JP2017081846A - Water-in-oil type emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an emulsion composition which is excellent in moisture retention, usability, formulation stability, and percutaneous absorption of an agent.SOLUTION: It was found that the problem can be solved by a water-in-oil type emulsion composition characterized by containing the following (a) and (b): (a) tranexamic acid or a salt thereof; and (b) a specific polyoxyalkylene-modified silicone; wherein, further, preferably, the polyoxyalkylene-modified silicone is PEG/PPG-19/19 dimethicone or the like, a crosslinked silicone is contained, the crosslinked silicone is dimethicone/vinyldimethicone)crosspolymer, diglycerin is contained, 6 mass% or more of ethanol is contained, and 50 mass% or more of water is contained.SELECTED DRAWING: None

Description

The present invention relates to an emulsified composition excellent in moisture retention, usability, formulation stability, and transdermal absorbability of a drug.

There are many women who use whitening cosmetics and sunscreen cosmetics in order to realize skin without freckles and freckles. Spots and freckles are caused by an increase in the amount of melanin pigment in the skin caused by the stimulation of ultraviolet rays, which is abnormally deposited in the skin. In order to prevent spots and freckles due to sunburn, sunscreen cosmetics containing titanium dioxide or the like having an ultraviolet protection function are generally used. However, sunscreen cosmetics are less effective for stains that have already been made. On the other hand, cosmetics containing whitening ingredients such as tranexamic acid, vitamin C derivatives, and resorcin derivatives, so-called whitening cosmetics, can be said to be very effective for stains that have already been made (for example, patents). Reference 1).

However, the whitening component has a great influence on the stability to the emulsified preparation because of its large blending amount and many salts. Of these, tranexamic acid is not easy to be incorporated into an emulsified preparation. Therefore, many emulsion preparations containing tranexamic acid have increased stability by increasing the amount of surfactant, and preparations with stickiness that are poor in usability. In addition, the emulsion stability of the preparation may inhibit the transdermal absorbability of the whitening component in the preparation, and it can be said that formulation in the preparation is very difficult.

As emulsion formulations, oil-in-water (O / W) emulsions and water-in-oil (W / O) emulsions are known. The oil-in-water emulsion is fresh and less sticky, and its usability is good. One water-in-oil emulsion is characterized by high moisture retention compared to an oil-in-water emulsion. It is very effective for skin that has been exposed to UV rays and dried. However, on the other hand, the stickiness is high and the usability is often not good. In the past, many studies have been conducted to solve these problems (for example, Patent Documents 1 and 2). However, there are no preparations that can solve all of these problems. That is, it has been difficult to obtain a water-in-oil emulsion having high moisturizing properties, no stickiness and good usability and high formulation stability and excellent percutaneous absorption of tranexamic acid.

JP 2012-72085 A JP 2014-1111584 A

An object of the present invention is to obtain a water-in-oil emulsion that has high moisturizing properties, has no stickiness, has good usability, has high formulation stability, and has excellent transdermal absorbability of tranexamic acid.

In view of such a situation, the present inventors used various raw materials used in the cosmetics field in combination, and as a result of earnest research aimed at solving the above problems, the following preparations were obtained. The present invention was completed by finding that a water-in-oil emulsion with high moisturizing properties, high stickiness and good usability, high stability of the formulation, and excellent transdermal absorbability of tranexamic acid can be realized. . That is, the present invention is as follows.

（一般式（１）において、Ｒ^１は独立して水素原子、炭素数１〜３のアルキル基、又はフェニル基を表し、Ｒ^２は下記一般式（２）で表される基を表し、Ｒ^３は独立して水素原子、炭素数１〜３のアルキル基、フェニル基、又は下記一般式（２）で表される基を表し、ｎは１００〜４００の整数を、ｍは１００〜４００の整数をそれぞれ表す。）

