JP3235673B2 - Water-in-oil emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-in-oil emulsion composition. More specifically, the present invention relates to a water-in-oil emulsion composition having good stability and feeling of use used in an external preparation for skin.

[0002]

2. Description of the Related Art Emulsified compositions used for external preparations for skin can be roughly classified into water-in-oil type (W / O type) and oil-in-water type (O / W type). Of these two main types of emulsified compositions, the W / O type has excellent effects such as high emollient ability and excellent drug absorption, but it is difficult to obtain a stable composition. Met.

In order to obtain a W / O type emulsified composition, the amount of an oil agent in the emulsified composition is usually larger than usual, and an emulsifier having a low HLB value such as α-monoglyceryl ether, diisostearic triglyceride, EO addition mole Attempts have been made to emulsify with a small number of EO adducts of silicon. However, a W / O-type emulsified composition having sufficient stability has not been obtained using only these emulsifiers and general-purpose oily bases. In addition, since a large amount of the oil agent is used, the oily feeling (oiliness) and stickiness are strong, and a satisfactory feeling of use has not been obtained.

[0004] As means for solving such problems,
JP-A-3-27597 discloses a W / O emulsion composition using a mono- or diester of N-long-chain acyl acidic amino acid and Na hyaluronate. However, Na hyaluronate has problems that it is very expensive, has a sticky feeling, and has a relatively low W / O type emulsification assisting ability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water-in-oil type emulsion composition having good stability and feeling of use.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in view of such circumstances, and have found that a water-soluble polymer having a sulfate group, an amino group or a peptide bond is used instead of Na hyaluronate. With excellent stability,
W / with excellent oily feeling and less sticky feeling
It has been found that an O-type emulsion composition can be obtained, and the present invention has been completed. That is, the present invention relates to (A) the following general formula (I)

Embedded image (In the formula, X and Y may be the same or different, but each is a sterol ester-forming residue, or one of X and Y is a sterol ester-forming residue and the other is a hydrogen atom or carbon number. It is an ester-forming residue of a liquid higher alkyl or alkenyl having 8 to 30 carbon atoms or a solid saturated monohydric alcohol having 12 to 38 carbon atoms, and has a COR of 8 to 30 carbon atoms.
22 is a long-chain acyl group, and n is 1 or 2. )
1 to 50% by weight of at least one mono- or diester of an N-long-chain acyl acidic amino acid represented by the formula (1), and at least one selected from (B) a water-soluble polymer having a sulfate ester group, an amino group or a peptide bond. 002-1
0% by weight of a water-in-oil emulsion composition.

The N-long-chain acylglutamic acid mono- or cholesteryl ester of the formula (I) is disclosed in
An ester compound disclosed in Japanese Patent No. 275697. The long-chain acyl group COR is an acyl group derived from a saturated or unsaturated fatty acid having 8 to 22 carbon atoms. For example, in addition to an acyl group formed by a fatty acid having a single composition such as lauric acid, palmitic acid, stearic acid, and oleic acid, , Palm oil fatty acids,
It may be an acyl group of a fatty acid (including a branched fatty acid) obtained from nature such as beef fatty acid and hardened tallow fatty acid. The acidic amino acid moiety is glutamic acid or aspartic acid and may be optically active or racemic.

Examples of the sterols used for X and Y include cholesterol, lanosterol, stigmasterol, hydrogenated products and blends thereof, and the liquid higher alkyl or alkenyl alcohol having 8 to 30 carbon atoms has 8 to 30 carbon atoms. Which is in the form of a liquid at room temperature and includes, for example, branched alcohols such as 2-octyldodecyl alcohol and isostearyl alcohol, and unsaturated alcohols such as oleyl alcohol. The solid higher alcohol having 12 to 38 carbon atoms is a saturated monohydric alcohol having 12 to 38 carbon atoms and presents a solid at normal temperature, and examples thereof include cetyl alcohol and behenyl alcohol.

The amount of component (A) to be added to the water-in-oil emulsion composition of the present invention varies depending on the use, but is selected from the range of 1 to 50% by weight. For example, in the case of cream 1-1
0%, especially 1-5% is preferred.

The water-soluble polymer having a sulfate group, amino group or peptide bond used in the present invention includes the following.

A high molecular polysaccharide having a sulfate ester group such as chondroitin sulfate (type A or C type) or dermatan sulfate; a high molecular polysaccharide having an amino group such as chitosan or partially deacetylated chitin; Examples of the hydrophilic polymer include α or γ-polyglutamate sodium, hydrolyzed collagen or a derivative thereof.

The amount of the component (B) to be added to the water-in-oil emulsion composition of the present invention varies depending on the use thereof,
It is selected from the range of 10% by weight, preferably 0.01%.
３3%.

The oil-in-water emulsion composition of the present invention can be used for pharmaceuticals and cosmetics.
The cosmetic composition can be composed for a wide variety of uses such as lotion, cream, and makeup.

