JPH1176799A - O/w/o multi-phase emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an O/W/O multi-phase emulsion having high aging stability and satisfactory usability. SOLUTION: In the O/W/O multi-phase emulsion contg. an O/W emulsion dispersed in outer phase oil 10, the O/W emulsion of an inner phase contains an amphiphilic substance and an N-long chain acyl acidic amino acid monosalt capable of forming gel at ordinary temp. or above in an amphiphilic substance- N-long chain acyl acidic amino acid monosalt-oil-water system, an oil component 14 and water 12, and the outer phase oil 10 contains an organically modified clay mineral and an emulsifier having an HLB of <=7. The weight ratio between the O/W emulsion and the outer phase oil 10 is 2:3 to 19:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an O / W / O type composite emulsion. More specifically, the present invention relates to an O / W / O type composite emulsion obtained by dispersing an O / W type emulsion in an external phase oil and having excellent temporal stability.

[0002]

2. Description of the Related Art An oil-in-water-in-oil emulsion composition in which an oil-in-water emulsion composition (hereinafter referred to as an O / W emulsion) is further emulsified and dispersed in an oil phase is an O / W / O composite emulsion. Or, it is called an O / W / O type multiple emulsion and has become important in various industrial uses such as cosmetics, foods, and pharmaceuticals.

[0003] That is, while a normal O / W emulsion is simply an oil phase dispersed in an aqueous phase,
As shown in FIG. 1, the particle structure of the O / W / O type composite emulsion has a structure in which an internal phase oil 14 is further dispersed in an aqueous phase 12 dispersed in an external phase oil 10.

For this reason, a simple O / W type or W / O
It is possible to provide a special feeling of use that cannot be obtained with a type emulsion.

On the other hand, in order to obtain a stable composite emulsion, for example, Japanese Patent Application Laid-Open No. 8-323188 discloses a method of preparing an O / W type fine emulsion as an internal phase using a hydrophilic nonionic activator. It describes a step of dispersing and emulsifying an O / W emulsion in an oily component that becomes an external phase oil containing an organically modified clay mineral, and a composite emulsion obtained by this preparation method is a union of an internal phase oil and an external phase oil. Is suppressed, and the stability over time is remarkably increased.

[0006]

However, usually,
It has been practiced to blend solid or semi-solid oil components such as higher alcohols and waxes in order to improve the familiarity of the cream.
In the case of the W / O type complex emulsion, when these solid and semi-solid oil components are blended with the internal phase O / W type emulsion or the external phase oil emulsified by using a nonionic surfactant, the stability with time is deteriorated. was there.

[0007] In view of the above viewpoint, the present inventors have proposed a stable O
As a result of intensive studies to obtain a / W / O type composite emulsion, the amphipathic substance composed of a specific combination and N-
A long-chain acyl acidic amino acid monosalt is contained in an O / W emulsion, and an organically modified clay mineral and H
An emulsifier having an LB of 7 or less is contained so that O
By dispersing the / W emulsion in the external phase oil, a solid or semi-solid oil can be stably blended into the O / W emulsion of the internal phase, and the base is improved in adaptability to the skin. / W / O type composite emulsion was found to be obtained, and the present invention was completed.

According to the present invention, the oil content contained in the O / W emulsion serving as the internal phase is not limited, and even when a solid or semi-solid oil component is contained in order to improve the usability, the stability over time is excellent. It is another object of the present invention to provide an O / W / O type composite emulsion.

[0009]

That is, the present invention relates to an O / W / O type composite emulsion in which an O / W type emulsion is dispersed in an external phase oil, wherein an O / W type emulsion of an internal phase is added to an amphiphilic compound. Substance-N-long-chain acyl-acid amino acid monosalt-oil-ampholyte selected from those capable of forming a gel at room temperature or higher in an aqueous system and an N-long-chain acyl-acid amino acid monosalt, an oily component, Water and an organically modified clay mineral and an emulsifier having an HLB of 7 or less in the external phase oil, wherein the weight ratio of the O / W emulsion to the external phase oil is 2: 3 to 19: 1. An object of the present invention is to provide an O / W / O type composite emulsion characterized by the following.

Further, the present invention provides the above O / W / O type composite emulsion, wherein the amphiphilic substance is a higher alcohol and / or a higher fatty acid having a carbon chain length of 12 or more. To provide.

Further, the present invention is characterized in that the N-long-chain acyl acidic amino acid monosalt contained in the O / W emulsion of the internal phase is N-stearoyl-L-glutamic acid monosalt. An O / W / O type composite emulsion is provided.

The present invention also provides an O / W emulsion of the internal phase containing an N-long-chain acyl acidic amino acid disalt, the content of which is based on the N-long-chain acyl acidic amino acid monosalt. An object of the present invention is to provide the O / W / O type composite emulsion described above, wherein the molar ratio is 0.25 times or less.

Furthermore, the present invention relates to the above-mentioned amphiphile and N
-O based on the total amount of long-chain acyl acidic amino acid monosalt
The present invention provides the above-mentioned O / W / O type composite emulsion, wherein the internal phase oil of the / W type emulsion is contained in an amount of 1/2 or more.

The present invention also relates to the present invention, wherein the amphipathic substance and N-
The above-mentioned O / W, wherein the long-chain acyl acidic amino acid monosalt is present at the oil droplet interface of the O / W emulsion, and its abundance is 90% or more of the total content by peak area ratio by DSC. / O type complex emulsion is provided.

