WO2020138420A1 - Water-in-oil emulsion composition containing nicotinamide - Google Patents

Abstract

Provided is a water-in-oil emulsion composition having an excellent feel on use. A water-in-oil emulsion composition containing (A) 3 mass% or more of nicotinamide; (B) one or more surfactants selected from the group consisting of silicone-based surfactants, sorbitan ester surfactants, polyglycerin ester surfactants, and glycerin ester surfactants; and (C) one or more oil-soluble thickeners selected from the group consisting of clay-based thickeners, dextrin fatty acid esters, inulin fatty acid esters, and amino acid-based oil gelling agents is prepared.

Description

Water-in-oil emulsion composition containing nicotinamide

The present invention relates to a water-in-oil emulsion composition containing nicotinic acid amide.

Nicotinic acid amide is one of the vitamins, and has been used as a component for promoting blood circulation, anti-inflammation, ceramide synthesis promotion, etc. in the skin care area, and as a whitening, anti-wrinkle and anti-aging agent. It is known that it also has an effect (for example, patent document 1).

An oil-in-water emulsion composition containing nicotinic acid amide, a specific active agent, and petrolatum has been proposed (Patent Document 2).

JP-A-2004-217629 Japanese Patent Laid-Open No. 2018-172304

On the other hand, the water-in-oil composition has excellent properties such as high moisture retention and water resistance, but on the other hand, it is difficult to impart sufficient stability due to problems such as easy separation, and the oil-in-water composition There are many formulation issues when compared to the product.

An object of the present invention is to provide a water-in-oil type emulsion composition containing a high concentration of nicotinic acid amide, which has good stability and usability.

As a result of repeated intensive studies to solve this problem, the present inventors have found that in the present invention,
(A) Nicotinic acid amide;
A water-in-oil type emulsion composition having an excellent feeling in use and excellent stability by using a water-in-oil type emulsion composition containing (B) a specific surfactant; and (C) an oil-soluble thickener. The present invention has been completed and the present invention has been completed.

That is, the present invention provides the following water-in-oil emulsion compositions.
Item 1.
(A) Nicotinic acid amide 3% by mass or more;
(B) one or more surfactants selected from the group consisting of silicone-based surfactants, sorbitan ester surfactants, polyglycerin ester surfactants, and glycerin ester surfactants; and (C) A water-in-oil emulsion composition containing an oil-soluble thickener, which is one or more selected from the group consisting of clay-based thickeners, dextrin fatty acid esters, inulin fatty acid esters, and amino acid-based oil gelling agents.
Item 2.
Item 2. The water-in-oil emulsion composition according to Item 1, wherein the content of the component (A) is 3 to 10% by mass.
Item 3.
The component (B) is PEG-10 dimethicone, PEG-3 dimethicone, PEG-12 dimethicone, PEG/PPG-19/19 dimethicone, polysilicone 13, PEG-9 polydimethylsiloxyethyl dimethicone, methylpolysiloxane cetylmethyl. Polysiloxane/poly(oxyethylene/oxypropylene)methyl polysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, bisbutyl dimethicone polyglyceryl-3, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, polyglyceryl-3 disiloxane dimethicone , Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, sorbitan oleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan sesquiisostearate, sorbitan isostearate, sorbitan tristearate, sorbitan sesquistearate, tristearin Acid sorbitan, polyglyceryl triisostearate-2, polyglyceryl isostearate-2, polyglyceryl-10 condensed ricinoleate, polyglyceryl-10 pentaisostearate, polyglyceryl pentaoleate-10, polyglyceryl pentastearate-10, polyglyceryl pentahydroxystearate- 10, condensed polyglyceryl-6 ricinoleate, polyglyceryl pentaisostearate-6, polyglyceryl pentaoleate-6, polyglyceryl pentahydroxystearate-6, glyceryl oleate, glyceryl sesquioleate, glyceryl trioleate, glyceryl sesquiisostearate, Item 3. The water-in-oil emulsion composition according to Item 1 or 2, which is one or more selected from the group consisting of glyceryl isostearate, glyceryl triisostearate, glyceryl stearate, glyceryl sesquistearate, and glyceryl tristearate.
Item 4.
The component (C) is dimethyl distearyl ammonium hectorite, benzyl dimethyl stearyl ammonium hectorite, distearyl dimethyl ammonium chloride treated aluminum magnesium silicate, dextrin palmitate, dextrin oleate, dextrin stearate, dextrin myristate, (palmitin. (Acid/ethylhexanoic acid) dextrin, (palmitic acid/hexyldecanoic acid) dextrin, and at least one member selected from the group consisting of inulin stearate, dibutyllauroylglutamide, and dibutylethylhexanoylglutamide. The water-in-oil emulsion composition according to any one of 1.
Item 5.
The water-in-oil emulsion composition according to any one of Items 1 to 4, further comprising (D) an ultraviolet absorber.
Item 6.
Item 6. The water-in-oil emulsion composition according to Item 5, wherein the total content of the component (D) is 20% by mass or less.
Item 7.
7. The water-in-oil emulsion composition according to any one of Items 1 to 6, further comprising (E) an ultraviolet protective agent.
Item 8.
The component (B) is two or more kinds of surfactants selected from the group consisting of silicone-based surfactants, sorbitan ester surfactants, polyglycerin ester surfactants, and glycerin ester surfactants. The water-in-oil emulsion composition according to any one of 1 to 7.
Item 9.
Item 8. The water-in-oil emulsion composition according to any one of Items 1 to 7, wherein the component (B) is a combination of at least two kinds of surfactants selected from silicone-based surfactants.
Item 10
The component (B) is one or more kinds of surfactants selected from (B)-1 component silicone surfactant, and (B)-2 component sorbitan stearate, sorbitan isostearate, sorbitan sesquiisostearate, Sorbitan oleate, sorbitan sesquioleate, glyceryl stearate, glyceryl sesquistearate, glyceryl isostearate, glyceryl sesquiisostearate, glyceryl oleate, glyceryl sesquioleate, polyglyceryl-10 pentastearate, polyglyceryl pentaisostearate-10, Item 8. A water-in-oil emulsion according to any one of items 1 to 7, which is a combination of one or more surfactants selected from the group consisting of polyglyceryl-10 pentahydroxystearate and polyglyceryl pentaoleate-10. Composition.
Item 11.
The (D) UV absorber is a salicylic acid-based UV absorber, a cinnamic acid-based UV absorber, a benzoylmethane-based UV absorber, a benzoate derivative UV absorber, a triazine derivative UV absorber, or a benzalmalonate derivative UV absorber. Item 11. Water-in-oil according to any one of Items 1 to 10, which is one or more selected from the group consisting of an agent, an octocrylene-based ultraviolet absorber, an imidazolesulfonic acid derivative ultraviolet absorber, and a benzophenone derivative ultraviolet absorber. Emulsion composition.
Item 12.
The ultraviolet absorber (D) is 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-4′-methoxydibenzoylmethane, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4,6-tris[ Item 1 to 11, which is one or more selected from the group consisting of 4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine and 2-phenylbenzimidazole-5-sulfonic acid. The water-in-oil emulsion composition according to any one of claims 1 to 5.

The present invention can provide a water-in-oil emulsion composition having excellent stability.

In the present specification, the unit "mass%" of the content is synonymous with "g/100g".

Formulations containing a high concentration of nicotinamide having various effects are very useful for producing multifunctional formulations, but water-in-oil emulsion compositions contain a high concentration of nicotinamide. If they are used, the formulation may become unstable, sticky, and sticky, which may affect the feeling of use. According to the present inventors, it is extremely difficult to obtain a water-in-oil emulsion composition that has both good stability and usability while containing a high concentration of nicotinic acid amide. Was found.

The conventional water-in-oil composition system cannot stably emulsify a high concentration of nicotinic acid amide, and contains a high concentration of nicotinic acid amide that achieves both good usability and sufficient stability. There is a need for a water-in-oil emulsion composition. For example, in a water-in-oil emulsion composition having a characteristic feeling of use by containing an emulsifying silicone elastomer, a surfactant, an ultraviolet absorber, etc., in addition to not having sufficient stability, It lacks general versatility because it has a characteristic feeling of use that is different from the general emulsified composition in that the aqueous phase is released when a shear stress is applied.

