JPH08985A - Preparation of emulsifier composition and water-in-oil-type emulsion by using the same - Google Patents

Abstract

PURPOSE:To prepare a water-in-oil-type emulsion with excellent stability and feeling of use even in a low viscosity region. CONSTITUTION:In preparing a water-in-oil-type emulsion, a surfactant compsn. wherein a nonionic surfactant (A) consisting of a partial ester of a polyhydric alcohol with at least three hydroxyl groups with a fatty acid and being liq. at ordinary temp. and a water soln. (B) contg. 1-40wt.% amino acid or its salt and 1-20wt.% non-reductive sugar alcohol with at least five hydroxyl groups in a molecule are mixed so as to make the wt. ratio of the nonionic surfactant in the component (A) to the component (B) water soln. to be 1:1 to 1:20, is used. In addition, emulsifying is performed by incorporating at first an emulsifying agent consisting of an ethylene oxide 20-60 adduct to a hydroxyfatty acid triglyceride and furthermore, mixing an emulsifying agent compsn. therein, and then, adding water therein.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an emulsifier composition and a method for preparing a water-in-oil emulsion using this emulsifier composition.

[0002]

BACKGROUND OF THE INVENTION Water-in-oil emulsions have generally been known to have many excellent properties in various fields, but in general, they are generally used in water for most purposes. An oil type emulsion was used.

Particularly in the case of cosmetics, the water-in-oil emulsion is applied to the skin to form an oil film on the stratum corneum, but does not impede skin breathing and does not easily run off against water or sweat. It is known that it has many excellent characteristics, but in reality, due to problems such as low stability, the proportion of water-in-oil emulsion products in current Japanese skin care products is high. Is very low.

In general, cosmetics and pharmaceuticals have a long warranty period of 1 to 2 years, and therefore gelling agents such as high-grade alcohol, various salts, fatty acid metal soaps and low molecular weight polyethylene are included in the product formulation. Since various efforts have been made to stabilize the viscosity by adding various additives such as, to increase the viscosity, most of the water-in-oil emulsion products currently on the market have high viscosity. It is the cream of.

However, the high-viscosity water-in-oil type cream has a problem of viscosity and, in addition to the viscosity of the oil-in-water type cream, it is more sticky and sticky because the continuous phase is oil. It has a bad feel on the skin and has been a serious problem as a skin external medicine or cosmetic.

Many studies have been made to date on such problems. For example, Japanese Patent Publication Sho 48-1
No. 5798 uses an emulsifier composition obtained by mixing an oleic acid monoglyceride and a 70% aqueous solution of sorbitol. In Japanese Patent Publication No. 53-21393, various amino acid aqueous solutions and lipophilic nonionic compounds are used. By using an emulsifier composition obtained by mixing a surfactant, in JP-B-60-26366, α-
Using monoalkyl glyceryl ether as an emulsifier,
It has been shown that a stable water-in-oil emulsion can be obtained by using a fatty acid metal salt or an organic acid salt in combination.

[0007]

However, any of the above-mentioned methods is mainly aimed at preparing an emulsion having a relatively high viscosity, and is not always satisfactory in terms of emulsion stability. . In particular, it is difficult to prepare a highly stable water-in-oil emulsion in a region where the viscosity is 1,000 centipoise or less at room temperature, particularly in a very low viscosity region of 200 centipoise or less.

The present invention relates to a water-in-oil type emulsion product, which has been limited in use due to its stability and feeling during use.
In order to solve these problems, the purpose is to use a specific emulsifier composition, which not only provides excellent feeling in use, but also has a very low viscosity which makes it difficult to maintain the stability of emulsion. Even in the field, it is to obtain a water-in-oil emulsion which can maintain high stability.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, have found that a specific nonionic surfactant which is lipophilic, an amino acid or a salt thereof and a specific sugar. By using an emulsifier composition obtained by mixing an aqueous solution containing an alcohol, an oil component and a specific emulsifier are mixed, and the above emulsifier composition is added thereto, and then water is added to emulsify the mixture. As a result, they have found that a water-in-oil emulsion having a high stability even in a very low viscosity region and having an excellent feel on the skin can be prepared, and completed the present invention.

