand, a water-in-oil emulsion composition having an oily component as an outer phase (continuous phase) is excellent in the effect of moisturizing the skin, but tends to cause a sticky feeling, and has a problem that it is difficult to express freshness.

  Various attempts have been made to eliminate the sticky feeling of the water-in-oil emulsion composition by increasing the ratio of the aqueous component of the inner phase (= inner water phase ratio). The problem with this method is that the emulsification system becomes unstable as the internal water phase ratio increases. In particular, when the internal water phase ratio is 70% by mass or more, the emulsification stability rapidly decreases. Therefore, in the prior art, by devising the types of surfactant and emulsifier, a high internal water phase water-in-oil emulsion composition having good stability has been produced.

In Patent Document 1, a silicone oil component is emulsified by combining a specific polyether-modified silicone and a sucrose fatty acid ester of HLB 4 or less to produce a high internal water phase water-in-oil emulsion composition having good stability. ing. However, since the polyether silicone exhibits a behavior as a polymer surfactant, a sticky feeling due to entanglement of polymer chains has occurred.
Moreover, in patent document 2, stability is favorable although it is a high internal water phase by using the dimethylpolysiloxane polyoxyethylene copolymer which contains 5-30 weight% of polyoxyethylene groups in one molecule as an emulsifier. A water-in-oil emulsion composition is produced. However, in order to maintain the stability, it is necessary to mix saccharides and / or inorganic salts and polyhydric alcohol, which causes a problem that the raw materials are limited.
And in patent document 3, the high internal water phase water-in-oil type emulsified cosmetics with favorable stability are produced by using a dimethylpolysiloxane polyoxyalkylene copolymer and dextrin fatty acid ester for an emulsifier. However, in the composition, it is necessary to occupy 30% by mass or more of the oil phase with the chain silicone oil.
In Patent Document 4, high glycerin monooleate and 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (commonly used name phytantriol) as an emulsifier are combined to provide high stability. A water-in-oil emulsion composition is produced. However, when the ratio of the impurities (glycerin fatty acid diester and / or glycerin fatty acid triester) contained in the glyceryl monooleate is 25 mass or more, there is a problem that stability is lowered.
Patent Document 5 discloses a high internal water phase water-in-oil emulsion composition containing glyceryl isostearate and 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol. However, the composition needs to contain 30% by mass of isoparaffin having 20 or less carbon atoms in the oil component, and the amount of glyceryl monoisostearate mixed in the glyceryl isostearate is also limited.

  As described above, the conventional high internal water phase water-in-oil emulsion composition may remain sticky even if the problem of emulsion stability is improved (Patent Document 1), or the reaction contained in the surfactant and the emulsifier. There are influences of by-products (Patent Documents 4 and 5), restrictions on the type and amount of oil (Patent Documents 1, 3, and 5), or the necessity of adding other components (Patent Document 2). There wasn't. Furthermore, even if the sticky feeling was reduced, high freshness as in the oil-in-water emulsion composition was not exhibited.

  Therefore, by emulsifying the emulsified particles at the time of application and releasing the water of the inner phase onto the skin, an attempt to express a remarkable freshness that overflows water while being a water-in-oil emulsion composition. Has been done. Such a feeling of use is caused by a phase inversion from a water-in-oil type to an oil-in-water type, and thus is called a phase inversion feeling (or a feeling of overflowing water).

Patent Documents 6 to 8 show that a high internal water phase water-in-oil type emulsified cosmetic produced using a specific cross-linked polyether-modified silicone as a main emulsifier exhibits an excellent phase inversion feeling during application. Has been.
However, all of the crosslinked polyether-modified silicones are difficult to disperse, and it has been necessary to form a three-dimensional structure in advance by swelling and kneading in low-viscosity silicone oil. Furthermore, since the temporal stability is not sufficient (Patent Document 6), an aqueous thickener (carboxymethylcellulose salt) is added to stabilize the inner aqueous phase (Patent Document 7), or a phase inversion feeling is exhibited. In order to make this happen, a specific ester oil is essential (Patent Document 8).

  Thus, the expression of the phase inversion feeling can solve the above-mentioned problem of feeling of use (strength of stickiness and lack of freshness) associated with the water-in-oil emulsion composition. In addition to requiring a complicated process for the pre-treatment, the kind of oil that can be blended is limited.

JP 2001-89356 A Japanese Patent No. 2654960 Japanese Patent No. 2791677 Japanese Patent No. 4681439 Japanese Patent No. 4629799 Japanese Patent No. 3784914 Japanese Patent No. 4150280 JP 2001-2521 A JP 2011-21007 A

  As described above, the phase inversion feeling is a feeling of use that is expressed when the emulsified particles are rapidly disintegrated by a physical pressure generated during coating. In the water-in-oil type emulsion system, the higher the inner water phase ratio and the larger the emulsion particle diameter of the inner phase, the easier the coalescence and disintegration of the emulsion particles occur. Therefore, the higher the internal water phase and the larger the emulsified particle size, the more remarkable the phase inversion during coating.