Furthermore, there is a water-in-oil type emulsion composition having improved stability at a relatively high temperature by combining an emulsifying silicone elastomer and a solidifying agent, but it cannot be said that the composition has sufficient stability and is solid. It contains a large amount of wax, giving it a squeaky feel.

The water-in-oil type emulsion composition of the present invention,
(A) Nicotinic acid amide 3% by mass or more;
(B) a surfactant, which is one or more selected from the group consisting of a silicone-based surfactant, a sorbitan ester surfactant, a polyglycerin ester surfactant, and a glycerin ester surfactant; and (C) clay. A water-in-oil type emulsion composition containing one or more oil-soluble thickeners selected from the group consisting of a system thickener, a dextrin fatty acid ester, an inulin fatty acid ester, and an amino acid oil gelling agent.

[(A) Nicotinic acid amide]
The nicotinic acid amide contained in the water-in-oil emulsion composition of the present invention is an amide compound of nicotinic acid (vitamin B ₃ /niacin) and is a water-soluble vitamin. Nicotinic acid amide may be an extract from a natural product or a product synthesized by a known method. Specifically, those listed in the 17th revised Japanese Pharmacopoeia can be used. It is known to have a blood circulation promoting action and a rough skin improving action, as well as a melanin production inhibiting action and a whitening effect.

In the water-in-oil type emulsion composition of the present invention, the content of the component (A) with respect to the total amount of the water-in-oil type emulsion composition is appropriately set depending on the balance with other components. With respect to the total amount of the water-in-oil type emulsion composition, the content of the component (A) is preferably 20% by mass or less, and more preferably from the viewpoint of alleviating the dryness, stickiness and irritation that may occur with nicotinic acid amide. It is 10 mass% or less, more preferably 8 mass% or less. Further, the content necessary for sufficiently imparting the effects of whitening, anti-aging and the like is such that the total content of the component (A) is 3% by mass or more based on the total amount of the water-in-oil emulsion composition. Is. The component (A) can be preferably 4% by mass or more, more preferably 5% by mass or more. With respect to the total amount of the water-in-oil type emulsion composition, the total content of the component (A) is preferably 3% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, further preferably It is 3% by mass to 10% by mass, and even more preferably 3% by mass to 8% by mass.

[(B) One or more surfactants selected from the group consisting of silicone-based surfactants, sorbitan ester surfactants, polyglycerin ester surfactants, and glycerin ester surfactants]
The surfactant contained in the water-in-oil emulsion composition of the present invention is selected from the group consisting of silicone-based surfactants, sorbitan ester surfactants, polyglycerin ester surfactants, and glycerin ester surfactants. One or more of them are listed. Although not limited thereto, the HLB value of such a surfactant is preferably 15 or less, more preferably 10 or less, even more preferably 9 or less, even more preferably 8 or less, most preferably 2- 6 surfactants.

Here, the HLB (Hydrophile-Lipophile Balance) in the present invention is an index showing the hydrophilic-lipophilic balance and is calculated by the following (Formula 1) by Oda and Teramura et al.
HLB=(Σ inorganic value/Σ organic)×10 (Equation 1)
Here, Σinorganic value/Σorganic property is called IOB (Inorganic-Organic balance), and is based on the “inorganic value” and the “organic value” set for each atom and functional group. It can be calculated by integrating the "inorganic value" and "organic value" of the atoms and functional groups that make up the organic compounds such as agents (Koshida Yoshio, "Organic Conceptual Diagram-Basic and Application-", See pages 11 to 17, Sankyo Publishing, published in 1984).

(Silicone type surfactant)
The silicone surfactant contained in the water-in-oil type emulsion composition of the present invention is not particularly limited as long as it is used as a component of a skin external preparation in the fields of medicines, quasi drugs or cosmetics.

The silicone-based surfactant is preferably a polyether-modified silicone-based surfactant, a polyether/alkyl co-modified silicone-based surfactant, a polyglycerin-modified silicone-based surfactant, or a polyglycerin-alkyl-co-modified silicone-based surfactant. An activator is exemplified. More specifically, PEG-10 dimethicone, PEG-3 dimethicone, PEG-12 dimethicone, PEG/PPG-19/19 dimethicone, polysilicone 13, which is a polyoxyethylene/methylpolysiloxane copolymer, and PEG-9. Polyether-modified silicone surfactants such as polydimethylsiloxyethyldimethicone; methylpolysiloxane/cetylmethylpolysiloxane/poly(oxyethylene/oxypropylene)methylpolysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyldimethicone Polyether/alkyl co-modified silicone surfactants; bisbutyldimethicone polyglyceryl-3, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, polyglyceryl-3 disiloxane dimethicone and other polyglycerin-modified silicone surfactants; lauryl polyglyceryl-3 Examples thereof include polyglycerin/alkyl co-modified silicone surfactants such as polydimethylsiloxyethyl dimethicone.

In the present invention, without limitation, PEG-10 dimethicone, PEG-3 dimethicone, PEG-12 dimethicone, PEG/PPG-19/19 dimethicone, polysilicone 13, PEG-9 polydimethylsiloxyethyl dimethicone, methyl polysiloxane. -Cetylmethylpolysiloxane-poly(oxyethylene-oxypropylene)methylpolysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, bisbutyldimethicone polyglyceryl-3, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, polyglyceryl-3 Disiloxane dimethicone or lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone is preferable, and among them, PEG-10 dimethicone, PEG-3 dimethicone, PEG-12 dimethicone, PEG/PPG-19/19 dimethicone, polysilicone 13, PEG-9 polydimethylsiloxyethyl dimethicone, methyl polysiloxane/cetylmethyl polysiloxane/poly(oxyethylene/oxypropylene)methyl polysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, or lauryl polyglyceryl-3 poly More preferred is dimethylsiloxyethyl dimethicone. Among these, PEG-10 dimethicone, PEG/PPG-19/19 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, or lauryl polyglyceryl-3 poly, from the viewpoint of stability and the like. Even more preferred is dimethylsiloxyethyl dimethicone, especially PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxy. Ethyl dimethicone is particularly preferred.

As the silicone-based surfactant, a commercially available product can be used or a synthetic product can be used.

Commercially available products include, but are not limited to, KF-6017, (HLB4.5, Shin-Etsu Chemical Co., Ltd.), KF-6019 (HLB4.5, Shin-Etsu Chemical Co., Ltd.), KF-6015 (HLB4.5, HLB4.5, Shin-Etsu Chemical Co., Ltd., SH3772M (HLB6, Toray Dow Corning) SH3775M (HLB5, Toray Dow Corning) BY-11-030 (HLB6, Toray Dow Corning), KF-6004 (HLB9) Shin-Etsu Chemical Co., Ltd.), KF-6011 (HLB14.5, Shin-Etsu Chemical Co., Ltd.), FZ-2222, FZ-2233, KF-6028, (HLB4, Shin-Etsu Chemical Co., Ltd.), ABIL EM90 (Made by Goldschmidt) ), KF-6048 (HLB3.5, Shin-Etsu Chemical Co., Ltd.), KF-6038 (HLB4.5, Shin-Etsu Chemical Co., Ltd.), KF-6104, KF6106 (HLB low, Shin-Etsu Chemical Co., Ltd.), KF-6100 (HLB). Naka, Shin-Etsu Chemical Co., Ltd.), KF-6105 (HLB low, Shin-Etsu Chemical Co., Ltd.) and the like.

In the present invention, the silicone surfactant may be used alone or in combination of two or more.

(Ester-based surfactant)
The ester-based surfactant that can be contained in the water-in-oil type emulsion composition of the present invention is not particularly limited as long as it is used as a component of, for example, a skin external preparation in the fields of medicine, quasi drugs or cosmetics.