That is, the first aspect of the present invention is: A) a nonionic surfactant which is liquid at room temperature and comprises a partial ester of a polyvalent alcohol having 3 or more hydroxyl groups and a fatty acid; and B) an amino acid. Alternatively, an aqueous solution containing 1 to 40% by weight of a salt thereof and 1 to 20% by weight of a non-reducing sugar alcohol having at least 5 or more hydroxyl groups in the molecule, and a nonionic surfactant of component A The present invention relates to an emulsifier composition, wherein an aqueous solution of component B is mixed in a weight ratio of 1: 1 to 1:20.

The second aspect of the present invention is to add to the oil the ethylene oxide 20 to 20 of hydroxy fatty acid triglyceride.
A method for preparing a water-in-oil emulsion, which comprises adding an emulsifier consisting of a 60 mol adduct, further mixing the emulsifier composition according to the first invention, and then adding water for emulsification. Is.

[0012]

Structure / Function of the Invention A used in the emulsifier composition of the present invention
The component is a lipophilic nonionic surfactant which is liquid at room temperature and is composed of a partial ester of polyhydric alcohol having 3 or more hydroxyl groups and a fatty acid. The above partial ester differs depending on the type of polyhydric alcohol. For example, in the case of glycerol having three hydroxyl groups, it is mainly a mixture of a monoester, a diester and a small amount of a triester. Is a mixture of monoesters, diesters with a small amount of triesters and tetraesters when 4 is diglycerol or sorbitan. Among these partial esters, as a material for forming a good emulsifier composition, a single partial ester or a mixture thereof is selected and used from those which are liquid at room temperature and are lipophilic.

Examples of the polyvalent alcohol having three or more hydroxyl groups constituting the partial ester include, for example, glycerol, diglycerol, triglycerol, tetraglycerol, hexaglycerol and octaglycerol. Le,
Examples thereof include decaglycerol, xylitol, sorbitol, mannitol, sorbitan, trimethylolpropane and pentaerythritol.

As the fatty acid which constitutes the partial ester,
For example, various known fatty acids such as caprylic acid, capric acid, lauric acid, oleic acid, isostearic acid, and linoleic acid can be used as long as the partial ester with the polyhydric alcohol is liquid at room temperature. Can be used. Among these fatty acids, cis-Δ9-octadecenoic acid is contained in an amount of 85% by weight or more, and cis-Δ9-octadecenoic acid is contained.
-High-purity oleic acid containing 90% by weight or more of unsaturated fatty acids is preferred.

As the partial ester of the component A, particularly preferable ones are glycerol monooleate, sorbitan monooleate, sorbitan dioleate, diglycerol monooleate derived from the above-mentioned high-purity oleic acid. , Diglycerol diolate, etc. Oleic acid of very high purity is introduced as an acyl group in these partial esters, so they have excellent oxidative stability as emulsifiers, and as a result of the enhanced orientation between surfactant molecules, skin permeability is improved. It is characterized by excellent functionality such as emulsion stability and emulsion stability. Compared with oleic acid derivatives that are generally commercially available at present, the stability of the emulsifier composition and the water-in-oil type prepared using it are It has the effect of significantly improving the stability of the emulsion.

The component B used in the emulsifier composition of the present invention is
It is an aqueous solution containing an amino acid or a salt thereof and a non-reducing sugar alcohol having at least 5 or more hydroxyl groups in the molecule. The amino acid or salt thereof can be selected and used from general food additives and those known as non-Japanese Pharmacopoeia drugs. Further, the non-reducing sugar alcohol can be selected and used from those generally used as foods and Japanese Pharmacopoeia, particularly xylitol, sorbitol, mannitol and maltitol. -Lol, laccitol and the like are preferably used.

Amino acids include glycine, alanine, arginine hydrochloride, asparagine, aspartic acid, glutamine, glutamic acid, histidine, leucine, isoleucine, proline, hydroxyproline, serine, threonine, valine, phenylalanine, and the like. Among them, neutral amino acids, particularly alanine and serine are preferable. These amino acids are usually in the L-form,
D-isomer which is the isomer thereof, and D which is a mixture thereof.
Even the L-form can be similarly used. Amino acid salts include monovalent metal salts such as sodium salts and potassium salts, and divalent metal salts such as calcium salts and magnesium salts. Particularly, sodium aspartate monohydrate and potassium aspartate dihydrate. , Sodium glutamate 1
Hydrates, potassium glutamate monohydrate and the like are preferably used.

