JP2855057B2 - Thickening gelling agent and thickening gel-like composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thickening gelling agent and a thickening gel-like composition, and more particularly to an aqueous thickening gelling agent and a thickening gel-like composition using a surfactant.

[0002]

2. Description of the Related Art In the fields of pharmaceuticals, cosmetics and the like, various aqueous thickening gelling agents have been used to maintain their dosage forms. For example, examples of organic compounds include polysaccharides, natural polymers such as casein, polyoxyethylene, and acrylic acid polymers.
Synthetic polymers such as montmorillonite, various clay minerals such as montmorillonite, and silica are appropriately selected and used according to the purpose and effect of the thickening gelling agent.

[0003]

When such thickening gelling agents are used in pharmaceuticals and cosmetics, they need to be highly safe for use on the human body, and at the same time, they are used for external application. In the case of the one used for, the feeling when used, that is, good usability is required. For this reason, the thickening gelling agent used for the above-mentioned purpose is required to have both high safety and favorable usability, and good thickening gelling ability, but it is required to have a conventional thickening gelling agent. Has not been known that sufficiently satisfies the above three points.

[0004] For example, a polymer-based polymer has relatively high safety, and exhibits good thickening gelling ability with a small amount of addition.
When used on the skin, it produces a "slimy feeling" peculiar to polymers, and has an unpleasant use feeling. Clay minerals have high thixotropy and provide a refreshing feeling of use, which is preferable in terms of usability, but is prone to syneresis and is unstable. Therefore, development of an aqueous thickening gelling agent excellent in safety, usability and thickening gelling ability has been desired.

On the other hand, in the oil-in-water emulsion composition, the above-mentioned aqueous thickening gelling agent is generally blended for improving the stability. However, in an oil-in-water emulsion composition using such a thickening gelling agent, for example, when applied to the skin, first, the thickening gelling agent in the external aqueous phase forms a film on the skin. And the oil phase will be placed on top of it. 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.

[0006] That is, when an oil-in-water emulsion composition such as a cosmetic is applied to the skin, it is desired that the effect is maintained for a long period of 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 aqueous thickening gelling agent which is excellent in safety and usability and can perform good thickening gelation. The present invention is to provide a thickened gel-like composition, and further, a thickened coating film having water repellency after use of an oil-in-water emulsion composition using the aqueous thickening gelling agent in an aqueous dispersion medium. It is to provide a gelling agent or a thickened gel-like composition.

[0008]

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 using sucrose fatty acid diester obtained by purification by solvent fractionation, it exhibits excellent thickening gelling ability,
Furthermore, it has been found that when this is used for an oil-in-water emulsion composition, the coating film after use has water repellency, and the water resistance of the coating film is improved. In other words, when a sucrose fatty acid diester having a relatively low molecular structure is present in the aqueous phase, an aggregate having a specific structure is formed, and the aggregate functions as if it were a water-soluble polymer. Was found to be a thickening gel.

[0009] Since sucrose fatty acid diesters are inherently relatively lipophilic, when the oil-in-water emulsion composition thickened and gelled by the aggregate is applied to, for example, the skin, the above-mentioned association is of course required. Since the coalescence is easily destroyed and returns to low hydrophilic sucrose fatty acid diester, their presence does not impair the water repellency of the oil-in-water emulsion composition, and can exhibit excellent water repellency together with the oil phase component. . The present inventors have also conducted a detailed study using pure sucrose fatty acid diester obtained by column chromatography purification,
Pure sucrose fatty acid diester is difficult to disperse in water and takes a long time to form a thickened gel, but it can be easily and uniformly dispersed using a sucrose fatty acid diester containing a small amount of ionic surfactant. I found that.

Further, when a higher fatty alcohol and / or a higher fatty acid is blended with the thickening gelling agent or the thickening gel composition in which the sucrose fatty acid diester forms an association in the aqueous phase, It was also found that performance was improved. That is, an aqueous thickening gelling agent according to claim 1 of the present application, the entire
Purity is 50% or more with respect to sucrose fatty acid ester
A sucrose fatty acid diester, an ionic surfactant,
Contains higher aliphatic alcohols and / or higher fatty acids
It is characterized by that.