The ester-based surfactant is preferably exemplified by a sorbitan ester surfactant, a polyglycerin ester surfactant, and a glycerin ester surfactant. Specifically, without limitation, sorbitan oleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan sesquiisostearate, sorbitan isostearate, sorbitan triisostearate, sorbitan stearate, sorbitan tristearate, sorbitan sesquistearate. And other sorbitan ester surfactants; polyglyceryl-2 triisostearate, polyglyceryl-2 isostearate, polyglyceryl-10 condensed ricinoleate, polyglyceryl-10 pentaisostearate, polyglyceryl-10 pentaoleate, polyglyceryl-10 pentastearate, penta Polyglyceryl ester surfactants such as polyglyceryl-10 hydroxystearate, polyglyceryl-6 condensed ricinoleate, polyglyceryl-6 pentaisostearate, polyglyceryl-6 pentaoleate, polyglyceryl-6 pentahydroxystearate; glyceryl oleate, sesquiolein Examples thereof include glyceryl ester surfactants such as glyceryl acid salt, glyceryl trioleate, glyceryl sesquiisostearate, glyceryl isostearate, glyceryl triisostearate, glyceryl stearate, glyceryl sesquistearate, and glyceryl tristearate.

In the present invention, without limitation, sorbitan oleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan sesquiisostearate, sorbitan isostearate, sorbitan triisostearate, sorbitan sesquistearate, tristearic acid. Sorbitan, Polyglyceryl-2 triisostearate, Polyglyceryl-2 isostearate, Polyglyceryl-10 condensed ricinoleate, Polyglyceryl-10 pentaisostearate, Polyglyceryl-10 pentaoleate, Polyglyceryl-10 pentastearate, Polyglyceryl pentahydroxystearate-10 , Condensed polyglyceryl ricinoleate-6, polyglyceryl pentaisostearate-6, polyglyceryl pentaoleate-6, polyglyceryl pentahydroxystearate-6, glyceryl oleate, glyceryl sesquioleate, glyceryl trioleate, glyceryl sesquiisostearate, isostearine Glyceryl acid, glyceryl triisostearate, glyceryl stearate, glyceryl sesquistearate, glyceryl tristearate, among them, sorbitan oleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan sesquiisostearate, sorbitan isostearate, Sorbitan stearate, polyglyceryl triisostearate-2, polyglyceryl isostearate-2, polyglyceryl-10 condensed ricinoleate, polyglyceryl-10 pentaisostearate, polyglyceryl pentaoleate-10, polyglyceryl pentastearate-10, polyglyceryl pentahydroxystearate -10, polyglyceryl-6 condensed ricinoleate, polyglyceryl pentaisostearate-6, polyglyceryl-6 pentaoleate, polyglyceryl-6 pentahydroxystearate, glyceryl oleate, glyceryl sesquioleate, glyceryl trioleate, glyceryl sesquiisostearate , Glyceryl isostearate, glyceryl triisostearate, glyceryl stearate, glyceryl sesquistearate, or glyceryl tristearate are more preferred. Among these, from the viewpoint of stability, condensed ricinoleic acid polyglyceryl-10, pentaisostearate polyglyceryl-10, pentaoleic acid polyglyceryl-10, pentastearic acid polyglyceryl-10, or pentahydroxystearic acid polyglyceryl-10 is even more preferable. ..

As the ester-based surfactant, a commercially available product can be used or a synthetic product can be used.

Commercially available products include, but are not limited to, NIKKOL SO-10V (manufactured by Nikko Chemicals), NIKKOL SO-15V (manufactured by Nikko Chemicals), NIKKOL SO-30V (manufactured by Nikko Chemicals), NIKKOL SI-15RV. (Manufactured by Nikko Chemicals), NIKKOL SI-10RV (manufactured by Nikko Chemicals), NIKKOL SS-10MV (manufactured by Nikko Chemicals), NIKKOL SS-15V (manufactured by Nikko Chemicals), NIKKOL DGTIS (manufactured by Nikko Chemicals), NIKKOL DGMIS (manufactured by Nikko Chemicals), NIKKOL Decagrin-PR20 (manufactured by Nikko Chemicals), NIKKOL Decagrin-5ISV (manufactured by Nikko Chemicals), NIKKOL Decagrin-5OV (manufactured by Nikko Chemicals), NIKKOL Decagrin-5SV (manufactured by Nikko Chemicals) ), NIKKOL Decaglin-5HS (manufactured by Nikko Chemicals), NIKKOL MGS-BMV (manufactured by Nikko Chemicals), NIKKOL MGS-AMV (manufactured by Nikko Chemicals), NIKKOL MGIS (manufactured by Nikko Chemicals), NIKKOL Nikko MMG. Manufactured) and the like.

Such a component (B) can contribute to both the stability of the formulation and the feeling of use even when the nicotinic acid amide of the component (A) is contained in a high concentration.

In the water-in-oil emulsion composition of the present invention, the total content of the component (B) with respect to the total amount of the water-in-oil emulsion composition is preferably 0.5% by mass or more, more preferably 1% by mass. % Or more, more preferably 1.5% by mass or more, even more preferably 2% by mass or more, and most preferably 3% by mass or more. The total content of the component (B) with respect to the total amount of the water-in-oil emulsion composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 8% by mass or less. Yes, even more preferably 6% by mass or less, and most preferably 4% by mass or less. When the total content of the component (B) is in the above range, it can function sufficiently as a surfactant and can obtain good stability. In addition, deterioration of the feeling of use such as stickiness is alleviated.

The total content of the component (B) with respect to the total amount of the water-in-oil emulsion composition is preferably 0.5 to 8% by mass, more preferably 0.5 to 5% by mass, and further preferably 1 to 5% by mass. , Even more preferably 2 to 5% by mass, most preferably 2 to 4% by mass.

In the water-in-oil emulsion composition of the present invention, the ratio of the total content of the component (B) to the component (A) is not particularly limited, but is preferably 1 part by mass of the total content of the component (A). The amount is 0.2 to 1 part by mass, more preferably 0.4 to 1.0 part by mass, still more preferably 0.4 to 0.8 part by mass.

The component (B) used in the water-in-oil emulsion composition of the present invention is at least one selected from silicone-based surfactants, sorbitan ester surfactants, polyglycerin ester surfactants, and glycerin ester surfactants. The surfactant is preferably PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, sorbitan stearate, isostearic acid. Sorbitan, sorbitan sesquiisostearate, sorbitan oleate, sorbitan sesquioleate, glyceryl stearate, glyceryl sesquistearate, glyceryl isostearate, glyceryl sesquiisostearate, glyceryl oleate, glyceryl sesquioleate, polyglyceryl pentastearate-10, More preferably, it is one or more surfactants selected from the group consisting of polyglyceryl pentaisostearate-10, polyglyceryl-10 pentahydroxystearate, and polyglyceryl pentaoleate-10. PEG-9 polydimethylsiloxyethyl dimethicone , PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, polyglyceryl-10 pentastearate, polyglyceryl pentaisostearate, polyglyceryl-10 pentahydroxystearate, pentaolein More preferably one or more surfactants selected from the group consisting of polyglyceryl acid-10, PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and More preferably, it is one or more surfactants selected from the group consisting of lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone.

The component (B) used in the water-in-oil emulsion composition of the present invention is at least two selected from silicone-based surfactants, sorbitan ester surfactants, polyglycerin ester surfactants, and glycerin ester surfactants. The surfactant is preferably at least one of PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone and stearin. Acid sorbitan, sorbitan isostearate, sorbitan sesquiisostearate, sorbitan oleate, sorbitan sesquioleate, glyceryl stearate, glyceryl sesquistearate, glyceryl isostearate, glyceryl sesquiisostearate, glyceryl oleate, glyceryl sesquioleate, pentastearin Acid polyglyceryl-10, pentaisostearate polyglyceryl-10, pentahydroxystearate polyglyceryl-10, pentaoleic acid polyglyceryl-10, more preferably at least one is PEG-9 polydimethylsiloxyethyl dimethicone, PEG -10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, polyglyceryl pentastearate-10, polyglyceryl pentaisostearate-10, polyglyceryl-10 pentahydroxystearate, polyglyceryl pentaoleate More preferably, at least one is selected from PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone. Even more preferably,

As one specific embodiment of the combination of two or more kinds of the component (B) used in the water-in-oil type emulsion composition of the present invention, and the component (B) as a constituent element, at least a silicone-based surfactant. A combination of two or more kinds of surfactants selected from is preferable. For example, but not limited to, two kinds selected from the group consisting of PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone. Can be a combination of.