  However, if the emulsified particles are coalesced or disintegrated before use and separated into an aqueous phase and an oil phase, it cannot be established as a commercial product. Therefore, in the conventional water-in-oil emulsion composition, when increasing the internal water phase ratio, the tendency to reduce the emulsion particle diameter of the internal water phase (preferably to 1 μm or less) was strong. There is also a report of a high inner water phase water-in-oil emulsion composition having an average emulsified particle size of 10 μm or more. In such a composition, the oil phase has high elasticity due to the incorporation of hydrophobic powder (preferably elastomer). It was given and could not express a phase inversion (Patent Document 9).

  Therefore, in order to produce a water-in-oil emulsion composition that is industrially useful and excellent in phase inversion, the emulsion particles in the inner aqueous phase are likely to coalesce and disintegrate (= low emulsion stability). However, it is necessary to control the emulsification stability exquisitely so that coalescence and destruction do not occur before use (= high stability over time).

  The present invention has solved the above-mentioned problems. Specifically, the inner aqueous phase ratio is 70 to 98% by mass and the inner aqueous phase has an emulsified particle diameter of 10 to 100 μm. An object of the present invention is to provide a water-in-oil emulsion composition that has good stability over time while having a prescription and form that easily breaks, and that the emulsified particles can be easily broken at the time of application and can exhibit a remarkable phase inversion. .

  As a result of intensive studies by the present inventors on the above-mentioned problems, 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, diglyceryl diisostearate, and polyoxyethylene / methylpolyethylene are used as emulsifiers. By using a siloxane copolymer in combination, even if the inner water phase ratio is 70 to 98% by mass and the average emulsified particle size of the inner water phase is 10 to 100 μm, the water-in-oil type has good stability over time. It has been found that an emulsified composition can be prepared. And the said water-in-oil emulsion composition does not have a sticky feeling, expresses an excellent phase inversion feeling at the time of application, and further finds that it has a moist feeling and an excellent moisturizing effect, thereby completing the present invention. It came to.

That is, the water-in-oil emulsion composition of the present invention includes the following components (A) to (E):
(A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (B) diglyceryl diisostearate (C) polyoxyethylene / methylpolysiloxane copolymer (D) aqueous component (E) The oil component is included, the total amount of the components (A) to (C) is 0.9% by mass or less with respect to the whole composition, and the mass of the component (D) is 70 to 98% by mass with respect to the whole composition. In addition, the average emulsified particle diameter is 10 to 100 μm.

  The water-in-oil emulsified composition according to the present invention has good stability over time, no stickiness, exhibits excellent phase inversion (= water overflow) at the time of application, and has a moist feeling. Excellent imparting and moisturizing effect.

It is a microscope picture which shows the emulsified particle diameter of the water-in-oil type emulsion composition (Example 12) of this invention.

<Constituents>
The water-in-oil emulsion composition according to the present invention comprises (A)-(E) as essential components. Hereinafter, each component will be described in detail.

[Component A: 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (common name: phytanetriol)]
3,7,11,15-tetramethyl-1,2,3-hexadecanetriol is a surfactant known by the common name of phytantriol. As a commercially available product, for example, “Phytantriol” manufactured by DSM Nutrition Japan Co., Ltd. can be used.
The blending amount of 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol is preferably 0.01 to 0.4% by mass, more preferably 0. 1 to 0.4% by mass, most preferably 0.3% by mass.

[Component B: Glyceryl diisostearate]
Examples of the glyceryl diisostearate used in the present invention include WOGEL-18DV (manufactured by Matsumoto Pharmaceutical Co., Ltd.).
The blending amount of glyceryl diisostearate 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 with respect to the entire composition. It is.

[Component C: Polyoxyethylene / methylpolysiloxane copolymer]
Examples of the polyoxyethylene / methylpolysiloxane copolymer used in the present invention include KF-6028 and KF6017P (both manufactured by Shin-Etsu Chemical Co., Ltd.).
The blending amount of the polyoxyethylene / methylpolysiloxane copolymer is preferably 0.05 to 0.3% by mass, more preferably 0.05 to 0.3% by mass, most preferably based on the entire composition. Preferably it is 0.1 mass%.

  In the components (A)-(C), the total amount of (A)-(C) is preferably 0.07-0.9% by mass or less, more preferably 0.4-0. 8 mass%, most preferably 0.7-0.8 mass%. If the amount is more than 0.9% by mass, a sticky feeling may be produced, and if it is less than 0.07% by mass, emulsification may be difficult.

[Component D: Aqueous component]
As the aqueous component (D) according to the present invention, an aqueous component that can be usually used for cosmetics and pharmaceuticals in addition to water can be used as long as the stability of the emulsion is not impaired. Examples of such aqueous components include alcohols, water-soluble polymers, humectants and the like.

  Examples of alcohols include ethanol, propanol, and isopropanol.

  Examples of water-soluble polymers include plant polymers such as gum arabic, carrageenan, pectin, agar, quince seed, and starch, microorganism polymers such as dextran and pullulan, carboxymethyl starch, and methylhydroxypropyl starch. Animal polymers such as starch polymers, collagen, casein, gelatin, starch polymers such as carboxymethyl starch and methylhydroxypropyl starch, alginic polymers such as sodium alginate, vinyl polymers such as carboxyvinyl polymer , Polyoxyethylene polymer, polyoxyethylene polyoxypropylene copolymer polymer, acrylic polymer such as sodium polyacrylate, polyacrylamide, bentonite, magnesium aluminum silicate, laponite It can be exemplified inorganic water-soluble polymers, and the like.