The concentration of the amino acid or its salt in the aqueous solution is 1 to 40% by weight. If it is less than 1% by weight, a stable emulsifier composition cannot be obtained, and the stability of the water-in-oil emulsion prepared using this composition decreases. The higher the concentration of the amino acid or its salt, the more the above stability is improved, but if it is higher than 40% by weight, crystals tend to precipitate. In the present invention, the sugar alcohol used in combination can prevent the precipitation of crystals of amino acid or a salt thereof and form a stable aqueous solution even at a high concentration, but in practice, the concentration range should not give a supersaturated state. Since this concentration depends on the solubility of the amino acid or its salt, it is preferable to set an appropriate concentration within the above range depending on the solubility of the selected amino acid or its salt.

The concentration of the non-reducing sugar alcohol in the aqueous solution is 1 to 20% by weight. If it is less than 1% by weight, the stability of the finally prepared water-in-oil emulsion may cause a problem. On the other hand, if it is more than 20% by weight, the solubility of the amino acid or its salt is likely to cause a problem, and as a result, it becomes difficult to obtain a stable water-in-oil emulsion having a low viscosity.

The emulsifier composition of the present invention comprises a lipophilic nonionic surfactant which is a liquid at room temperature and which is composed of the partial ester of the component A, and an aqueous solution of the component B in a weight ratio of the former to the latter. Mix so that it becomes 1: 1 to 1:20,
By stirring this until a strong gel-like composition is obtained, a gel-like water-in-oil type emulsifier composition can be usually obtained. The stronger the agitation, the better the gel state can be obtained.At that time, if the emulsifier composition has a high temperature with a stirrer, the stirring may be performed while cooling to keep the temperature at room temperature or lower. Good.

The mixing ratio of A component and B component is B
Amino acid or its salt in ingredients, non-reducing sugar alcohol
The optimum ratio is appropriately selected according to the kind of the resin and its concentration. For example, the B component is L-sodium glutamate 1
In the case of an aqueous solution of 5% by weight of hydrate and 5% by weight of laccitol, the weight ratio of A component: B component is preferably in the range of 1: 2 to 1:10. Also, 40% by weight of L-sodium glutamate monohydrate and 20% of lactide
In the case of an aqueous solution of wt%, the weight ratio of A component: B component is 1 :.
It is preferable that the range is from 2 to 1:15.

In the present invention, the above-mentioned emulsifier composition is used to prepare the final water-in-oil emulsion. In this method, first, an emulsifier consisting of 20 to 60 mol of an ethylene oxide adduct of hydroxy fatty acid triglyceride is added to oil and mixed by stirring, and then the above emulsifier composition is mixed and dispersed, and then water is added. In addition, it is mixed by stirring to emulsify, and by this method, a water-in-oil emulsion having low viscosity and high stability can be prepared.

As the oil component, ester-based oily bases conventionally used in cosmetics and the like, and non-ester-based oily bases also often used in cosmetics can be widely used. Particularly preferred is an esterified product of high-purity oleic acid containing cis-Δ9-octadecenoic acid in an amount of 85% by weight or more and cis-Δ9-unsaturated fatty acid in an amount of 90% by weight or more, such as glyceryl trioleate or diglycero-. Rutetraoleate, Ethyloleate, Decyloleate
Ester-based oily base such as oleate, oleyl oleate, trimethylol propane trioleate, or
It is preferable to use a mixture of this oily base and one or more non-ester oily bases selected from squalane, squalene, liquid paraffin and polybutene.

In the 20 to 60 mol ethylene oxide adduct of hydroxy fatty acid triglyceride, examples of the hydroxy fatty acid include castor oil and hydrogenated castor oil. The amount of the ethylene oxide adduct of triglyceride used is preferably about 1 to 5% by weight in the total formulation (in the total amount of the water-in-oil emulsion). Further, in addition to the ethylene oxide adduct of triglyceride and the above-mentioned oil component, at a ratio of 1 to 10% by weight in the total formulation, 3
A partial ester of a polyhydric alcohol having one or more hydroxyl groups and a fatty acid may be added, which can further enhance the stability of the water-in-oil emulsion.

