JP3250877B2 - Water-repellent oil-in-water emulsion composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-in-water emulsion composition, and more particularly to a water-repellent oil-in-water emulsion composition in which a coated film after use has water repellency.

[0002]

2. Description of the Related Art It is well known that emulsified compositions are used in the fields of pharmaceuticals, cosmetics, etc., and particularly when used as an external preparation for the skin, a refreshing feeling can be obtained. An oil-in-water emulsion composition in which an oil component is dispersed is widely used. However, the oil phase is only dispersed in the water phase, and the oil phase may be separated during long-term storage due to the specific gravity of the two. Therefore, it is necessary to maintain the dosage form by increasing the viscosity of the aqueous phase and, in some cases, causing it to gel, and various aqueous thickening gelling agents have been used for this purpose. For example, organic compounds include polysaccharides, natural polymers such as casein, polyoxyethylene, synthetic polymers such as acrylic acid polymers, and inorganic compounds include various clay minerals such as montmorillonite and silica. It is appropriately selected and used depending on the purpose and effect of the thickening gelling agent.

[0003]

However, in such an oil-in-water emulsion composition using such a thickening gelling agent, for example, when applied to the skin, first, the thickening gel in the external aqueous phase The agent forms a film on the skin, on which the oil phase is located. In addition, since the thickening gelling agent itself is hydrophilic, the oil phase is also washed out together with the thickening gelling agent at the time of washing with water, and sufficient water resistance cannot be obtained despite the fact that the oil is blended. However, there was a problem in the retention on the coated surface.

[0004] That is, when an oil-in-water emulsion composition such as cosmetics is applied to the skin, it is desired that the effect is maintained for a long time. Since the oil-in-water emulsion composition has low water resistance, the oil-in-water emulsion composition is easily exfoliated by sweating, a water bath or the like in summer, and it is extremely difficult to maintain the effect for a long time. Also, in the winter season, dry, open air conditions and water work tend to cause cracks, red tinge, rough skin, etc. The oil-in-water emulsified composition containing the thickening gelling agent has a problem that its effect on the skin is limited due to its low retention on the skin.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide an oil-in-water emulsion composition, which has good thickening gelling ability, usability, and stability. It is an object of the present invention to provide a water-repellent oil-in-water emulsion composition in which a coating film after use exhibits water repellency and the coating film has excellent water resistance.

[0006]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to achieve the above object, sucrose fatty acid esters widely used in food additives, cosmetics, etc. and having good safety have been obtained. When a sucrose fatty acid diester obtained by purification by solvent fractionation and a higher aliphatic alcohol and / or a higher fatty acid are used as a thickening gelling agent for an aqueous phase in an oil-in-water emulsion composition, excellent thickening gelation is obtained. While demonstrating the ability
It has been found that the coated film after use of the oil-in-water emulsion composition has water repellency, and the water resistance of the coated film is improved.

That is, when a sucrose fatty acid diester not having a high molecular structure and a higher aliphatic alcohol and / or a higher fatty acid are present in an aqueous phase, an aggregate having a specific structure is formed. It was found that the system thickened and gelled by functioning like a water-soluble polymer. And sucrose fatty acid diesters and higher aliphatic alcohols and the like are relatively high in lipophilicity, so that when the oil-in-water emulsion composition thickened and gelled by the aggregate is applied to the skin, for example, Needless to say, the above aggregates are easily destroyed and return to low hydrophilic sucrose fatty acid diesters, higher aliphatic alcohols, etc., so that their presence does not impair the water repellency of the oil-in-water emulsion composition and is excellent together with the oil phase component. It can exhibit high water repellency.

The present inventors also conducted detailed studies using pure sucrose fatty acid diesters obtained by column chromatography purification. As a result, it was difficult to disperse pure sucrose fatty acid diesters in water and to increase the viscosity. It took a long time to gel, but it was clarified that sucrose fatty acid diester containing a small amount of an ionic surfactant easily and uniformly dispersed. That is, the water-repellent oil-in-water emulsified composition according to claim 1 of the present application contains sucrose fatty acid in the aqueous phase.
Esters and higher fatty alcohols and / or higher fats
An acid and an ionic surfactant;
35% by weight or less of sucrose fatty acid diester in the acid ester
Sucrose fatty acid monoester and sucrose fat
Containing the acid triester in a ratio of 1: 3 to 1:20
It is characterized by. And the water repellency according to claim 2 of the present application
The oil-in-water emulsion composition contains sucrose fatty acid ester in the aqueous phase.
And higher fatty alcohols and / or higher fatty acids, and
The sucrose fatty acid ester
Contains at least 35% by weight of sucrose fatty acid diester
Sucrose fatty acid monoester and sucrose fatty acid triester
It is characterized by containing an ester in a ratio of 1: 3 to 1:20.
To be

[0009] Then, claim 3 Symbol mounting repellent oil-in-water emulsion composition of the present application, the water-repellent oil-in-water emulsion composition according to claim 1 or 2, sucrose fatty acid diester in the aqueous phase And the molar ratio of the higher aliphatic alcohol and / or higher fatty acid is 1: 1 to 1: 5, and the amount of the ionic surfactant is 0.4 to 20% by mole based on the total amount of the mixture.
It is characterized by containing. 4. Symbol placement repellent oil-in-water emulsion composition comprises a sucrose fatty acid ester in the aqueous phase,
Higher fatty alcohols and / or higher fatty acids and ions
The sucrose fatty acid ester
Medium, containing 50% by weight or more of sucrose fatty acid diester,
The sucrose fatty acid diester and higher fatty alcohol and
And / or higher fatty acid forms an aggregate having a molar ratio of 1: 2 in the aqueous phase.
It is characterized by forming. And Claim 5
The water-repellent oil-in-water emulsion composition of sucrose fatty acid in the aqueous phase
Esters and higher fatty alcohols and / or higher fats
An acid and an ionic surfactant;
35% by weight of sucrose fatty acid diester in fatty acid ester
Containing sucrose fatty acid monoester and sucrose fat
Containing fatty acid triesters in a ratio of 1: 3 to 1:20,
The sucrose fatty acid diester and higher fatty alcohol and
And / or the higher fatty acid forms an aggregate having a molar ratio of 1: 2 in the aqueous phase.
It is characterized by having.