  Examples of the humectant include 1,3-butylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, xylitol, maltitol, maltose, D-mannitol, glucose, fructose, sodium chondroitin sulfate, Examples include sodium hyaluronate, sodium lactate, glucosamine, cyclodextrin and the like.

  The compounding quantity of the (D) aqueous component in the water-in-oil emulsion composition of the present invention is 70 to 98% by mass with respect to the entire composition. If it is less than 70% by mass, it is difficult to obtain excellent phase inversion, and if it exceeds 98% by mass, the stability over time is lowered and phase separation is likely to occur before use.

[Component E: Oily component]
As (E) oily component which concerns on this invention, the oily component which can be normally used for cosmetics and a pharmaceutical can be used in the range which does not impair the stability of an emulsion.

  Examples of liquid oily components include chain silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, and dodeca Examples include cyclic silicone oils such as methylcyclohexasiloxane.

  Solid oily components include cocoa butter, coconut oil, horse oil, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hardened castor oil, macadamia nut oil fatty acid phytosteryl, etc., paraffin wax (linear hydrocarbon) , Hydrocarbons such as microcrystalline wax (branched saturated hydrocarbon), ceresin wax, mole, montan wax, Fischer-Trops wax, beeswax, lanolin, carnauba wax, candelilla wax, rice bran wax (rice wax), gay wax, nukarou , Montan wax, capock wax, bayberry wax, shellac wax, sugarcane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, hard lanolin, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE choleste Ethers, lanolin fatty acid polyethylene glycol, waxes such as POE hydrogenated lanolin alcohol, higher fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, and higher grades such as cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, cetostearyl alcohol Alcohol etc. are mentioned.

  Further, as polar oils, 2-ethylhexanoic acid, glyceryl triisostearate, isodecyl neopentanoate, tripropylene glycol pivalate, di-N-lauroyl-L-glutamate (phytosteryl 2-octyldodecyl, glyceryl tri-2-ethylhexanoate) , Tetra-2-ethylhexanoic acid pentaerythritol, tetra (behenic acid / benzoic acid / ethylhexanoic acid) pentaerythritol, tri (caprylic / capric acid) glyceryl, diisostearyl malate, macadamia nut oil, polyglyceryl triisostearate 2, Ethylhexyl ethylhexanoate, ethylhexyl palmitate, cetyl octanoate, hexyl laurate, isopropyl myristate, octyl palmitate, isocetyl stearate, isostearic acid An ester oil typified by sopropyl, octyl isopalmitate, isodecyl isostearate, 2-ethylhexyl succinate, diethyl sebacate and the like, jojoba oil, meadowfoam oil, isostearic acid and the like can be blended.

  Furthermore, hydrocarbon oils such as liquid paraffin, squalane, squalene, paraffin, isoparaffin, heavy liquid isoparaffin, isododecane, isohexadecane, and olefin oligomer can be blended as the nonpolar oil.

  The compounding quantity of the (E) oil-based component in the water-in-oil type emulsion composition of this invention is 1.1-29.93% by mass with respect to the whole composition, Preferably it is 7-20 mass%. If the blending amount of the oil component is less than 1.1% by mass, the moist feeling and the moisturizing effect may be inferior, and if it exceeds 29.93% by mass, a sticky feeling is generated and the phase inversion feeling is also inferior.

  In the water-in-oil emulsion composition of the present invention, in addition to the components (A) to (D), the water-in-oil emulsion composition for cosmetics and pharmaceuticals is usually used within the range not impairing the effects of the present invention. The other components used in can be blended. Examples of such components include UV protection agents, sequestering agents, antioxidants, preservatives, thickeners, fragrances, powders, coloring materials, herbal medicines, and other various medicinal ingredients as needed. can do.

Examples of UV protection agents include, for example, benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic acid UV absorbers such as methyl anthranilate, salicylic acid UV absorbers such as octyl salicylate, isopropyl paramethoxycinnamate, Cinnamic acid UV absorbers such as octyl paramethoxycinnamate, UV absorbers such as urocanic acid and ethyl urocanate, benzophenone UV absorbers such as 2-hydroxy-4-methoxybenzophenone and dihydroxybenzophenone, benzotriazole Examples include ultraviolet absorbers and ultraviolet absorbers such as 2-phenylbenzimidazole-5-sulfonic acid.
Examples of the sequestering agent include sodium edetate and sodium metaphosphate.

Examples of the antioxidant include ascorbic acid, α-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like.
Examples of preservatives include benzoic acid, salicylic acid, paraoxybenzoic acid esters (methylparapene, ethylparaben, butylparaben, etc.), sorbic acid, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, Examples thereof include trichlorocarbanilide, photosensitizer, phenoxyethanol and the like.

  Examples of the powder include mica, talc, kaolin, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, lithia mica, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silica. Acid (silica), aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, aluminum oxide, barium sulfate, bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide , Zinc oxide, mica titanium (titanium oxide coated mica), fish phosphorus foil, bismuth oxychloride, boron nitride, red 228, red 226, blue 404, polyethylene powder, polymethyl methacrylate powder, polyamide resin powder (nylon Powder), cellulose powder, organopolysiloxane elastomer, aluminum Umm powder, mention may be made of copper powder and the like.