Further, the present invention relates to the above-mentioned amphiphilic substance and N
-The above-mentioned O / W / O composite emulsion, wherein the total amount of the long-chain acyl acidic amino acid monosalt is 0.2% by weight or more based on the aqueous phase of the O / W emulsion. It is.

Further, in the present invention, the organically modified clay mineral is obtained by treating a water-swellable clay mineral with a quaternary ammonium-type cationic surfactant and a nonionic surfactant. The above-mentioned O / W / O type composite emulsion is provided.

Further, the present invention provides an O / W emulsion by adding an oily component to be an internal phase oil to an aqueous phase containing an N-long-chain acyl acidic amino acid monosalt and subjecting it to high-pressure emulsification or ultrasonic treatment. Adjusting the O / W emulsion and dispersing and emulsifying the O / W emulsion in an oily component which is an external phase oil containing an organically modified clay mineral and an emulsifier having an HLB of 7 or less. It is intended to provide a method for producing an O-type composite emulsion.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

The amphiphilic substance blended in the O / W emulsion used as the internal phase in the present invention has a surface activity, but itself has a strong hydrophobicity and does not have the surface activity as a general surfactant. For example, higher fatty acids, higher fatty alcohols, monoglycerides, glycerol monoalkyl ethers, monoalkylamines, sterols, free N-long-chain acyl acidic amino acids and the like can be used. Preferred are higher fatty acids, higher fatty alcohols, and N-long-chain acyl acidic amino acids, and particularly preferable are higher fatty acids and / or higher fatty alcohols.

The higher fatty acids and higher fatty alcohols are
Those having 12 or more carbon atoms are preferred, and those having 16 or more carbon atoms are particularly preferred. Further, the N-long-chain acyl acidic amino acid preferably has a long-chain acyl group having 12 or more carbon atoms, and particularly preferably has 16 or more carbon atoms. If the number of carbon atoms is small, problems such as insufficient emulsification stability may be caused.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid (behenic acid), oleic acid, 12-hydroxystearic acid, undecylenic acid, tallic acid, isostearic acid, linoleic acid, Linoleic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and the like can be mentioned, and higher aliphatic alcohols include, for example, higher alcohols corresponding to these higher fatty acids.

Examples of N-long-chain acyl acidic amino acids include N-stearoyl-L-glutamic acid, N-palmitoyl-L-glutamic acid, and N-myristoyl-L-amino acid.
Glutamic acid, N-lauryl-L-glutamic acid, N-
Coconut oil-L-glutamic acid, N-stearoyl-L-aspartic acid, N-palmitoyl-L-aspartic acid, N-myristoyl-L-aspartic acid, N-lauryl-L-aspartic acid, N-coconut oil-L- Aspartic acid and the like.

The mono-salt of N-long-chain acyl acidic amino acid to be mixed in the O / W emulsion is defined as one of a plurality of carboxyl groups of the N-long-chain acyl acidic amino acid in which one carboxyl group is neutralized to form a salt. Means what became. N-
A long-chain acyl acidic amino acid is an amino acid in which a long-chain acyl group is covalently bonded to a nitrogen atom of an acidic amino acid, and the long-chain acyl group bonded to the acidic amino acid may be either linear or branched, Moreover, it does not matter whether it is saturated or unsaturated. The long-chain acyl group preferably has 12 or more carbon atoms, particularly preferably 16 or more. If the number of carbon atoms is small and the chain length is short, sufficient emulsion stability may not be obtained.

The N-long-chain acyl acidic amino acid monosalt used in the present invention includes, for example, N-stearoyl-L-glutamic acid monosalt, N-palmitoyl-L-glutamic acid monosalt, N-myristoyl-L-glutamic acid monosalt N-lauroyl-L-glutamic acid monosalt, N-coconut oil-L-glutamic acid monosalt, N-stearoyl-L
-Aspartic acid monosalt, N-palmitoyl-L-aspartic acid monosalt, N-myristoyl-L-aspartic acid monosalt, N-lauroyl-L-aspartic acid monosalt, N-coconut oil-L-aspartic acid monosalt And the like. The counter ion of the N-long-chain acyl acidic amino acid is not particularly limited, but is preferably, for example, sodium, potassium, triethanolamine or the like.

The N-long-chain acyl acidic amino acid has at least two carboxyl groups in the molecule. -The form is changed to long-chain acyl acidic amino acid monosalt, N-long-chain acyl acidic amino acid disalt. For example, when the N-long chain acyl acidic amino acid is N-stearoyl-L-glutamic acid,
When one amino group and two carboxyl groups are present in one molecule and the neutralization ratio is 0, (1-a) in FIG.
It is considered that all exist in an acidic form as in When the mixture is neutralized by adding an alkali, for example, sodium hydroxide, the proportion of the monosodium salt type (1-b) gradually increases, and at a neutralization ratio of 50%, all N-stearoyl-L- Glutamic acid is considered to be in the monosodium salt form (1-b). When sodium hydroxide is further added, the monosodium salt type becomes disodium salt type (1-
c), and it is considered that all the N-stearoyl-L-glutamic acids are in the disodium salt type (1-c) at a neutralization ratio of 100%.

