JPH1171227A - Water-in-oil emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in preservation stability and moisture retention and useful as a cosmetic such as skin cream by including a specific cholesterol ester of a fatty acid, a specified organopolysiloxane co- modified with a polyoxyalkylene and an alkyl, and a water-soluble salts. SOLUTION: The objective composition is obtained by including (A) an iso- type fatty acid cholesterol ester of formula I [(n) is 6-32] and/or an anti-iso type fatty acid cholesterol ester of formula II, (B) an organopolysiloxane co- modified with a polyoxyalkylene and an alkyl of formula III [(m) is 1-5; (x) is 5-50; (y) is 1-30; (z) is 20-200; (p) is 2-20; (q) is 1-5; (r) is 2-20; (n) is 2-20] and/or an organopolysiloxane modified with the polyoxyalkylene of formula IV [(s) is 300-700; (t) is 1-10; (u) is 1-5; (v) is 20-30; (w) is 20-30], and (C) water-soluble salts.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an improved water-in-oil type emulsion composition, and more particularly to a water-in-oil type emulsion composition having excellent storage stability at high temperatures and excellent moisturizing properties.

[0002]

2. Description of the Related Art Conventionally, water-in-oil type emulsion compositions have high water repellency, water resistance and sweat resistance, and have been used for products such as hand creams, makeup cosmetics, sun care cosmetics, and hair cosmetics. I have. Further, the water-in-oil type emulsion composition is superior to the oil-in-water type emulsion composition in protecting the skin and maintaining flexibility, and has recently been used as a water-in-oil type emulsion composition using a silicone surfactant. Research has been done.

[0003]

However, the emulsification stability of a water-in-oil type emulsion composition using a silicone-based surfactant is not yet sufficient, and although its improvement is strongly desired, However, a water-in-oil type emulsion composition excellent in storage stability, particularly storage stability at high temperatures, and moisture retention has not been obtained.

Until now, for example, Japanese Patent Publication No. 55-39
576 discloses a technique relating to an organic silicon-containing emulsion composition using a water-in-oil organic surfactant and a polydiorganosiloxane-polyoxyalkylene copolymer, but it is not sufficient in storage stability. It was difficult. JP-A-4-370152 discloses a technique relating to an organic silicon-containing emulsion composition using a polyoxyalkylene-modified organopolysiloxane, methylphenylpolysiloxane, and volatile dimethylpolysiloxane. Because of the limited oil content, it was difficult to prepare an emulsion composition having a satisfactory feel.

An object of the present invention is to provide a water-in-oil type emulsion composition having excellent storage stability, especially storage stability at high temperatures, and moisture retention.

[0006]

Means for Solving the Problems As a result of investigations for solving the above-mentioned problems, the present inventors have found that a specific fatty acid cholesterol ester and a specific polyoxyalkylene alkyl co-modified organopolysiloxane and / or polyoxyalkylene are used. It has been found that a water-in-oil emulsion composition containing a modified organopolysiloxane and a water-soluble salt achieves the object. That is, the present invention provides the following general formula (1)

[0007]

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(Wherein, n is 6 to 32 in the general formula) and / or a cholesterol ester of an iso-type fatty acid represented by the following general formula (2):

[0009]

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(Wherein, n represents 6 to 32 in the general formula) and a cholesterol ester of an anteiso-type fatty acid represented by the following general formula (3):

[0011]

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(Wherein, in the general formula, m is 1 to 5, x is 5 to 50, y is 1 to 30, and z is 2
0 to 200, p is 2 to 20, q is 1 to 5, r is 2 to 20, and n is 2 to 20. And / or a polyoxyalkylene alkyl co-modified organopolysiloxane represented by the following general formula (4):

[0013]

Embedded image (However, in the general formula, m is 1 to 5, and s is 300
７００700, t is 1１〜10, u is 1５5, v is 20〜30, and w is 20２０30. A) a water-in-oil type emulsion composition comprising at least one modified organopolysiloxane selected from the group of polyoxyalkylene-modified organopolysiloxanes represented by the formula (1) and water-soluble salts.