Examples of the medicinal component include vitamin A oil, retinol, retinol palmitate, pyridoxine hydrochloride, benzyl nicotinate, nicotinic acid amide, nicotinic acid dl-α-tocopherol, magnesium ascorbate phosphate, vitamin D ₂ , dl- Vitamins such as α-tocopherol, pantothenic acid and biotin; anti-inflammatory agents such as azulene and glycyrrhizin; whitening agents such as arbutin, 4-methoxysalicylic acid, tranexamic acid, ethylvitamin C and magnesium ascorbate phosphate, and hormones such as estradiol Astringents such as zinc oxide and tannic acid; refreshing agents such as L-menthol and camphor; and other lysozyme chloride, pyridoxine hydrochloride, sulfur and the like. Furthermore, various extracts showing various medicinal effects can be blended.

  The said component is an illustration and is not limited to these. Further, these components can be appropriately combined and blended in accordance with a prescription according to a desired form.

<Manufacturing method>
As a method for producing a water-in-oil emulsion composition according to the present invention, first, an oil phase component (components (A)-(C), (E), and other hydrophobic components) and an aqueous phase component (component ( D) and other hydrophilic components) are heated and mixed to prepare a uniform mixture. Next, in a state where the mixture of oil phase components is stirred using a stirring and mixing device, the mixture of water phase components is gradually added to the mixture of oil phase components and emulsified (= emulsification step). The water-in-oil emulsion composition of the present invention can be obtained.

  The emulsified particle diameter in the water-in-oil emulsion composition of the present invention can be controlled by various methods, but the most general and preferable method is a method of controlling by the stirring conditions in the emulsification step. Generally, the larger the number of rotations of the stirring and mixing apparatus used in the emulsification step and the longer the stirring time, the greater the load due to shearing, collision, and cavitation, so that the formed emulsified particles become finer. Therefore, the emulsified particle size of the water-in-oil emulsion composition according to the present invention is controlled to the target particle size range by complexly adjusting the agitation conditions such as the type of agitation / mixing device, its rotation speed, and agitation time. can do.

Examples of the stirring and mixing device used in the stirring and mixing include, for example, a high-speed emulsifying device such as a homodisper, a homomixer, a homogenizer, and a microfluidizer, a dispermixer including a sawtooth stirring blade, and an impeller type including a rotating blade. A stirrer etc. are mentioned. Although any of the stirring and mixing devices can be used to produce a water-in-oil emulsion composition having an emulsified particle size specified in the present invention, it is particularly preferable to use a high-speed emulsification device represented by homodispers.
In the examples of the present application, water-in-oil emulsification with an average emulsified particle size of 10 to 20 μm is performed by stirring for 30 to 180 seconds at a rotation speed of 3000 to 6000 rpm using a homodisper (manufactured by PRIMIX Corporation). The composition was adjusted.

<Emulsified particle size>
The emulsion particle diameter in the water-in-oil emulsion composition of the present invention, that is, the particle diameter of water droplets dispersed in the oil phase is 10 to 100 μm, preferably 10 to 30 μm, and most preferably 20 μm. If the emulsified particle size is less than 10 μm, an excellent phase inversion may not be obtained. Moreover, when an emulsified particle diameter exceeds 100 micrometers, the temporal stability of the said emulsion composition will become low and may not be suitable as a product.
The term “emulsified particle size” used in the present application is a measurement of the particle size of about 100 emulsified particles arbitrarily selected in the micrograph of the emulsified composition, and the emulsified particles obtained from the measured values. Represents the average diameter.

The water-in-oil emulsion composition according to the present invention can be widely applied to cosmetics, pharmaceuticals, and quasi drugs, but is particularly suitable for cosmetics. Examples of application to cosmetics include cosmetic liquids, milky lotions, creams, foundations, eye shadows, eyeliners, mascaras, and other application examples include skin external ointments.
These products can be manufactured according to conventional methods, but the present invention is not limited to these products.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Further, the blending amount is expressed in mass% unless otherwise specified.

<Evaluation criteria>
The compositions prepared in the examples were evaluated for stability over time and feeling of use according to the following criteria.
Time stability The water-in-oil emulsion composition was allowed to stand at 0 ° C. or 25 ° C. for 4 weeks, and then the stability was visually evaluated based on the following criteria.
◎: No oil droplets or separation confirmed ○: Oil droplet confirmed △: Confirmed separation ×: Confirmed separation within 30 minutes after production
Phase inversion feeling at the time of phase inversion sense applied for (= overflowing feeling of water), asked to apply the sample to the face in 10 professional panelists, were asked to evaluate the feeling of use in accordance with the following criteria.
A: Nine or more panelists answered that there was a phase inversion feeling during application.
○: 7 or more and less than 9 panelists answered that there was a phase inversion feeling during application.
Δ: 5 or more and less than 7 panelists answered that there was a phase inversion during coating.
X: Less than 5 panelists answered that there was a phase inversion feeling during application.
No sticky feeling Regarding the lack of sticky feeling during use, 10 professional panels applied samples to the face, and evaluated the feeling of use according to the following criteria.
A: Nine or more panelists answered that there was no stickiness during use.
○: 7 or more and less than 9 panelists answered that there was no stickiness during use.
Δ: 5 or more and less than 7 panelists answered that there was no stickiness during use.
×: Less than 5 panelists answered that there was no stickiness during use.
Moist for moist feeling of the skin of the light-sensitive use, asked to apply the sample to the face in 10 professional panelists, were asked to evaluate the feeling of use in accordance with the following criteria.
A: Nine or more panelists answered that the skin was moist during use.
○: 7 or more and less than 9 panelists answered that the skin was moist during use.
Δ: 5 or more and less than 7 panelists answered that the skin was moist during use.
X: Less than 5 panelists answered that the skin was moist during use.
The moisturizing effect of the skin in a moisturizing effect use, asked to apply the sample to the face in 10 professional panelists, were asked to evaluate the feeling of use in accordance with the following criteria.
A: Nine or more panelists answered that there was a moisturizing effect during use.
○: 7 or more and less than 9 panelists answered that there was a moisturizing effect during use.
Δ: 5 or more and less than 7 panelists answered that there was a moisturizing effect during use.
X: Less than 5 panelists answered that there was a moisturizing effect during use.