As described above, the form of the N-long-chain acyl acidic amino acid changes depending on the neutralization ratio, and the acidic form of the N-long-chain acyl acidic amino acid is used as the amphiphilic substance of the present invention as described above. It is possible. For example, when an alkali is used in combination with N-stearoyl-L-glutamic acid so as to have a neutralization rate of 25%, the molar ratio of the acidic form and the monosalt form of N-stearoyl-L-glutamic acid is 1%. , Each of which can function as an amphiphile and an N-long chain acyl acidic amino acid monosalt used in the present invention.

On the other hand, the N-long-chain acyl acidic amino acid disalt also forms an association with the amphipathic substance, but the N-long-chain acyl acidic amino acid disalt forms an association with the amphipathic substance as compared with the association formed between the monosalt and the amphiphile. The strength is so low that a sufficient effect cannot be exhibited. When a disalt is used, the pH of the system becomes 11 or more, which is a strong alkali, and is not suitable for practical use. Accordingly, when the N-long-chain acyl acidic amino acid and the alkali of the neutralizing agent are separately added to form an N-long-chain acyl acidic amino acid monosalt in the system, the alkali is excessively added. N-
Care must be taken because the proportion of long-chain acyl acidic amino acids present in the di-salt form increases and the abundance of the mono-salt form decreases.

The amount of the alkali is preferably adjusted so that the amount of the di-salt in the O / W emulsion is not more than 0.25 times the molar amount of the mono-salt. It is preferable to mix them so as to be twice or less. When the abundance of the disalt increases, the pH of the system does not become weakly acidic, pH stability or emulsion stability decreases,
In addition, when applied to the skin, a cream-like feeling may not be obtained. In addition, as the alkali of the neutralizing agent for neutralizing the N-long-chain acyl acidic amino acid,
Examples include potassium hydroxide, sodium hydroxide, triethanolamine and the like.

In the present invention, among the above amphipathic substances and N-long-chain acyl acidic amino acid monosalts, the amphipathic substance-N-long-chain acyl acidic amino acid monosalt-oil-water system can be used at room temperature or higher. Gel-forming amphiphile -N-
A combination of long chain acyl acidic amino acid monosalts is used. In the combination of an amphiphile-N-long-chain acyl acidic amino acid monosalt that forms a gel at an aqueous system and at a normal temperature or higher, there is no particular limitation as long as each compounding amount capable of forming a gel is used. Preferably 1 carbon atom
A combination of 6 or more higher fatty acids and / or higher aliphatic alcohols and N-stearoyl-L-glutamic acid monosalt is preferred.

FIG. 3 is a conceptual diagram showing an O / W emulsion. In FIG. 3, an oil phase 14 is dispersed in an aqueous phase 12, and an amphiphilic substance 20 and an N-long-chain acyl acidic amino acid monosalt 30 are provided at an interface between the aqueous phase 12 and the oil phase 14. It is present, and the dispersed state of the oil phase 12 in the aqueous phase 10 is stabilized. The aqueous phase 12 further contains N-
Long-chain acyl acidic amino acid monosalt 30 and amphiphile 2
0, the N-long chain acyl acidic amino acid monosalt 30 and part of the amphiphile 20 form a lamellar structure 40 in the aqueous phase, a gel structure is established, and the base solidifies. ing.

An association between an amphiphile and an N-long-chain acyl acidic amino acid monosalt in water to form a gel;
The abundance of the long-chain acyl acidic amino acid monosalt and the amphiphilic substance at the oil droplet interface or in the aqueous phase can be confirmed by DSC (differential scanning calorimetry) measurement. In the present invention, the amphipathic substance and the N-long-chain acyl acidic amino acid monosalt are present at the oil droplet interface of the O / W emulsion, and the abundance is 90% of the total content by the peak area ratio by DSC.
% Is preferable.

The total amount of the amphiphilic substance and the N-long-chain acyl acidic amino acid monosalt is preferably 0.2% by weight or more based on the aqueous phase of the O / W emulsion.

The compounding ratio of the amphiphile and the N-long-chain acyl acidic amino acid monosalt can be adjusted as appropriate, but is preferably 1: 1 to 1: 5, more preferably 1: 2 to 1: 4.

The amount of the internal phase oil in the O / W emulsion is at least 1/2 times, preferably at least equal to the total amount of the amphiphilic substance and the N-long-chain acyl acidic amino acid monosalt. When the amount of the oil phase is less than の of the amphiphilic substance, the stability over time of the emulsified state tends to deteriorate.

The compounding amount of the amphiphilic substance is preferably 25% by weight or less, more preferably 10% by weight, based on the total amount of the O / W emulsion. The compounding amount of the salt is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total amount of the O / W emulsion.

In the O / W emulsion, the weight ratio of the oil phase to the aqueous phase is preferably less than 1: 1.

The organically modified clay mineral blended in the external phase oil of the present invention is a kind of colloidal hydrous aluminum silicate having a three-layer structure and generally has the following general formula (1):

Embedded image (X, Y) _2-3 (Si, Al) ₄ O ₁₀ (OH) ₂ Z _1/3 · nH ₂ O where X = Al, Fe (III), Mn (III), Cr ( III) Y = Mg, Fe (II), Ni, Zn, Li Z = K, Na, Ca Water swellable clay minerals obtained by treating with a quaternary ammonium salt type cationic surfactant It is.