As the above-mentioned partial ester, a lipophilic nonionic surfactant which is liquid at room temperature, which is the same as the component A constituting the emulsifier composition, and which is completely the same as the component A is used. can do. Particularly preferred is glycerol monooleate or glycero-derived from high-purity oleic acid containing 85% by weight or more of cis-Δ9-octadecenoic acid and 90% by weight or more of cis-Δ9-unsaturated fatty acid. Lugiolate, diglycero
It is recommended to use rumonooleate, diglycerol-ludiolate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, mannitol monooleate, mannitol lediolate, mannitol rutriolate, etc. .

In the preparation of the water-in-oil emulsion, the use ratio of oil and water is appropriately selected according to the purpose of use of the emulsion. In particular, in the present invention, since the viscosity of the emulsion can be set to a low viscosity range of 1,000 centipoise or less at room temperature, preferably 200 centipoise or less, the use ratio of oil and water is selected in a wide range accordingly. be able to. Generally, oil:
The weight ratio of water may be 90:10 to 10:90. Further, in the preparation of this emulsion, the mixing amount of the emulsifier composition of the present invention is 1 to 20 in the total formulation.
It is preferable to set the ratio to the percentage by weight, preferably 3 to 10% by weight.

The water-in-oil emulsion prepared in this way has the characteristic that it is excellent in stability even in the above-mentioned extremely low viscosity region. For example, it is oil-soluble in the oil phase. By adding a water-soluble active ingredient to the aqueous phase, it can be used for cosmetics having excellent skin permeability, flexibility and a feeling of use, pharmaceuticals used on the skin, or pesticides. it can.

[0028]

Industrial Applicability According to the present invention, it is possible to prepare a water-in-oil emulsion which exhibits a high stability even in a considerably low viscosity range and has an excellent feeling on skin.

[0029]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these.

Example 1 As component A, glycerol monooleate [NOFABLE GO-901, manufactured by NOF CORPORATION], acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-unsaturated Fatty acid content 94% by weight] 5 parts were used. As component B, 3 parts of sodium L-glutamate monohydrate (manufactured by Ajinomoto Co., Inc.) and 1 part of mannitol (manufactured by Towa Kasei Co., Ltd.) were dissolved in 6 parts of purified water. An aqueous solution was used. This A component and B
Creamix CLM-0.8S
Using [manufactured by M-Technik Co., Ltd.], the mixture was stirred and mixed at 10,000 rpm for 10 minutes to obtain an emulsifier composition X ₁ which was water-in-oil type.

Example 2 As component A, diglycerol monooleate [NOFABLE PGO-9021L manufactured by NOF CORPORATION], acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-unsaturated Fatty acid content 94% by weight] 5 parts were used. As the B component, 4 parts of L-sodium glutamate monohydrate (manufactured by Ajinomoto Co., Inc.) and laccit-
An aqueous solution prepared by dissolving 1 part of RU [“MILCHEN” manufactured by Towa Kasei Kogyo Co., Ltd.] in 5 parts of purified water was used. The components A and B were stirred and mixed in the same manner as in Example 1 to obtain an emulsifier composition X ₂ .

Example 3 Glycerol monooleate [NOFABLE GO-991P manufactured by NOF CORPORATION] as component A, acyl group composition: cis-Δ9-octadecenoic acid content 99% by weight,
5 parts of cis-Δ9-unsaturated fatty acid content of 99% by weight and glycerol dioleate [NOFAB manufactured by NOF Corporation]
LE GO-902P ", acyl group composition: cis-Δ9-
Octadecenoic acid content 88% by weight, cis-Δ9-unsaturated fatty acid content 94% by weight] 5 parts were used. As component B, 4 parts of sodium L-aspartate monohydrate (manufactured by Ajinomoto Co., Inc.) and 1 part of xylitol (“Xylitol” manufactured by Towa Kasei Co., Ltd.) were dissolved in 12 parts of purified water. An aqueous solution was used. The components A and B were stirred and mixed in the same manner as in Example 1 to obtain an emulsifier composition X ₃ .

Example 4 As a component A, sorbitan monooleate [NOFABLESO-901, manufactured by NOF CORPORATION], acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-unsaturated fatty acid Content 94% by weight] 5 parts were used.
Further, as the B component, L-serine [manufactured by Ajinomoto Co., Inc.] 3
And 1 part of sorbitol (“Solvitt D-Powder” manufactured by Towa Kasei Kogyo Co., Ltd.) were dissolved in 6 parts of purified water to prepare an aqueous solution. The components A and B were used in Example 1
The mixture was stirred and mixed in the same manner as in to obtain an emulsifier composition X ₄ .