[0014]

Embodiments of the present invention will be described below in detail. Conventionally, branched fatty acid cholesterol esters used as cosmetic raw materials are composed of isostearic acid. This isostearic acid
Although the branch position and the branched alkyl chain length are not specified,
Most is 2-heptylundecanoic acid. The branched fatty acid cholesterol ester used in the present invention is composed of iso-type and anteiso-type fatty acids. That is, it is limited to fatty acids having a methyl group at the 2-position from the terminal [the above-mentioned general formula (1)] and the 3-position from the terminal [the above-mentioned general formula (2)]. The branched fatty acid cholesterol ester of the present invention differs from conventionally known compounds in that the branch position and the branched alkyl chain length are specified.

The branched fatty acid cholesterol ester used in the present invention does not need to be separated into an iso form and an ante iso form, but may be separated. Further, these branched fatty acid cholesterol esters may be a mixture with other fatty acid cholesterol esters, or may be composed of only the branched fatty acid cholesterol esters. The total carbon number of these iso-type fatty acids and anteiso-type fatty acids has a low melting point and is in a range of forming a liquid crystal structure.
And preferably has 12 to 28 carbon atoms in total.

The cholesterol ester of iso-fatty acid and / or anteiso-fatty acid used in the present invention includes, for example, YOFCO CLE-NH (containing cholesterol ester of iso-fatty acid and anteiso-fatty acid) of Nippon Seika Co., Ltd. Examples thereof include, but are not limited to, chemically synthesized products such as cholesterol ester of 15-methylheptadecanoic acid (anteiso type),
Those derived from human vernix can also be used. The above-mentioned YOFCO CLE-NH of Nippon Seika Co., Ltd. is obtained by esterifying lanolin fatty acid obtained by saponifying and decomposing wool fat with cholesterol by a known method, and has a composition having 12 to 30 carbon atoms. It contains about 35% by weight of cholesterol esters of iso-fatty acids and about 40% by weight of cholesterol esters of anteiso-type fatty acids having 11 to 31 carbon atoms, and the remainder contains cholesterol esters of straight-chain fatty acids having 12 to 30 carbon atoms. It is what is done.

For the above-mentioned human vernix derived from human vernix, the vernix is wiped off from the neonatal skin immediately after childbirth using, for example, cotton wool, and the cotton wool is then washed with chloroform / methanol (2:
A fatty acid cholesterol ester fraction obtained by silica gel column chromatography using hexane and benzene as a developing solvent,
It contains about 40% by weight of a cholesterol ester of an iso-fatty acid having 14 to 26 carbon atoms, about 20% by weight of a cholesterol ester of an anteiso-type fatty acid having 15 to 25 carbon atoms, and the remainder is a cholesterol ester of an unsaturated fatty acid. .

The amount of the cholesterol ester of the above-mentioned iso-fatty acid and / or anteiso-fatty acid is 0.005-20 based on the total amount of the water-in-oil emulsion composition.
% By weight (hereinafter abbreviated as wt%) is preferred.

The polyoxyalkylenealkyl-co-modified organopolysiloxane and polyoxyalkylene-modified organopolysiloxane used in the present invention are both known substances, and any one or a combination of two or more of these substances is known. Can be used. Examples of the polyoxyalkylene alkyl co-modified organopolysiloxane represented by the general formula (3) used in the present invention include, for example, ABILE manufactured by Goldschmidt-Tah Co., Ltd.
M90 and the like can be mentioned, but it is not limited thereto. Further, the above general formula (4) used in the present invention.
The polyoxyalkylene-modified organopolysiloxane represented by is, for example, Silicon BY22-008 manufactured by Toray Dow Corning Co., Ltd., but is not limited thereto. The compounding amount of one or more modified organopolysiloxanes selected from the group of polyoxyalkylene alkyl co-modified organopolysiloxanes and / or polyoxyalkylene-modified organopolysiloxanes used in the present invention is determined based on the water-in-oil emulsion composition. 0.05-5 wt% is preferable based on the total amount.