Specifically, for example, montmorillonite,
A montmorillonite group (naturally occurring or synthetic (in this case, the (OH) group in the formula is replaced with fluorine)) such as saponite and hectorite (commercially available products include veegum, kunipia, laponite, etc.) and sodium silicic mica And clay minerals such as synthetic mica known as sodium or lithium teniolite (commercially available products include dimonite: Topy Industries, Ltd.) and the like, and are obtained by treating with a quaternary ammonium salt type cationic surfactant.

The quaternary ammonium salt type cationic surfactant used for organically modifying the water-swellable clay mineral is represented by the following general formula (Formula 2).

[0040]

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.

Furthermore, when the organically modified clay mineral used in the present invention is treated with the above-mentioned quaternary ammonium salt type cationic surfactant, it is most preferred to treat it together with a nonionic surfactant. , Polyoxyethylene 2
３０30 mol addition ｛hereinafter abbreviated as POE (2-30). ｝ Oleyl ether, POE (2-35) stearyl ether, POE (2-20) lauryl ether, POE (1
-20) alkyl phenyl ether, POE (6-1)
8) ether-type activators such as behenyl ether, POE (5-25) 2-decylpentadecyl ether, POE (3-30) 2-decyltetradecyl ether, POE (8-16) 2-octyldecyl ether; And PO
E (4-60) hydrogenated castor oil, POE (3-14) fatty acid monoester, POE (6-30) fatty acid diester, POE (5-20) sorbitan fatty acid ester and other ester-type activators, and further POE (2 30) Ethers such as glyceryl monoisostearate, POE (10-60) glyceryl triisostearate, POE (7-50) hydrogenated castor oil monoisostearate, POE (12-60) hydrogenated castor oil triisostearate, etc. Ethylene oxide addition type surfactants such as ester type surfactants and polyhydric alcohol fatty acid ester type surfactants such as glycerin fatty acid esters such as decaglyceryl tetraolate, hexaglyceryl triisostearate, diglyceryl diisostearate and glyceryl monooleate Activators. Among these, polyglycerin fatty acid esters of diglycerin or higher such as decaglyceryl tetraolate, hexaglyceryl triisostearate, diglyceryl diisostearate, POE (2-12) lauryl ether, POE (6-15) behenyl Ether, PO
E (5-20) 2-decylpentadecyl ether, PO
E (5-17) 2-decyltetradecyl ether, PO
POE such as E (8-16) 2-octyldecyl ether
Addition ether type activator, and POE (10-20))
Hardened castor oil, POE (5-14) oleic acid monoester, POE (6-20) oleic acid diester, PO
POE such as E (5-10) sorbitan olein ester
Non-ionic surfactants of ethylene oxide addition type such as addition ester type activators, POE (3 to 15) glyceryl monoisostearate, POE (10 to 40) glyceryl triisostearate and other POE addition ether ester activators. It is preferable to use one kind or two or more kinds.

The organically modified clay mineral used in the present invention is:
For example, the above-mentioned water-swellable clay mineral and a quaternary ammonium salt type cationic surfactant (and a nonionic surfactant) are dispersed and stirred in a low boiling point solvent such as water, acetone or a lower alcohol to carry out low stirring. Obtained by removing the boiling solvent.

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.

Representative examples of the organically modified clay mineral preferably used in the present invention include dimethylalkylammonium hectorite, benzyldimethylstearylammonium hectorite, and aluminum magnesium silicate treated with distearyldimethylammonium chloride. Examples of commercially available products include Benton 38 (montmorillonite treated with distearyl dimethyl ammonium chloride: National Red).

The organically modified clay mineral accounts for 0.1% of the total amount of the external phase oil.
-10% by weight. Preferably, 0.5 to 5.0
% By weight. If the amount is less than 0.1% by weight, the effect of adding the organically modified clay mineral cannot be obtained, and a stable composite emulsion cannot be obtained. If it exceeds 10% by weight,
The prepared O / W / O type composite emulsion may have problems in practical use such as high viscosity, poor spread, roughness, lack of transparency, and the like.

Further, in the external phase oil, an emulsifier having an HLB of 7 or less must be blended together with the organically modified clay mineral. For example, surfactants sorbitan monolaurate, sorbitan monooleate, sorbitan monoisostearate, sorbitan fatty acid esters such as sorbitan tristearate, glycerol monostearate,
Glycerin fatty acid esters such as glycerol monooleate, POE (5), POE (7.5), POE (1
0) Polyoxyethylene hardened castor oil such as hardened castor oil, and a polyether-based silicone surfactant. In particular, a polyether-based silicon surfactant is preferable, and specifically, has a structure represented by the following chemical formula “Chemical Formula 3”.

Embedded image (Wherein, R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m is an average of 1 to 150, n is an average of 1 to 50,
a and b represent a number of 0 to 35 on average)

The emulsifier having an HLB of 7 or less is preferably blended in an amount of 0.1 to 15% by weight based on the total amount of the external phase oil. Note that H
The emulsifier having an LB of 7 or less may be contained in a state of being adsorbed on the organically modified clay mineral of the essential component. That is, usually, when an O / W / O type composite emulsion is produced, an organically modified clay mineral and an emulsifier having an HLB of 7 or less are separately added.
The emulsifier having an HLB of 7 or less may be treated with a surfactant having an LB of 7 or less and admixed with the organic modified clay mineral adsorbed.