Example 5 As component A, sorbitan monooleate [“NONION OP-80R” manufactured by NOF CORPORATION, acyl group composition:
Cis-Δ9-octadecenoic acid content 55% by weight, cis-Δ
9-unsaturated fatty acid content 82% by weight] 5 parts were used. As component B, 3 parts of sodium L-glutamate monohydrate (manufactured by Ajinomoto Co., Inc.) and 1 part of maltitol (“AMALTY” manufactured by Towa Kasei Co., Ltd.) were dissolved in 6 parts of purified water. An aqueous solution was used. The components A and B were stirred and mixed in the same manner as in Example 1 to give an emulsifier composition X ₅
Got

Comparative Example 1 Sorbitan monooleate [NOFA manufactured by NOF CORPORATION]
BLE SO-901 ", acyl group composition: cis-Δ9-
An aqueous solution prepared by dissolving 6 parts of purified water in 5 parts of octadecenoic acid content of 88% by weight, cis-Δ9-unsaturated fatty acid content of 94% by weight, and 4 parts of laccitol [TOWA KASEI KOGYO CO., LTD. And were mixed by stirring in the same manner as in Example ₁ to obtain an emulsifier composition Y ₁ .

Comparative Example 2 10 parts of sorbitan monocaprylate [Nonion CP-08R manufactured by NOF CORPORATION] and 1 part of L-serine [manufactured by Ajinomoto Co.] were dissolved in 9 parts of purified water. Aqueous solution,
The mixture was stirred and mixed in the same manner as in Example 1 to obtain an emulsifier composition Y ₂ .

Comparative Example 3 5 parts of polyoxyethylene sorbitan monooleate [Nonion OT-221 manufactured by NOF CORPORATION, ethylene oxide addition mole number 20] and L-sodium glutamate monohydrate [Ajinomoto ( Co., Ltd.] and 1 part of laccitol [“MILCHEN” manufactured by Towa Kasei Kogyo Co., Ltd.] in 6 parts of purified water were stirred and mixed in the same manner as in Example 1 to prepare an emulsifier composition. Item Y ₃ was obtained.

Examples 6 to 10 As an oil component, oleyl oleate [N Oil and Fat Co., Ltd. "N
OFABLE OO-9080 ", acyl group composition: cis-Δ9-octadecenoic acid content 72% by weight, cis-Δ9-
Using 6 parts of unsaturated fatty acid content of 88% by weight and 6 parts of squalene (“Super squalene” manufactured by SQUATECK Co., Ltd.), these oil components were heated to 50 ° C. to produce polyoxyethylene hydrogenated castor oil [Japan Oil & Fat Co., Ltd. "Uniol HC
-40 ", ethylene oxide addition mole number 40] 0.5
2 parts of the emulsifier compositions X _{1 to} X ₅ obtained in Examples 1 to ₅ were mixed and dispersed in the oil phase, followed by stirring with purified water 8 parts. Parts were gradually added, and at room temperature, 5 kinds of water-in-oil emulsions were prepared by stirring and mixing at 8,000 rpm for 10 minutes using CLEAMIX CLM-0.8S [manufactured by M-Technik Co., Ltd.]. did.

Examples 11 to 15 Glycerol trioleate [NOFABLEGO-903, manufactured by NOF CORPORATION], acyl group composition: cis-Δ9-octadecenoic acid content 72% by weight, cis-Δ9-unsaturated Fatty acid content 88% by weight] 12 parts,
To this oil, sorbitan sesquioleate [NOFABLE SO-902, manufactured by NOF CORPORATION, acyl group composition: cis-Δ9-octadecenoic acid content 72% by weight, cis-Δ9-unsaturated fatty acid content 88% by weight] 1.6 parts,
0.4 parts of polyoxyethylene hydrogenated castor oil [NOIL HC-40, manufactured by NOF CORPORATION, ethylene oxide addition mole number 40] heated to 50 ° C. was added and sufficiently stirred. Emulsifier composition X ₁ obtained in Examples 1 to 5
X ₅ : 1 part was mixed and dispersed in the oil phase, and then 6 parts of purified water was gradually added to the mixture with stirring.
The mixture was stirred and mixed in the same manner as above to prepare five types of water-in-oil emulsions.