[0010] water-repellent oil-in-water emulsified composition according to claim 6 Symbol mounting is claim in 1-5 repellent oil-in-water emulsion composition according to, higher aliphatic sucrose fatty acid diester alcohols and / or higher Neither the sucrose fatty acid diester nor the higher fatty alcohol and / or the higher fatty acid, which is observed in DSC (indicative scanning calorimetry) when the molar ratio of the fatty acid is 1: 2, and Is characterized by having an endothermic peak at the same position as the endothermic peak which is not a component. Repellent oil-in-water emulsified composition according to claim 7 Symbol mounting, in water-repellent oil-in-water emulsion composition according to claim 1-6, sucrose fatty acid diester and higher aliphatic alcohols and / or higher fatty water It is characterized by being associated in a phase and forming a lamellar structure.

[0011] 8 Symbol mounting repellent oil-in-water emulsion composition claims, claim in 1-7 repellent oil-in-water emulsion composition according to, higher aliphatic sucrose fatty acid diester alcohols and / or higher Fatty acids are associated in an aqueous phase to form a lamellar structure in which the subcell structure is hexagonal. 9. Symbol mounting repellent oil-in-water emulsion composition, in water-repellent oil-in-water emulsion composition according to claim 1-8, the contact angle to water, characterized in that at least 60 °.

Hereinafter, the configuration of the present invention will be described in detail. The water-repellent oil-in-water emulsion composition according to the present invention comprises a sucrose fatty acid diester usually used as a nonionic surfactant, a higher aliphatic alcohol and / or a higher fatty acid, and an ionic surfactant. By using the oil-in-water emulsion composition as a thickening gelling agent, the coated film after use shows water repellency. Therefore, the essential components of the water-repellent oil-in-water emulsion composition of the present invention are three or four of sucrose fatty acid diester, higher fatty alcohol and / or higher fatty acid, and ionic surfactant.

The sucrose fatty acid diester used in the present invention is a fatty acid having a saturated or unsaturated, straight or branched chain having 12 to 22 carbon atoms, and the two fatty acids may be different. Even if other sucrose fatty acid esters in the sucrose fatty acid diester, such as sucrose fatty acid monoester and sucrose fatty acid triester are contained as impurities, the water-repellent oil-in-water emulsion composition according to the present invention can be obtained, The impurity content is at most 50%, preferably 40% or less, more preferably 30% or less. However, when the monoester and the triester coexist as impurities, and the ratio of the monoester to the triester is in the range of 1: 3 to 1:20, the diester content may be less than 50%. In this case, the content of the diester is 35% or more, preferably 40% or more.

Generally, commercially available sucrose fatty acid esters are mixtures of monoesters, diesters, triesters, and other impurities. In order to obtain a high-purity sucrose fatty acid diester used in the present invention, a solvent is required. It needs to be purified by fractionation or column chromatography. If purified by column chromatography, a highly purified product having a diester purity of 99% or more can be obtained.
Sucrose fatty acid diester alone is very difficult to disperse in water. For this reason, it is preferable to use an ionic surfactant in combination for good dispersion in water.

Examples of the ionic surfactant include fatty acid soaps, ether carboxylic acids and salts thereof, alkane sulfonates, sulfonates of higher fatty acid esters, dialkyl sulfosuccinates, sulfonates of higher fatty acid amides, and alkyl allyl sulfones. Acid sulfate, higher alcohol sulfate, secondary higher alcohol sulfate, alkyl and alkyl allyl ether sulfate, sulfate of glycerin fatty acid ester, sulfate of higher fatty acid alkylolamide, sulfated oil, phosphoric acid Anionic surfactants such as ester salts, amino acids, collagen hydrolysates and higher fatty acid condensates, collagen hydrolyzate derivatives, and alkylamine salts, polyamine or alkanolamine fatty acid derivatives, alkyltrimethylammonium A cationic surfactant such as dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, alkylisoquinolinium salt, dialkylmorpholinium salt and the like can be used. 12 ~
22 ionic surfactants, and particularly preferred are anionic or cationic surfactants having a lipophilic group having 12 to 22 carbon atoms. However, if the amount of the water-soluble ionic surfactant increases, water repellency cannot be obtained. Therefore, the blending amount of the water-soluble ionic surfactant is a mixture of a sucrose fatty acid diester and a higher aliphatic alcohol and / or a higher fatty acid. It is preferably from 0.4 to 20 mol%, more preferably from 1 to 8 mol%, based on the total amount.

The higher aliphatic alcohol and / or higher fatty acid used in the present invention has a fatty chain having 1 carbon atom.
It has two or more saturated or unsaturated, straight or branched chains, and one or more of these may be used. For example, cetanol, stearyl alcohol, behenyl alcohol, batyl alcohol, stearic acid, behenic acid and the like can be mentioned.

In the water-repellent oil-in-water emulsion composition of the present invention, a sucrose fatty acid diester and a higher aliphatic alcohol and / or a higher fatty acid form an association in a water phase at a molar ratio of 1: 2, and a thickening gel The mixing ratio of the essential components is not particularly limited as long as the chemical conversion ability and the water repellency are exhibited, but preferably the sucrose fatty acid diester is 10 mol% or more and 50 mol% or more.
Mol% or less, higher fatty alcohol and / or higher fatty acid is 50 mol% to 90 mol%, more preferably 25 mol% to 45 mol% of sucrose fatty acid diester, higher fatty alcohol and / or higher fatty acid Is from 55 mol% to 75 mol%. And as a compound molar ratio of a sucrose fatty acid diester and a higher aliphatic alcohol and / or a higher fatty acid, preferably 1: 1 to 1
The ratio is 1: 5, more preferably 1: 1.5 to 1: 3.