The oily components used for the internal phase oil of the O / W type emulsion used in the present invention and the external phase oil of the O / W / O type composite emulsion of the present invention include, for example, avocado oil, camellia oil, turtle oil, macadamia nut Oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, evening primrose oil, eno oil, soybean oil, peanut oil Oil, teaseed oil, kaya oil, rice bran oil,
Liquid oils and fats such as sinagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, glyceryl trioctanoate, glycerin triisopalmitate, cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, and mutton Solid fats and oils such as hardened beef tallow, palm kernel oil, lard, beef tallow, beef tallow, hardened oil, beef leg fat, mokuro, hardened castor oil, beeswax,
Candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin,
Waxes such as sugar cane wax, isopropyl lanolin fatty acid, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, etc., liquid paraffin , Ozokerite, squalene, pristane, paraffin, ceresin, squalane, petrolatum, microcrystalline wax and other hydrocarbons, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristate Myristyl, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate,
Myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate,
Neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexylate, tri-2 -Glyceryl ethylhexylate, trimethylolpropane triisostearate, cetyl-2-ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimyristate, glyceride tri-2-heptylundecanoate, methyl ester of castor oil fatty acid, oil of oleic acid , Cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate,
Diisopropyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sepate, 2-hexyldecyl myristate, palmitic acid And synthetic esters such as -2-hexyldecyl, 2-hexyldecyl adipate, diisopropyl sebacylate, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate and triethyl citrate. In the present invention, there is no limitation on the oil content that can be blended, and there is an advantage in that solid and semi-solid oil content can be blended stably.

In addition to these oily components, chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane and methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexa Siloxane, cyclic polysiloxane such as tetramethyltetrahydrogencyclotetrasiloxane, amino-modified silicone oil, epoxy-modified silicone oil, epoxy
Silicone oils such as polyether-modified silicone oils, polyether-modified silicone oils, carboxy-modified silicone oils, alcohol-modified silicone oils, alkyl-modified silicone oils, ammonium salt-modified silicone oils, fluorine-modified silicone oils and other modified silicone oils, and trimethylsiloxysilicone Highly polymerized methylpolysiloxane such as silicone resin having a three-dimensional structure such as acid, highly polymerized dimethylpolysiloxane, highly polymerized methylphenylpolysiloxane, highly polymerized methylvinylpolysiloxane, and highly polymerized amino modified methylpolysiloxane Silicone resin such as polysiloxane, perfluorocarbon or perfluoropolyether such as perfluorodecalin, perfluorohexane, tripafluoro-n-butylamine, vitamin A and derivatives thereof , Vitamin D and its derivatives, vitamin E and its derivatives, vitamins such as vitamin K and its derivatives, sterols, it is also possible to incorporate natural and synthetic perfumes.

Further, in the oil phase, as a substance which is hardly soluble in water, an ultraviolet absorber, a preservative such as paraben, ubiquinone,
Vitamins such as vitamin P, bactericides such as chlorhexidine hydrochloride, trichlorocarbanilide, and Irgassan DP300, and drugs such as dexamethasone acetate can be added.

The water constituting the O / W emulsion of the internal phase and the O / W / O complex emulsion of the present invention is, for example, vitamin B group, vitamin C and its derivatives, pantothenic acid and its Derivatives, water-soluble active substances such as vitamins such as biotin, sodium glutamate, arginine, aspartic acid, citric acid, tartaric acid,
Buffers such as lactic acid, chelating agents such as EDTA, water-soluble ultraviolet absorbers, and water-soluble components such as various dyes can be added. The aqueous phase may contain alcohols such as ethanol and isopropanol, and salts such as NaCl.

In the O / W / O type composite emulsion of the present invention, the weight ratio of the internal phase O / W type emulsion to the external phase oil is from 2: 3 to 19: 1, preferably from 3: 2 to 19: 1.
17: 3. If the weight ratio of the O / W emulsion to the oil phase is more than 2: 3, the viscosity of the prepared composite emulsion is low, and the emulsion stability over time may be poor. If the weight ratio of the O / W emulsion to the oil phase is more than 19: 1, the phase is inverted during the stirring emulsification, and the O / W / O emulsion and the O / W emulsion are mixed. However, the O / W / O type composite emulsion of the present invention cannot be obtained.

Specific examples of UV absorbers, polyhydric alcohols, and other humectants that can be blended to give the O / W / O type composite emulsion of the present invention an ultraviolet absorbing effect and a moisturizing effect are as follows. It is.