In the examples, the following products were used.
* 1: Synthelan 4 (Nikko Chemicals)
* 2: NIKKOL CIO (manufactured by Nikko Chemicals Co., Ltd.)
* 3: RA-G-308 (Nippon Seika Co., Ltd.)
* 4: PE-MC wax (manufactured by Nikko Rica Corporation)
* 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 (DSM Nutrition Japan Co., Ltd.)
* 8: Sunsoft O-30S (manufactured by Taiyo Chemical Co., Ltd.)
* 9: WOGEL-18DV (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: Mixture of poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer (50%) and light liquid isoparaffin (50%) * 14: ABIL EM90 (manufactured by Degussa)

<Measurement of emulsion particle size>
In order to make it easy to distinguish the outline of each emulsified particle, the emulsion composition is diluted with cetyl 2-ethylhexanoate (Nikko Chemicals) and then photographed using a microscope (BX51, Olympus). I took a picture. FIG. 1 shows a part of a photograph taken for Example 12 (emulsified particle size = 15 μm). The particle diameter of about 100 emulsified particles arbitrarily selected on the photograph thus obtained was measured, and an average value was calculated.

[Test Example 1]
High internal water phase water-in-oil emulsion compositions were prepared according to the formulations shown in Table 1, and the stability over time and the feeling in use were evaluated.

Formulated with (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) glyceryl diisostearate, and (C) polyoxyethylene / methylpolysiloxane copolymer as surfactants In addition, the composition (Example 1-5) containing (D) an aqueous component and (E) an oil component is excellent in stability over time, has no stickiness, and exhibits a noticeable phase inversion during coating. In addition, the skin was moist and moisturized. On the other hand, the composition of Comparative Example 1-3 lacking even one of the surfactants (A) to (C) cannot form a stable emulsification system and causes phase separation. It was. Further, (D) the composition of Comparative Example 4 not containing an aqueous component (= the composition of Example 1 excluding component (D)), or (E) the composition of Comparative Example 5 not containing an oily component. (= Excluding component (E) from the composition of Example 1 and making up with purified water), an emulsification system could not be formed (Comparative Examples 4 and 5).
Therefore, (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) glyceryl diisostearate, and (C) a polyoxyethylene / methylpolysiloxane copolymer are combined ( D) A water-in-oil type that is excellent in stability over time and phase inversion, without stickiness, and also has a moisturizing effect and moisturizing effect when emulsified with an aqueous component and (E) an oil component. It became clear that an emulsified composition could be prepared.

As described above, a water-in-oil emulsion composition in which 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (component (A) of the present invention) and glyceryl monooleate are combined as an emulsifier. In the product, when the ratio of the glycerin fatty acid diester and / or the glycerin fatty acid triester contained in the monooleic acid glycerin is 25% or more, there is a problem that the stability is poor (Patent Document 4). However, even when the composition of Example 1 of the present application was mixed with glyceryl monooleate containing 55% by mass of glycerin dioleate and glyceryl trioleate, the stability was not impaired (Example 4).
In addition, in a composition using a dimethylpolysiloxane polyoxyethylene copolymer containing 5 to 30% by weight of a polyoxyethylene group in one molecule as an emulsifier, saccharides and / or inorganic salts are used to maintain the emulsion stability. The blending of the polyhydric alcohol was indispensable (Patent Document 2), but even if the polyhydric alcohol was excluded from the composition of Example 2 of the present application, no effect on the stability was observed (Example 5). .
Further, the composition of the present invention (Example 1-6) was prepared in the same manner as in Patent Documents 6-8 by using a crosslinked polyether-modified silicone (methylphenylpolysiloxane crosslinked methylphenylpolysiloxane; diphenylsiloxyphenyltrimethicone (about 84). %) And (dimethicone / phenylvinyldimethicone) cross-polymer (about 16% by mass) as an emulsifier, the stability is remarkably higher, and in addition, a phase inversion feeling is obtained. It became clear that it was even better.
In the compositions of Patent Documents 1, 3, and 6-8, it is essential to add silicone oil. However, even in the composition of Example 6 of the present invention that does not contain silicone oil, excellent stability over time and usability are obtained. It has been.
Therefore, the present invention does not require a complicated pretreatment step of the emulsifier, and further, it is possible to achieve both excellent phase inversion and good stability over time without limiting the type of oil. It was done.

[Test Example 2]
Next, the influence of the internal water phase ratio on the stability over time and the feeling in use was examined.