If the sucrose fatty acid diester and the higher fatty alcohol and / or higher fatty acid are blended in the aqueous phase within this range, the molar ratio of sucrose fatty acid diester to higher fatty alcohol and / or higher fatty acid is 1: 2. Is formed. Further, the total amount of the sucrose fatty acid diester, the higher aliphatic alcohol and / or the higher fatty acid, and the ionic surfactant is preferably 1 to 25% by weight based on the total amount of the water-repellent oil-in-water emulsion composition, More preferably, 2
~ 15%.

A thickening gelling agent is prepared by changing the mixing ratio of the sucrose fatty acid diester and the higher aliphatic alcohol, and 5% of the thickening gelling agent is used to prepare an oil-in-water type emulsified composition which has been emulsified in advance. The mixture was mixed at a ratio of 95%, and the relationship between the mixing ratio and the gel hardness was examined. When sucrose stearic acid diester is used as the sucrose fatty acid diester and stearyl alcohol is used as the higher aliphatic alcohol, as shown in FIG. The fraction is about 0.5 to 0.83, that is, the molar ratio of sucrose fatty acid diester: higher aliphatic alcohol is in the range of 1: 1 to 1: 5, and preferably the molar fraction is about 0.6. 0.75, that is, the molar ratio is 1: 1.5 to 1: 3. It is understood that the thickening gelling ability is maximized when the molar ratio is about 0.67, that is, when the molar ratio is 1: 2. Similar results can be obtained by using higher fatty acids or mixtures thereof instead of higher aliphatic alcohols.

Such a thickening gelling ability is derived from an association of a sucrose fatty acid diester and a higher aliphatic alcohol and / or a higher fatty acid formed in an aqueous phase at a molar ratio of 1: 2. Can be confirmed by DSC (scanning calorimeter). That is, when the water-repellent oil-in-water emulsion composition is measured by DSC (scanning calorimeter), FIG.
As shown in Table 2, Tc (solid-liquid transition) of an endothermic peak derived from the used sucrose fatty acid diester (hereinafter, this peak is referred to as Ps) or an endothermic peak (Pa) derived from higher aliphatic alcohol and / or higher fatty acid. In addition to the endothermic peak at (temperature), a new endothermic peak (referred to as Pc) is observed in a higher temperature portion than these. When the molar ratio of sucrose fatty acid diester is more than 1: 2, Ps and Pc are observed, and as the molar ratio approaches 1: 2, Ps decreases and Pc increases. When the molar ratio is around 1: 2, Ps or Pa disappears and becomes Pc only. When the higher aliphatic alcohol and / or higher fatty acid is more than 1: 2, Pa is observed in addition to Ps. Will be done.

Accordingly, this Pc is an endothermic peak of an aggregate formed at a molar ratio of sucrose fatty acid diester to higher aliphatic alcohol and / or higher fatty acid of 1: 2. The present inventors performed X-ray analysis to elucidate the structure of the aggregate. As a result of measuring the emulsified composition having a molar ratio of sucrose fatty acid diester: higher aliphatic alcohol and / or higher fatty acid of 1: 2 by small-angle X-ray diffraction,
As shown in FIG. 3, the surface spacing is about 4.1 ° around 21.5 degrees.
Was observed, and it was confirmed that an aggregate composed of hexagonal (α-structure) subcells was formed.

Therefore, it is understood that the water-repellent oil-in-water emulsion composition of the present invention has the following structure with respect to the structure of the aggregate formed in the aqueous phase. That is, in the aqueous phase, as shown in FIG. 1, sucrose fatty acid diester molecules and higher fatty alcohol and / or higher fatty acid molecules are arranged in a molar ratio of 1: 2, and in such an arrangement, a hexagonal subcell structure is formed. have. The hydrophilic group and the hydrophobic group of each molecule are adjacent to each other with the same direction due to their affinity, and such an arrangement is continuous to form a layer, with the hydrophilic group facing the aqueous phase and the hydrophobic group facing each other. It forms a lamellar structure.

The above-mentioned aggregate having a molar ratio of sucrose fatty acid diester: higher aliphatic alcohol and / or higher fatty acid of 1: 2 is formed at least in a molar ratio of sucrose fatty acid diester: higher fatty alcohol of 1: 1 or more. The fluidity of the aqueous phase is restricted by being dispersed in the aqueous phase, and the system becomes a thickened gel. However, when the molar ratio of the sucrose fatty acid diester is higher than the above molar ratio, an excess of the sucrose fatty acid diester is present. When the molar ratio of the higher aliphatic alcohol and / or higher fatty acid is higher than 1: 2, the excess of the higher fatty acid becomes higher. The presence of aliphatic alcohols and / or higher fatty acids tends to reduce the thickening gelling ability.

In the oil-in-water emulsified composition in which the above-mentioned aggregate having a molar ratio of 1: 2 is formed in the aqueous phase and the gel is thickened and gelled, a conventional thickening gelling agent such as a hydrophilic polymer is used. The water repellency of the coating film, which cannot be obtained with the oil-in-water emulsion composition, can be obtained.
That is, the water-repellent oil-in-water emulsified composition of the present invention has a refreshing feeling of use characteristic of the oil-in-water emulsified composition, and has a sticky or drawback when a hydrophilic polymer is blended. The coating film after use shows good water repellency without any slimy feeling and without impairing the water repellency of the oil content, and has excellent water resistance, so it has excellent holding properties on the skin etc. It has the feature of.

