JPH10194924A - Water-in-oil type emulsified composition and skin lotion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-in-oil type emulsified composition having extremely excellent temperature stability by adding a specific compound or its salt to a system using an organic-modified clay mineral as a emulsifier. SOLUTION: This water-in-oil type emulsified composition comprises an organic-modified clay mineral obtained by treating a water-swelling clay mineral which is one kind of colloidal water-containing aluminum silicate having three- layer structure of formula I (X is Al, etc.; Y is Mg, etc.; Z is K, etc.) with a quaternary ammonium salt type cationic surfactant of formula II (R1 is an alkyl, etc.; R2 is methyl, etc.; R3 and R4 are each an alkyl, etc.; X is halogen, etc.) and a nonionic surfactant, an amino acid or its salt, oil content and water, L-Arginine or its hydrochloride, L-glutamic acid or its sodium salt is preferably used as the amino acid or its salt. The formulation amount of the amino acid or its salt is preferably 0.01-10.0wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water-in-oil emulsion composition (W / O emulsion composition) and an external preparation for skin containing the same. More specifically, a water-in-oil emulsion composition which has excellent temperature stability and can be widely used as an external phase oil component from polar oils to non-polar oils, and has extremely excellent temperature stability and usability containing the same. Skin external preparation.

[0002]

2. Description of the Related Art Conventionally, a water-in-oil type using an organically modified clay mineral obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant as an emulsifier. Emulsified compositions are known (Patent Publication No. 2-14098).

[0003]

The inventors of the present invention have conducted further studies on a water-in-oil type emulsion composition using the above-mentioned organically modified clay mineral as an emulsifier. As a result, an amino acid or a salt thereof is added to this system. Surprisingly, the stability is improved even more unexpectedly, and the skin external preparation using this water-in-oil type emulsion composition has an unexpected effect of giving an excellent feeling of use that is light and non-sticky. The present inventors have found out and completed the present invention based on this finding.

An object of the present invention is to provide a water-in-oil type emulsion composition having extremely excellent temperature stability and a skin external preparation using the same which is extremely excellent in temperature stability and usability.

[0005]

That is, the present invention relates to an organically modified clay mineral obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant. An object of the present invention is to provide a water-in-oil emulsion composition comprising one or more selected from amino acids or salts thereof, an oil component and water.

Further, the present invention provides the above-mentioned water-in-oil emulsion composition, wherein the amino acid or a salt thereof is L-arginine or a hydrochloride thereof, L-glutamic acid or a sodium salt thereof. Is what you do.

Further, the present invention provides the above-mentioned water-in-oil emulsion composition, wherein the content of the amino acid or a salt thereof is 0.01 to 10.0% by weight. is there.

The present invention also provides a skin external preparation characterized by containing the above-described water-in-oil emulsion composition.

Hereinafter, the configuration of the present invention will be described in detail. The organically modified clay mineral used as an emulsifier in the present invention is obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant.
The water-swellable clay mineral is a kind of colloidal hydrated aluminum silicate having a three-layer structure, and is generally represented by the following general formula [Chemical Formula 1].

## STR1 ## _{(X, Y) 2 ~ 3} (Si, Al) 4 O 10 (OH) 2
Z _1/3 · nH ₂ O, where X = Al, Fe〓, Mn〓, Cr〓 Y = Mg, Fe〓, Ni, Zn, Li Z = K, Na, Ca Montmorillonite, natural or synthetic, such as montmorillonite, savonite, hectorite, etc. (in this case, those in which the (OH) group in the formula is replaced with fluorine) (commercially available products include veegum, kunipiaraponite, etc.) and Examples thereof include sodium silicic mica, and synthetic mica known as sodium or lithium teniolite (a commercially available product is Dimonite; Topy Industries, Ltd.).

A quaternary ammonium salt type cationic surfactant used for treating the water-swellable clay mineral is represented by the following general formula (2):

Embedded image (Wherein, R ₁ is an alkyl group or benzyl group having 10 to 22 carbon atoms, R ₂ is a methyl group or an alkyl group having 10 to 22 carbon atoms, R ₃ and R ₄ are an alkyl group or hydroxy group having 1 to 3 carbon atoms) An alkyl group, X represents a halogen atom or a methyl sulfate residue.)