Examples 16 to 20 As an oil component, oleyl oleate [N Oil and Fat Co., Ltd. "N
OFABLE OO-9990 ", acyl group composition: cis-Δ9-octadecenoic acid content 99% by weight, cis-Δ9-
Unsaturated fatty acid content 99% by weight] 6 parts, squalene [Squateck Co., Ltd. "Super Squalene" 3 parts, and squalane [Squateck Co., Ltd. "Super Squalane" 3 parts, To these oils, sorbitan trioleate [NOFABLE SO-9 manufactured by NOF CORPORATION]
93 ", acyl group composition: cis-Δ9-octadecenoic acid content 99% by weight, cis-Δ9-unsaturated fatty acid content 99% by weight] 0.8 parts, and glycerol monooleate [NOFABLEGO manufactured by NOF Corporation] -991 ", acyl group composition: cis-Δ9-octadecenoic acid content 99% by weight, cis-Δ9-unsaturated fatty acid content 99% by weight] 1.2 parts and 5
0.4 parts of polyoxyethylene hydrogenated castor oil [NOIL HC-40, manufactured by NOF CORPORATION, ethylene oxide addition mole number 40] heated to 0 ° C. was added and sufficiently stirred, and Emulsifier compositions X _{1 to} X obtained in Examples 1 to 5
₅ : 1 part was mixed and dispersed in the oil phase, and 10 parts of purified water was gradually added to the oil phase with stirring.
The mixture was stirred and mixed in the same manner as above to prepare five types of water-in-oil emulsions.

Examples 21 to 25 As the oil component, diglycerol tetraoleate [“NOFABLE PGO-9024L” manufactured by NOF CORPORATION], acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-non Saturated fatty acid content 94% by weight] 6 parts and polybutene [Nippon Oil & Fat Co.
6 parts of "X" and sorbitan trioleate [NOFABLE SO-9 manufactured by NOF CORPORATION].
03 ", acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-unsaturated fatty acid content 94% by weight] and 1 part of sorbitan sesquioleate (NOFABLE SO- manufactured by NOF Corporation). 902 ", acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-unsaturated fatty acid content 94% by weight] 1 part,
0.4 parts of polyoxyethylene hydrogenated castor oil [“NOIL HC-40” manufactured by NOF CORPORATION, ethylene oxide addition mole number 40] heated to ℃ was added and sufficiently stirred, and then, Emulsifier composition X ₁ obtained in Examples 1 to 5
X ₅ : 1 part was mixed and dispersed in the oil phase, and then 6 parts of purified water was gradually added to the mixture with stirring.
The mixture was stirred and mixed in the same manner as above to prepare five types of water-in-oil emulsions.

Comparative Examples 4 to 8 As an oil component, oleyl oleate [NOF CORPORATION, "N
OFABLE OO-9080 ", acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-
12 parts of unsaturated fatty acid content of 94% by weight was used, and sorbitan sesquioleate [N.
OFABLE SO-902 ", acyl group composition: cis-
Δ9-octadecenoic acid content 88% by weight, cis-Δ9-unsaturated fatty acid content 94% by weight] 1 part, and sufficiently stirred, to which the emulsifier composition X ₁ obtained in Examples 1 to 5 was added.
X ₅ : 1 part was mixed and dispersed in the oil phase, and then, while stirring, 6 parts of polyoxyethylene hydrogenated castor oil [manufactured by NOF CORPORATION, “UNIOR HC-4”] was previously added to 6 parts of purified water.
0 ", ethylene oxide addition mole number 40] 0.4 part was dissolved at 50 ° C., then cooled to room temperature, gradually added, and stirred and mixed in the same manner as in Examples 6 to 10 to obtain 5 kinds of oil. A water emulsion was prepared.