The water repellency can be evaluated by measuring the contact angle with water. The larger the contact angle, the higher the water repellency. However, when the water repellent oil-in-water emulsion composition of the present invention is used, it is generally used. It shows extremely high water repellency when the contact angle is 60 ° or more. In order to obtain the water-repellent oil-in-water type emulsion composition according to the present invention, the following method can be mentioned. That is, after mixing and dissolving sucrose fatty acid diester, higher aliphatic alcohol and / or higher fatty acid, and ionic surfactant in a solvent such as chloroform, the solvent is distilled off to obtain a uniform thickening gelling agent. This can be added to and mixed with the emulsion prepared in advance to obtain the water-repellent oil-in-water emulsion composition of the present invention.
Alternatively, the thickening gelling agent may be dissolved in an aqueous phase such as water or an aqueous solvent to form a thickened gel composition, which may be added to and mixed with an emulsion prepared in advance. The thickening gelling agent does not need to be made uniform in advance as described above, but may be made uniform in advance in order to shorten the preparation time when preparing the thickened gel composition. Examples of the aqueous solvent include ethyl alcohol, isopropyl alcohol, methyl alcohol, propylene glycol, 1,3-butylene glycol, glycerin, ethylene glycol, polyethylene glycol, and these. And the like.

The water-repellent oil-in-water emulsion composition of the present invention also forms an association of the above essential components with the above-mentioned molar ratio of 1: 2 in the process of producing the oil-in-water emulsion composition such as cosmetics and pharmaceuticals. It can be obtained by appropriately compounding it in a compounding ratio. For example, there is a method in which a higher aliphatic alcohol and / or a higher fatty acid is added to an oil phase, and after emulsification with an aqueous phase, a sucrose fatty acid diester and an ionic surfactant are mixed. The sucrose fatty acid diester and the ionic surfactant may be added to the aqueous phase in advance, but in that case, problems such as thickening during emulsification are likely to occur. In addition, the sucrose fatty acid diester is consumed as a surfactant in the emulsification process, and the amount of the sucrose fatty acid diester required to form an aggregate in the aqueous phase is insufficient. In order to obtain, sucrose fatty acid diester for forming an aggregate after emulsification must be added.

[0027] The method for producing the water-repellent oil-in-water emulsion composition of the present invention may be a method of preparing a uniform thickening gelling agent as described above, or a method of separately mixing essential components. However, an aggregate having a molar ratio of 1: 2 is formed, and the peak of the aggregate is confirmed in DSC. The water-repellent oil-in-water emulsion composition of the present invention has a hardness that is not changed or separated, and is very stable over time, and the coated film after use is water-repellent. And an oil-in-water type emulsified composition having excellent holding properties on a coated surface.

The water-repellent oil-in-water emulsified composition of the present invention may contain other substances according to the intended use and purpose. For example, if applied to cosmetics, fragrances and preservatives , Vitamins, powders, pigments, drugs and the like. Examples of the inorganic powder include talc, titanium oxide, kaolin, silicic anhydride, silicate, zinc oxide, calcium carbonate, magnesium carbonate, red iron oxide, yellow iron oxide, chromium oxide, carbon black, ultramarine, mica, sericite, and nylon. Powder, polyethylene powder, cellulose powder,
Acrylic resins, titanium dioxide, iron oxide and the like can be mentioned.

Examples of inorganic pigments include talc, kaolin, calcium carbonate, zinc oxide, titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, titanium coated mica, bismuth oxychloride, red iron oxide, binder pigment , Gunjo Pink, chromium hydroxide, titanium mica, yellow iron oxide,
Chromium oxide, aluminum cobalt oxide, navy blue, black iron oxide, carbon black, silicic anhydride, magnesium silicate, bentonite, mica, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, light calcium carbonate, heavy calcium carbonate, light Magnesium carbonate, heavy magnesium carbonate, niramine, etc. are listed.These inorganic powders and inorganic pigments may be blended as they are, but those which have been hydrophobized by silicone treatment, fluorine treatment, metal soap treatment, activator treatment, etc. You may mix.

Examples of the oil component include silicone oils such as dimethylpolysiloxane, methylpolysiloxane, cyclic siloxane, and trimethylsilicic acid, higher fatty acids such as palmitic acid, stearic acid and behenic acid, and sterols such as cholesterol. , Liquid paraffin, ozokerite, ceresin wax, paraffin wax, microcrystal wax, vaseline, hydrocarbons such as squalane, tallow, pork oil, almond oil, avocado oil, olive oil, cacao oil, sesame oil, cottonseed oil, castor oil, palm kernel oil, Fats and oils such as coconut oil, palm oil, wood wax, peanut oil, etc., waxes such as beeswax, spermaceti, lanolin, candelilla wax, carbanana wax, esters such as diethyl phthalate, dibutyl phthalate, cholesterol isostearate and the like. Can be used with silicone oil or hydrocarbon oil. If placed further usability, it tends to improve the water repellency was observed.

These oil phases contain an oil-soluble drug, an antioxidant,
An ultraviolet absorber such as octyl methoxycinnamate and a lipophilic surfactant can also be blended. In addition, the water-repellent oil-in-water emulsion composition of the present invention can be used as cosmetics and pharmaceuticals of various dosage forms as long as its effects are not impaired, and can be blended. Creams, emulsions, lotions, and other cosmetics It can be applied to O / W emulsified compositions such as makeup cosmetics, skin external preparation cream, cleansing and the like.

[0032]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the embodiments. In addition, unless otherwise specified, the compounding amount is shown in% by weight.
First, a production example of a sucrose fatty acid diester used in the present invention will be described.