Examples of the ultraviolet absorbent include para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester,
N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PA
Benzoic acid-based ultraviolet absorbers such as BA methyl ester and N, N-dimethyl PABA octyl ester; anthranil-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; amyl salicylate; menthyl salicylate; homomenthyl salicylate; octyl salicylate; Phenyl salicylate, benzyl salicylate, p
Salicylic acid ultraviolet absorbers such as isopropanol salicylate, octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropyl Cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate,
2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-
Cinnamic acid ultraviolet absorbers such as cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, and 2,4-dihydroxy Benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,
4'-dimethoxybenzophenone, 2,2'4,4'-
Tetrahydroxybenzophenone, 2-hydroxy-4
-Methoxybenzohephenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4
-Phenylbenzophenone, 2-ethylhexyl-4 '
-Phenylbenzophenone-2-carboxylate, 2
-Hydroxy-4-n-octoxybenzophenone, 4
Benzophenone-based ultraviolet absorbers such as -hydroxy-3-carboxybenzophenone, 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-
d, l-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'- t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'methylphenylbenzotriazole,
Dibenzalazine, dianisoylmethane, 4-methoxy-
4'-t-butyldimenzoylmethane, 5- (3,3-
Dimethyl-2-norbornylidene) -3-pentane-2
UV absorbers such as -ON.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-
Butylene glycol, pentamethylene glycol, 2-
Dihydric alcohols such as butene-1,4-diol, hexylene glycol and octylene glycol; trihydric alcohols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol; and tetravalent alcohols such as pentaerythritol Alcohols, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, polyhydric alcohols such as diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, triglycerin, tetraglycerin, polyglycerin, etc. Coalescence, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol nomobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether Le, ethylene glycol mono -2
-Methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether,
Dihydric alcohol alkyl ethers such as ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol, dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Dibutyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Dihydric alcohol alkyl ethers such as ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoether Phenyl ether acetate, ethylene glycol diazibate, ethylene glycol disuccinate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate DOO, dihydric alcohol ether esters such as propylene glycol monophenyl ether acetate and the like.

Examples of the humectant include chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate and the like. Sodium lactate, bile acid and the like are used to such an extent that the viscosity of the base is not lost. Monosalts, dl-pyrrolidone carboxylic acid monosalts, short-chain soluble collagen, liquid extract of St. John's wort, extract of Achillea millefolium, etc. can also be added.

The method for preparing the O / W emulsion serving as the internal phase is not particularly limited, and any method may be used as long as a stable emulsion can be obtained. It is adjusted by stirring with an emulsifier such as a mixer. When a high shearing force is applied to an emulsifier, for example, a high pressure emulsification treatment or an ultrasonic treatment with a nanomizer, manton gourin, French press, colloid mill, microfluidizer, ultrasonic emulsifier, etc.
The internal phase oil is finely and stably blended to obtain a cream having a glossy and smooth appearance, and the O / W /
It is particularly suitable for preparing an O-type composite emulsion.

Further, the obtained O / W type emulsion was
The O / W / O composite emulsion of the present invention can be obtained by mixing and emulsifying with stirring into an external phase oil containing an organically modified clay mineral and an emulsifier having an HLB of 7 or less. The emulsifying machine used at this time is not particularly limited, but a disperser (TK HOMD DISPER; TOKUSHU KIKA KOGYO CO., LT
It is preferable to use D) and the like.

The use of the O / W / O type composite emulsion of the present invention is not particularly limited, but it is preferably used as cosmetics, pharmaceuticals, quasi-drugs and the like, for example, as products such as creams, emulsions and ointments. Used.

[0061]

The present invention will be described in more detail with reference to the following examples. Note that the present invention is not limited to the following embodiments. In addition, the compounding component of each formulation represents weight%.

Using the components shown in the following tables, O / W emulsions of Production Examples and O / W / O composite emulsions of Examples and Comparative Examples using the same were produced by a conventional method. The storage stability when left at room temperature or 50 ° C. for one month and the usability by sensory evaluation of 10 panelists were evaluated according to the following criteria.

[Storage stability] A: Emulsified particles are uniform and no abnormality is observed at all under microscopic observation. ：: Some variation in emulsified particles was observed under a microscope, but no abnormality was observed with the naked eye. Δ: Some variation in emulsified particles is observed with the naked eye. ×: Abnormality such as oil floating or coarsening of emulsified particles is observed with the naked eye.

[Usability] ：: All of the ten panels specialized in evaluation answered “good” or “no stickiness”. ：: Eight or more and less than ten panel members who evaluated the evaluation replied “good” or “no stickiness”. Δ: 6 or more and less than 8 panelists who evaluated the evaluation answered “good” or “no stickiness” as good. ×: Less than 6 panelists specialized in evaluation answered “good” or “no stickiness” as good.

"Production Examples 1-4: O / W emulsion"

[Table 1] ---------------------------------------------- -------------------------- Ingredients / Production example 1 2 3 4 --------------- -------------------------------------------------- ------- (a) Amphiphile and N-long-chain acyl acidic amino acid monosalt, or surfactant behenyl alcohol --44 N-stearoyl-L-chlorotamic acid Na --22 POE (10) Hardened castor oil 2 2--(b) Oil phase Liquid paraffin 2016 16 12 12 Vaseline-22 2 Microcrystalline wax-22 2 Methyl alcohol 0.1 0.1 0.1 0.1 Ethyl alcohol 0.1 0.1. 1 0.1 0.1 butyl alcohol 0.1 0.1 0.1 0.1 (c) Aqueous phase ion-exchanged water Remaining Remaining Remaining Remaining 1,3 polyethylene glycol 10 10 10 10 NaCl 0.5 0.5 0.5 0.5 Arbutin 222 2 Trehalose 0.1 0.1 0.1 0.1 --------------------------- --------------------------------------------- "Production method" (a ) And (b) were mixed and uniformly dissolved, and then component (c) was added, followed by stirring and emulsification. In Production Examples 1 to 3, emulsification was performed using a homogenizer.
Was emulsified under high pressure using a Nanomizer.