For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, behenyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyldimethylammonium chloride, stearyldimethylammonium chloride Aralkyl dimethyl ammonium chloride, behenyl dimethyl ammonium chloride, cetyl diethyl ammonium chloride, stearyl diethyl ammonium chloride, stearyl diethyl ammonium chloride, aralkyl diethyl ammonium chloride, behenyl diethyl ammonium chloride,
Benzyl dimethyl myristyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, benzyl dimethyl stearyl ammonium chloride, benzyl dimethyl behenyl ammonium chloride, benzyl dimethyl ethyl cetyl ammonium chloride, benzyl dimethyl ethyl stearyl ammonium chloride, distearyl dimethyl ammonium chloride, dibehenyl dihydroxy Ethyl ammonium chloride, the corresponding bromide, and the like, and dipalmityl uropyr ethyl ammonium methyl sulfate, and the like, and one or more of these are arbitrarily selected and treated.

The nonionic surfactant used for treating the water-swellable clay mineral has an HLB value of 2 to 16%.
And 3 to 12 are more preferable.
For example, addition of 2 to 30 moles of polyoxyethylene (hereinafter abbreviated as POE (2 to 30)). ｝ Oleyl ether, P
OE (2-35) stearyl ether, POE (2-2
0) lauryl ether, POE (1-20) alkyl phenyl ether, POE (6-18) behenyl ether, POE (5-25) 2-decyl pentadecyl ether, POE (3-30) 2-decyl tetradecyl ether, POE (8-16) 2-octyldecyl ether,
And POE (4-60) hydrogenated castor oil, POE (3-14) fatty acid monoester, P
OE (6-30) fatty acid diester, POE (5-2)
0) ester-type activators such as sorbitan fatty acid esters,
POE (2-30) glyceryl monoisostearate, POE (10-60) glyceryl triisostearate, POE (7-50) hydrogenated castor oil monoisostearate, POE (12-60) hydrogenated castor oil triiso Ethylene oxide addition type surfactants such as ether ester type activators such as stearate and polyvalent such as glycerin fatty acid esters such as decaglyceryl tetraolate, hexaglyceryl triisostearate, diglyceryl diisostearate and glyceryl monooleate. Alcohol fatty acid ester type surfactants are exemplified. Among these, polyglycerin fatty acid esters of diglycerin or higher such as decaglyceryl tetraolate, hexaglyceryl triisostearate, diglyceryl diisostearate, POE (2 to 12) lauryl ether, POE (6
-15) POE-added ether type activity such as behenyl ether, POE (5-20) 2-decylpentadecyl ether, POE (5-17) 2-decyltetradecyl ether, POE (8-16) 2-octyldecyl ether, etc. Agent, and POE (10-20)) hydrogenated castor oil, PO
E (5-14) oleic acid monoester, POE (6 ~
20) POE addition ester type activators such as oleic acid diester, POE (5-10) sorbitan olein ester, POE such as POE (3-15) glyceryl monoisostearate, POE (10-40) glyceryl triisostearate Particularly preferred are nonionic surfactants of the ethylene oxide addition type, such as addition ether ester activators. One or more of these nonionic surfactants are arbitrarily selected and used.

The organically modified clay mineral used in the present invention is:
For example, the above water-swellable clay mineral, the quaternary ammonium salt type cationic surfactant and the nonionic surfactant are dispersed and stirred in a low boiling point solvent such as water, acetone or lower alcohol, or A water-swellable clay mineral and a quaternary ammonium salt-type cationic surfactant are treated in a low-boiling solvent to obtain a cation-modified clay mineral, then treated with a nonionic surfactant, and then the low-boiling solvent is removed. It is obtained by doing. In addition, an organically modified clay mineral and a nonionic surfactant treated only with a quaternary ammonium salt type cationic surfactant are added to a water-in-oil emulsion composition to form a water-in-oil emulsion composition. It is also possible to treat with a non-ionic surfactant.

When the quaternary ammonium salt type cationic surfactant and the nonionic surfactant penetrate between the layers, the interlayer distance of the water-swellable clay mineral is widened. By measuring the interval, the presence or absence of adsorption of the quaternary ammonium salt type cationic surfactant and the nonionic surfactant can be confirmed.

When the organically modified clay mineral is subjected to Soxhlet extraction using chloroform, ether, etc., the surfactant between the layers is washed away, and the extract is subjected to gas chromatography analysis, thermal decomposition temperature measurement or thermal decomposition amount analysis. The presence of a surfactant can be confirmed by measurement (DTA-TG measurement) or the like.