Further, as another specific embodiment of a combination of two or more kinds of the component (B) used in the water-in-oil type emulsion composition of the present invention,
(B)-1 component One or more surfactants selected from silicone-based surfactants, and (B)-2 component sorbitan stearate, sorbitan isostearate, sorbitan sesquiisostearate, sorbitan oleate, sesquioleic acid. Sorbitan, glyceryl stearate, glyceryl sesquistearate, glyceryl isostearate, glyceryl sesquiisostearate, glyceryl oleate, glyceryl sesquioleate, polyglyceryl pentastearate-10, polyglyceryl pentaisostearate-10, polyglyceryl pentahydroxystearate-10 , And at least one surfactant selected from the group consisting of polyglyceryl pentaoleate-10, and at least (B)-1 component PEG-9 polydimethylsiloxyethyl dimethicone, PEG -10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, one or more surfactants selected from the group consisting of lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, (B)-2 components sorbitan stearate, isostearic acid Sorbitan, sorbitan sesquiisostearate, sorbitan oleate, sorbitan sesquioleate, glyceryl stearate, glyceryl sesquistearate, glyceryl isostearate, glyceryl sesquiisostearate, glyceryl oleate, glyceryl sesquioleate, polyglyceryl pentastearate-10, More preferably, it contains a surfactant selected from the group consisting of polyglyceryl pentaisostearate-10, polyglyceryl pentahydroxystearate-10, and polyglyceryl pentaoleate-10.

Above all,
(B)-1 component selected from the group consisting of PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone One of the above-mentioned surfactants and (B)-2 component selected from polyglyceryl pentastearate-10, polyglyceryl pentaisostearate-10, polyglyceryl pentahydroxystearate-10, and polyglyceryl pentaoleate-10 It is even more preferable to contain the above surfactants.

In addition, three or more kinds of surfactants selected from the components (B)-1 and (B)-2 can be used in an appropriate combination according to the feeling of use of the intended preparation. For example, the B-1 component is selected from the group consisting of PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, and lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone 1 Two or more kinds of surfactants selected from polyglyceryl pentastearate-10, polyglyceryl pentaisostearate-10, polyglyceryl pentahydroxystearate-10, and polyglyceryl pentaoleate-10 as component B-2. A combination of activators, selected as the component B-1 from the group consisting of PEG-9 polydimethylsiloxyethyl dimethicone, PEG-10 dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone 1 or more surfactants selected from the group consisting of polyglyceryl pentastearate-10, polyglyceryl pentaisostearate-10, polyglyceryl pentahydroxystearate-10, and polyglyceryl pentaoleate-10 as component B-2 1 For example, a combination of two or more kinds of surfactants can be exemplified.

[(C) One or more oil-soluble thickeners selected from the group consisting of clay-based thickeners, dextrin fatty acid esters, inulin fatty acid esters, and amino acid oil gelling agents]
The oil-soluble thickener contained in the water-in-oil type emulsion composition of the present invention is not particularly limited as long as it is used as a component of an external preparation for skin in the fields of medicines, quasi drugs or cosmetics.

The oil-soluble thickener contained in the water-in-oil emulsion composition of the present invention is selected from the group consisting of clay-based thickeners, dextrin fatty acid esters, inulin fatty acid esters, and amino acid-based oil gelling agents 1. There are more than one species. At least one selected from the group consisting of clay-based thickeners, dextrin fatty acid esters, and inulin fatty acid esters is preferable.

(Clay-based thickener)
In the present specification, the “clay thickener” means an organic modified clay mineral, and examples thereof include quaternary ammonium salt type cation modified clay mineral. Specific examples include dimethyl distearyl ammonium hectorite, dimethyl alkyl ammonium hectorite, dimethyl distearyl ammonium bentonite, benzyl dimethyl stearyl ammonium hectorite, distearyl dimethyl ammonium chloride treated aluminum magnesium silicate, and the like.

In the present invention, although not limited, such organically modified clay mineral is preferably dimethyl distearyl ammonium hectorite, dimethyl alkyl ammonium hectorite, dimethyl distearyl ammonium bentonite, or benzyl dimethyl stearyl ammonium hectorite, among which, Dimethyl distearyl ammonium hectorite or benzyl dimethyl stearyl ammonium hectorite is more preferred, and dimethyl distearyl ammonium hectorite is even more preferred.

As the clay-based thickener, a commercially available product can be used or a synthetic product can be used.

Commercially available products include, but are not limited to, Benton 38V, Benton 38VCG (manufactured by Elementis Japan KK), Benton 27 (manufactured by Elementis Japan KK).

(Dextrin fatty acid ester)
In the present specification, examples of the dextrin fatty acid ester include dextrin derivatives such as dextrin palmitate, dextrin oleate, dextrin stearate, dextrin myristate, (palmitic acid/ethylhexanoic acid) dextrin, and (palmitic acid/hexyldecanoic acid) dextrin. It is illustrated.

In the present invention, although not limited, such dextrin fatty acid ester is preferably a dextrin derivative such as dextrin palmitate, dextrin myristic acid, dextrin (palmitic acid/ethylhexanoic acid), and dextrin (palmitic acid/hexyldecanoic acid), More preferable are dextrin palmitate, dextrin myristate, and (palmitic acid/hexyldecanoic acid) dextrin.

As the dextrin fatty acid ester, a commercially available product can be used or a synthetic product can be used.

Commercially available products include, but are not limited to, Leopard KL2 (manufactured by Chiba Flour Milling Company), Leopearl TL2 (manufactured by Chiba Flour Milling Company), Leopearl MKL2 (manufactured by Chiba Flour Milling Company), Leopearl TT2 (Chiba Milling Company) , Leopearl WX (manufactured by Chiba Flour Milling Company), Leopearl ISK2 (manufactured by Chiba Flour Milling Company), Leopearl ISL2 (manufactured by Chiba Flour Milling Company) and the like.

(Inulin fatty acid ester)
In the present invention, the inulin fatty acid ester includes, but is not limited to, inulin stearate, inulin palmitate, and inulin myristate, and inulin stearate is particularly preferable.

The fatty acid inulin can be a commercially available product or can be synthesized and used.

Commercially available products include, but are not limited to, Leopard ISK2 (Chiba Flour Milling Co.), Leopard ISL2 (Chiba Flour Milling Co.) and the like.

(Amino acid oil gelling agent)
In the present invention, the amino acid oil gelling agent is not limited, and examples thereof include dibutyl lauroyl glutamide and dibutyl ethyl hexanoyl glutamide.

As the amino acid oil gelling agent, a commercially available product can be used or a synthetic product can be used.

The commercially available products include, but are not limited to, GB-21 (manufactured by Ajinomoto Co.) and EB-21 (manufactured by Ajinomoto Co.).

Such a component (C) can contribute to both the stability of the preparation and the feeling of use even when the nicotinic acid amide of the component (A) is contained in a high concentration.

The oil-soluble thickener of the present invention is an oil-soluble thickener that is at least one selected from the group consisting of clay-based thickeners, dextrin fatty acid esters, inulin fatty acid esters, and amino acid-based oil gelling agents. In particular, benzyl dimethyl stearyl ammonium hectorite, dimethyl distearyl ammonium hectorite, inulin stearate, (palmitic acid/ethyl hexanoic acid) dextrin, palmitic acid dextrin, myristic acid dextrin, dibutyl lauroyl glutamide, and dibutyl ethyl hexanoyl glutamide. It is preferable to contain one or more oil-soluble thickeners selected from the group consisting of the following: dimethyl distearyl ammonium hectorite, inulin stearate, (palmitic acid/ethylhexanoic acid) dextrin, dextrin palmitate, and It is more preferable to contain one or more oil-soluble thickeners selected from the group consisting of dextrin myristate, dimethyl distearyl ammonium hectorite, inulin stearate, (palmitic acid/ethylhexanoic acid) dextrin, and palmitin. It is even more preferable to contain one or more oil-soluble thickeners selected from the group consisting of acid dextrins, and one or more oil-soluble selected from the group consisting of dimethyl distearyl ammonium hectorite and inulin stearate. It is particularly preferred to include a thickening agent.

