JPH08126833A - Water-in-oil type emulsion - Google Patents

Abstract

PURPOSE: To prepare a water-in-oil type emulsion containing amino acids and their salts, having an excellent dermatologic action on the skin, and excellent in stability and usability. CONSTITUTION: This water-in-oil type emulsion contains (A) a water-in-oil type emulsion composition composed of (a) a material which is liquid at ordinary temp. and selected from a group of a partial ester of a polyhydric alcohol having at least >=3 hydroxyl groups in the molecule and a fatty acid and the one obtained by adding 1-10mol ethylene oxide to a hydroxy fatty triglyceride, and (b) an aq. solution containing >=0.1% one ore more kinds of amino acids and/or their salts and having 1:1 to 1:46 weight ratio of (b) to (a), (B) 0.1-10% organic modified clay mineral and (C) 1-20% silicone oil.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-in-oil emulsion excellent in usability, which contains an amino acid and / or a salt thereof having an excellent effect on skin and a silicone oil.

[0002]

2. Description of the Related Art Conventionally, amino acids and / or
Or salts thereof, because they have an excellent effect on the skin, it is desired to blend these into cosmetics, as a technique for stably blending in water-in-oil emulsion, Japanese Patent Publication No. 53-213
No. 93 “water-in-oil type emulsifier composition” is available. This technology
(i) A substance which is liquid at room temperature selected from the group consisting of a partial ester of a polyhydric alcohol having at least 3 or more hydroxyl groups in the molecule and a fatty acid, and 1 to 10 moles of ethylene oxide added to hydroxy fatty acid triglyceride. And (ii) an aqueous solution containing one or more amino acids and / or salts thereof in an amount of 0.1% or more, and the ratio of (i) to (ii) is 1: 1 to 1:46 by weight.
And a water-in-oil type emulsifier composition.

[0003]

However, a water-in-oil emulsion using this emulsifier composition has been desired to be further improved in terms of stickiness during use, weight of elongation and the like. The present invention solves such conventional problems and provides a water-in-oil emulsion which contains an amino acid and / or a salt thereof having an excellent effect on the skin and is excellent in stability and usability. The purpose is to

[0004]

Means for Solving the Problems As a result of intensive studies to solve the problems of the prior art, the inventors of the present invention have found that a water-in-oil emulsion obtained by using the water-in-oil type emulsifier composition described above is an organically modified clay mineral. The present invention has been completed by discovering that the silicone oil, which was difficult to be blended by the prior art, can be stably blended by blending the compound (1), and that the stickiness during use and the weight of elongation can be greatly improved. That is, the present invention is
(A) (a) Liquid at room temperature selected from the group consisting of partial ester of polyhydric alcohol having at least 3 or more hydroxyl groups in the molecule and fatty acid and hydroxy fatty acid triglyceride to which 1 to 10 mol of ethylene oxide is added. The substance to be exhibited and (b) an aqueous solution containing 0.1% or more of one or more amino acids and / or salts thereof, and the weight ratio of (a) to (b) is 1: 1 to 1: 1.
Water-in-oil emulsifier composition which is 46, (B) organically modified clay mineral 0.1-10.0%, and (C) silicon oil 1-20%
It is a water-in-oil emulsion containing and.

Next, the structure of the present invention will be described in detail. In the present invention, it is important that the fatty acid partial esters of polyhydric alcohol used in the water-in-oil emulsifier composition (A) are liquid at room temperature. This is because substances that are solid at room temperature, such as glycerol monostearate and sorbitan monostearate, do not separate into two layers and form an effective gel even when mixed with an aqueous amino acid solution.

The fatty acid partial ester of polyhydric alcohol which is liquid at room temperature can be derived from the following substances. The polyhydric alcohols used have 3 or more hydroxyl groups and are glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin,
Octaglycerin, nonaglycerin, decaglycerin,
Trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, sorbitol and the like.
Fatty acids that react with these polyhydric alcohols to form partial esters are selected from caprylic acid, capric acid, oleic acid, linoleic acid, ricinoleic acid, isooctanoic acid, isomyristic acid, isopalmitic acid, and isostearic acid. obtain.