In the composition (Example 7-10) containing all the components (A)-(E) of the present application and having an internal water phase ratio of 70-97.9% by mass (Example 7-10), the effects of the present invention (good stability with time, stickiness) It can be seen that there is no sense of sensation, and excellent moisturizing effect, moist feeling, and phase inversion feeling are all manifested. In particular, the composition of Example 10 is stable over time at both a high temperature (50 ° C.) and a constant temperature (0 ° C.) despite the extremely high internal water phase with an internal water phase ratio of 97.9%. It was confirmed to be good.
On the other hand, in the composition having an inner water phase ratio of 49% by mass (Comparative Example 7), the stability over time was good but the feeling of stickiness was reduced, and the result was inferior to the phase inversion. In the water-in-oil emulsion composition of the invention, the internal water phase ratio is preferably in the range of 70-98% by mass, more preferably 80-95% by mass, and most preferably 85-90% by mass. I can say that.

[Test Example 3]
As described above, in a high inner water phase water-in-oil emulsification system, the larger the emulsion particle size of the inner phase, the better the phase inversion feeling, but there is a concern that the stability over time is lowered. Then, the internal water phase ratio was fixed to a high internal water phase state of about 86% by mass in the emulsified composition of the present application, and the influence of the emulsified particle size of the internal phase on the stability over time and the phase inversion was examined.

  Formulated with (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) glyceryl diisostearate, and (C) polyoxyethylene / methylpolysiloxane copolymer as surfactants In the composition, the stability over time was good in the range of the emulsified particle diameter of 1 to 100 μm (Comparative Examples 8, 9 and Examples 11-14). Among these, the emulsified particle diameter was excellent also in the phase inversion feeling. Was a composition of 10-100 μm (Examples 11-14). Therefore, in the high inner water phase water-in-oil type emulsion composition of the present invention, good stability over time is obtained by setting the emulsion particle size of the inner phase to 10-100 μm, preferably 10-30 μm, and most preferably 20 μm. As a result, it was clarified that both a remarkable phase inversion feeling can be realized.

  On the other hand, any or all of the surfactants (A) to (C) were replaced with poly (oxyethylene / oxypropylene) methylpolysiloxane or cetyl dimethicone copolyol, which are general-purpose lipophilic surfactants. In the composition, in any emulsified particle size of 1 to 100 μm, no result was obtained in which both the stability over time and the phase inversion feeling were good (Comparative Example 10-15). The composition with an average emulsified particle size of 1 μm (Comparative Example 10) and 3 μm (Comparative Example 11) has good stability over time but no phase inversion feeling, and 10 μm (Comparative Example 12) and 15 μm (Comparative Example 13). Although a phase inversion feeling was obtained with the composition, the stability over time was inferior. Furthermore, with the compositions of 30 μm (Comparative Example 14) and 100 μm (Comparative Example 15), an emulsion system could not be formed and phase separation occurred.

As described above, in the conventional high inner water phase water-in-oil type emulsion system, when the emulsion particle diameter is 10 μm or more, the emulsion particles are likely to coalesce or collapse, and this tendency becomes more prominent as the emulsion particle diameter increases. It becomes. On the other hand, in the high inner water phase water-in-oil type emulsion system prepared using the components (A) to (C) of the present application, the emulsion particle size is more stable with time in the 10-30 μm system than in the 1-3 μm system. The result was excellent.
Therefore, the combination of (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) glyceryl diisostearate, and (C) a polyoxyethylene-methylpolysiloxane copolymer is It was revealed that the emulsion particles having a low curvature of the interface film (= specifically, emulsion particles having a particle diameter of 10 to 100 μm) are very suitable for stabilization.

[Test Example 4]
Next, the amount of components (A)-(C) was examined.

(A)-(C) total is 0.45 mass% (Example 15), 0.75 mass% (Example 16), 0.8 mass% (Example 17), 0.85 mass% (implementation) The composition of Example 18) was excellent in stability with time and phase inversion, without stickiness, and also with a moist feeling and a moisturizing effect. On the other hand, in the composition (Comparative Example 16) in which the sum of (A)-(C) is 0.95% by mass, a decrease in phase inversion feeling was observed. Therefore, in order to produce a high internal water phase water-in-oil emulsion composition having excellent phase inversion and no stickiness, the total amount of (A)-(C) is 0. It can be seen that the content may be 07-0.9 mass%, more preferably 0.4-0.8 mass%, and most preferably 0.7-0.8 mass%.
If the sum of (A)-(C) is within the above range, each blending amount of (A), (B), (C) may be set to any value, but preferably (A) is 0. 0.01-0.4 mass%, (B) is 0.01-0.7 mass%, (C) is 0.05-0.3 mass%, and more preferably (A) is 0.1- 0.4 mass%, (B) is 0.2-0.6 mass%, (C) is 0.05-0.3 mass%, most preferably (A) is 0.3 mass%, (B) is 0.4 mass% and (C) is 0.1 mass%.