In the water-in-oil type emulsion composition of the present invention, the total content of the component (C) with respect to the total amount of the water-in-oil type emulsion composition may be appropriately adjusted depending on the type and combination of the component (C) to be used. From the viewpoint of being suppressed, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. The total content of the component (C) with respect to the total amount of the water-in-oil type emulsion composition is preferably 0.1% by mass or more, and more preferably 0.2, from the viewpoint of providing better stability. The content is at least mass%, more preferably at least 0.5 mass%, and even more preferably at least 1 mass%.

The total content of the component (C) with respect to the total amount of the water-in-oil type emulsion composition is preferably 0.5 to 5% by mass, more preferably 0.5 to 5% by mass from the viewpoint of providing better thermal stability. It is 3% by mass, more preferably 0.5 to 2% by mass.

In the water-in-oil emulsion composition of the present invention, the ratio of the content of the component (C) to the component (A) is not particularly limited, but is preferably 0 with respect to the total content of the component (A) of 1 part by mass. 0.05 to 1.0 parts by mass, more preferably 0.1 to 0.8 parts by mass, even more preferably 0.1 to 0.6 parts by mass, even more preferably 0.1 to 0.5 parts by mass, most preferably It is preferably 0.1 to 0.4 parts by mass.

[UV absorber]
The water-in-oil type emulsion composition of the present invention, from the viewpoint of improving the feeling of use, stability, etc., unless the effects of the present invention are impaired, the above-mentioned (A) component, (B) component, and (C) component, Besides, (D) an ultraviolet absorber may be contained. The ultraviolet absorber used in the present invention is not particularly limited as long as it is used as a component of, for example, a skin external preparation in the fields of medicines, quasi drugs or cosmetics. The UV absorber is not limited, but preferably salicylic acid UV absorbers, cinnamic acid UV absorbers, benzoylmethane UV absorbers, benzoic acid ester derivative UV absorbers, triazine derivative UV absorbers, benzal It may be a malonate derivative UV absorber, an octocrylene-based UV absorber, an imidazolesulfonic acid derivative UV absorber, a benzophenone derivative UV absorber, or the like.

Specifically, as the UV absorber, salicylic acid-based UV absorbers such as 2-ethylhexyl salicylate, homomenthyl salicylate, or ethylene glycol salicylate; diparamethoxycinnamic acid mono-2-ethylhexanoate glyceryl, paradihydroxypropylbenzoic acid. Cinnamic acid UV absorbers such as ethyl or 2-ethylhexyl paramethoxycinnamate; Benzoylmethane UV absorbers such as 4-tert-butyl-4'-methoxydibenzoylmethane; 2-[4-(diethylamino )-2-Hydroxybenzoyl]benzoic acid hexyl ester and other benzoic acid ester derivative UV absorbers; 2-methoxyhexyl dimethoxybenzylidenedioxoimidazolidinepropionate; 2,2′-methylenebis[6-(2H-benzotriazol-2) Iyl)-4-(1,1,3,3-tetramethylbutyl)phenol]; 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4 Triazines such as -methoxyphenyl)-1,3,5-triazine, diethylhexylbutamidotriazone, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine Derivatives; benzalmalonate derivative UV absorbers such as dimethicodiethylbenzalmalonate; Octocrylene UV absorbers such as 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester; 2-phenyl Imidazolsulfonic acid derivative UV absorbers such as benzimidazol-5-sulfonic acid and disodium phenyldibenzimidazoletetrasulfonic acid; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5 -Sulfonic acid and salts thereof, benzophenone derivative UV absorbers such as dihydroxydimethoxybenzophenone, dihydroxybenzophenone, or tetrahydroxybenzophenone.

In the present invention, although not limited, examples of such an ultraviolet absorber include 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl-4′-methoxydibenzoylmethane, 2-[4-(diethylamino)- 2-Hydroxybenzoyl]benzoic acid hexyl ester, dimethoxybenzylidene dioxoimidazolidine propionate 2-ethylhexyl, 2,2′-methylenebis[6-(2H-benzotriazol-2yl)-4-(1,1,3) ,3-Tetramethylbutyl)phenol], 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5- Triazine, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, dimethicodiethylbenzalmalonate, 2-cyano-3,3-diphenylpropa-2 -Enoic acid 2-ethylhexyl ester and 2-phenylbenzimidazole-5-sulfonic acid are preferred, 2-methoxyhexyl paramethoxycinnamate, 4-tert-butyl-4'-methoxydibenzoylmethane, 2-[4 -(Diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1 ,3,5-triazine, 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, 2-phenylbenzimidazole-5-sulfonic acid are more preferable. , 2-Methylhexyl paramethoxycinnamate, 2-[4-(diethylamino)-2-hydroxybenzoyl]benzoic acid hexyl ester, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy} -Phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine are further More preferable.

The ultraviolet absorber can be a commercially available product or can be synthesized and used.

Commercially available products are not limited, but Uvinul MC80 (manufactured by BASF), Parsol 1789 (manufactured by DSM Nutrition Japan), and the like can be appropriately combined and used.

In the water-in-oil type emulsion composition of the present invention, the total content of the ultraviolet absorber relative to the total amount of the water-in-oil type emulsion composition is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably Is 10% by mass or less.

The total content of the ultraviolet absorber with respect to the total amount of the water-in-oil emulsion composition is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 6% by mass or more, even more preferably Is 7% by mass or more.

The total content of the ultraviolet absorber with respect to the total amount of the water-in-oil emulsion composition is preferably 1 to 20% by mass, more preferably 3 to 20% by mass, still more preferably 5 to 20% by mass, and particularly preferably It is 6 to 20% by mass, most preferably 7 to 15% by mass.

In the water-in-oil type emulsion composition of the present invention, the ratio of the content of the ultraviolet absorber to the component (A) is not particularly limited, but it is preferably 0. 0 with respect to the total content of the component (A) of 1 part by mass. The amount is 6 to 2 parts by mass, more preferably 1 to 2 parts by mass, still more preferably 1.4 to 2 parts by mass.

[UV protection agent]
The water-in-oil type emulsion composition of the present invention, from the viewpoint of improving the feeling of use, stability, etc., unless the effects of the present invention are impaired, the above-mentioned (A) component, (B) component, and (C) component, In addition to the above, it may further contain (E) an ultraviolet protective agent. Specific examples thereof include fine particle titanium oxide, fine particle zinc oxide, iron oxide, and cerium oxide, but are not limited thereto. In the present invention, the ultraviolet protective agent (E) is preferably, but not limited to, fine particle titanium oxide or fine particle zinc oxide. These (E) UV protection agents may be surface-treated.

Examples of the type of surface treatment agent used for the surface treatment include amphipathic components, silicone components, silane compounds, fatty acid components, alkyl titanates, and the like, but are not particularly limited thereto, and these surface treatment agents include 1 You may use 1 type, or 2 or more types. Examples of the amphipathic component of the surface treatment agent include metal soap, perfluoroalkylethyl phosphate diethanolamine salt, fluoroalkyl acrylate/polyalkylene glycol acrylate polymer, perfluoropolyether phosphoric acid, perfluoropolyether chain. Examples thereof include anionic or cationic polymers (polyurethane-27 or polyurethane-26), hydrogenated lecithin, acylated amino acids, α-tocopherol phosphate ester salt, etc., which have a hydrophilic part and a hydrophobic part, and are powders. It may be a monomer type or a polymer type as long as it exhibits a sorption property. Examples of the silicone component of the surface treatment agent include dimethylpolysiloxane, methylhydrogenpolysiloxane, α-monoalkoxypolydimethylsiloxane, α-dialkoxypolydimethylsiloxane, α-trialkoxypolydimethylsiloxane, and triethoxysilylethyl. Examples thereof include polydimethylsiloxyethyl dimethicone, triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone and amodimethicone. Examples of the silane compound of the surface treatment agent include triethoxycaprylylsilane, aminopropyltriethoxysilane, perfluorooctylethyltriethoxysilane, and perfluorooctyltriethoxysilane. Examples of the fatty acid component of the surface treatment agent include stearic acid, isostearic acid, oleic acid, hydroxystearic acid, myristic acid and the like. Examples of the alkyl titanate as the surface treatment agent include pyrophosphoric acid type alkyl titanate, phosphorous acid type alkyl titanate, amino acid type alkyl titanate, and long chain carboxylic acid type alkyl titanate. Specific examples of the alkyl titanate include isopropyl triisostearoyl titanate.