[0007] These partial esters generally refer to monoesters, diesters, triesters and some tetraesters, pentaesters, etc., individually or as a mixture thereof. When a mixture is used, the preferable mixing ratio depends on the type of carboxylic acid and the number of hydroxyl groups of the polyhydric alcohol. For example, in a glycerol ester having three hydroxyl groups, those having a fatty acid having 8 carbon atoms mainly consisting of a mixture of diesters and triesters and those having 18 carbon atoms mainly consisting of a mixture of monoesters and diesters are preferable. Further, in fatty acids having 18 carbon atoms, esters having different hydroxyl groups, for example, glycerol or trimethylolpropane having 3 hydroxyl groups are mainly a mixture of mono and diesters, and diglycerol having 4 hydroxyl groups are mainly mono and diesters. Mixtures of some triesters are also preferred, which in the case of sorbitol with 6 hydroxyl groups mainly consist of diesters, triesters and some tetraesters. That is,
As the number of hydroxyl groups in the polyhydroxyl compound increases, the content of triester or tetraester gradually increases.

Of these partial esters, particularly preferable ones are glycerin mono-2-heptyl undecanoate, trimethylolpropane mono-2-heptyl undecanoate, diglycerin di-2-heptyl undecanoate, glycerin mono-9. -Methylheptadecanoate, trimethylolpropane mono-9-methylheptadecanoate, diglycerin di-9-methylheptadecanoate, pentaerythritol di9-methylheptadecanoate, glycerin monooleate, trimethylolpropane monooleate , Diglycerin diolate, glycerin diricinolate, sorbitan mono (di) oleate, sorbitan di (tri) oleate and the like.

Next, an ethylene oxide adduct of hydroxy fatty acid triglyceride is also a compound involved in the present invention. Hydroxy fatty acid triglyceride ethylene oxide adducts include ethylene oxide adducts of castor oil or hydrogenated castor oil, with a blend of at least about 1 mole to about 10 moles of ethylene oxide adduct being preferred.

As the substance which forms a water-in-oil type emulsifier composition in the presence of an amino acid or a salt thereof, the above-mentioned partial ester of a polyhydric alcohol having at least 3 or more hydroxyl groups and a fatty acid, and hydroxy. In addition to ethylene oxide adduct of fatty acid triglyceride,
Partial ester of polyhydric alcohol and fatty acid with 1 to 10 mol of ethylene oxide added, or partial ester of polyhydric alcohol with 1 to 10 mol of ethylene oxide and fatty acid, also selected from those which are liquid at room temperature Can be done. Specific examples of the former include ethylene oxide 1 to 1 such as glycerin di-2-heptyl undecanoate, glycerin-diolate, sorbitan di-2-heptyl undecanoate, sorbitan diolate.
An example is a 0 mol adduct. Specific examples of the latter include glycerin or sorbitol, ethylene oxide 1-
A compound obtained by partially esterifying 2-heptylundecanoic acid or oleic acid can be mentioned as the compound added with 10 mol.
Both are the same as the substance (A) (a) in the present invention,
Mix with an aqueous solution of an amino acid or its salt to form a water-in-oil emulsifier composition.

Next, in the present invention, the amino acids or salts thereof used in the water-in-oil emulsifier composition (A) are the following general food additives, amino acids known as non-pharmaceutical drugs or It may be selected from the salts. L-amino acid; L-alanine, β-alanine, L-arginine hydrochloride, L-asparagine monohydrate, L-aspartic acid, L-citrulline, L-glutamic acid, L-glutamic acid hydrochloride, L-glutamine, glycine , L-histidine, L-histidine hydrochloride monohydrate, L-hydroxyproline, L-isoleucine, L-leucine, L
-Lysine, L-lysine hydrochloride, L-ornithine hydrochloride,
L-proline, L-phenylalanine, L-serine, L
-Threonine, L-tryptophan, L-tyrosine, L
-Valine, L-doper and L-alpha aminobutyric acid. Of course, the same applies to the D isomer and DL isomer as isomers. Among these, particularly preferable are glycine, L-hydroxyproline, L-alanine and β.
An aqueous solution of alanine, L-proline, L-serine with suitable concentrations. Next, as the metal salt of the amino acid, a monovalent metal salt, that is, a salt of sodium, potassium, lithium, 2
There are calcium and magnesium salts of valent metal salts. Among these, particularly preferred are suitable concentrations of L-sodium aspartate monohydrate, potassium L-aspartate dihydrate, sodium L-glutamate monohydrate, and potassium L-glutamate monohydrate. It is an aqueous solution.