[Test Example 5]

Table 5 shows the results of examining the blending amounts of the low-viscosity silicone oil and the olefin oligomer in the composition of the present application.
Low viscosity (kinematic viscosity at 25 ° C. of 3 centistokes (cs) or less) Silicone oil in the oil phase 7.2 mass% (Example 19), 8.0 mass% (Example 20), or 14.8 When a composition containing% by mass (Example 21) was prepared, all had excellent effects (phase inversion, no stickiness, moist feeling, and moisturizing effect) of the present invention, and the stability over time was also good. It was. Moreover, in any composition containing 0.5 mass% (Example 19), 18.5 mass% (Example 21), and 20.0 mass% (Example 20) of an olefin oligomer in an oil phase, it is excellent. Effect and good stability over time.
Therefore, the composition of the present invention is different from conventional water-in-oil type emulsion compositions that require the blending of silicone oil and specific hydrocarbon oil (Patent Documents 1, 3, 5-8), and silicone oil. Even if the oil phase is 10% by mass or less of the oil phase and / or the olefin oligomer is 1% by mass or more of the oil phase, the effect (phase inversion, no stickiness, moist and moisturizing effect) and stability over time It has been shown that is not compromised.

  In Table 5, the results of the composition of Example 20 are more excellent in the temporal stability than the compositions of Examples 19 and 21. Therefore, in the composition according to the present invention, silicone oil and olefin oligomer having a kinematic viscosity of 3 centistokes (cs) or less are less than 10% by mass (the silicone oil) and 1% by mass or more (olefin) in the oil phase, respectively. Oligomer), more preferably 6-9 mass% (the silicone oil) and 15-20 mass (olefin oligomer), it is considered that the stability over time is further increased.

  In Table 5, the results of the composition of Example 20 are more excellent in the temporal stability than the compositions of Examples 19 and 21. Therefore, in the composition according to the present invention, silicone oil and olefin oligomer having a kinematic viscosity of 3 centistokes (cs) or less are less than 10% by mass (the silicone oil) and 1% by mass or more (olefin) in the oil phase, respectively. Oligomer), more preferably 6-9 mass% (the silicone oil) and 15-20 mass (olefin oligomer), it is considered that the stability over time is further increased.

  Below, the formulation example of the water-in-oil type emulsion composition which concerns on this invention is shown. In any composition, good aging stability and excellent phase inversion feeling were exhibited, there was no stickiness, and the moisturizing effect and moisturizing effect were also excellent.

[Prescription Example 1: Cream]
<Prescription>
Ingredient Amount (% by mass)
(1) Olefin oligomer (* 1) 2.5
(2) Cetyl 2-ethylhexanoate (* 2) 4.0
(3) Vaseline 2.0
(4) 80% polyethylene wax / 20% microcrystalline wax mixture (* 4) 1.0
(5) Isohexadecane 2.0
(6) Decamethyltetrasiloxane (* 5) 1.0
(7) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (* 7) 0.3
(8) Diglyceryl diisostearate (* 9) 0.4
(9) Polyoxyethylene / methylpolysiloxane copolymer (* 11)
0.1
(10) Glycerin 5.0
(11) Dipropylene glycol 3.0
(12) Methylparaben 0.1
(13) Sodium chloride 1.0
(14) Purified water residue <Production method>
In the above formulation, the oil phase components (1) to (9) are heated and mixed at 80 ° C., and the mixture (room temperature) of the water phase components (10) to (14) is gradually added while stirring with a homodisper. It was adjusted.

[Prescription Example 2: Cosmetic liquid]
<Prescription>
Ingredient Amount (% by mass)
(1) Olefin oligomer (* 1) 1.0
(2) Glyceryl tri-2-ethylhexanoate (* 3) 2.0
(3) Dimethylpolysiloxane (* 6) 2.0
(4) Isododecane 2.0
(5) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (* 7) 0.3
(6) Diglyceryl diisostearate (* 9) 0.45
(7) Polyoxyethylene / methylpolysiloxane copolymer (* 11)
0.05
(8) Glycerin 7.0
(9) 1,3-butylene glycol 4.0
(10) Dipropylene glycol 3.0
(11) Polyethylene glycol 6000 1.0
(12) Carboxymethylcellulose 0.3
(Serogen F-SR, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(13) Phenoxyethanol 0.35
(14) Sodium chloride 1.0
(15) Citric acid 0.02
(16) Na citrate 0.08
(17) Citric acid 3Na 0.03
(18) Fragrance 0.1
(19) Purified water residue <Production method>
In the above formulation, the oil phase components (1) to (7) were mixed, and the mixture (room temperature) of the water phase components (8) to (19) was gradually added while stirring with a homodisper.

[Prescription Example 3: Whitening Cream]
<Prescription>
Ingredient Amount (% by mass)
(1) Olefin oligomer (* 1) 2.0
(2) Cetyl 2-ethylhexanoate (* 2) 2.0
(3) Dimethylpolysiloxane (* 6) 2.0
(4) Isodecyl pivalate 2.0
(5) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (* 7) 0.3
(6) Diglyceryl diisostearate (* 9) 0.3
(7) Polyoxyethylene / methylpolysiloxane copolymer (* 10)
0.1
(8) Deodorized polybutene-P (manufactured by Nikko Rica Corporation) 2.0
(9) Glycerin triisostearate 1.0
(San Spaul GTI (S), Taiyo Kagaku Co., Ltd.)
(10) Tranexamic acid 2.0
(11) Carboxymethylcellulose 0.2
(Serogen F-SR, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(12) Sodium pyrosulfite 0.01
(13) EPI ocher # 1P 0.0005
(14) Fragrance 0.05
(15) Phenoxyethanol 0.35
(16) Sodium chloride 1.0
(17) Citric acid 0.02
(18) Na citrate 0.08
(19) Citric acid 3Na 0.03
(20) Purified water residue <Production method>
In the above formulation, the oil phase components (1) to (9) were mixed, and the mixture (room temperature) of the water phase components (10) to (20) was gradually added while stirring with a homodisper.