The total content of the ultraviolet protective agent with respect to the total amount of the water-in-oil emulsion composition is preferably 3 to 10% by mass. By blending in this range, it is possible to improve the ultraviolet protection effect while achieving both the feeling of use and the stability.

Further, in the present invention, although not limited, the (D) ultraviolet absorber and the (E) ultraviolet protector may be compounded, supported or encapsulated in another component, and the combination thereof is not particularly limited. ..

[Base or carrier]
The water-in-oil type emulsion composition of the present invention, from the viewpoint of improving the feeling of use, stability, etc., unless the effects of the present invention are impaired, the above-mentioned (A) component, (B) component, and (C) component, In addition to the above, a base or carrier may be included. Examples of the base or carrier include, but are not limited to, cellulose derivatives; polyvinylpyrrolidone; carrageenan; polyvinyl butyrate; polyethylene glycol; glycol ethers; lower alcohols such as ethanol and isopropanol; Known components to be added to the external skin preparations such as cosmetics and pharmaceuticals can be used.

In the water-in-oil type emulsion composition of the present invention, an oil component functioning as a base or carrier can be used. Examples of such a base or carrier include hydrocarbons such as paraffin and petrolatum; ester oils such as isopropyl myristate; oils and fats derived from animals and plants such as evening primrose oil; waxes such as beeswax; methyl polysiloxane. Siloxanes, alkyl-modified silicones such as caprylyl methicone, cross-linked methyl polysiloxanes, cross-linked alkyl-modified silicones, acrylic silicones, and silicones such as silicone resins, but are not limited thereto. Well-known ingredients to be added to external preparations for skin such as pharmaceuticals can be used.

The base or carrier may be used alone or in combination of two or more.

[Additive]
In the water-in-oil emulsion composition of the present invention, within the range that does not impair the effects of the present invention, known additives to be added to pharmaceuticals, quasi drugs, or cosmetics, for example, antioxidants and thickeners. Preservatives, pH adjusters, stabilizers, irritation reducing agents, preservatives, coloring agents, fragrances, powders and/or pearlescent agents can be added.

Examples of the antioxidant include dibutylhydroxytoluene, butylhydroxyanisole, sorbic acid, sodium sulfite, ascorbic acid, ascorbic acid derivative, tocopherol, tocopherol derivative, erythorbic acid, and L-cysteine hydrochloride. To be

As the thickener, for example, guar gum, locust bean gum, carrageenan, xanthan gum, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, alkyl methacrylate acrylate copolymer, (hydroxyethyl acrylate/acryloyldimethyltaurine Na) copolymer, (Na acrylate/acryloyl dimethyl taurine Na) copolymer, polyacrylic acid amide, polyethylene glycol, alginic acid, macrogol, sodium chondroitin sulfate, and a cellulosic thickener such as hydroxyethyl cellulose.

Examples of preservatives and preservatives include benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, isobutyl paraoxybenzoate, isopropyl paraoxybenzoate, butyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, and paraoxybenzoate. Benzyl benzoate, methyl paraoxybenzoate, phenoxyethanol, benzyl alcohol, chlorobutanol, sorbic acid and its salts, chlorhexidine gluconate, caprylhydroxysamic acid, propynyl butylcarbamate and 1,2-pentanediol, 2,4- Hexanediol, 1,2-hexanediol, 1,2-octanediol and the like can be mentioned.

Examples of pH adjusters include inorganic acids, organic acids, and organic bases.

Examples of the stabilizer include sodium polyacrylate, dibutylhydroxytoluene, butylhydroxyanisole and the like.
Examples of the irritation reducing agent include licorice extract and sodium alginate.

Examples of the colorant include pigment grade titanium oxide, zinc oxide, iron oxide, organic pigments, talc, sericite, mica, synthetic mica, chromium oxide, and Gunjou.

Further, powder may be blended for the purpose of improving the feel and imparting a makeup effect, and specifically, boron nitride, silica, alumina, aluminum hydroxide, metal soap, silicone powder, amino acid, polymethylmethacryl Methyl acid etc. are mentioned. 

The additives can be used alone or in combination of two or more. In addition, the present invention is not limited to these, and known components that are blended in external preparations for skin such as cosmetics and pharmaceuticals can be appropriately used.

[Other active ingredients]
The water-in-oil type emulsion composition of the present invention may contain other active ingredients within a range that does not impair the effects of the present invention. Specific examples of the active ingredient include, for example, a cooling component, a moisturizing component, an anti-inflammatory component, an antibacterial or bactericidal component, a vitamin, an amino acid or a derivative thereof, a cell activating component, an antiaging component, a blood circulation promoting component, a keratin softening component, Examples include whitening ingredients and astringent ingredients.

Examples of the cooling component include camphor, menthol, borneol, eugenol, cineol, thymol, bisabolol, α-pinene, sesquiterpene such as monoterpene such as limonene, diterpene, eucalyptus oil, peppermint oil, clove oil, cinnamon barley. Essential oils such as oil, peppermint oil, mint oil, tea tree oil, chamomile oil, rosemary oil, lemon oil, orange oil, thyme oil, sage oil, clove oil and the like can be mentioned.

Examples of moisturizing ingredients include high molecular compounds such as sodium hyaluronate, heparin analogs, sodium chondroitin sulfate, collagen, elastin, keratin, chitin, and chitosan or hydrolysates thereof; glycine, aspartic acid, arginine, etc. Amino acids; natural moisturizing factors such as sodium lactate, urea, and sodium pyrrolidonecarboxylate; lipids such as ceramides and phospholipids; macromolecules with phospholipid polar groups such as MPC polymers; polyoxypropylene methyl glucoside; PPG- 10 methyl glucose, PEG/PPG/polybutylene glycol 8/5/3 glycerin; trimethylglycine (betaine); hydroxyethyl urea; acrylic acid/acrylamide/dimethyldiallylammonium chloride copolymer; and coix seed extract, mugwort leaf Extracts, chamomile extract, hamamelis extract, birch sap, hamcho extract, lilac extract, tea extract, lavender oil, and plant extract extracts such as perilla extract; animal extracts such as placenta extract.

As the anti-inflammatory component, for example, a component derived from a plant (for example, Conflict-), allantoin, glycyrrhizic acid or its derivative, glycyrrhetinic acid or its derivative, zinc oxide, pyridoxine hydrochloride, tocopherol acetate, salicylic acid or its derivative, Examples include azulene, steroids and ε-aminocaproic acid.

Examples of the antibacterial or bactericidal component include chlorhexidine, salicylic acid, benzalkonium chloride, acrinol, sulfur, resorcin, ethanol, benzethonium chloride, adapalene, benzoyl peroxide, clindamycin, cresol, gluconic acid and its derivatives, and povidone-yo. -Phosphate, potassium iodide, iodine, isopropylmethylphenol, triclocarban, triclosan, photosensitizer No. 101, photosensitizer No. 201, paraben, phenoxyethanol, 1,2-pentanediol, alkyldiaminoglycine hydrochloride, chlorhexidine gluconate, and Examples include zinc paraphenol sulfonate, picrotone olamine, and miconazole.

Examples of vitamins include retinol derivatives (retinol, retinol acetate, retinol palmitate, etc.) retinoic acid, tocopheryl retinoate, and other vitamin A; tocopherol, tocopherol acetate, and other vitamin Es; riboflavin Such as vitamin B2; nicotinic acids other than nicotinamide; vitamin Cs such as ascorbic acid, ascorbate, ascorbic acid derivative; vitamin Ds; vitamin Ks, γ-oryzanol, vitamin B1s; pyridoxine hydrochloride, etc. Vitamin B6s; vitamin B12s; folic acid; pantothenic acids such as panthenol; biotins; and vitamin-like acting factors such as carnitine and pyrroloquinoline quinone.