Comparative Examples 9 to 13 As the oil component, diglycerol tetraoleate [“NOFABLE PGO-9024L” manufactured by NOF CORPORATION], acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-non Saturated fatty acid content 94% by weight] 12 parts was added to this oil, and sorbitan sesquioleate [NOFABLE SO-902, manufactured by NOF CORPORATION], acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, Cis-Δ9-unsaturated fatty acid content 94% by weight] 1 part and polyoxyethylene sorbitan monooleate [Nonion OT-221 manufactured by NOF CORPORATION, polysorbate 80, ethylene oxide addition mole number 20] 0.5
And 1 part of the emulsifier compositions X _{1 to} X ₅ obtained in Examples 1 to ₅ are mixed and dispersed in the oil phase, and then stirred with purified water. Gradually add 6 parts,
Then, the mixture was stirred and mixed in the same manner as in Examples 6 to 10 to prepare five types of water-in-oil emulsions.

Comparative Examples 14 to 18 As oil components, 8 parts of medium-chain fatty acid triglyceride [“PANACET 800” manufactured by NOF CORPORATION] and 4 parts of squalane (“Super squalane” manufactured by SQUATEC Co., Ltd.) And 3 parts by weight of the emulsifier compositions X _{1 to} X ₅ obtained in Examples 1 to ₅ were added to and dispersed in the oily component, and then 6 parts of purified water was gradually added while stirring. The mixture was stirred and mixed in the same manner as in No. 10 to 10 to prepare five types of water-in-oil emulsions.

Comparative Examples 19 to 21 As an oil component, oleyl oleate [N Oil and Fat Co., Ltd. "N
OFABLE OO-9080 ", acyl group composition: cis-Δ9-octadecenoic acid content 72% by weight, cis-Δ9-
12 parts of unsaturated fatty acid content of 88% by weight were used, and sorbitan sesquioleate [N.
OFABLE SO-902 ", acyl group composition: cis-
Δ9-octadecenoic acid content 72% by weight, cis-Δ9-unsaturated fatty acid content 88% by weight] 1 part and glycerol monooleate [NOFABLE GO-manufactured by NOF Corporation]
901 ", acyl group composition: cis-Δ9-octadecenoic acid content 72% by weight, cis-Δ9-unsaturated fatty acid content 88% by weight] and 1 part of polyoxyethylene hydrogenated castor oil [NOF Co., Ltd. "Uniol HC-4
0 ", by adding the moles of ethylene oxide added 40] 0.4 parts thoroughly stirred, which in Comparative Examples 1 to 3 obtained in the emulsifier composition Y ₁ to Y _3: a mixture of 1 part oil After being dispersed in the phase, 6 parts of purified water was gradually added with stirring, and the mixture was stirred and mixed in the same manner as in Examples 6 to 10 to prepare three types of water-in-oil emulsions.

Comparative Example 22 Glycerol trioleate [NOFABLEGO-903 manufactured by NOF CORPORATION] as an oil component, acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-unsaturated fatty acid content 94 wt%] 12 parts,
To this oil, sorbitan sesquioleate [NOFABLE SO-902, manufactured by NOF CORPORATION, acyl group composition: cis-Δ9-octadecenoic acid content 88% by weight, cis-Δ9-unsaturated fatty acid content 94% by weight] 2 copies and 50
0.4 parts of polyoxyethylene hydrogenated castor oil [“NOIL HC-40” manufactured by NOF CORPORATION, ethylene oxide addition mole number 40] heated to 0 ° C. was added in advance with sufficient stirring. 0.1 part of L-sodium glutamate monohydrate (manufactured by Ajinomoto Co., Inc.) and 6 parts of purified water and laccitol (“MILCHEN” manufactured by Towa Kasei Co., Ltd.)
What melted 0.1 part was gradually added, and the mixture was stirred and mixed in the same manner as in Examples 6 to 10 to prepare a water-in-oil emulsion.

Comparative Example 23 Glycerol trioleate [“NOFABLEGO-903” manufactured by NOF CORPORATION], acyl group composition: cis-Δ9-octadecenoic acid content 72% by weight, cis-Δ9-unsaturated fatty acid content 88 wt%] 12 parts,
Sorbitan monooleate [Nippon Yushi Co., Ltd.]
Made by "NOFABLE SO-901", acyl group composition:
Cis-Δ9-octadecenoic acid content 72% by weight, cis-Δ
9-unsaturated fatty acid content 88% by weight] 1 part, glycero-
Lumonooleate [NOFABLE manufactured by NOF CORPORATION]
GO-901 ”, acyl group composition: cis-Δ9-octadecenoic acid content 72% by weight, cis-Δ9-unsaturated fatty acid content 88% by weight] and 1 part of polyoxyethylene hydrogenated castor oil [Japan YUIO Co., Ltd. "Uniol HC
-40 ", ethylene oxide addition mole number 40] 0.4
And 6 parts of purified water were gradually added while sufficiently stirring, and the mixture was stirred and mixed in the same manner as in Examples 6 to 10 to prepare a water-in-oil emulsion.