（一般式（２）において、Ｒ^４は水素原子又は炭素数１〜３のアルキル基を表し、ａは１〜５の整数を、ｂは１０〜３０の整数を、ｃは１０〜３０の整数をそれぞれ表す。）
＜２＞ 前記（ｂ）のポリオキシアルキレン変性シリコーンが、ＰＥＧ／ＰＰＧ−１９／１９ジメチコン、ＰＥＧ／ＰＰＧ−１８／１８ジメチコン、ＰＥＧ／ＰＰＧ−３０／１０ジメチコンであることを特徴とする＜１＞に記載の油中水型乳化組成物。
＜３＞ さらに架橋型シリコーンを含有することを特徴とする＜１＞又は＜２＞に記載の油中水型乳化組成物。
＜４＞ 前記架橋型シリコーンが、（ジメチコン／ビニルジメチコン）クロスポリマーであることを特徴とする＜１＞〜＜３＞の何れか一つに記載の油中水型乳化組成物。
＜５＞ さらにジグリセリンを含有することを特徴とする＜１＞〜＜４＞の何れか一つに記載の油中水型乳化組成物。
＜６＞ さらにエタノールを６質量％以上含有することを特徴とする＜１＞〜＜５＞の何れか一つに記載の油中水型乳化組成物。
＜７＞ 水を５０質量％以上含有することを特徴とする＜１＞〜＜６＞の何れか一つに記載の油中水型乳化組成物。 <1> A water-in-oil emulsion composition containing the following (a) and (b):
(A) tranexamic acid or a salt thereof (b) a polyoxyalkylene-modified silicone represented by the following general formula (1)

(In General Formula (1), R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group; R ² represents a group represented by the following General Formula (2); ³ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a group represented by the following general formula (2), n is an integer of 100 to 400, and m is 100 to 400. Each represents an integer.)

(In General Formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer of 1 to 5, b is an integer of 10 to 30, and c is an integer of 10 to 30. Represents each.)
<2> The polyoxyalkylene-modified silicone (b) is PEG / PPG-19 / 19 dimethicone, PEG / PPG-18 / 18 dimethicone, or PEG / PPG-30 / 10 dimethicone <1 > The water-in-oil type emulsion composition as described in>.
<3> The water-in-oil emulsion composition according to <1> or <2>, further comprising a crosslinked silicone.
<4> The water-in-oil emulsion composition according to any one of <1> to <3>, wherein the crosslinked silicone is a (dimethicone / vinyl dimethicone) crosspolymer.
<5> The water-in-oil emulsion composition according to any one of <1> to <4>, further comprising diglycerin.
<6> The water-in-oil emulsion composition according to any one of <1> to <5>, further comprising 6% by mass or more of ethanol.
<7> The water-in-oil emulsion composition according to any one of <1> to <6>, wherein the composition contains 50% by mass or more of water.

ADVANTAGE OF THE INVENTION According to this invention, the emulsification composition excellent in moisture retention, usability, formulation stability, and the transdermal absorbability of a medicine can be provided.

<1> Tranexamic acid or salt thereof of the present invention The tranexamic acid or salt thereof of the present invention may be any one that is generally used in cosmetics and the like. As content, 0.01-5 mass% is preferable with respect to the water-in-oil emulsion composition whole quantity, and 1-2 mass% is more preferable.

<2> Polyoxyalkylene-modified silicone of the present invention The polyoxyalkylene-modified silicone of the present invention is represented by the general formula (1).

In the general formula (1), R1 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. is there. R2 represents a group represented by the following general formula (2). R3 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a group represented by the following general formula (2), preferably an alkyl group having 1 to 3 carbon atoms, or the following general group. It is group represented by Formula (2), More preferably, it is a methyl group. n represents an integer of 100 to 400, and m represents an integer of 100 to 400.

In General formula (2), R4 represents a hydrogen atom or a C1-C3 alkyl group, Preferably it is a C1-C3 alkyl group, More preferably, it is a methyl group. a represents an integer of 1 to 5, b represents an integer of 10 to 30, and c represents an integer of 10 to 30, respectively.

The polyoxyalkylene-modified silicone represented by the general formula (1) may be any one that is generally used in cosmetics and the like. Moreover, the thing with low HLB is preferable, and the thing of 1-4 is specifically preferable. Here, HLB (Hydrophilic-Lypophilic Balance) refers to a value calculated from the Griffin equation. Specific examples include PEG / PPG-19 / 19 dimethicone, PEG / PPG-18 / 18 dimethicone, and PEG / PPG-30 / 10 dimethicone, with PEG / PPG-19 / 19 dimethicone being preferred. The content is preferably 0.2 to 5% by mass, more preferably 1 to 3% by mass with respect to the total amount of the water-in-oil emulsion composition. If the content is less than 0.2% by mass, it may be difficult to form a water-in-oil emulsion, and if the content is more than 5% by mass, the usability may be impaired.