The content of the quaternary ammonium salt type cationic surfactant in the organically modified clay mineral used in the present invention is 60 to 140 milliequivalents (hereinafter abbreviated as meq) to 100 g of the water-swellable clay mineral. Is preferred. The content of the nonionic surfactant in the organically modified clay mineral is preferably from 5 to 200 g, more preferably from 15 to 170 g, per 100 g of the water-swellable clay mineral.

The amount of the organically modified clay mineral to be added to the water-in-oil emulsion composition of the present invention is 0.25 to 5% by weight, and 0.5 to 3% by weight based on the total amount of the emulsion composition. preferable.

The amino acids and salts thereof used in the present invention are D- and L-form amino acids and salts thereof, for example, alanine, glycine, arginine, lysine, tryptophan, serine, glutamine, glutamic acid, asparagine, aspartic acid, tyrosine, Threonine, cysteine, phenylalanine, histidine, leucine, isoleucine, methionine, proline, valine and the like,
One kind or two or more kinds are arbitrarily selected and used. Particularly preferred are L-arginine and its hydrochloride, L-glutamic acid and its sodium salt.

The amount of the amino acid or salt thereof to be incorporated in the water-in-oil emulsion composition of the present invention is 0.001 to 20% by weight, and 0.01 to 10% by weight based on the total amount of the emulsion composition. preferable. In the present invention, temperature stability and usability can be surprisingly improved by blending an amino acid or a salt thereof with the water-in-oil emulsion composition.

As the oil used in the present invention, all common oils used in cosmetics, quasi-drugs, pharmaceuticals, etc. can be used, and the range can be widely used from polar oils to non-polar oils. . Examples of oil components include hydrocarbon oils such as liquid paraffin, squalane, isoparaffin, and branched paraffin; ester oils such as isopropyl myristate and cetyl isooctanoate; decamethylpentasiloxane; dimethylpolysiloxane; Examples include silicone oils such as siloxane.
In addition, waxes such as petrolatum, microcrystalline, lanolin, and beeswax can be added as long as the effects of the present invention are not impaired.

The amount of the oil component to be incorporated in the water-in-oil emulsion composition of the present invention is 5 to 90% by weight based on the total weight of the emulsion composition.
And preferably 10 to 80% by weight.

Other water-soluble components can be added to water, which is an essential component of the present invention, as long as the effects of the present invention are not impaired.

The water-in-oil emulsion composition of the present invention can be produced by a conventional method by blending an oil-soluble substance and a water-soluble substance in addition to the above-mentioned essential components, if necessary, as long as the effects of the present invention are not impaired. I can do it. For example, a drug, a humectant, a thickener, a preservative, a metal-sequestering agent, a component used in ordinary cosmetics, quasi-drugs, and pharmaceuticals such as fragrances are blended, and the skin of a water-in-oil emulsion composition is formed by an ordinary method. An external preparation can be manufactured. In addition, the said essential component is mix | blended with all the skin external preparations which are water-in-oil emulsion compositions, respectively. The external preparation for skin of the present invention is used as cosmetics such as skin cosmetics and hair cosmetics, quasi-drugs, and pharmaceuticals.

[0024]

Next, the present invention will be described in more detail by way of examples. The present invention is not limited by this. The numbers in the examples represent% by weight.

First, an example of the preparation of an organically modified clay mineral used as an emulsifier in the present invention is shown below. "Preparation Example 1" 45 g of benzyldimethylstearyl ammonium chloride (corresponding to about 100 meq) and POE (6)
An aqueous solution 50 in which 30 g of lauryl ether is dissolved at 50 ° C.
To 0 ml, 100 g of Vegum (trade name of Vanderbilt U.S.A.), which is a water-swellable clay mineral, was added, and sufficiently dispersed and mixed with a disper for about 30 minutes. Next, after removing water with a filter, it was dried for about 24 hours to obtain an organically modified clay mineral used in the present invention.

Example 1: Water-in-oil emulsion composition 1 part of the organically modified clay mineral obtained in Production Example 1 was mixed with 30 parts of cetyl isooctanoate to form an oil phase in advance, and then 70 parts of water And 1 part of L-arginine hydrochloride were added at room temperature and stirred and emulsified with a homomixer to produce a water-in-oil emulsion composition of the present invention.