[Prescription Example 4: Cream]
<Prescription>
Ingredient Amount (% by mass)
(1) Coco Alkane 7.5
(VEGELIGHT 1214, manufactured by BIOSYNISH)
(2) Caprylic acid palm oil alkyl 2.0
(CETIOL C5, manufactured by BASF)
(3) (Caprylic acid / Capric acid) Caprylyl 2.0
(CETIOL RLF, manufactured by BASF)
(4) Purified murmuru butter 2.0
(Refined Murmur Butter, manufactured by Koei Kogyo Co., Ltd.)
(5) Partially hydrogenated jojoba oil 1.0
(Hoba Cream M-40, manufactured by Koei Kogyo Co., Ltd.)
(6) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (* 7) 0.3
(7) Diglyceryl diisostearate (* 9) 0.4
(8) Polyoxyethylene / methylpolysiloxane copolymer (* 11)
0.1
(9) Glycerin 5.0
(10) Dipropylene glycol 3.0
(11) Methylparaben 0.1
(12) Sodium glutamate 1.0
(13) Perfume appropriate amount (14) Purified water Residue <Production method>
In the above formulation, the oil phase component (1)-(8) is heated and mixed at 80 ° C., and the mixture (room temperature) of the water phase component (9)-(14) is gradually added while stirring with a homodisper. It was adjusted.

[Component B: Diglyceryl diisostearate ]
As a diglyceryl diisostearate used for this invention, WOGEL-18DV (made by Matsumoto Pharmaceutical Co., Ltd.) etc. are mentioned as an example.
The amount of diglyceryl diisostearate 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 with respect to the entire composition. %.

(A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) diglyceryl diisostearate , and (C) a polyoxyethylene / methylpolysiloxane copolymer as surfactants The composition (Example 1-5) containing (D) an aqueous component and (E) an oily component is excellent in stability over time, has no stickiness, and exhibits a noticeable phase inversion during coating. Was excellent in moisturizing skin and moisturizing effect. On the other hand, the composition of Comparative Example 1-3 lacking even one of the surfactants (A) to (C) cannot form a stable emulsification system and causes phase separation. It was. Further, (D) the composition of Comparative Example 4 not containing an aqueous component (= the composition of Example 1 excluding component (D)), or (E) the composition of Comparative Example 5 not containing an oily component. (= Excluding component (E) from the composition of Example 1 and making up with purified water), an emulsification system could not be formed (Comparative Examples 4 and 5).
Therefore, (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) diglyceryl diisostearate , and (C) a polyoxyethylene / methylpolysiloxane copolymer are combined. Water emulsification of (D) aqueous component and (E) oily component is excellent in stability over time and phase inversion, without stickiness, and also has excellent moisturizing effect and moisturizing effect It was revealed that a mold emulsion composition can be prepared.

(A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) diglyceryl diisostearate , and (C) a polyoxyethylene / methylpolysiloxane copolymer as surfactants In the blended composition, the stability over time is good when the emulsified particle diameter is in the range of 1-100 μm (Comparative Examples 8, 9, and Examples 11-14). Among these, the emulsified particles are also excellent in phase inversion feeling. The composition had a diameter of 10-100 μm (Examples 11-14). Therefore, in the high inner water phase water-in-oil type emulsion composition of the present invention, good stability over time is obtained by setting the emulsion particle size of the inner phase to 10-100 μm, preferably 10-30 μm, and most preferably 20 μm. As a result, it was clarified that both a remarkable phase inversion feeling can be realized.

As described above, in the conventional high inner water phase water-in-oil type emulsion system, when the emulsion particle diameter is 10 μm or more, the emulsion particles are likely to coalesce or collapse, and this tendency becomes more prominent as the emulsion particle diameter increases. It becomes. On the other hand, in the high inner water phase water-in-oil type emulsion system prepared using the components (A) to (C) of the present application, the emulsion particle size is more stable with time in the 10-30 μm system than in the 1-3 μm system. The result was excellent.
Therefore, the combination of (A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol, (B) diglyceryl diisostearate , and (C) a polyoxyethylene-methylpolysiloxane copolymer is It was revealed that the emulsion particles having a low curvature of the interface film (= specifically, emulsion particles having a particle diameter of 10 to 100 μm) are very suitable for stabilization.

Claims (1)

The following components (A) to (E):
(A) 3,7,11,15-tetramethyl-1,2,3-hexadecanetriol (B) diglyceryl diisostearate (C) polyoxyethylene / methylpolysiloxane copolymer (D) aqueous component (E) Contains oily ingredients,
The mass of the aqueous component of component (D) is 70-98% by mass relative to the entire composition,
The average emulsified particle size of the inner aqueous phase is 10-100 μm, and
The total amount of components (A), (B), (C) is 0.07-0.9 mass% with respect to the entire composition;
A water-in-oil emulsion composition characterized by the above.