The aqueous thickener according to claim 2 of the present application.
The gelling agent is the thickening gelling agent according to claim 1,
Sucrose fatty acid diester is higher than higher fatty alcohol
At least equimolar to the total amount of lower fatty acids, and
Of the ionic surfactant to the total amount of the mixture of 0.4 to
It is characterized by containing 20 mol%.

[0012] The thickened gel-like composition according to the third aspect is characterized in that
The purity of sucrose fatty acid ester is 50% or more.
Sucrose fatty acid diester, ionic surfactant,
Containing higher aliphatic alcohols and / or higher fatty acids,
The sucrose fatty acid diester is hexagonal
In the form of an aggregate having a lamellar structure consisting of
Sign.

A thickened gel composition according to claim 4
Is a thickened gel-like composition according to claim 3,
The aqueous thickening gelling agent according to 1 or 2 was blended in the aqueous phase.
And features.

[0014] The thickened gel-like composition according to claim 5 is characterized in that
Item 3. The thickened gel composition according to Item 3 or 4,
(Suggested scanning calorimetry) of sucrose fatty acid diester
It is characterized by having an endothermic peak of the aggregate. Also,
The thickened gel-like composition according to claim 6 is the same as that of claims 3 to 5.
The thickened gel-like composition according to any of the above, wherein the composition is water
It is a medium oil type emulsified composition.

Hereinafter, the configuration of the present invention will be described in detail. The aqueous thickening gelling agent and the thickening gel-like composition according to the present invention,
The sucrose fatty acid diester, which is usually used as a nonionic surfactant, forms an aggregate in an aqueous phase to thicken and gel the system. And if this is applied to the oil-in-water emulsion composition, the water repellency of the oil component is not impaired, and the coated film after use of the oil-in-water emulsion composition shows water repellency, Has water resistance.
The sucrose fatty acid diester used in the present invention has 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 such as sucrose fatty acid monoester and sucrose fatty acid triester are contained as impurities in the sucrose fatty acid diester, the thickening gelling agent or the thickened gel according to the present invention is used. Although a composition is obtained, the content of impurities is at most 50%, preferably at most 40%, more preferably at most 30%. However, when a monoester and a triester coexist as impurities, the ratio of the monoester to the triester is 1: 3.
If it is within the range of １ ： 1: 20, the diester content is 5
It may be less than 0%, in which case the diester content is at least 35%, preferably at least 40%.

For sucrose fatty acid diesters, Tc (a solid-liquid transition concentration of each sucrose fatty acid ester in a solution, which is measured by, for example, DSC (scanning calorimeter) as an important factor for gelling or thickening. Can be). The thickening agent may be used even if the sucrose fatty acid diester has a low Tc, and the sucrose fatty acid diester may be used as a gelling agent having a high Tc.

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 must be used. 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 salts Cationic surfactants such as dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, dialkylmorpholinium salts, and the like can be used. Preferably, the lipophilic group has 12 carbon atoms. ~
22 ionic surfactants, and particularly preferred are anionic or cationic surfactants having a lipophilic group having 12 to 22 carbon atoms.

In order for the thickening gelling agent or the thickening gel composition of the present invention to form an aggregate in the aqueous phase and to form a thickened gel, an ionic surfactant is required for the sucrose fatty acid diester. Is preferably incorporated in an amount of 0.4 mol% to 20 mol%, more preferably 1 mol% to 8 mol%. When the amount of the water-soluble ionic surfactant increases, water repellency cannot be obtained, and when the amount of the ionic surfactant is low, the sucrose fatty acid diester is hardly dispersed.