Production Example 1 Sucrose stearic acid diester
100 g of commercially available sucrose stearic acid ester, which is said to contain about 30% monoester, is weighed into a purified 1 L beaker, and a mixed solution of 855 ml of methanol and 45 ml of water is added thereto. Dissolve the sample once with. Thereafter, the solution is kept at 44 ° C. and separated into two phases, and then the upper layer (solution phase)
Fractionate. The main component of the lower layer (solid phase) is a triester, and the upper layer mainly contains a monoester and a diester. Water is added to the upper layer so that the ethanol concentration becomes about 80 v / v%, the temperature is raised to 60 ° C., a precipitate is formed at 25 ° C., and the precipitate is collected. The upper layer is mainly composed of monoester, and the precipitate is mainly composed of diethyl ether. Is dissolved in 720 ml of methanol, 180 ml of water is added to the solution, and the mixture is stirred, kept at 25 ° C. and left standing to form a precipitate, and the precipitate is collected. Was repeated to obtain a composition containing about 80% or more of sucrose stearic acid diester. Ingredients other than sucrose stearic acid diester include sucrose stearic acid monoester, triester,
Stearic acid, sodium stearate and the like.
The yield based on the raw sucrose fatty acid ester was about 33.
%Met.

Production Example 2 Sucrose oleic acid mono and die
50 g of commercially available sucrose oleate ester, which is said to contain about 70% of monoester, was weighed and added to a purified 1 L beaker of Steal, and a mixed solution of 760 ml of methanol and 190 ml of water was added to dissolve the mixture at -20 ° C. And let it stand for two-phase separation, then settle down (lower layer)
Fractionate. Here, the upper layer is mainly composed of monoester, and the precipitate (lower layer) is mainly composed of a mixture of diester and triester. 760 ml of methanol and 190 parts of water were added to the separated precipitate.
Add and dissolve the mixed solution of ml, leave at −20 ° C., separate again into two phases, and separate the precipitated portion. This operation is repeated twice. Here, the upper layer is mainly composed of monoester, and the precipitate (lower layer) is mainly composed of diester and triester. The upper layer obtained in and was concentrated to obtain sucrose oleic acid monoester. The purity of the sucrose oleate monoester was about 95%, and the yield was about 65% based on the raw sucrose oleate. The lower layer obtained in (1) and (2) is dissolved in a 97% methanol solution, and left at room temperature to separate the upper layer. The upper layer obtained in step was concentrated and dried to obtain sucrose oleic acid diester. The purity of the sucrose oleic diester was 65% or more, and the yield based on the raw sucrose oleic ester was about 25%.

Production Example 3 Sucrose stearic acid diester
Column chromatography - purified chloroform 400ml column chromatography commercially as solvent by - swollen gel 200g for, packed in a column chromatography tube was about 10g added sucrose stearic acid ester obtained by the production method 1. Stepwise elution was performed using the following solvents in order. i) methanol: chloroform = 8: 92 (volume ratio) 1L ii) methanol: chloroform = 15: 85 (volume ratio)
1L iii) Methanol: chloroform = 25: 75 (volume ratio) 1L The eluate was fractionated in 70 ml portions, and sucrose stearic acid diester was confirmed by gas chromatography and TLC for each fraction. When the diester fraction is concentrated, about 4 g
Of sucrose stearic acid diester (purity: 98% or more) was obtained.

Production Example 4 Sucrose oleic acid diester
Purification by column chromatography Using 400 ml of chloroform as a solvent, 200 g of commercially available silica gel for column chromatography was swollen, filled in a column chromatography tube, and about 10 g of sucrose oleate obtained by Production Method 2 was added. Stepwise elution was performed using the following solvents in order. i) Methanol: chloroform = 6: 94 (volume ratio) 1L ii) Methanol: chloroform = 12: 88 (volume ratio)
1L iii) Methanol: chloroform = 20: 80 (volume ratio) 1L The eluate was fractionated in 70 ml portions, and sucrose oleic diester was confirmed by gas chromatography and TLC for each fraction. When the diester fraction was concentrated, about 2.5
g of sucrose oleic acid diester (purity of 98% or more) was obtained.

Production Example 5 Sucrose stearic acid diester
In a purified 1 L beaker, 100 g of commercially available sucrose stearic acid ester, which is said to contain about 30% monoester, is weighed, and a mixed solution of 800 ml of methanol and 100 ml of water is added, and the sample is once dissolved at a temperature near the boiling point of the solvent. . Thereafter, a precipitate is formed at 35 ° C., and the precipitate is collected,
A composition containing about 40% sucrose stearic diester and 50% sucrose stearic triester was obtained. Ingredients other than sucrose stearic acid diester and sucrose stearic acid triester were sucrose stearic acid monoester, stearic acid, and sodium stearate. The yield based on the starting sucrose fatty acid ester was about 75%.

Next, an example of a water-repellent oil-in-water emulsion composition using the sucrose fatty acid diester produced as described above and a higher aliphatic alcohol and / or a higher fatty acid will be described. Example 1 1) Purified water 79.5 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.5 4) Dimethyl polysiloxane 5.0 5) Stearyl alcohol 2.0 6) Sucrose stearic diester 3. 0 Here, sucrose stearic acid diester was obtained according to Production Example 5. 1) to 5) were heated and stirred to emulsify, and 6) was added to obtain a gel oil-in-water emulsion composition. This emulsified composition was stable at 37 ° C., 25 ° C., and 0 ° C. for at least one month, and had a refreshing feeling of use, was excellent in usability, and had a water repellency of ◎. In addition, DSC measurement confirmed that an aggregate having the molar ratio of 1: 2 was formed.