The above Examples 6 to 25 and Comparative Examples 4 to 2
Each water-in-oil emulsion prepared in 3 was heated at room temperature (25 ° C) using Rheomat 115 manufactured by Contrabass.
As a result of measuring the viscosity in Example 1, all of Examples 6 to 25 have low viscosities of 200 centipoise or less, and Comparative Examples 4 to 23 have almost the same viscosity or 200 centipoise. It was a little over. As a specific example, the measured viscosities at 25 ° C. and 40 ° C. of several types of water-in-oil emulsions using the emulsifier compositions X ₁ and X ₃ obtained in Examples 1 and ₃ are shown in Table 1 below. .

[0049]

[Table 1]

Next, for each water-in-oil emulsion prepared in Examples 6 to 25 and Comparative Examples 4 to 23, immediately after the emulsion was prepared, the procedure was as follows.
The stability and usability were evaluated. These results are
The following Table 2 (Examples 6 to 25) and Table 3 (Comparative Example 4 to)
23). In addition, the type of the emulsifier composition used is also shown in each table for reference.

<Stability> Water-in-oil emulsion 5 ml
Was placed in a polypropylene spitz tube (sterilized) with a lid of 15 ml, and the stability at each temperature was evaluated.
After 1 day and 10 days from the preparation, ∘ indicates that no separation was visually observed, and ∘ indicates that the oil phase was slightly separated,
The case where the separation of the aqueous phase was observed was evaluated as Δ, the case where the separation of both the oil phase and the water phase was observed was evaluated as ×, and the case where the two phases were almost separated was evaluated as XX.

<Usability> Twenty healthy men and women were panelists, and the feeling of spread and dryness on the skin when water-in-oil emulsion was applied to the back of the hand was evaluated according to the following criteria. . In the table, "N" is a stretch and "S" is a refreshing feeling. ◎: 16 or more people answered that they are good ○: 12 to 15 people who answered that they are good △: 7 to 11 people who answered that they are good ×: 6 people or less who answered that they are good

[0053]

[Table 2]

[0054]

[Table 3]

As is clear from the results shown in Tables 2 and 3, the emulsifier compositions X _{1 to} X ₅ of the present invention were used, and polyoxyethylene hydrogenated castor oil was added to the oil,
After mixing with the emulsifier composition X _{1 to} X ₅ described above,
It can be seen that by the method of adding water and emulsifying, a water-in-oil emulsion having a low viscosity and excellent stability and usability can be prepared.

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Claims (4)

[Claims] 1. A nonionic surfactant which is liquid at room temperature and which comprises A) a partial ester of polyhydric alcohol having 3 or more hydroxyl groups and a fatty acid, and B) an amino acid or a salt thereof in an amount of 1 to 40. 1 to 20% by weight and a non-reducing sugar alcohol having at least 5 or more hydroxyl groups in the molecule
An emulsifier composition comprising a non-ionic surfactant of component A and an aqueous solution of component B mixed in a weight ratio of 1: 1 to 1:20. 2. The nonionic surfactant of component A, wherein the fatty acid forming the partial ester contains cis-Δ9-octadecenoic acid in an amount of 85% by weight or more, and cis-Δ9.
-The emulsifier composition according to claim 1, which consists of high-purity oleic acid containing 90% by weight or more of unsaturated fatty acids. 3. Addition of 20 to 60 mol of ethylene oxide of hydroxy fatty acid triglyceride to oil, mixing the emulsifier composition according to claim 1 or 2, and then adding water for emulsification. A method for preparing a water-in-oil emulsion comprising: 4. The oil component comprises an esterified product of high-purity oleic acid containing 85% by weight or more of cis-Δ9-octadecenoic acid and 90% by weight or more of cis-Δ9-unsaturated fatty acid, or The method for preparing a water-in-oil emulsion according to claim 3, comprising a mixture of the esterified product and one or more selected from squalane, squalene, liquid paraffin, and polybutene.