The thickening gelling agent of the present invention is characterized in that sucrose fatty acid diester forms an aggregate having a stable lamellar structure with a wide water replenishing interval in the aqueous phase, so that the aqueous phase can be gelled. . The fact that the thickening gelling agent or the thickening gel-like composition of the present invention forms an aggregate in the aqueous phase is determined by DSC
(Scanning calorimeter). When a thickened gel composition obtained by dissolving sucrose fatty acid diester in water using an ionic surfactant is measured by DSC (scanning calorimeter), one endothermic peak (hereinafter, this peak is referred to as Ps). Was found, indicating that the sucrose fatty acid diester formed an aggregate in the aqueous phase. When the DSC (scanning calorimeter) is measured on the thickened gel composition of the present invention, this Ps is recognized.

[0022] The present inventors determined that the structure of the above-mentioned aggregate was obtained by subjecting the above composition to X-ray diffraction using a small-angle X-ray diffraction method.
Line analysis was performed. As a result, it was confirmed that an aggregate composed of hexagonal (α-structure) subcells was formed. Therefore, in the thickening gelling agent or the thickening gel composition of the present invention, the structure of the aggregate formed in the aqueous phase,
It is understood that it has the following structure. That is, in the aqueous phase, sucrose fatty acid diester molecules are arranged as shown in FIG. 1, and in such an arrangement, they have a hexagonal subcell structure. 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 thickening gelling agent of the present invention can easily thicken and gel the aqueous phase by uniformly dispersing a small amount of the thickening gelling agent in the aqueous phase. It is at least 1% by weight, preferably at least 2% by weight, more preferably at least 3% by weight, based on the composition to be gelatinized. As the amount of the thickening gelling agent increases, the gel hardness also increases.

Further, the present inventors have found that when a thickening gelling agent or a thickening gel composition containing the sucrose fatty acid diester and an ionic surfactant is used in combination with a higher aliphatic alcohol and / or a higher fatty acid, It has been found that the thickening gelling ability is further improved. The compounding ratio at which the thickening gelling ability is improved is such that sucrose fatty acid diester is at least 50 mol%
Less than 0%, higher fatty alcohols and / or higher fatty acids are more than 0 mol% and 50 mol% or less, and 0.4 to 20 mol% of the ionic surfactant is based on the total amount of these mixtures.
Mol% or less, preferably 75 mol% or more and less than 100 mol% of sucrose fatty acid diester, and more than 0 mol% and 25 mol% or less of higher aliphatic alcohol and / or higher fatty acid, and more preferably sucrose fatty acid diester. Is 8
0 mol% or more and less than 100 mol%, and higher fatty alcohols and / or higher fatty acids are more than 0 mol% and 20 mol% or less.

In the thickening gelling agent or the thickening gel composition containing the higher aliphatic alcohol and / or higher fatty acid, the endothermic peak of the aggregate of the sucrose fatty acid diester is measured by DSC (scanning calorimeter). (Ps) is observed. However, as the blending ratio of the higher aliphatic alcohol and / or higher fatty acid increases, Ps decreases, and instead, the endothermic peak observed in a high temperature portion becomes higher than Ps. The higher aliphatic alcohol and / or higher fatty acid used in the present invention has a saturated or unsaturated, straight or branched chain having 12 or more carbon atoms. The above may be used. For example, cetanol, stearyl alcohol,
Behenyl alcohol, batyl alcohol, stearic acid, behenic acid and the like.

As a method for obtaining a thickening gelling agent according to the present invention, a uniform thickening gelling agent can be obtained by mixing and dissolving the above essential components in a solvent such as chloroform and then distilling off the solvent. The essential component does not need to be made uniform in advance, but may be made uniform in advance in order to shorten the preparation time when preparing the thickened gel composition. The thickened gel composition of the present invention can be obtained by dissolving the thickening gelling agent in water or an aqueous phase such as an aqueous solvent. Such aqueous solvents include, for example, ethyl alcohol, isopropyl alcohol, methyl alcohol, propylene glycol
Glycerol, 1,3-butylene glycol, glycerin, ethylene glycol, polyethylene glycol, or an aqueous solution thereof.