The oil-in-water emulsion composition of the present invention comprises
In addition to the components (A) and (B), as long as they are used in ordinary skin external preparations, they may be blended in a range that does not impair the effect. For example, saturated and unsaturated fatty acids and higher alcohols obtained therefrom,
Squalane, castor oil and its derivatives, beeswax, lanolin and its derivatives, including liquid and purified lanolin, cholesterol and its derivatives, jojoba oil, macadamia nut oil, carnauba wax, sesame oil, cocoa oil, palm oil, mink oil, wood wax, candelilla Oily bases derived from animals and plants such as wax and whale wax, oil bases derived from petroleum and minerals such as paraffin, microcrystalline wax, liquid paraffin, petrolatum, ceresin, etc., and oily bases such as silicones, resin acids, esters and ketones Components, surfactants, thickeners and the like can be arbitrarily added.

The aqueous phase component includes polyhydric alcohols such as glycerin, ethylene glycol, 1,3-butylene glycol, and propylene glycol, polyamino acid derivatives and salts thereof, polyethylene glycol, gum arabic, xanthan gum, and carboxyvinyl polymer. , Hydroxyethylcellulose, water-soluble polymers such as acylated proteins; sorbitol, sugar alcohols such as mannitol, and alkylene oxide adducts thereof; citric acid,
Organic acids such as succinic acid, lactic acid and pyroglutamic acid and salts thereof; lower alcohols such as ethanol and propanol; and urea.

The water-in-oil emulsion composition of the present invention may optionally contain, as an emulsifier, an emulsifier having a relatively low HLB, such as α-monoglyceryl ether, diisostearic acid triglyceride, and an EO adduct of silicon. can do.

Further, as the agents to be incorporated in the oil-in-water emulsion composition of the present invention, those generally incorporated in external medicines and cosmetics can be mentioned, such as antiseptics, ultraviolet absorbers, whitening agents, antiperspirants and deodorants. Preparations, vitamin preparations, hair restorers and the like.

[0018]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Production Example 1 Synthesis of N-lauroyl-L-glutamic acid monocholesterol ester N-lauroyl-L-glutamic acid was placed in a 1000 ml flask.
165 g (0.5 mol) and 300 ml of toluene were charged, and 194 g (0.5 mol) of cholesterol was further added. Then, 0.5 ml of sulfuric acid was added as a catalyst, and the mixture was heated to 130 to 140 ° C. to carry out an esterification reaction for about 4 hours. After repeated washing with water, toluene was distilled off to obtain 320 g of a waxy compound. This compound has an acid value of 82.4 and a saponification value of 161.3, which indicates that it is a monoester.

Production Example 2 Synthesis of N-cocoyl-L-glutamic acid dicholesterol ester 365 g of N-cocoylglutamic acid dichloride was placed in a reaction vessel.
(1 mol), 1000 g of toluene and 100 g of pyridine were added, and 392 g (1 mol) of cholesterol dissolved in 500 g of toluene was gradually added. The reaction is carried out at 80 ° C. for 1 hour with stirring. After removing the precipitate of pyridine hydrochloride by filtration, toluene was distilled off under reduced pressure to obtain a wax-like compound. This ester compound has an acid value of 3.0 and a saponification value of 110.5,
N-cocoyl-L-glutamic acid dicholesterol ester was obtained.

Production Example 3 1 mol of N-lauroyl-L-glutamic acid and a mixed alcohol (0.6 mol of cholesterol, 1 mol of 2-octyldodecyl alcohol, 0.4 mol of behenyl alcohol) were charged into a reaction vessel, and 200 ml of toluene was added thereto. Then, the mixture was heated and stirred, and 1 ml of sulfuric acid as a catalyst was added.
The reaction was continued with heating and stirring for about an hour. During this time, by-product water was sufficiently removed. After the completion of the reaction, the mixture was neutralized with an aqueous solution of potassium hydroxide, and toluene was distilled off to obtain a mixture of the desired three types of esters. Acid value = 3.06, saponification value = 121.87, pH (1
%) = 5.55, and the molar ratio (%) of each ester group was 30:50:20.

Production Example 4 A reaction vessel was charged with 1 mol of N-stearoyl-L-glutamic acid and a mixed alcohol (0.4 mol of phytosterol, 1.2 mol of 2-octyldodecyl alcohol, 0.4 mol of stearyl alcohol), and 200 ml of toluene was added thereto. Then, the mixture was heated and stirred, 1 ml of a catalyst, paratoluenesulfonic acid, was added, and the mixture was heated and stirred at 90 to 140 ° C. for about 4 hours to react. During this time, by-product water was sufficiently removed. After the completion of the reaction, the mixture was neutralized with an aqueous solution of potassium hydroxide, and toluene was distilled off to obtain a mixture of the desired three types of esters. Acid value = 3.0
6, saponification value = 121.87, pH (1%) = 5.55, and the ratio of each ester was 20:60:20.