In the present specification, the water repellency of the coating film of the emulsion composition was evaluated by measuring the contact angle with water. The contact angle was measured at about 25 ° C. using an automatic contact angle meter CA-Z (manufactured by Kyowa Interface Science Co., Ltd.) after applying the test emulsion composition to a glass plate to a thickness of 0.35 mm and drying. The water repellency was evaluated according to the following criteria. ◎: contact angle of 80 ° or more ○: contact angle of 60 to less than 80 ° △: contact angle of 40 to less than 60 ° ×: contact angle of less than 40 °

Comparative Example 1 1) Purified water 81.5 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.5 4) Dimethylpolysiloxane 5.0 5) Montmorillonite (aqueous thickener) 3.0 1 ) To 4) were heated and stirred to emulsify, and 5) was added to obtain an oil-in-water emulsion composition. This emulsified composition is at 37 ° C., 25
Although it was stable at 0 ° C. and 0 ° C. for one month or more, the water repellency was ×.

Comparative Example 2 1) Purified water 83.5 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.5 4) Dimethyl polysiloxane 5.0 5) Acrylic acid polymer (water-soluble polymer thickener) ) 1.5 6) Caustic potassium 0.5 1) to 4) were heated and stirred to emulsify, and 5) and 6) were added to homogenize to obtain an oil-in-water emulsion composition. This emulsion composition was stable at 37 ° C., 25 ° C., and 0 ° C. for at least one month, respectively, but the water repellency was ×.

Comparative Examples 3 to 5 1) Purified water 83.5 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.5 4) Dimethyl polysiloxane 5.0 5) Stearyl alcohol 1.5 1) to 5 ) Was heated and stirred, and then the following commercially available sucrose fatty acid ester (3.0%) was added at 70 ° C, and the obtained oil-in-water emulsion compositions were compared by emulsification.

[0043]Comparative Example 3  Commercially available sucrose stearic acid ester (monoester 30
%, 70% or more of diester).
The water repellency of the oil-in-water emulsion composition was Δ.Comparative Example 4  Commercially available sucrose stearate (monoester 50
%, 50% or more of diester).
The water repellency of the oil-in-water emulsion composition was x.Comparative Example 5  Commercially available sucrose stearic acid ester (monoester 70
%, 30% or more of diester).
The water repellency of the oil-in-water emulsion composition was x.

Example 2 Nutrition cream 1) Liquid paraffin 30.0 wt% 2) Pluronic 4.0 3) Vitamin E acetate 0.2 4) Paraben 0.2 5) Fragrance 0.1 6) Stearic acid 5 7) Purified water residue 8) Glycerin 30.0 9) Sucrose oleic acid diester 2.5 Here, sucrose oleic acid diester was obtained according to Production Example 4, and a small amount of sodium oleate was used. contains. 1) to 6) and 7) to 8) are separately heated to 70 ° C., and 1) to 6) are added to 7) to 8) with stirring, emulsified, and 9) is added, mixed, stirred and cooled. To obtain a nourishing cream. The water repellency of this nutritional cream was ○. In addition, DSC measurement confirmed that an aggregate having the molar ratio of 1: 2 was formed.

Example 3 Hand cream 1) Squalane 20.0 wt% 2) Polyoxyethylene sorbitan fatty acid ester 4.0 3) Vaseline 15.0 4) Vitamin E acetate 0.2 5) Paraben 0.2 6) Fragrance 0 .17) Stearyl alcohol 0.75 8) Behenyl alcohol 0.75 9) Purified water residue 10) Propylene glycol 10.0 11) Sucrose stearic acid diester 3.0 Here, sucrose stearic acid diester is a production example. 5 and contains a small amount of sodium stearate. 1) to 8) and 9) to 10) separately for 7
The mixture was heated to 0 ° C., and 1) to 8) were added to 9) to 10) while stirring to emulsify. 11) was added, mixed and stirred, and cooled to obtain a hand cream. The water repellency of this hand cream was ○. In addition, DSC measurement confirmed that an aggregate having the molar ratio of 1: 2 was formed.

Example 4 Gel Whitening Cosmetic <Gel Formula> 1) 0.5% by weight of stearic acid 2) Triethanolamine 0.3 3) Behenyl alcohol 2.0 4) Remaining amount of purified water 5) Diester of sucrose stearic acid 3.0 Here, the sucrose stearic acid diester is obtained by Production Example 5. 1) to 4) were heated and dissolved at 60 ° C., 5) was added thereto, mixed and stirred, and cooled to obtain a gel.

<Emulsification Formula> 1) Squalane 40.0 wt% 2) Stearic acid 0.5 3) Paraben 0.1 4) Fragrance 0.1 5) Triethanolamine 0.3 6) Propylene glycol 20.0 7) Arbutin 3.0 8) Remaining amount of purified water An emulsion was prepared by the usual method with the above composition, and the above gel 7
0 g and 30 g of the emulsion were mixed and cooled to 25 ° C. to obtain a gel whitening cosmetic. The water repellency of this gel whitening cosmetic was ○. In addition, DSC measurement confirmed that an aggregate having the molar ratio of 1: 2 was formed.

Example 5 Sunscreen cream 1) Beeswax 2.0 wt% 2) Shortening 2.0 3) Cetostearyl alcohol 2.0 4) Olive oil 14.8 5) 2-Ethylhexyl p-dimethylaminobenzoate 4.0 6) 2-Hydroxy-4-methoxybenzophenone 1.0 7) Fragrance 0.1 8) Paraben 0.1 9) Ethanol 5.0 10) Purified water residue 11) Potassium stearate 0.4 12) Propylene glycol 5.0 13) Sucrose oleic acid diester 2.0 Here, sucrose oleic acid diester was obtained by Production Example 4. 1) to 8) and 9) to 12) were separately heated and stirred at 70 ° C, and 1) to 8) were added to 9) to 12).
Was added to the mixture while stirring to emulsify, and 13) was added thereto, followed by mixing and stirring, followed by cooling to obtain an O / W sunscreen cream.
The water repellency of this cream was ○. In addition, DSC measurement confirmed that an aggregate having the molar ratio of 1: 2 was formed.