Water-in-oil type emulsifier composition (A) in the present invention
Is an aqueous solution of amino acids or salts thereof at various concentrations,
It is obtained by simply mixing the fatty acid partial esters of polyhydric alcohols or the ethylene oxide adducts of hydroxy fatty acid triglycerides in the appropriate proportions and continuing stirring until a water-in-oil gel is formed.

In the present invention, an aqueous solution of an amino acid or a salt thereof is added to a fatty acid partial ester of a polyhydric alcohol or an ethylene oxide adduct of hydroxycarboxylic acid triglyceride while gradually stirring to obtain an emulsion having a desired hardness or viscosity. It is desirable to continue the addition and stirring until a gel is obtained. At this time, it is a feature of the present invention that all the operations can be completed at room temperature. This is because the amino acid or its salt can be encapsulated in a water-insoluble complex without being decomposed or condensed by heating.

Although the amino acids or salts thereof have different solubilities in water, it is necessary to use an aqueous solution of 0.1% or more for the water-in-oil emulsion of the present invention. If it does not reach this concentration, the resulting composition is not fluid or long-term stability cannot be expected. Furthermore, the preferred state of obtaining the object of the present invention is that the amino acid or its salt is well soluble in water. Therefore, a highly concentrated aqueous solution gives a more reliable and somewhat transparent and stable water-in-oil emulsion. However, in a supersaturated aqueous solution, amino acid crystal precipitation occurs, which is not practical. For example, regarding L-sodium glutamate monohydrate, which is mentioned as one of the most preferable ones in the present invention, the desired water-in-oil content is obtained by adding an aqueous solution containing a concentration of 5% to 40%. A type emulsion can be obtained. A high concentration of 40% or more is not practical, and a low concentration of less than 5% results in a fluid water-in-oil emulsifier composition.

Furthermore, in the water-in-oil type emulsifier composition (A) of the present invention, (a) a mixture of fatty acid partial esters of polyhydric alcohol and / or ethylene oxide adduct of hydroxy fatty acid triglyceride and (b) amino acid and / or
Alternatively, the quantitative ratio of the salt to the aqueous solution has an appropriate ratio depending on the concentration of the aqueous solution. For example, in the case of the above-mentioned sodium L-glutamate monohydrate, in the case of a 5% aqueous solution, the compounding ratio of (a) to (b) is 1: 1 to 1: 1 by weight.
22, preferably in the range of 1: 2 to 1:10, 40
% Aqueous solution (a) to (b) is mixed in a weight ratio of 1: 1.
The desired product can be obtained in the range of ˜1: 46, preferably 1: 2 to 1:15.

The excess amount of the aqueous solution of the amino acid or its salt added to the inner phase of the water-in-oil type emulsifier composition (A) destroys the gel structure. The compounding ratio of (a) to (b) also varies within a certain range depending on the solubility of each of the other amino acids or salts thereof, but is 1: 1 to 1:46, and the preferable ratio is: The weight ratio is in the range of 1: 2 to 1:15. Here, particularly preferable combinations include glycine, β-alanine, L-hydroxyproline, L-proline, L-serine, sodium L-aspartate monohydrate, and potassium L-aspartate dihydrate. , L-sodium glutamate monohydrate, L-
It consists of an aqueous solution of potassium glutamate monohydrate and a highly concentrated aqueous solution whose concentration is closer to supersaturation, and fatty acid partial esters of polyhydric alcohols, and the ratio of the ester mixture to the aqueous solution of amino acids or their salts is 1: 1. ˜1: 46, preferably a mixture consisting of a ratio of 1: 2 to 1:15.

In order to obtain the water-in-oil emulsion which is stable and has excellent usability by adding the water-in-oil type emulsifier composition described above, it is necessary to further add an organically modified clay mineral. The organically modified clay mineral used in the present invention is a kind of colloidal hydrous aluminum silicate having a three-layer structure and is generally represented by the following general formula 1.

[0018]

Embedded image (X, Y) _2-3 (Si, Al) ₄ O ₁₀ (OH)
₂ Z _1/3 · nH ₂ 0 However, X = Al, Fe (III), Mn (III), Cr (II
I) Y = Mg, Fe (II), Ni, Zn, Li Z = K, Na, Ca

Specifically, natural or synthetic montmorillonites such as montmorillonite, saponite, and hectorite (wherein the (OH) group in the formula is replaced with fluorine) (veegum, kunipia, laponite as commercial products) Etc.) and sodium mica known as sodium silicic mica, or synthetic mica known as sodium or lithium teniolite (commercially available Dimonite: Topy Industries Co., Ltd., etc.) and other clay minerals, and quaternary ammonium salt type cation interfaces. Obtained by treating with an activator. The quaternary ammonium salt type cationic surfactant used here is
It is represented by the following general formula 2.