The water-soluble salts used in the present invention may be any salts that readily dissolve in water at room temperature. For example, inorganic salts such as sodium chloride, magnesium chloride, sodium sulfate, potassium nitrate, ammonium nitrate, sodium citrate, potassium acetate, sodium succinate,
Examples thereof include salts of organic acid salts such as sodium aspartate and the like, and salts of organic bases such as ethanolamine hydrochloride and arginine hydrochloride. When incorporated in the composition, it is preferable to add them as an aqueous solution of the salt. The compounding amount of the water-soluble salts is preferably from 0.1 to 20% by weight, particularly preferably from 0.5 to 10% by weight, based on the total weight of the composition. This range is preferable because storage stability is improved.

The water-in-oil emulsion composition of the present invention is obtained by using the above-mentioned cholesterol ester of an iso-fatty acid and / or anteiso-fatty acid, the above-mentioned specific modified organopolysiloxane, and water-soluble salts in combination. It has high moisture retention and storage stability at high temperatures.

The water-in-oil type emulsion composition of the present invention may contain, in addition to the above-mentioned raw materials, tar pigments, coloring pigments such as iron oxide, preservatives such as paraben and phenoxyethanol, dimethylpolysiloxane and methylphenylpolysiloxane. Hydrocarbons such as silicone oil, liquid paraffin, squalane, paraffin, and petrolatum; waxes such as beeswax, jojoba oil and carnauba wax; triglycerides such as glyceryl triisostearate, glyceryl trioctanoate, and glyceryl tri-2-ethylhexanoate; myristin Ester oils such as octyldodecyl acid, isocetyl myristate, neopentyl glycol dioctanoate, and cetyl palmitate; higher alcohols such as cetanol, behenyl alcohol, and stearyl alcohol; sterols such as cholesterol and phytosterol. Lumpur acids, olive oil, macadamia nut oil, vegetable oils such as castor oil, process oil such hardened oil, stearic acid, myristic acid, fatty acids such as isostearic acid, sodium cetyl sulfate, N- stearoyl -
L-glutamate, anionic surfactant such as glycyrrhizinate, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene hydrogenated castor oil, polyhydric alcohol fatty acid ester, Nonionic surfactants such as polyglycerin fatty acid ester, modified silicone and sucrose ester; cationic surfactants such as tetraalkylammonium salt; amphoteric surfactants such as betaine type, sulfobetaine type and sulfoamino acid type; lecithin and lysozyme Natural surfactants such as phosphatidylcholine, white pigments such as titanium oxide and zinc oxide, antioxidants such as dibutylhydroxytoluene, glycerin, 1,3-butylene glycol, dipropylene glycol, propylene glycol, and sorby , Maltitol, polyhydric alcohols such as diglycerin, chelating agents such as edetic acid, xanthan gum, carboxyvinyl polymer, thickeners such as carrageenan, potassium hydroxide, diisopropanolamine, neutralizing agents such as triethanolamine, Hyaluronic acid, biopolymers such as collagen, chamomile, aloe, peach, carrot, plant extracts such as licorice, amino acids such as serine and threonine, ultraviolet absorbers such as hydroxymethoxybenzophenone sulfonate, etc. It can be appropriately blended within the range achieved.

Examples of the dosage form of the water-in-oil emulsion composition of the present invention include creams, emulsions, lotions, packs, massages, and makeups.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.

(1) Storage stability test used in the present invention,
(2) Each test method of the moisture retention test is as follows.

(1) Storage stability test After the sample was left standing at 45 ° C. for 2 days, the emulsified state and appearance were observed, and when abnormalities were recognized (when oil separated or particles became coarse), × ”, and after standing for 10 days,
The case where abnormalities are observed is indicated by “△”, the case where abnormalities are observed after standing for 1 month is indicated by “○”, and the abnormalities are not observed even after standing for 1 month (emulsions with uniform and homogeneous emulsified state) Is excellent, and is represented by “◎”.