Further, other components can be blended with the thickened gel composition to make cosmetics, pharmaceuticals and the like.
For example, gels, lotions, serums and the like can be prepared by adding components such as water-soluble drugs. Or,
The thickening gel-like composition may be added to and mixed with a previously prepared emulsion or solubilized product to prepare a cream, an emulsion, a lotion or the like. These are also the thickened gel compositions of the present invention.

[0028] The thickened gel composition of the present invention may also be obtained by appropriately mixing the essential components in a mixing ratio for forming an association in the process of producing a thickened gel composition such as cosmetics or pharmaceuticals. Can be. 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,
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, it is necessary to add a sucrose fatty acid diester to form an aggregate after emulsification.

When the thickening gelling agent or the thickening gel composition of the present invention is applied to the emulsifier composition as described above, the aggregate is formed, and the peak of the aggregate of the sucrose fatty acid diester in DSC is obtained. Is confirmed. In such an oil-in-water emulsion composition, the water repellency of the coating film, which cannot be obtained by the conventional oil-in-water emulsion composition using a thickening gelling agent such as a hydrophilic polymer, can be obtained. That is, it has a refreshing feeling of use which is a characteristic of the oil-in-water emulsion composition, and has no sticky or slimy feeling which is a drawback when a hydrophilic polymer is blended, and furthermore, the oil content is further reduced. The coating film after use exhibits good water repellency without impairing water repellency, and has excellent water resistance, so that it has excellent retention on skin and the like.

The water repellency can be evaluated by measuring the contact angle with water. The larger the contact angle, the higher the water repellency. However, the oil-in-water emulsion composition has a very high water repellency of 60 ° or more. Is shown. The thickened gel composition of the present invention is a very stable thickened gel composition with little change in hardness or separation. The thickened gel composition of the present invention can also contain other substances according to the intended use and purpose. For example, if applied to cosmetics, fragrances, preservatives, vitamins, powders , Pigment and the like.

Examples of the inorganic powder include talc, titanium oxide, kaolin, silicic acid anhydride, silicate, zinc oxide, calcium carbonate, magnesium carbonate, red iron oxide, yellow iron oxide, chromium oxide, carbon black, ultramarine, mica, and cellulite Site, nylon powder, polyethylene powder, cellulose powder, acrylic resin, titanium dioxide, iron oxide and the like. Examples of the 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, caking pigment, gunjou 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 dimethylpolysiloxane, methylpolysiloxane, cyclic siloxane, silicone oil such as 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 is improved water repellency.

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.

[0034]

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 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 Purification of sucrose stearic acid diester 100 g of a commercially available sucrose stearic ester assumed to contain about 30% of a monoester was weighed into a 1 L beaker, and a mixed solution of 855 ml of methanol and 45 ml of water was weighed. In addition, the sample is dissolved once at a temperature near the boiling point of the solvent. 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 99% 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 99% or more) could be collected.

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, examples of the thickening gelling agent and the gel 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. Examples 1 to 3 <Preparation of thickening gel-like composition> Sucrose stearic acid diester (containing a small amount of sodium stearate as an ionic surfactant) obtained in Production Example 1 was used as a thickening gelling agent. A gel having the composition shown in Table 1 below was prepared. The preparation method is that after adding purified water to sucrose stearic acid diester and heating to 60 ° C. to sufficiently swell,
The gel was obtained by standing at room temperature. <Gel Hardness> The hardness of the gel at 25 ° C. of the thickened gel-like composition was measured by a card tension meter. Table 1 shows the results.

[0040]

Table 1 Example 1 Example 2 Example 3シ ョ Sucrose stearic acid diester 1.0% 3.0 5.0 ──────────────────────────────────── Water 99.0% 97.0 95.0 ────────────────────────────────────ゲ ル Immediately after gel hardness 1 917 One month later 1 10 14 １４よ う As is clear from the above results, all gels A good product having no change in hardness and no separation even after a lapse of months was obtained.

