JPH05279651A - Thickening-gelling agent - Google Patents

Abstract

PURPOSE:To provide the subject agent containing a sucrose fatty acid diester and a small amount of an ionic surfactant, exhibiting excellent thickening and gelling properties and excellent in safety and usage. CONSTITUTION:The objective thickening and gelling agent contains (A) >=50wt.%, preferably 72 to 97wt.% sucrose fatty acid diester (e.g. sucrose stearic acid diester) and (B) >=0.5wt.%, preferably 1 to 8wt.% ionic surfactant. As the component (B), e.g. a sulfonic acid salt of a higher fatty acid ester and an alkyltrimethylammonium salt of a higher fatty acid ester are exemplified, where the carbon number of the lipophilic group is preferably 12 to 22. In addition, for improving the thickening and gelling properties of this agent, an amphiphatic substance such as a higher fatty acid or a higher fatty alcohol is preferably added. In order to obtain a gel by using the agent, >=3wt.% as its concentration and uniform distribution in water are recommendable.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thickening gelling agent, and more particularly to a thickening gelling agent using a surfactant.

[0002]

2. Description of the Related Art In the fields of pharmaceuticals, cosmetics, etc., various aqueous thickening gelling agents are used to maintain the dosage form.
For example, polysaccharides, natural polymers such as casein, synthetic polymers such as polyoxyethylene and acrylic acid polymers are used as organic compounds, and various clay minerals such as montmorillonite and silica are used as inorganic compounds. , Which is appropriately selected and used according to the intended effect of the thickening gelling agent.

[0003]

When such a thickening gelling agent is used in medicines and cosmetics, it is of course required to have high safety for use in the human body, but at the same time, it is required to be applied externally to the skin. In the case of those used for, the feel when used, that is, the ease of use is required. Therefore, the thickening gelling agent used for the above purpose is required to have both high safety and preferable usability, and good thickening gelling ability. Was not known to sufficiently satisfy the above three points.

[0004] For example, a polymer type is relatively safe and exhibits a good thickening and gelling ability when added in a small amount.
When used on the skin, it produces a "slickness" peculiar to polymers, and has an unpleasant usability. Clay minerals have high thixotropy and give a refreshing after-use feeling, which is preferable in terms of usability, but they are likely to cause syneresis and are unstable. The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is to provide a thickening gelling agent which is excellent in safety and usability and can perform good thickening gelation. ..

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors in order to achieve the above-mentioned object, sucrose fatty acid ester which is widely used in food additives, cosmetics and the like and has good safety is selected. It was found that the sucrose fatty acid diester purified by solvent fractionation gives an aqueous thickening gelling agent having excellent thickening and gelling ability, and having good safety and usability. Furthermore, as a result of an examination using pure sucrose fatty acid ester obtained by column chromatography purification, it was found that the addition of a small amount of an ionic surfactant to sucrose fatty acid diester produces thickening gelation ability. It became clear. That is, the thickening gelling agent according to claim 1 of the present application is characterized by containing a sucrose fatty acid diester and an ionic surfactant. The constituent features of the present invention will be described in more detail below. The two essential components are the sucrose fatty acid diester and the ionic surfactant described above.

The fatty acid in the sucrose fatty acid diester is a saturated or unsaturated, straight or branched chain having 12 to 22 carbon atoms, and the two fatty acids may be different. Even if the sucrose fatty acid diester contains other sucrose fatty acid ester, for example, sucrose fatty acid monoester or sucrose fatty acid triester as an impurity, the thickened gel is formed. The maximum content of impurities is 50%,
It is preferably 40% or less, more preferably 30% or less. However, in the case where monoester and triester coexist as impurities, the content of diester may be less than 50% as long as the ratio of monoester and triester is in the range of 1: 3 to 1:20. The diester content in this case is 35% or more, preferably 40%. Regarding sucrose fatty acid diester, Tc (which indicates the solid-liquid transition temperature of each sucrose fatty acid ester in a solution and can be measured by, for example, DSC (differential calorimeter)) is an important factor for gelation or thickening. Is mentioned.

That is, as a thickener, T of a diester is used.
It is preferably c or more, and the gelling agent is preferably Tc or less of the diester. Pure sucrose fatty acid diester (purity of 99% or more separated by column chromatography) alone does not disperse in water and does not function as a thickening gelling agent, but sucrose fatty acid diester has a small ionic interface. By adding the active substance, it is uniformly dispersed and becomes a good thickening gelling agent.

As the ionic surfactant, fatty acid soap, ether carboxylic acid and its salt, alkane sulfonate, sulfonate of higher fatty acid ester, dialkyl sulfosuccinate, sulfonate of higher fatty acid amide, alkyl allyl sulfone Acid salt, higher alcohol sulfate ester salt, secondary higher alcohol sulfate ester salt, alkyl and alkyl allyl ether sulfate ester salt, glycerin fatty acid ester sulfate ester salt, higher fatty acid alkylolamide sulfate ester salt, sulfated oil, phosphoric acid Anionic surfactants such as ester salt, amino acid, collagen hydrolyzate and higher fatty acid condensate, collagen hydrolyzate derivative, and alkylamine salt, polyamine or alkanolamine fatty acid derivative, alkyltrimethylammonium salt A cationic surfactant such as a dialkyldimethylammonium salt, an alkyldimethylbenzylammonium salt, an alkylpyridinium salt, an alkylisoquinolinium salt or a dialkylmorpholinium salt can be used, and the lipophilic group preferably has 12 carbon atoms. ~
The ionic surfactant having 22 carbon atoms, and particularly preferable one is an anionic or cationic surfactant having 12 to 22 carbon atoms in the lipophilic group.