[0020]

Embedded image

For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethyl. Ethyl ammonium chloride,
Aralkyldimethylethylammonium chloride, behenyldimethylethylammonium chloride, myristyldiethylmethylammonium chloride, cetyldiethylmethylammonium chloride, stearyldiethylmethylammonium chloride, aralkyldiethylmethylammonium chloride, behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, Benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride,
Benzyl methyl ethyl cetyl ammonium chloride, benzyl methyl ethyl stearyl ammonium chloride,
Dibehenyldihydroxyethylammonium chloride,
And corresponding bromide and the like, and further dipalmitylpropylethylammonium methylsulfate and the like. In carrying out the present invention, one or more of these are arbitrarily selected.

Typical organic modified clay minerals include dimethylalkylammonium hectorite, benzyldimethylstearylammonium hectorite, distearyldimethylammonium chloride treated aluminum magnesium silicate and the like. As a commercial product,
Benton 38 (montmorillonite treated with distearyl dimethyl ammonium chloride: National Red Co.) and the like. These montmorillonite type organically modified clay minerals are
It is preferable to add 0.1 to 10.0% by weight of the total amount of the water-in-oil emulsion, and more preferably 0.1 to 4.
0% by weight is compounded. If it is less than 0.1% by weight, it is difficult to obtain sufficient stability, and if it is added up to 10.0% by weight, sufficient stability can be obtained.
It is not preferable in terms of usability, such as poor removal to the fingers and heavy elongation on the skin.

In order to further improve usability, it is necessary to add silicone oil. The silicone oil used in the present invention is, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, decamethylpolysiloxane, dodecamethylpolysiloxane, tetramethyltetrahydrogenpolysiloxane, amino acid. A modified silicone is mentioned. As a dimethylpolysiloxane oil, the viscosity at 25 ° C. is 0.65 to 5000
cst, methylphenylpolysiloxane oil having a viscosity at 25 ° C. of 10 to 1000 cst,
Examples of the cyclic dimethylpolysiloxane oil include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane. The blending amount of these oil components is not particularly limited, but the total amount is preferably 1 to 20%. If it is less than 1%, the usability-improving effect is not seen so much, and if it exceeds 20%, stability is not preferable.

The oil component used in the water-in-oil emulsion of the present invention includes avocado oil, camellia oil, macadamia nut oil, corn oil, mink oil, as animal and vegetable oil.
Olive oil, rapeseed oil, egg yolk oil, sesame oil, wheat germ oil,
Castor oil, linseed oil, safflower oil, cottonseed oil, soybean oil,
Peanut oil, tea seed oil, rice bran oil, jojoba oil, germ oil, and the like, hydrocarbon-based oil components include liquid paraffin, ozokerite, squalene, squalane, lanolin derivatives, pristane, ceresin, vaseline, microcrystalline wax, and the like. . Further, as the esters,
Isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate,
Butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 1,2-hydroxystearate, di2 -Ethylene glycol ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, di-2-
Ethylhexyl trimethylolpropane, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexylate, glyceryl tri-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2
-Ethylhexyl palmitate, glycerin trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, cetostearyl alcohol, acetoglyceride,
2-Heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-myristic acid Hexyldecyl, 2-hexyldecyl palmitate, adipine 2-hexyldecyl, diisoprovir sebacate, ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, triglycerin, glyceryl trioctanoate, glyceryl triisopalmitate. Etc. The blending amount of these oil components is not particularly limited, but it is an amount capable of obtaining a water-in-oil emulsion, and is a total amount of 0.
1 to 70% by weight is preferable.

[0025]

EXAMPLES Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this. Prior to the examples, the evaluation method adopted in each example will be described.