<3> Crosslinkable silicone of the present invention The crosslinkable silicone of the present invention may be any one that is generally used in cosmetics and the like. The cross-linked silicone is a silicone containing a three-dimensional bond, and examples thereof include cross-linked methyl polysiloxane and cross-linked polyether-modified silicone. As this cross-linked methylpolysiloxane or cross-linked polyether-modified silicone, (dimethicone / vinyl dimethicone) cross polymer, (dimethicone / phenyl vinyl dimethicone) cross polymer, dimethicone polyol cross-polymer, etc. are known as cross-linked polyether-modified silicone. ing. Cross-linked methylpolysiloxane is preferred (dimethicone / vinyl dimethicone) and a cross-polymer is more preferred.

These cross-linked silicones are known compounds and can be produced according to conventional methods. For example, in the case of a cross-linked methylpolysiloxane, it can be produced by dealcoholizing dimethoxydimethylsiloxane and vinyldimethylmethoxysiloxane, followed by addition polymerization using a polymerization initiator such as azobisisobutyronitrile. Can do. Other cross-linked silicones can also be produced in accordance with this by polymerizing the monomer appropriately with the corresponding one.

In addition, some of such crosslinked silicones are already on the market, and such commercially available products can also be used. Preferred commercially available products are silicone KSG-16 (manufactured by Shin-Etsu Silicone Co., Ltd.), which is a dimethicone solution (about 25% by mass) of cross-linked methylpolysiloxane, and phenyltrimethicone solution (about 15% by mass) of cross-linked methylphenyl polysiloxane. Silicone KSG-18 (manufactured by Shin-Etsu Silicone Co., Ltd.), dimethicone solution of crosslinked polyether-modified silicone (about 27% by mass), or silicone KSG-21 or silicone KSG-210 (both Shin-Etsu Silicone Co., Ltd.) And the like). In addition, silicone KSG-31, silicone KSG-32, silicone KSG-33 (all manufactured by Shin-Etsu Silicone Co., Ltd.), which are solutions of crosslinked alkyl polyether-modified silicone, can also be used.

The content is preferably from 0.1 to 5 mass%, more preferably from 0.5 to 2 mass%, based on the total amount of the water-in-oil emulsion composition.

<4> Ethanol of the Present Invention The crosslinked silicone of the present invention may be any one that is generally used in cosmetics and the like. 6-15 mass% is preferable with respect to the water-in-oil type emulsion composition whole quantity, and, as for content, 8-10 mass% is more preferable.

<5> Diglycerin of the Present Invention The diglycerin of the present invention is not particularly limited as long as it is generally used in cosmetics and the like. The content is preferably from 0.1 to 10% by mass, more preferably from 4 to 6% by mass, based on the total amount of the water-in-oil emulsion composition.

<6> Water of the Present Invention The water of the present invention may be anything that is generally used in cosmetics and the like. Ion exchange water, purified water, hot spring water, aromatic distilled water, etc. may be used. The content is preferably 50% by mass or more with respect to the total amount of the water-in-oil emulsion composition.

<7> Water-in-oil emulsion composition of the present invention The water-in-oil emulsion composition of the present invention is not particularly limited as long as it is externally administered to the skin, and includes, for example, quasi drugs. Suitable cosmetics, skin external goods and the like can be suitably exemplified. Of these, cosmetics are particularly preferred. In addition, the water-in-oil emulsion composition of the present invention can take any of the conventionally known emulsion dosage forms, essence dosage forms, cream dosage forms, and powder-containing dosage forms. As the cosmetic, any of basic cosmetics, hair cosmetics, and makeup cosmetics can be applied, but it is particularly preferable to apply to basic cosmetics.