Test Example 1 Component (A) 3% Component (B) 0.03% Liquid paraffin 12% Glycerin 5% Polydimethylsiloxane (200 cPs) 3% POE dimethylsiloxane (HLB = 7) 3% Decamethylcyclopentasiloxane 3% Triglyceryl diisostearic acid 0.5% Salt 0.5% Methyl parahydroxybenzoate 0.2% Purified water Residue

With respect to the emulsified composition of the above composition containing the components (A) and (B) shown in Table 1, the emulsion stability, feeling of use and viscosity were evaluated. Table 1 shows the results. The performance evaluation was performed by the following method.

Emulsion stability The emulsified composition was stored at 40 ° C., and the emulsified state was visually evaluated. Evaluation criteria were as follows: ×: separated immediately after emulsification, Δ: separated within 1 week at 40 ° C., ○: stabilized at 40 ° C. for 1 week or more.

Feeling of Use After applying 0.2 g to the forearms of 10 male and female panelists, stickiness was determined by sensory evaluation. Evaluation criteria: -2
(Sticky) to 2 (not sticky).

Viscosity The viscosity was measured with a B-type viscometer (DVL-B manufactured by Toki Sangyo Co., Ltd.). The measurement was performed at 25 ° C. and 12 rpm.

[0028]

[Table 1]

Use Example 1 Emulsion (W / O type) Ester compound of Production Example 4 2 (% by weight) Partially deacetylated chitin 0.01 Glyceryl trioctanoate 10 Squalane 5 Glycerin 5 Polydimethylsiloxane (200 cPs) 3 POE Dimethylsiloxane (HLB = 7) 3 Decamethylcyclopentasiloxane 3 α-monoglyceryl ether 0.5 Salt 0.5 Methyl parahydroxybenzoate 0.2 Purified water Residue

An emulsion of the above composition was prepared. This emulsion is W
/ O type, and had a lotion-like viscosity, and was excellent in stability.

Usage Example 2 Nutritional cream (W / O type) Ester compound of Production Example 2 3 (% by weight) Hydrolyzed collagen 0.5 Water-soluble chitin 0.1 Squalane 10 Macadamia nut oil 5 Hardened oil 4 Stearic acid 3 Triglyceryl Diisostearic acid 3 Behenyl alcohol 2 2-Pyrrolidone-5-carboxylic acid Na 2 2-Pyrrolidone-5-carboxylic acid lauryl ester 1 Dimethylsiloxane (5000 cPs) 1.5 Tocopherol acetate 0.2 Purified water Residue

A nutritional cream having the above composition was produced. This nutritional cream was W / O type, and was excellent in use feeling and emulsion stability.

Usage Example 3 Ointment base (W / O type) Ester compound of Production Example 2 5 (% by weight) Chondroitin sulfate Na 0.01 Liquid paraffin 15 1,3-butylene glycol 5 Vaseline 5 Stearic acid 3-2-pyrrolidone -5-carboxylic acid lauryl ester 2 triglyceryl distearic acid 0.5 purified water residue

An ointment base having the above composition was prepared. This ointment base was not sticky, and was excellent in usability and stability.

[0035]

The water-in-oil emulsion composition of the present invention has excellent emulsion stability and feeling of use and can be suitably used as an external preparation for skin.

Continuation of the front page (56) References JP-A-3-275697 (JP, A) JP-A-63-96111 (JP, A) JP-A-62-187406 (JP, A) JP-A-62-191039 (JP) , A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K ⁷ /00-7/50 A61K 9/00-9/72 A61K 47/00-47/48

Claims (4)

(57) [Claims] (A) The following general formula (I) (In the formula, X and Y may be the same or different, but are either a sterol ester-forming residue, or one of X and Y is a sterol ester-forming residue and the other is a hydrogen atom, carbon atom 8 A liquid higher alkyl or alkenyl of from 30 to 30 or an ester forming residue of a solid saturated monohydric alcohol having from 12 to 38 carbon atoms;
22 is a long-chain acyl group, and n is 1 or 2. (B) chondroitin sulfate, dermatan sulfate, chitosan, water-soluble chitin, partially deacetylated chitin, α or γ- A water-in-oil emulsion composition comprising 0.002 to 10% by weight of at least one water-soluble polymer obtained from polyglutamic acid, hydrolyzed collagen or a derivative thereof. 2. The water-in-oil emulsion composition according to claim 1, wherein the water-soluble polymer is chondroitin sulfate or dermatan sulfate. 3. The water-in-oil emulsion composition according to claim 1, wherein the water-soluble polymer is water-soluble chitin or partially deacetylated chitin. 4. The water-in-oil emulsion composition according to claim 1, wherein the water-soluble polymer is α or γ-polyglutamic acid or hydrolyzed collagen.