(2) Moisturizing test (method for measuring the water content of the stratum corneum) In the upper arm of 20 persons, the water content of the stratum corneum before and 15 minutes after the application of the sample was measured by Skicon-2 based on the method of Tagami et al.
00 (manufactured by IBS), and the evaluation was performed based on the number of persons whose numerical value increased after application.

In the present invention, isoform fatty acids and / or
Or as a cholesterol ester of anteiso type fatty acid, manufactured by Nippon Seika Co., Ltd. (YOFCO CLE-NH)
(Hereinafter abbreviated as NH) and cholesterol ester of 15-methylheptadecanoic acid were used.

Examples 1 to 6 and Comparative Examples 1 to 4 [Skin Cream] Skin creams, which are W / O emulsions, having the compositions shown in Table 1 (the blending amount is wt%) were prepared. Various tests were performed.

[0030]

[Table 1]

(1) Preparation Method After the components (A) and (B) are uniformly dissolved in advance at about 60 ° C., the component (B) is added to the component (A) with stirring and emulsified and dispersed. And cooled to about 30 ° C. to prepare each skin cream.

(2) Characteristics The test results of each sample are shown in the lower column of Table 1. As shown in this table, Examples 1 to 6 of the present invention are Comparative Examples 1 and 2 containing no specific branched fatty acid cholesterol ester, Comparative Example 3 containing no modified polysiloxane, and Comparative Examples containing no water-soluble salts. Compared with Example 4, storage stability at high temperature and excellent moisture retention were shown. In addition, since the storage stability of Comparative Examples 2-4 was bad, the moisture retention test was not performed.

Examples 7 to 13 and Comparative Examples 5 to 7 [Skin Creams] Each skin cream, which is a W / O emulsion, having the composition shown in Table 2 (the blending amount is wt%) was prepared. Various tests were conducted.

[0034]

[Table 2]

(1) Preparation Method After the components (A) and (B) are previously uniformly dissolved at about 60 ° C., the component (B) is added to the component (A) with stirring, and the mixture is emulsified and dispersed. It was cooled to about 30 ° C. to prepare a skin cream.

(2) Characteristics The test results of each sample are shown in the lower column of Table 2. As shown in this table, Examples 7 to 13 of the present invention are Comparative Example 5 not containing the modified polysiloxane, Comparative Example 6 not containing the specific branched fatty acid cholesterol ester, and Comparative Examples not containing the water-soluble salts. Compared to No. 7, storage stability at high temperatures and excellent moisture retention were exhibited. In addition, since the storage stability of Comparative Example 5 and Comparative Example 7 was poor, the moisture retention test was not performed.

[0037]

As described above, the water-in-oil type emulsion composition of the present invention has a storage stability, particularly at high temperatures.
It is excellent in moisture retention and extremely useful.

Claims (1)

[Claims] [Claim 1] The following general formula (1) (However, in the general formula, n is represented by 6 to 32).
Or the following general formula (2): (However, in the general formula, n is represented by 6 to 32.) A cholesterol ester of an anteiso-type fatty acid represented by the following general formula (3): (However, in the general formula, m is 1 to 5 and x is 5 to 5
0, y is 1 to 30, z is 20 to 200, p is 2 to 20, q is 1 to 5, and r is 2 to
20 and n is represented by 2 to 20. And / or a polyoxyalkylene alkyl co-modified organopolysiloxane represented by the following general formula (4): (However, in the general formula, m is 1 to 5, and s is 300
７００700, t is 1１〜10, u is 1５5, v is 20〜30, and w is 20２０30. A water-in-oil type emulsion composition comprising at least one modified organopolysiloxane selected from the group of polyoxyalkylene-modified organopolysiloxanes represented by the formula (1) and water-soluble salts.