The water-in-oil emulsion composition of the present invention may contain optional components that are usually used in cosmetics in addition to the above components. Optional ingredients include, for example, macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, palm oil, palm oil, liquid lanolin, hardened palm oil, hardened oil Oil, wax, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, microcrystallin, oil, wax, liquid oil, waxy wax, liquid paraffin, squalane, pistol Hydrocarbons such as wax, higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, cetyl alcohol, stearyl alcohol, isostearyl alcohol , Behenyl alcohol, octyldodecanol, higher alcohol such as myristyl alcohol, cetostearyl alcohol, cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, malic acid Diisostearyl, di-2-ethylhexanoic acid ethylene glycol, dicaprate neopentyl glycol, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, tri Synthetic ester oils such as trimethylolpropane isostearate and pentane erythritol tetra-2-ethylhexanoate, dimethylpolysiloxane, methylphenylpolysiloxa , Chain polysiloxanes such as diphenylpolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine Oil agents such as silicone oil such as modified polysiloxane such as modified polysiloxane, anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, alkyl sulfate triethanolamine ether, chloride Cationic surfactants such as stearyltrimethylammonium, benzalkonium chloride, laurylamine oxide, imidazoline-based amphoteric surfactants (2-cocoyl-2-imidazolinini) Umhydroxide-1-carboxyethyloxy disodium salt), betaine surfactants (alkyl betaines, amide betaines, sulfobetaines, etc.), amphoteric surfactants such as acylmethyltaurine, sorbitan fatty acid esters (sorbitan mono) Stearates, sorbitan sesquioleate, etc.), glycerin fatty acids (glyceryl monostearate, etc.), propylene glycol fatty acid esters (propylene glycol monostearate, etc.), hardened castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters ( POE sorbitan monooleate, polysoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid ester (POE-glycerin monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldodecyl ether, etc.), POE alkyl phenyl ethers (POE nonylphenyl ether) ), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), Sho Nonionic surfactants such as sugar fatty acid esters and alkyl glucosides, polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, propylene glycol Polyol, dipropylene glycol, diglycerin, isoprene glycol, 1,2-pentanediol, 2,4-hexylene glycol, 1,2-hexanediol, 1,2-octanediol and other polyhydric alcohols, pyrrolidone carvone Moisturizing ingredients such as sodium acid, lactic acid, sodium lactate, guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, curdlan, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, chondroitin Sulfuric acid, dermatan sulfate, glycogen, heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucoitin sulfate, hydro Xiethyl guar gum, carboxymethyl guar gum, dextran, keratosulfate, locust bean gum, succinoglucan, caronic acid, chitin, chitosan, carboxymethylchitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, sodium polyacrylate, polyethylene Thickeners such as glycol and bentonite, surface may be treated, powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica), aluminum oxide, barium sulfate Surface may be treated, bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide inorganic pigments, surface may be treated, titanium mica, fish Phosphorous foil, bismuth oxychloride, etc. Red, No. 202, Red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201 No., Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204, and the like, polyethylene powder, polymethyl methacrylate, nylon powder, organopolysiloxane elastomer , Organic powders such as cellulose powder, urethane powder, silk powder, etc., powder coated with a bio-component-like polymer such as a copolymer of methacryloyloxyalkylphosphorylcholine and alkyl methacrylate, ethanol, Lower alcohols such as isopropanol, vitamin A or derivatives thereof, vitamin B6 hydrochloride, vitamin B6 Ripalmitate, vitamin B6 dioctanoate, vitamin B2 or derivatives thereof, vitamin B such as vitamin B12, vitamin B15 or derivatives thereof, vitamin E such as α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, vitamin D Vitamins such as vitamin H, pantothenic acid, and pantethine can be preferably exemplified, and can be blended as optional components.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to a following example.

<Manufacture example 1> Manufacture of the water-in-oil emulsion composition of this invention The water-in-oil emulsion composition of this invention was prepared according to prescription shown in Table 1 Example 1 of this invention. That is, (A) was heated at a temperature of 60 ° C. to uniformly dissolve, and then (B) was added while stirring with a homomixer. In addition, referring to Example 1, Example 2-16 and Comparative Examples 1 and 2 were similarly prepared. It shows in Tables 1-3.