"Examples 1-2 and Comparative Examples 1-2: O / W
/ O emulsion "

[Table 2] ---------------------------------------------- -------------------------- Ingredients / Comparative Examples / Examples Comparative Example 1 Comparative Example 2 Example 1 Example 2 ---- -------------------------------------------------- ------------------ O / W emulsion Emulsion of Production Example 1 78---Emulsion of Production Example 2-78--Emulsion of Production Example 3--78- Emulsion of Production Example 4-78 External phase oil Cyclic silicone oil 20 20 20 20 HLB 7 or less emulsifier Dimethyl siloxane methyl (POE) siloxane 11 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 1 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 11 -------------------------------------------------- ----------------- [Storage stability] Room temperature ○ △ ○ ◎ 50 ℃ ○ × ○ ◎ ----------------- -------------------------------------------------- ----- [Usability] Familiar △ △ ○ ◎ Non-stickiness △ △ ○ ◎ ------------------------------------------- ----------------------------- "Preparation method" Mix each component, emulsify using homogenizer, O / W A / O type composite emulsion was produced.

According to Table 2, in Examples 1 and 2 using the O / W emulsion containing the amphipathic substance and the N-long-chain acyl acidic amino acid monosalt, solid and semi-solid oils were blended. Also, an O / W / O type composite emulsion having good storage stability and excellent usability can be produced.
On the other hand, in Comparative Examples 1 and 2, even if a solid or semi-solid oil component is blended for the purpose of improving the usability, a stable emulsion cannot be obtained and the usability is not improved. Also,
Example 2 subjected to high-pressure emulsification has extremely excellent storage stability and usability.

Next, “Table 3” was prepared in the same manner as described above.
All of the O / W emulsions of Production Examples 5 to 8 shown in Table 1 were subjected to high-pressure emulsification treatment using a nanomizer to produce O / W / O emulsions shown in Table 4. Comparative Examples 3 and 4 are examples using an amphiphilic substance and a surfactant in a compounding amount that does not form a gel at room temperature or higher in an amphiphilic substance-surfactant-oil-water system.

"Production Examples 5 to 8: O / W emulsion"

[Table 3] ---------------------------------------------- -------------------------- Ingredients / Production example 5 6 7 8 --------------- -------------------------------------------------- ------- (a) Amphiphile and N-long-chain acyl acidic amino acid monosalt stearyl alcohol 3 0.2 21 behenyl alcohol 4 0.2 21 N-stearoyl-L-chlorotamic acid Na 111 1 (b) Oil phase Methylpolysiloxane 3 12.4 7 10 Methylhydrogen 0.1 0.1 0.1 0.1 Ethylhydrogen 0.1 0.1 0.1 0.1 0.1 Polyethylene 0.1 0.1 0.1 0.1 (c) Aqueous phase Ion-exchanged water Remaining Remaining Remaining Remaining Remaining Glycerin 5.55 5 L-sodium alkionate 2 2 2 2 Fructose 2 2 2 2 ------------- -------------------------------------------------- ---------

[Examples 3 and 4, Comparative Examples 3 and 4: O / W /
O-type emulsion "

[Table 4] ---------------------------------------------- -------------------------- Ingredients / Comparative Example / Example Comparative Example 3 Comparative Example 4 Example 3 Example 4 ---- -------------------------------------------------- ------------------ O / W emulsion Emulsion of Production Example 5 78---Emulsion of Production Example 6-78--Emulsion of Production Example 7--78- Emulsion of Production Example 8-78 External phase oil Cyclic silicone oil 20 20 20 20 HLB 7 or less emulsifier Dimethyl siloxane methyl (POE) siloxane 11 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1ponpon Copolymer -------------------------------------------------- ----------------- [Storage stability] Room temperature × △ ◎ ◎ 50 ℃ × × ◎ ◎ ----------------- -------------------------------------------------- ----- [Usability] familiar × × ◎ ◎ No tatters × × ◎ ◎ ------------------------------------------- -----------------------------

Although the storage stability and the usability of Examples 3 and 4 were very good, Comparative Example 3 produced agglomerates of solid oil over time, and Comparative Example 4 produced oil floating over time. The usability was poor. As can be seen from Comparative Examples 3 and 4, even when the same amphiphile and N-long-chain acyl acidic amino acid monosalt as in Examples 3 and 4 were used, the amount of the amphiphile- When a gel is not formed at room temperature or higher in an N-long-chain acyl acidic amino acid monosalt-oil-water system, an O / W / O type composite emulsion having good storage stability and usability cannot be obtained.

Next, “Table 5” was prepared in the same manner as described above.
All of the O / W emulsions of Production Example 9 shown in Table 6 were subjected to high-pressure emulsification using a nanomizer to produce O / W / O composite emulsions shown in Table 6. Comparative Examples 5 and 6 are examples in which the weight ratio of the O / W emulsion to the external phase oil is out of the range of the present invention.

[0073]

[Table 5] "Production Example 9: O / W emulsion" ----------------------------------- ---------- Ingredients Production Example 9 ----------------------------------- ---------- (a) Amphiphile and N-long-chain acyl acid amino acid monosalt cetanol 8 N-stearoyl-L-quartamic acid Na 5 (b) oil phase squalane 5-pentaerythritol-2- Ethyl hexanoate 2 Vitamin E-acetate 0.1 butyl human peroxytoluene 0.05 methyl paraben 0.1 ethyl paraben 0.1 butyl paraben 0.1 (c) Aqueous phase ion-exchanged water Remainder 1,3 1 Erythritol 1.0 ---------------------------------------------

[Examples 5 to 8, Comparative Examples 5 to 6: O / W /
"O-type emulsion" The emulsion of Production Example 9 was used in the O / W-type emulsion, and the O / W-type emulsion shown in "Table 6" and the O /
Similarly to the W / O type composite emulsion, the O / W / O type composite emulsions of Examples 5 to 8 and Comparative Examples 5 to 6 were produced and evaluated.