Examples of the amino acid or its derivative include betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, cystine. , Methionine, leucine, isoleucine, valine, histidine, taurine, γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid, carnitine, carnosine, and creatine.

Examples of the cell activating component include amino acids; vitamins; α-hydroxy acids such as glycolic acid and lactic acid; tannin; flavonoids; saponin; allantoin; and Photosensitizer No. 301.
As the antiaging component, for example, hydrolyzed soybean protein, retinoid (retinol and its derivatives, retinoic acid, retinal, etc.), pangaminic acid, kinetin, ursolic acid, turmeric extract, sphingosine derivative, silicon, silicic acid, Examples thereof include N-methyl-L-serine and mevalonolactone.

Examples of the blood circulation promoting component include plants (for example, Panax ginseng, ashitaba, arnica, ginkgo, fennel, ginkgo, Dutch oak, chamomile, roma-chamomile, carrot, gentian, burdock, rice, hawthorn, shiitake mushroom, hawthorn, hazelnut , Senkyu, senburi, thyme, clove, chimp, touki, tounin, spruce, carrot, garlic, butcher-bloom, grape, button, horse chestnut, melissa, yuzu, yokuinin, rosemary, rosehip, chimp, Components derived from spruce, spruce, peach, apricot, walnut, and corn); and glucosyl hesperidin.

Examples of the keratin softening component include lanolin, urea, α-hydroxy acid and sulfur.
Examples of the whitening component include ascorbic acid and its derivative, arbutin, and tocopherol, tranexamic acid, hydroquinone, kojic acid, salicylic acid derivative, placenta extract, linoleic acid and a plant component having a whitening effect (for example, Yukinoshita, aloe). Etc.) and the like.
Examples of the astringent component include zinc paraphenol sulfonate, zinc oxide, menthol, and ethanol.

Other active ingredients may be used alone or in combination of two or more. In addition, the present invention is not limited to these, and known components that are blended in external preparations for skin such as cosmetics and pharmaceuticals can be appropriately used.

[Production method]
The method for producing the water-in-oil type emulsion composition of the present invention is not particularly limited, and the stirring method at the time of emulsification, the emulsification temperature, the feeding order of the oil phase and the aqueous phase, the feeding speed and the like may be appropriately set.

Specifically, a method of preparing an oil phase and a water phase, respectively, which are mixed after heating and melting if necessary, gradually adding water to the oil phase at room temperature, and emulsifying by mechanical stirring force such as a homogenizer, and the like can be mentioned. However, it is not particularly limited thereto.

A step of swelling the oil-soluble thickener may be included in the manufacturing process, and examples thereof include, but are not limited to, heat dispersion, mechanical disintegration, preliminary stirring in the oil phase, and the like.

[Formulation form]
The water-in-oil emulsion composition of the present invention is a drug, a quasi drug, or a base or carrier usually used for cosmetics, and, if necessary, mixed with an additive, a drug, a quasi drug, Alternatively, it can be a water-in-oil type emulsion composition for cosmetics.

The form of the water-in-oil type emulsion composition for pharmaceuticals is not particularly limited, and examples thereof include solutions, suspensions, emulsions, creams, ointments, gels, liniments, lotions, patches and aerosols. And so on. These preparations can be produced according to the method described in the 17th revised Japanese Pharmacopoeia general rules. Among them, solutions, suspensions, emulsions, creams, ointments, gels, lotions and patches are preferable, and creams, emulsions, ointments, lotions and gels are more preferable.

When using a water-in-oil type emulsion composition for quasi-drugs or cosmetics, the same forms as the above-mentioned drugs can be used. Other than the above, a stick agent, a sheet agent obtained by impregnating a non-woven fabric with a chemical solution, and the like can be given. Among them, solutions, suspensions, emulsions, creams, ointments, gels, lotions, sticks and sheets are preferable, and creams, emulsions, ointments, gels or lotions are more preferable.

The water-in-oil type emulsion composition of the present invention contains an oily base and an aqueous base, and typically can be in the form of a cream or emulsion.

Specific examples of the use in the case of a water-in-oil emulsion composition for quasi-drugs or cosmetics include, for example, lotion, emulsion, gel, cream, beauty essence, sunscreen cosmetic, pack, and mask. , Basic creams such as hand creams, all-in-one gels and body creams; and face makeup cosmetics such as BB creams, foundations and makeup bases, lip cosmetics such as lipsticks, lip balms, lip glosses and lip liners. Cosmetics for hair such as styling agents and the like. Among these, the water-in-oil type emulsion composition for skin is particularly preferable. That is, the water-in-oil type emulsion composition of the present invention can be used as a skin-water-in-oil type emulsion composition for pharmaceuticals, quasi drugs, or cosmetics. The formulation form of the water-in-oil emulsion composition is the same as that of the water-in-oil emulsion composition of the present invention. Also, usable bases or carriers, additives, active ingredients, and preferable ones thereof are the same as in the case of the water-in-oil type emulsion composition of the present invention.

The mass ratio of the oil phase to the water phase in the present invention may be appropriately set and is not limited, but from the viewpoint of obtaining better stability and feeling in use, oil phase:water phase=3:7 to 7:3. Is preferred, and an oil phase:water phase=4:6 to 6:4 ratio is particularly preferred.

[container]
The water-in-oil type emulsion composition of the present invention can be used by being housed in a container having a shape and a material selected appropriately according to the purpose of use and application. Specific containers include, for example, spray type, bottle type, tube type, jar type, drop type, dispenser type, stick type, pouch bags, and cheer packs. Since the water-in-oil type emulsion composition of the present invention can be used in a preferable state from the viewpoint of easy ejection from a container, it is possible to increase the degree of freedom in designing a formulation containing a high concentration of nicotinic acid amide. .. In other words, even a high-concentration nicotinic acid amide-containing preparation can be easily used in a wide variety of containers such as sprays, bottles, tubes, and dispensers, as well as jars and sticks, thus providing flexibility in product design. It is possible to secure the above, and it is very usefully applicable particularly to tube type, dispenser type and bottle type containers.

Moreover, examples of the material of the container include polyethylene terephthalate, polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.), ABS resin, ethylene vinyl alcohol resin, polystyrene, glass, and metal (aluminum, etc.). Further, these materials may be subjected to various coating treatments in consideration of strength, flexibility, weather resistance, stability of components, etc., or these materials may be combined, for example, by mixing, or laminated. It can be used as a container material. Of these, polypropylene, polyethylene (HDPE, LDPE, LLDPE, etc.), ethylene vinyl alcohol resin, and metal (aluminum, etc.) are preferably used.

[How to use]
The water-in-oil type emulsion composition of the present invention can be suitably used for the purpose of promoting blood circulation, anti-inflammation, and ceramide synthesis in expectation of physiological activity of nicotinic acid amide. In addition, whitening, anti-wrinkle and anti-aging effects can be expected, and it is useful as a multi-functional preparation including a whitening agent and a sunscreen.

The container for containing the composition and the method of using the composition are the same as those of the water-in-oil emulsion composition of the present invention.

[How to improve usability]
The present invention also includes a method for improving the usability of a water-in-oil emulsion composition containing (A) nicotinic acid amide. According to the present invention, one selected from the group consisting of (A) nicotinic acid amide; (B) silicone-based surfactant, sorbitan ester surfactant, polyglycerin ester surfactant, and glycerin ester surfactant. By using the above; and (C) the water-in-oil type emulsion composition containing the oil-soluble thickener, it is possible to improve the usability of the water-in-oil type emulsion composition. Here, improving the feeling of use means, for example, in the case of a cream or the like, when applied to the skin, it spreads well and has good familiarity, non-greasiness, moisturizing, maintaining appropriate softness, etc. Point to.

[Other]
The water-in-oil type emulsion composition of the present invention is also excellent in stability. Here, the term “excellent in stability” means that stability is assured, for example, at high temperature or at low temperature, although not limited thereto. Specifically, it means that separation or the like is suppressed even when at least the water-in-oil emulsion composition is stored.