[Evaluation Method] Usability (freshness, spread, cream fingers, etc.) was evaluated by a specialized panel based on the following evaluation criteria. Refreshing ◎ ……… Refreshing ○ ……… Slightly refreshing △ ………… Slightly sticky × ……… Sticky spread ◎ ……… Slightly spread ○ ……… Slightly spread △ ……… Slightly spread out × ……… Which cream finger has a heavy spread ◎ ………… Which cream finger is good ○ ……… Which cream finger is slightly good △ ……… Cream finger Which is slightly bad × ……… Cream finger Two months after the badness of the cream, the following evaluations were performed on the stability at 50 ° C., 37 ° C., room temperature and 0 ° C. Appearance ◎ ……… No abnormality ○ ……… Slight oil floating in some areas △ ………… Oil floating × ……… Separation

Examples 1 to 6 and Comparative Examples 1 to 4 First, water-in-oil emulsifier compositions having the following compositions were prepared. ───────────────────────────────── (i) (ii) ─────────── ────────────────────── Purified water 50 parts 184 parts Monosodium L-glutamate 20 46 Diglyceroldiolate 5 5 ────────── ──────────────────────── * Dissolve monosodium L-glutamate in water, stir and mix the aqueous solution with diglyceroldiolate, A water-in-oil emulsifier composition is obtained. (The same applies to Examples 7 and 8. Next, using the obtained water-in-oil emulsion, a water-in-oil emulsion having the composition shown in Table 1 was prepared and evaluated. The emulsion preparation method is as follows: (2), (3),
(4) and (5) were melted at 70 ° C, (1) was added, and (6) was added to the homogeneously dispersed mixture with a homomixer.
After uniform dispersion with a homomixer, (7) was gradually added and uniformly dispersed with a homomixer, the emulsified particles were prepared, and the mixture was cooled to room temperature with a heat exchanger to obtain a water-in-oil emulsion. Example 1
Table 1 shows the compositions and the evaluation results of Comparative Examples 1 and 2.

[0028]

[Table 1]

Example 7 (1) Water-in-oil type emulsifier composition (Note 1) 15.0% by weight (2) Liquid paraffin 20.0 (3) Dimethyl polysiloxane 20.0 (4) Ceresin 5. 0 (5) Benton 27 2.0 (6) Water 38.0 (7) Preservative Suitable amount (8) Perfume Suitable amount (Note 1) Pentaerythritol di-9-methylheptadecanoate 5.0 parts L-Glutamic acid Sodium monohydrate 4.0 L-serine 1.0 Water 40.0 (2) (3) (4) (7) (8) dissolved in 70 ^OC , (5) was added and homogenized. After uniformly dispersing with a mixer, (1) is added and further dispersed with a homomixer. (6) was gradually added to this, and the mixture was uniformly dispersed with a homomixer. The emulsified particles were adjusted and cooled to room temperature with a heat exchanger to obtain a water-in-oil emulsion.

Example 8 (1) Water-in-oil type emulsifier composition (Note 2) 20.0% by weight (2) Squalane 10.0 (3) Methylphenylpolysiloxane 20.0 (4) Beeswax 2 .0 (5) Benton 27 4.0 (6) Water 44.0 (7) Preservative proper amount (8) Perfume proper amount (Note 2) Glycerol monooleate (40% α-monoglyceride) 4.0 parts L-Ballin 0 0.4 Water 7.6 (2) (3) (4) (7) (8) dissolved in 70 ^OC was added with (5), and the mixture was homogenized with a homomixer, then (1) was added. In addition, the mixture is uniformly dispersed with a homomixer. (6) was gradually added to this, and the mixture was uniformly dispersed with a homomixer. The emulsified particles were adjusted and cooled to room temperature with a heat exchanger to obtain a water-in-oil emulsion.

[0031]

According to the present invention, a water-in-oil emulsion containing an amino acid and / or a salt thereof having an excellent action on the skin and having a refreshing usability was obtained.

Claims (2)

[Claims] 1. A selected from the group consisting of (A) (a) a partial ester of a polyhydric alcohol having at least three or more hydroxyl groups in the molecule and a fatty acid, and a hydroxy fatty acid triglyceride to which 1 to 10 mol of ethylene oxide is added. It consists of a substance that is liquid at room temperature and (b) an aqueous solution containing 0.1% or more of one or more amino acids and / or salts thereof, and the ratio of (a) to (b) is 1 by weight. A water-in-oil emulsifier composition of 1: 1 to 1:46,
A water-in-oil emulsion containing (B) 0.1 to 10.0% of an organically modified clay mineral and (C) 1 to 20% of silicon oil. 2. The water-in-oil emulsion according to claim 1, wherein the water-in-oil emulsifier composition (A) and the organically modified clay mineral are used.
A water-in-oil emulsion in which the compounding ratio of (B) is in the range of 1: 0.1 to 1:10.