<DSC Measurement> The gel composition of Example 3 was measured by DSC (scanning calorimeter). The results are shown in FIG. In FIG. 2, the main peak at 49 ° C. is that of pure sucrose stearic acid diester, and that slightly appearing at 56 ° C. is the peak of sucrose stearic acid triester contained as an impurity. . From the above, the thickening gelling agent or the thickened gel composition of the present invention forms an aggregate of sucrose fatty acid diester in the aqueous phase, and the presence of this aggregate causes the system to become a thickened gel. It became clear to do.

<X-Ray Analysis> In order to investigate the structure of the aggregate observed by the DSC measurement, the thickened gel composition of Example 3 was subjected to a structural analysis by a small-angle X-ray diffraction method. As a result, as shown in FIG. 3, a peak having a plane spacing of 4.1 angstrom was observed around 21.5 degrees. This indicates that an aggregate having a hexagonal crystal structure (α structure) is formed in the composition.

Accordingly, it is understood that the sucrose fatty acid diester in the thickening gelling agent or the thickening gel composition of the present invention has a structure as shown in FIG. 1 in the aqueous phase.
That is, sucrose fatty acid diesters (for example, sucrose stearic acid diester) are arranged as shown in FIG. 1, and in such an arrangement, they have a hexagonal subcell structure. 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.

Example 4 Higher aliphatic alcohol and / or
Is the effect of higher fatty acids <Preparation of thickened gel-like composition> sucrose stearic diester (containing about 1% of sodium stearate as an ionic surfactant) obtained in Production Example 3 and higher fatty alcohol Were mixed in various mixing ratios, and once dissolved in chloroform, concentrated, and the chloroform was distilled off to obtain a uniform thickening gelling agent. The obtained thickening gelling agent was mixed and dissolved in a ratio of 5% and purified water at a ratio of 95% to prepare a gel composition.

<Gel Hardness> The gel hardness of the above gel composition at 25 ° C. was measured with a card tension meter, and the relationship between the blending molar ratio and the gel hardness was examined. FIG. 4 shows the results. As is clear from FIG. 4, in the thickening gelling agent according to the present invention, the mole fraction of the higher aliphatic alcohol and / or higher fatty acid is 0.5 or less, that is, the sucrose fatty acid diester is 50 to 100% by mole. %, The higher aliphatic alcohol and / or higher fatty acid has a thickening gelling ability in a range of more than 0 mol% and 50 mol% or less,
In particular, when the molar fraction is 0.2 or less, that is, when the sucrose fatty acid diester is 80 mol% or more and less than 100 mol%, and the higher aliphatic alcohol and / or higher fatty acid is more than 0 mol% and 20 mol% or less, It is understood that the gel hardness is further improved as compared with the case where no higher aliphatic alcohol and / or higher fatty acid is contained.

<DSC Measurement> The gel composition was measured by DSC (scanning calorimeter).
FIG. 5 shows the results. As is apparent from FIG. 5, even when the higher aliphatic alcohol and / or higher fatty acid was blended, the first embodiment was measured by DSC (scanning calorimeter).
Endothermic peaks of the sucrose fatty acid diester aggregates were observed in the same manner as in Nos. 3 to 3, indicating that the sucrose fatty acid diesters formed aggregates.

Example 5 Gel Essence 1) 4.6% by weight of sucrose stearic acid diester 2) Potassium stearate 0.1 3) Stearyl alcohol 0.3 Here, sucrose stearic acid diester was prepared according to Production Example 5. Obtained and contains a small amount of sodium stearate. After dissolving 1) to 3) in chloroform, evaporate to dryness. Glycerin 5 was added to the dried sample.
% And 90% purified water to make the mixture uniform, and then various water-soluble drugs were added to obtain a gel-like serum. This gel-like serum is a stable gel-like composition in which the gel hardness changes over time or does not separate, and is refreshing,
It had good usability. In addition, DSC measurement confirmed that the sucrose fatty acid diester formed an aggregate.

Example 6 1) Purified water 81.9 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.1 4) Dimethyl polysiloxane 5.0 5) Stearyl alcohol 0.1 6) Sucrose stearic acid Diester 3.0 Here, sucrose stearic acid diester is obtained by Production Example 5, and contains a small amount of sodium stearate. 1) to 5) are heated and stirred to emulsify,
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, respectively, was excellent in usability with a refreshing feeling, and had a water repellency of ◎. In addition, DSC measurement confirmed that the sucrose fatty acid diester formed an aggregate.