Example 6 Sunscreen lotion 1) Vaseline 10.0 wt% 2) Olive oil 15.0 3) Oleic acid 1.5 4) Octyl methoxycinnamate 3.0 5) Paraben 0.1 6) Fragrance 0. 17) Purified water residue 8) Potassium oleate 0.3 9) Silicon-treated titanium oxide 6.0 10) Propylene glycol 5.0 11) Sucrose stearic acid diester 3.0 Here, sucrose stearic acid diester is , Obtained according to Production Example 5. 1) to 6) and 7) to 10)
Separately heated and stirred at 70 ° C., and 1) to 6) to 7) to 1
After 0) was added with stirring to emulsify, 11) was added, mixed and stirred, and cooled to obtain an O / W sunscreen lotion. The water repellency of this lotion was ○. Also, D
In the SC measurement, it was confirmed that an aggregate having a molar ratio of 1: 2 was formed.

Example 7 Pre-Make Lotion 1) Liquid paraffin 10.0 wt% 2) Trimethylsiloxysilicate 3.0 3) Behenyl alcohol 0.5 4) Stearyl alcohol 0.5 5) Fragrance 0.1 6) Paraben 0. 17) Purified water residue 8) Potassium stearate 0.3 9) Polyethylene glycol 3.0 10) Spherical cellulose powder 1.0 11) Propylene glycol 8.0 12) Sucrose oleic acid diester 1.5 Sucrose oleic acid diester was obtained according to Production Example 4. 1) to 6) and 7) to 11) are separately heated and stirred at 70 ° C., and 1) to 6) in 7) to 11).
Was added to the mixture while stirring to emulsify. Then, 12) was added thereto, mixed and stirred, and cooled to produce a pre-made lotion. This lotion was stable at 37 ° C., 25 ° C., and 0 ° C. for more than one month each. In addition, the water repellency was ○ while having a refreshing feeling. And, it showed higher water repellency than the conventional O / W type pre-made lotion, and when the powdery foundation was applied repeatedly, the makeup durability was improved as compared with the case without the lotion. In addition, DSC measurement confirmed that an aggregate having the molar ratio of 1: 2 was formed.

Example 8 Foundation 1 1) Cyclic polysiloxane 10.0 wt% 2) Trimethylsiloxysilicate 3.0 3) Stearyl alcohol 1.0 4) Fragrance 0.1 5) Paraben 0.1 6) Purified water residue Quantity 7) Sodium stearate 0.2 8) Titanium dioxide 5.8 9) Talc 4.2 10) Iron oxide 2.1 11) Propylene glycol 8.0 12) Sucrose oleic acid diester 1.5 The sugar oleic acid diester was obtained according to Production Example 4. 1) to 5) and 6) to 11) are separately heated and stirred at 70 ° C., and then 1) to 5) in 6) to 11).
Was added and emulsified while stirring, and 12) was added thereto, followed by mixing and stirring, and then cooled to produce a foundation. This foundation was stable at 37 ° C., 25 ° C., and 0 ° C., respectively, for one month or more. In addition, the contact angle was 98 ° C., which was very high in water repellency as compared with the conventional O / W type foundation, and the cosmetic durability was improved while having a refreshing usability. In the DSC measurement, the molar ratio was 1:
It was confirmed that an aggregate of No. 2 was formed.

Example 9 Foundation 2 1) 7.0% by weight of dimethylpolysiloxane 2) Methylphenylsiloxane 5.0 3) Squalane 5.0 4) Behenyl alcohol 1.0 5) Fragrance 0.1 6) Paraben 0.17 8) Polyoxyethylene sorbitan fatty acid ester 4.0 9) Silicon-treated titanium dioxide 5.8 10) Silicon-treated sacite 4.2 11) Silicon-treated iron oxide 2.1 12) Butylene glycol 5.0 13) Sucrose stearic acid diester 2.5 Here, sucrose stearic acid diester is obtained by Production Example 5, and contains a small amount of sodium stearate. 1) to 6) and 7) to 12) are separately heated and stirred to be uniform, and 1) to 6) are added to 7) to 12) with stirring, emulsified, and then 13) is added and mixed and stirred. After cooling, a foundation was produced. This foundation was stable at 37 ° C., 25 ° C., and 0 ° C., respectively, for one month or more. In addition, the contact angle was 101 ° C., which was a very high level of water repellency as compared with the conventional O / W type foundation, and the cosmetic durability was improved while having a refreshing feeling. In the DSC measurement, the molar ratio was 1: 2.
It was confirmed that an aggregate was formed.

Comparative Example 6 Pre-Make Lotion 1) Dimethyl polysiloxane 7.0 wt% 2) Cetyl alcohol 5.0 3) Fragrance 0.1 4) Paraben 0.1 5) Purified water balance 6) Potassium stearate 3 7) Polyethylene glycol 5.8 8) Propylene glycol 4.2 9) Acrylic acid polymer 2.1 10) Caustic potassium 5.0 1) to 4) and 5) to 8) are separately heated at 70 ° C. )
After emulsifying 1) to 4) with stirring in to 8), 9),
10) was added, mixed and stirred, and cooled to produce a pre-made lotion. This pre-made lotion is 37 ℃,
It was stable at 25 ° C. and 0 ° C. for at least one month, respectively, but the water repellency was ×.

Comparative Example 7 Foundation 1) Cyclic polysiloxane 10.0 wt% 2) Liquid paraffin 8.0 3) Cetyl alcohol 1.0 4) Fragrance 0.1 5) Paraben 0.1 6) Purified water balance 7) Sodium stearate 0.2 8) Titanium dioxide 5.8 9) Talc 4.2 10) Iron oxide 2.1 11) Propylene glycol 8.0 12) Bentonite 1.2 1) -5) and 6) -11) Were separately heated and stirred at 70 ° C., and 1) to 5) were added to 6) to 11) while stirring to emulsify. Then, 12) was added, mixed and stirred, and cooled to produce a foundation. This pre-made lotion is 3
Each of them was stable at 7 ° C., 25 ° C., and 0 ° C. for one month or more, but the water repellency was ×.