"Example 2: Water-in-oil emulsion composition" One part of the organically modified clay mineral obtained in Production Example 1 was mixed with 30 parts of decamethylpentasiloxane to form an oil phase in advance, and then 70 parts of water was added. One part of sodium L-glutamate was added at room temperature and stirred and emulsified with a homomixer to produce a water-in-oil emulsion composition of the present invention.

Next, a skin external preparation comprising the water-in-oil type emulsion composition of the present invention was produced, and its temperature stability and usability were evaluated. In addition, what was obtained according to Production Example 1 was used as the organically modified clay mineral.

Example 3 Moisture Cream (1) Squalane 20.0 (2) Cetyl isooctanoate 8.5 (3) 1.0 g of Vegum was added to 0.2 g of benzyldimethyl ammonium chloride and distearyl dimethyl ammonium Organically modified clay mineral obtained by treating with 0.1 g of chloride and 0.2 g of POE (10) glycerol triisostearate 1.5 (4) L-arginine hydrochloride 0.1 (5) Perfume appropriate amount (6) ) Paraoxybenzoic acid 0.2 (7) Glycerin 10.0 (8) Water 59.7 "Preparation method" (1) to (5) are mixed and dispersed to prepare an oil phase in advance. Next, a solution obtained by uniformly dissolving (6) to (9) was added to the oil phase while gradually stirring with a disper to obtain a moisture cream of the present invention.

“Example 4: Night Cream” (1) Squalane 30.0 (2) Lanolin 1.0 (3) Microcrytalin wax 1.0 (4) 0.5 g of Benton 38 was POE (14) Diolein Organically modified clay mineral obtained by treating with 0.05 g of acid ester 0.6 (5) Sodium L-glutamate 1.0 (6) Butyl parahydroxybenzoate 0.1 (7) Suitable amount of perfume (8) Pyrrolidone carboxylic acid Sodium acid 4.0 (9) Propylene glycol 5.0 (10) Water 57.3 "Preparation method" The night cream of the present invention was obtained in the same manner as in Example 3.

Comparative Example 1 Moisture Cream A moisture cream was produced in the same manner as in Example 3 except that L-arginine hydrochloride was omitted from the formulation of Example 3.

Comparative Example 2: Night Cream A night cream was produced in the same manner as in Example 4 except that sodium L-glutamate was omitted from Example 4.

Table 1 shows the results of temperature stability of Examples 1, 2, 3, and 4 and Comparative Examples 1 and 2, and the results of actual use tests by six women-only panels of Examples 3 and 4 and Comparative Examples 1 and 2. Shown in The results of the temperature stability test were evaluated by the appearance after standing for one month, and the actual use test was evaluated by the following evaluation criteria. “Temperature stability” ○: No separation is observed at all △: Almost no separation is observed ×: Separation of liquid phase (oil phase or aqueous phase) occurs “Usability” A: Smooth and moist feeling without stickiness B: Smooth feel C: Moist feel

[0034]

[Table 1] From Table 1, it can be seen that the water-in-oil emulsion composition and the external preparation for skin of the present invention have excellent temperature stability, and also have excellent usability that can give a smooth and moist feeling without stickiness. You can see that.

According to the present invention, a water-in-oil emulsion composition having excellent temperature stability can be provided. The water-in-oil emulsified composition of the present invention requires only a small amount of the organically modified clay mineral used as an emulsifier, and it is also possible to use a highly polar oil component which has conventionally been difficult to mix. Furthermore, since the water-in-oil emulsion composition of the present invention has reduced stickiness, which is the feeling of use of the conventional water-in-oil emulsion composition, and has a low elongation when applied to the skin, the skin has excellent usability. An external preparation can be provided.

Claims (4)

[Claims] An organically modified clay mineral obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and a nonionic surfactant, and one or more selected from amino acids or salts thereof. A water-in-oil type emulsion composition comprising two or more, an oil component and water. 2. The water-in-oil emulsion composition according to claim 1, wherein the amino acid or a salt thereof is L-arginine or a hydrochloride thereof, L-glutamic acid or a sodium salt thereof. 3. The content of the amino acid or a salt thereof,
The water-in-oil emulsion composition according to claim 1 or 2, wherein the content is 0.01 to 10.0% by weight. 4. An external preparation for skin, comprising the water-in-oil emulsion composition according to claim 1, 2, or 3.