In the method of the present invention, one selected from the group consisting of (A) nicotinic acid amide; (B) a silicone-based surfactant, a sorbitan ester surfactant, a polyglycerin ester surfactant, and a glycerin ester surfactant. The conditions and the like of the above; and (C) the water-in-oil type emulsion composition containing the oil-soluble thickener are the same as those used in the above-mentioned water-in-oil type emulsion composition. Furthermore, the product obtained by this method can be used once or several times a day in accordance with the intended use, according to the known or commonly used usage and dose.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

[Test Example 1] Stabilization Evaluation The compositions of Examples and Comparative Examples described in the table were prepared, and the state of the preparation for 1 hour after the production and the state after storage were observed.
The compositions of Examples and Comparative Examples were prepared by heating and dissolving the oil phase and the water phase, respectively, and bringing both phases to room temperature, and then using a homomixer while gradually containing the water phase in the oil phase. It was carried out by sufficiently stirring the resulting mixture to obtain the desired water-in-oil type emulsion composition.

(Stability)
Immediately after production and after storage at room temperature for 24 hours after production, the formulation was visually evaluated to determine whether or not it had sufficient stability.

<Evaluation criteria>
× Not emulsifiable, and separation and surface separation occurred immediately after production.
○ Immediately after production, a uniform emulsion state was maintained throughout.
◎ Even after being stored for 24 hours, a uniform emulsion state was maintained as a whole.

(Heat load test (thermal stability))
In order to evaluate the stability under the heat load test, the compositions of Examples and Comparative Examples were filled in 30 mL glass bottles and stored in a constant temperature bath at 50°C.
After 3 days and 2 weeks, the test preparation was taken out of the constant temperature bath, returned to room temperature, and visually evaluated for appearance to determine whether the compositions of Examples and Comparative Examples had long-term stability. did.

<Evaluation criteria>
× After 3 days, the separation was largely generated, and the properties were greatly changed, which had an influence on the feeling of use.
Δ After 3 days, some separation or separation on the surface occurred, but this did not affect the feeling of use and was within the range of no major problems in terms of properties.
○ Even after 3 days, a uniform emulsion state was maintained as a whole.
◎ Even after 2 weeks, a uniform emulsion state was maintained as a whole.
Here, even in the case of Δ, when it was stored at 25° C., the entire uniform emulsified state was maintained even after 2 weeks.

First, the stability of the composition was verified with and without nicotinic acid amide.

From the results in Table 1, if nicotinic acid amide is not contained, a sufficiently good emulsified state can be achieved without combining the components (B) and (C). Further, when the nicotinic acid amide had a low concentration, no problem was found in the stability. However, it was found that the high concentration of nicotinic acid amide as in the composition of Comparative Example 1 makes the emulsified state unstable and makes it difficult to prepare a stable preparation.

Next, the compositions of Examples and Comparative Examples shown in Tables 2 to 7 were prepared and evaluated.

In Examples 1 to 3, even when the nicotinic acid amide (A) was contained at a high concentration, by combining the components (B) and (C), the state immediately after the production and the stability were improved, and the water-in-oil type emulsion compositions were obtained. On the other hand, in Comparative Examples 1 to 3 in which the oil-soluble thickener was not contained, separation occurred immediately after the production. In Comparative Example 4 containing the ether-based surfactant polyethylene glycol dipolyhydroxystearate, separation occurred immediately after the production.
Further, the water-in-oil type emulsion compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were used on the skin and the feeling of use was evaluated. As a result, the water-in-oil type emulsion compositions of Examples are the oils of Comparative Examples. It was confirmed that, as compared with the water-in-water emulsion composition, no precipitation was observed, the formulation spread well, and the composition was not sticky. Hereinafter, also in the examples, the feeling of use was evaluated in the same manner.

In Examples 4 to 10, a water-in-oil type emulsion composition having good stability and heat stability immediately after production and a good feeling in use was obtained. Particularly, by using a silicone-based surfactant and a polyglycerin ester surfactant having an HLB of 2 to 6, it was confirmed that the thermal stability was good.

The compositions of Examples 5, 11-13, which contained the oil-soluble thickener, had high stability and thermal stability. Separation was confirmed immediately after production in the composition of Comparative Example 5 containing a water-soluble thickener instead of the oil-soluble thickener.
Regarding the thermal stability, the compositions of Examples 5 and 11 maintained good stability even under considerably severe conditions of 50° C. for 2 weeks, and therefore, inulin stearate or dimethyl distearyl ammonium hectorite. It has been confirmed that it is particularly preferable to contain one or more oil-soluble thickeners selected more.

As a result of investigating the content of the oil-soluble thickener, a water-in-oil emulsion composition having good stability and thermal stability immediately after production was obtained for each of the compositions of Examples.

As a result of examining the content of the ultraviolet absorber, a water-in-oil type emulsion composition having good stability and thermal stability immediately after production was obtained in Examples.

In each of the examples, a water-in-oil type emulsion composition having a good feeling in use and excellent stability and heat stability was obtained.

Prescription examples are shown in Tables 8 to 9 below.

Claims (7)

1. (A) Nicotinic acid amide 3% by mass or more;
   (B) a surfactant, which is one or more selected from the group consisting of a silicone-based surfactant, a sorbitan ester surfactant, a polyglycerin ester surfactant, and a glycerin ester surfactant; and (C) clay. A water-in-oil emulsion composition containing an oil-soluble thickener, which is one or more selected from the group consisting of a system thickener, a dextrin fatty acid ester, an inulin fatty acid ester, and an amino acid oil gelling agent.
2. The water-in-oil emulsion composition according to claim 1, wherein the content of the component (A) is 3 to 10% by mass.
3. The component (B) is PEG-10 dimethicone, PEG-3 dimethicone, PEG-12 dimethicone, PEG/PPG-19/19 dimethicone, polysilicone 13, PEG-9 polydimethylsiloxyethyl dimethicone, methylpolysiloxane cetylmethyl. Polysiloxane/poly(oxyethylene/oxypropylene)methyl polysiloxane copolymer, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, bisbutyl dimethicone polyglyceryl-3, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, polyglyceryl-3 disiloxane dimethicone , Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone, sorbitan oleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan sesquiisostearate, sorbitan isostearate, sorbitan tristearate, sorbitan sesquistearate, tristearin Acid sorbitan, polyglyceryl triisostearate-2, polyglyceryl isostearate-2, polyglyceryl-10 condensed ricinoleate, polyglyceryl-10 pentaisostearate, polyglyceryl pentaoleate-10, polyglyceryl pentastearate-10, polyglyceryl pentahydroxystearate- 10, condensed polyglyceryl-6 ricinoleate, polyglyceryl pentaisostearate-6, polyglyceryl pentaoleate-6, polyglyceryl pentahydroxystearate-6, glyceryl oleate, glyceryl sesquioleate, glyceryl trioleate, glyceryl sesquiisostearate, The water-in-oil emulsion composition according to claim 1 or 2, which is one or more selected from the group consisting of glyceryl isostearate, glyceryl triisostearate, glyceryl stearate, glyceryl sesquistearate, and glyceryl tristearate. ..
4. The component (C) is dimethyl distearyl ammonium hectorite, benzyl dimethyl stearyl ammonium hectorite, distearyl dimethyl ammonium chloride treated aluminum magnesium silicate, dextrin palmitate, dextrin oleate, dextrin stearate, dextrin myristate, (palmitin. Acid/ethylhexanoic acid) dextrin, (palmitic acid/hexyldecanoic acid) dextrin, inulin stearate, dibutyl lauroyl glutamide, and dibutyl ethyl hexanoyl glutamide. The water-in-oil emulsion composition according to any one of 3 above.
5. The water-in-oil emulsion composition according to any one of claims 1 to 4, further comprising (D) an ultraviolet absorber.
6. The water-in-oil emulsion composition according to claim 5, wherein the total content of the component (D) is 20 mass% or less.
7. The water-in-oil emulsion composition according to any one of claims 1 to 6, which further comprises (E) an ultraviolet protective agent.