[0055]

As described above, the oil-in-water emulsion composition according to the present invention can be used in the presence of an ionic surfactant in the presence of a sucrose fatty acid diester, a higher aliphatic alcohol and / or a higher fatty alcohol.
Alternatively, the higher fatty acid forms an aggregate having a molar ratio of 1: 2 in the aqueous phase, so that it has good thickening gelling ability, stability, and usability, and the coated film after use exhibits water repellency. And has the feature of being excellent in retention on the coated surface.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the blending mole fraction of sucrose fatty acid diester and higher aliphatic alcohol and gel hardness in the water-repellent oil-in-water emulsion composition according to one embodiment of the present invention.

FIG. 2 is a DSC chart of the water-repellent oil-in-water type emulsified composition according to one embodiment of the present invention when the mixing ratio of sucrose fatty acid diester to higher aliphatic alcohol is changed.

FIG. 3 is a chart of a water-repellent oil-in-water emulsion composition according to one embodiment of the present invention, which is measured by a small-angle X-ray diffraction method.

FIG. 4 is a diagram illustrating an association in which a sucrose fatty acid diester and a higher aliphatic alcohol and / or a higher fatty acid are formed in an aqueous phase in the water-repellent oil-in-water emulsion composition according to one embodiment of the present invention. FIG.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shigenori Kumagai 1050 Nippa-cho, Kohoku-ku, Yokohama, Kanagawa Prefecture Inside the Shiseido First Research Center (72) Inventor Shinichi Anzai 1050 Nippa-cho, Kohoku-ku, Yokohama, Kanagawa Shiseido Co., Ltd. First Research Center (72) Inventor Hideo Nakajima 1050 Nippa-cho, Kohoku-ku, Yokohama, Kanagawa Prefecture Shiseido Co., Ltd. First Research Center (56) References JP-A-4-253903 (JP, A JP-A-1-176444 (JP, A) JP-A-60-183029 (JP, A) JP-A-60-115509 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 7/00-7/50

Claims (9)

(57) [Claims] 1. A sucrose fatty acid ester in an aqueous phase,
Aliphatic alcohol and / or higher fatty acid and ionic
A surfactant, and in the sucrose fatty acid ester,
Contain 50% by weight or more of sucrose fatty acid diester
A water-repellent oil-in-water emulsion composition characterized by the following. 2. A sucrose fatty acid ester in an aqueous phase,
Aliphatic alcohol and / or higher fatty acid and ionic
A surfactant, and in the sucrose fatty acid ester,
Contains 35% by weight or more of sucrose fatty acid diester, and
Sucrose fatty acid monoester and sucrose fatty acid triester
Characterized by containing at a ratio of 1: 3 to 1:20.
Aqueous oil-in-water emulsion composition. 3. The water-repellent oil-in-water emulsion composition according to claim 1 , wherein the molar ratio of the sucrose fatty acid diester to the higher aliphatic alcohol and / or higher fatty acid in the aqueous phase is 1: 1 to 1. 1: 5, wherein the water-repellent oil-in-water emulsion composition contains 0.4 to 20 mol% of the ionic surfactant relative to the total amount of these mixtures. 4. A sucrose fatty acid ester in a water phase,
Aliphatic alcohol and / or higher fatty acid and ionic
A surfactant, and in the sucrose fatty acid ester,
Containing 50% by weight or more of sucrose fatty acid diester,  The sucrose fatty acid diester and higher fatty alcohol and
And / or higher fatty acids form an aggregate having a molar ratio of 1: 2 in the aqueous phase.
Water-repellent oil-in-water emulsion composition characterized by being formed
object. 5. A sucrose fatty acid ester in a water phase,
Aliphatic alcohol and / or higher fatty acid and ionic
A surfactant, and in the sucrose fatty acid ester,
Contains 35% by weight or more of sucrose fatty acid diester, and
Sucrose fatty acid monoester and sucrose fatty acid triester
In a ratio of 1: 3 to 1:20,  The sucrose fatty acid diester and higher fatty alcohol and
And / or higher fatty acids form an aggregate having a molar ratio of 1: 2 in the aqueous phase.
Water-repellent oil-in-water emulsion composition characterized by being formed
object. 6. The water-repellent oil-in-water type emulsion composition according to claim 1, wherein the molar ratio of sucrose fatty acid diester to higher aliphatic alcohol and / or higher fatty acid is 1: 2, and DSC ( Neither the sucrose fatty acid diester nor the higher aliphatic alcohol and / or the higher fatty acid, which is observed in the suggestive scanning calorimetry), and has an endothermic peak at the same position as the endothermic peak that is not any other component. A water-repellent oil-in-water emulsion composition characterized by the following. 7. The water-repellent oil-in-water emulsion composition according to claim 1, wherein the sucrose fatty acid diester and the higher aliphatic alcohol and / or the higher fatty acid are associated in an aqueous phase,
A water-repellent oil-in-water emulsion composition characterized by having a lamellar structure. 8. The water-repellent oil-in-water emulsion composition according to claim 1, wherein the sucrose fatty acid diester and the higher aliphatic alcohol and / or the higher fatty acid associate in an aqueous phase,
A water-repellent oil-in-water emulsion composition, characterized in that its subcell structure forms a hexagonal lamellar structure. 9. The water-repellent oil-in-water emulsion composition according to claim 1, wherein the water-repellent oil-in-water emulsion composition has a contact angle with water of 60 ° or more.