[0075]

[Table 6] ---------------------------------------------- ---------- Examples / Comparative Examples O / W type emulsion amount External phase oil amount -------------------------- ------------------------------ Example 5 50% by weight 50% by weight Example 6 60 40 Example 7 70 30 Example Example 8 80 20 Comparative Example 5 35 65 Comparative Example 6 97 3 ------------------------------------ --------------------

"Evaluation of Properties of Emulsion"

[Table 7] ---------------------------------------------- -------------------------- Emulsion form Storage stability Storage stability (room temperature) (room temperature) (50 ℃) ----- -------------------------------------------------- ----------------- Example 5 O / W / O ○ Example 6 O / W / O ○ Example 7 O / W / O Example 8 O / W / O ◎ ○ Comparative Example 5 O / W / O × × Comparative Example 6 O / W / O + O / W × × --------------------- -------------------------------------------------- -

In Comparative Example 5, an O / W / O emulsion was formed immediately after emulsification because the weight ratio of the O / W emulsion to the external phase oil was larger than 2: 3. ,
Compared with Examples 5 to 8, storage stability was poor, and oil floating was observed in both room temperature storage and 50 ° C storage. Further, as shown in Comparative Example 6, when the weight ratio of the O / W emulsion to the oil phase is more than 19: 1, when the O / W emulsion is in excess, the phase is inverted during emulsification and dispersion to prepare. It was confirmed that the emulsion contained both O / W / O type and O / W type emulsions.

[0078]

According to the present invention, it is possible to obtain an O / W / O composite emulsion having high stability over time and good usability.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of an O / W / O complex emulsion.

FIG. 2 is a diagram showing a neutralized state of N-stearoyl-L-glutamic acid.

FIG. 3 is a conceptual diagram of an O / W emulsion used in the present invention.

[Description of Symbols] 10: External phase oil 12: Aqueous phase 14: Internal phase oil 20: Amphiphilic substance 30: N-long-chain acyl acidic amino acid monosalt 40: Lamellar structure

Claims (9)

[Claims] 1. An O / W / O type composite emulsion in which an O / W type emulsion is dispersed in an external phase oil,
/ W emulsion contains an amphipathic substance-N-long-chain acyl acidic amino acid monosalt-oil-water, an amphipathic substance selected from those capable of forming a gel at room temperature or higher, and N
A long-chain acyl acidic amino acid monosalt, an oily component, and water, and the organic phase-modified clay mineral and HLB7 are contained in the external phase oil.
An O / W / O type composite emulsion comprising the following emulsifier, wherein the weight ratio of the O / W type emulsion to the external phase oil is 2: 3 to 19: 1. 2. The amphiphilic substance has a carbon chain length of 1 carbon atom.
2. The O / W / O complex emulsion according to claim 1, wherein the O / W / O complex emulsion is at least two higher alcohols and / or higher fatty acids. 3. The mono-salt of N-long-chain acyl acidic amino acid contained in the O / W emulsion of the internal phase is N-stearoyl-L-glutamic acid mono-salt. O / W / O type complex emulsion. 4. An N / O emulsion in the O / W emulsion of the internal phase.
A long-chain acyl acidic amino acid disalt, the content of which is not more than 0.25 times the molar ratio of N-long-chain acyl acidic amino acid monosalt,
4. The O / W / O complex emulsion according to 2 or 3. 5. The internal phase oil of the O / W emulsion is contained in an amount of at least 1/2 times the total amount of the amphiphilic substance and the N-long-chain acyl acidic amino acid monosalt. The O / W / O type composite emulsion according to claim 1, 2, 3, or 4. 6. The amphipathic substance and the N-long-chain acyl acidic amino acid monosalt are present at the oil droplet interface of the O / W emulsion, and the abundance is 90% of the total content by the peak area ratio by DSC. Claims 1 and 2,
The O / W / O type composite emulsion according to 3, 4 or 5. 7. The total amount of the amphipathic substance and the N-long-chain acyl acidic amino acid monosalt is at least 0.2% by weight based on the aqueous phase of the O / W emulsion. The O / W / O type composite emulsion according to 1, 2, 3, 4, 5 or 6. 8. The organically modified clay mineral is obtained by treating a water-swellable clay mineral with a quaternary ammonium-type cationic surfactant and a nonionic surfactant. The O / W / O type composite emulsion according to claim 1, 2, 3, 4, 5, 6, or 7. 9. A step of adding an oily component to be an internal phase oil to an aqueous phase containing an N-long-chain acyl acidic amino acid monosalt and subjecting it to high-pressure emulsification treatment or ultrasonic treatment to prepare an O / W emulsion. Dispersing and emulsifying the O / W emulsion in an oily component which is an external phase oil containing an organically modified clay mineral and an emulsifier having an HLB of 7 or less. O / W / described in 5, 6, 7 or 8
A method for producing an O-type composite emulsion.