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 59 ° ×: contact angle of less than 39 °

Comparative Example 1 1) Purified water 81.9 wt% 2) Propylene glycol 10.0 3) Sodium stearate 0.1 4) Dimethyl polysiloxane 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 82.9% by weight 2) Propylene glycol 10.0 3) Sodium stearate 0.1 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 6 1) Purified water 84.9% by weight 2) Propylene glycol 10.0 3) Sodium stearate 0.1 4) Dimethylpolysiloxane 5.0 1) to 5) An oil-in-water emulsion composition obtained by adding and emulsifying 3.0% of the following commercially available sucrose fatty acid ester at 70 ° C. was compared.

[0053]Comparative Example 3 Commercially available sucrose stearate (monoester 10
%, 90% or more of diester), uniform gel
An oil-in-water emulsion composition was not obtained.Comparative Example 4 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 5 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 6 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 7 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 2 7) Remaining purified water 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 the sucrose fatty acid diester formed an aggregate.

Example 8 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 0.17) Stearyl alcohol 0.1 8) Behenyl alcohol 0.1 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 the sucrose fatty acid diester formed an aggregate.

Example 9 Gel Whitening Cosmetic <Gel Formula> 1) Stearic acid 2.0 wt% 2) Triethanolamine 1.0 3) Behenyl alcohol 0.2 4) Remaining amount of purified water 5) Sucrose stearic acid diester 3.0 Here, sucrose stearic acid diester is obtained according to Production Example 5, and contains a small amount of sodium stearate. 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 0.2 3) Paraben 0.1 4) Fragrance 0.1 5) Triethanolamine 0.1 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 the sucrose fatty acid diester formed an aggregate.

Example 10 Sunscreen cream 1) Beeswax 2.0 wt% 2) Shortening 2.0 3) Cetostearyl alcohol 0.2 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 0.1 12) Propylene glycol 5.0 13) Sucrose oleic acid diester 2.0 Here, sucrose oleic acid diester is obtained according to Production Example 4, and contains a small amount of sodium oleate. 1) to 8) and 9) to 12) separately at 70 ° C
After heating and stirring, 1) to 8) were added to 9) to 12) while stirring to emulsify, 13) was added, mixed and stirred, and cooled to obtain an O / W sunscreen cream. The water repellency of this cream was ○. In addition, DSC measurement confirmed that the sucrose fatty acid diester formed an aggregate.

Example 11 Sunscreen lotion 1) Vaseline 10.0 wt% 2) Olive oil 15.0 3) Oleic acid 0.1 4) Octyl methoxycinnamate 3.0 5) Paraben 0.1 6) Fragrance 0. 17) Purified water residue 8) Potassium oleate 0.2 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 the sucrose fatty acid diester formed an aggregate.

Example 12 Pre-Make Lotion 1) Liquid paraffin 10.0 wt% 2) Trimethylsiloxysilicate 3.0 3) Behenyl alcohol 0.06 4) Stearyl alcohol 0.06 5) Fragrance 0.1 6) Paraben 17) Purified water residue 8) Potassium stearate 0.05 9) Polyethylene glycol 3.0 10) Spherical cellulose powder 1.0 11) Propylene glycol 8.0 12) Sucrose oleic 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 the sucrose fatty acid diester formed an aggregate.

Example 13 Foundation 1 1) Cyclic polysiloxane 10.0 wt% 2) Trimethylsiloxysilicate 3.0 3) Stearyl alcohol 0.1 4) Fragrance 0.1 5) Paraben 0.1 6) Purified water residue Amount 7) Sodium stearate 0.5 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 addition, DSC measurement confirmed that the sucrose fatty acid diester formed an aggregate.