<Test Example 1> The moisture retention evaluation test was conducted in a room at 20 ° C. and 50% relative humidity for 20 panelists. For the skin on the inner side of the forearm, the measurement site was washed with warm water at 37 ° C. for 30 seconds, allowed to rest for 20 minutes, and then measured with SKICON-200EX (manufactured by IBS) (initial value). Thereafter, the water-in-oil emulsion composition shown in Tables 1 to 3 was applied once a day, and after one week, the skin moisture content was measured again by the same procedure. The amount of increase (μS) in the measured value after 1 week with respect to the initial value is shown in Tables 1 to 3.

<Test Example 2> Usability Evaluation Five special panels used the water-in-oil emulsion compositions shown in Tables 1 to 3, and evaluated stickiness. The evaluation criteria are shown below. The results are shown in Tables 1-3.
1: There is no stickiness and there is no problem in usability.
2: There is not much stickiness and there is no problem in usability.
3: A feeling of stickiness is slightly felt, but the problem is small in terms of usability.
4: There is a sticky feeling, which is a problem in terms of usability.

<Test Example 3> Stability evaluation The water-in-oil emulsion compositions shown in Tables 1 to 3 were stored at 40 ° C for 3 months, and the stability at 1 month and 3 months was visually evaluated. The evaluation criteria are shown below. The results are shown in Tables 1-3.
1: Stable with no emulsification failure 2: Transparency is slightly higher, but stable without oil re-shrinking.
3: Very little oil is showing on the preparation surface.
4: The water phase and the oil phase are separated. Cannot be used as a topical skin preparation.

<Test Example 3> Evaluation of transdermal absorbability Evaluation of transdermal absorbability was performed by the following method. A panel of 10 persons was provided with a 1 cm × 1 cm portion on the inner side of the forearm, and 7 μL of the test sample, which was the water-in-oil emulsion composition prepared above, was applied to each panel and allowed to stand at 20 ° C. for 1 hour. The skin was wiped off with absorbent cotton impregnated with), this absorbent cotton was extracted three times with 100 ml of THF, the amount of tranexamic acid recovered was quantified by high performance liquid chromatography, and the percutaneous absorption was evaluated by the recovery rate (value) The lower the value, the higher the transdermal absorbability). Each water-in-oil emulsion composition was evaluated twice, and the average is shown in Tables 1-3.

From the results shown in Tables 1 to 3, the present invention is a water-in-oil emulsion that has high moisture retention, has no stickiness, has good usability, has high formulation stability, and has excellent transdermal absorbability of tranexamic acid. I know that there is.

INDUSTRIAL APPLICATION This invention can be utilized for the emulsion composition excellent in moisture retention, usability, formulation stability, and the transdermal absorbability of a medicine.

Claims (7)

A water-in-oil emulsion composition comprising the following (a) and (b):
(A) tranexamic acid or a salt thereof (b) a polyoxyalkylene-modified silicone represented by the following general formula (1)

(In General Formula (1), R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group; R ² represents a group represented by the following General Formula (2); ³ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a group represented by the following general formula (2), n is an integer of 100 to 400, and m is 100 to 400. Each represents an integer.)

(In General Formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer of 1 to 5, b is an integer of 10 to 30, and c is an integer of 10 to 30. Represents each.) The polyoxyalkylene-modified silicone (b) is PEG / PPG-19 / 19 dimethicone, PEG / PPG-18 / 18 dimethicone, or PEG / PPG-30 / 10 dimethicone. A water-in-oil emulsion composition. The water-in-oil emulsion composition according to claim 1, further comprising a cross-linked silicone. The water-in-oil emulsion composition according to any one of claims 1 to 3, wherein the crosslinked silicone is a (dimethicone / vinyl dimethicone) crosspolymer. Furthermore, diglycerin is contained, The water-in-oil emulsion composition as described in any one of Claims 1-4 characterized by the above-mentioned. Furthermore, ethanol is contained 6 mass% or more, The water-in-oil emulsion composition as described in any one of Claims 1-5 characterized by the above-mentioned. The water-in-oil emulsion composition according to any one of claims 1 to 6, comprising 50% by mass or more of water.