Example 14 Foundation 2 1) Dimethylpolysiloxane 7.0 wt% 2) Methylphenylsiloxane 5.0 3) Squalane 5.0 4) Behenyl alcohol 0.1 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 addition, DSC measurement confirmed that the sucrose fatty acid diester formed an aggregate.

Comparative Example 7 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 4. 0 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 to 8), 9),
10) was added, mixed and stirred, and cooled to produce a pre-made lotion. This pre-made lotion is 37 ℃,
At 25 ° C. and 0 ° C., each was stable for one month or more, but the water repellency was poor.

Comparative Example 8 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 1.0 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) with stirring to emulsify. 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 ×.

[0065]

As described above, the thickening gelling agent or the thickening gel composition according to the present invention provides an excellent thickening agent by forming an association of sucrose fatty acid diester in an aqueous phase. It exhibits gelling ability, safety, stability, and usability, and when it is applied to an oil-in-water emulsion composition, the coating film after use exhibits water repellency, and has a feature that the retention property is improved. .

[Brief description of the drawings]

FIG. 1 is an explanatory view of an aggregate formed by a sucrose fatty acid diester in an aqueous phase in a thickened gel composition according to one embodiment of the present invention.

FIG. 2 is a DSC chart of a thickened gel composition containing sucrose stearic acid diester according to one embodiment of the present invention.

FIG. 3 shows a small angle X in a thickened gel composition containing sucrose stearic acid diester according to one embodiment of the present invention.
FIG. 4 is a chart measured by a line diffraction method.

FIG. 4 is a diagram showing the relationship between the mixing molar fraction of sucrose fatty acid diester and higher aliphatic alcohol and gel hardness in the thickened gel composition according to one example of the present invention.

FIG. 5 is a DSC chart of the thickened gel composition according to one embodiment of the present invention when the mixing ratio of the sucrose fatty acid diester to the higher aliphatic alcohol is changed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI A61K 47/14 A61K 47/14 F (72) Inventor Kazuhiro Yamaguchi 1050 Nippacho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Daiichi Research Co., Ltd. Inside the center (72) Inventor Toshihiro Tanaka 1050 Nippa-cho, Kohoku-ku, Yokohama-shi, Kanagawa Prefecture Shiseido First Research Center (72) Inventor Shigenori Kumagai 1050 Nippa-cho, Kohoku-ku, Yokohama-shi, Kanagawa Shiseido Co., Ltd. (56) References JP-A-5-279651 (JP, A) JP-A-55-25430 (JP, A) JP-A-60-115509 (JP, A) (58) Fields surveyed ( Int.Cl. ⁶ , DB name) C09K 3/00 103 A61K 7/00 A61K 47/14

Claims (6)

(57) [Claims] Claims: 1. The purity of all sucrose fatty acid esters is
50% or more sucrose fatty acid diester, an ionic surfactant, and a higher aliphatic alcohol and / or higher fatty acid.
An aqueous thickening gelling agent comprising a fatty acid . 2. The aqueous thickening gelling agent according to claim 1, wherein the sucrose fatty acid diester is a higher aliphatic alcohol.
At least equimolar to the total amount of higher fatty acids and
The ionic surfactant was added in an amount of 0.1 to the total amount of these mixtures.
An aqueous thickening gelling agent comprising 4 to 20 mol% . 3. The purity of all sucrose fatty acid esters is
50% or more sucrose fatty acid diester and ionic
Surfactant and higher aliphatic alcohol and / or higher
A fatty acid, wherein the sucrose fatty acid diester is in an aqueous phase.
Forms lamellar aggregates composed of hexagonal subcells
Thickened gel composition characterized in that it forms. 4. The thickened gel composition according to claim 3,
The aqueous thickening gelling agent according to claim 1 or 2 in an aqueous phase.
A thickened gel-like composition characterized by being blended . 5. The thickened gel composition according to claim 3, which has an endothermic peak of an aggregate of sucrose fatty acid diesters by DSC (indicative scanning calorimetry). Gel composition. 6. The thickened gel composition according to any one of claims 3 to 5, wherein the composition is an oil-in-water emulsion composition.
Thickened gel composition characterized Rukoto.