It is preferable to add an amphipathic substance in order to enhance the thickening and gelling ability of the above thickening and gelling agent, and those hydrophobic groups preferably have 12 or more carbon atoms, more preferably higher grades. Fatty acids and higher aliphatic alcohols. An amphipathic substance has surface activity, but is itself highly hydrophobic and not as surface active as a general surfactant, for example, higher fatty acid, higher aliphatic alcohol.
And monoglycerides, glycerol monoalkyl ethers, monoalkylamines, and compounds having a sterol skeleton (cholesterol, phytosterol) and the like. As a composition for thickening and gelling, sucrose fatty acid diester is 50% or more and 99.6% or less, ionic surfactant is 0.4% or more and 20% or less, and amphipathic substance is 0% or more and 40% or less, Preferably sucrose fatty acid diester is 72
% To 97%, ionic surface-active substance is 1% to 8
% Or less, and the amphipathic substance is 10% or more and 20% or less.

As an example of the composition, FIG. 1 shows a gelling region diagram when sucrose stearate diester is selected as the sucrose fatty acid diester, sodium stearate is selected as the ionic surfactant, and stearic acid is selected as the amphipathic substance. It was The portion surrounded by the solid line in the figure corresponds to the gel region. The thickening gelling agent of the present invention is excellent in safety because it uses sucrose fatty acid diester commonly used in cosmetics and foods as a main component, and gels water by adding a small amount of gelling agent. There is an advantage that you can. That is, by uniformly dispersing the thickening gelling agent of the present invention in water in an amount of 1% or more, preferably 2% or more, more preferably 3% or more, a good gel with good usability can be obtained.
As the concentration of gelling agent increases, the hardness of the gel increases.
Furthermore, even if a part of water is replaced with a water-soluble solvent, a gel similar to the above gel can be obtained.

Examples of the water-soluble solvent include ethyl alcohol, isopropyl alcohol, methyl alcohol, propylene glycol, 1,3-butylene glycol, glycerin, ethylene glycol and polyethylene glycol. Be done. The ionic surfactant on the above gel,
Alternatively, various emulsions or solubilized products prepared using a nonionic surface-active substance may be added and mixed to prepare a cream, an emulsion or the like. It is also possible to mix other substances depending on the use and purpose. For example, for application to cosmetics, fragrances, preservatives, vitamins, powders, pigments and the like can be mixed. As inorganic powder,
For example, 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 blue, mica, sericite, nylon powder, polyethylene powder, Cellulose powder, acrylic resin, titanium dioxide, iron oxide, etc. may be mentioned.

Examples of the inorganic pigment include talc, kaolin, calcium carbonate, zinc white, titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine blue, titanium coated mica, bismuth oxychloride, red iron oxide, and caking pigment. , Gunjo pink, chromium hydroxide, mica titanium, yellow iron oxide,
Chromium oxide, cobalt aluminum oxide, navy blue, black iron oxide, carbon black, silicic acid 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 and the like can be mentioned.

[0013]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited to the embodiments. The blending amount is shown by weight unless otherwise specified. First, a production example of sucrose fatty acid diester, which is characteristic of the present invention, will be described. Production Example 1 Purification of sucrose stearate diester 100 g of a commercially available sucrose stearate ester, which is said to contain about 30% of monoester, was weighed in a 1 L beaker, and a mixed solution of 855 ml of methanol and 45 ml of water was added. In addition, the sample is once dissolved at a temperature near the boiling point of the solvent. After that, the solution was kept warm at 44 ° C and separated into two phases, and then the upper layer (solution phase)
To collect. The main component of the lower layer (solid phase) is triester, and the upper layer mainly contains monoester and diester. Water is added to this upper layer so that the concentration of ethanol is about 80 v / v%, and the mixture is heated to 60 ° C., a precipitate is formed at 25 ° C., and the precipitate is fractionated. The upper layer is composed mainly of monoester and the precipitate is composed mainly of die ether. The precipitate obtained in 1. is dissolved in 720 ml of methanol, 180 ml of water is added to the solution, and the mixture is stirred and kept warm at 25 ° C. and left to stand to form a precipitate, and the precipitate is fractionated. The above operation was repeated, and a composition containing about 80% or more of sucrose stearate diester could be obtained. As the inclusions present other than sucrose stearate diester, sucrose stearate monoester, triester,
Examples include stearic acid and sodium stearate.
The yield based on the raw material sucrose fatty acid ester is about 33.
%Met.

Production Example 2 Sucrose oleic acid mono and die
50 g of commercially available sucrose oleate, which is said to contain about 70% of monoester, was weighed in a purified 1 L beaker of Stell and dissolved by adding a mixed solution of 760 ml of methanol and 190 ml of water to -20 ° C. After leaving it to stand, and separating it into two phases, the precipitation part (lower layer)
To collect. Here, the upper layer contains a monoester, and the precipitate (lower layer) contains a mixture of a diester and a triester as a main component. 760 ml of methanol and 190 of water were added to the collected precipitate.
A mixed solution of ml is added to dissolve it, and the mixture is allowed to stand at -20 ° C to separate into two phases again, and the precipitated portion is separated. This operation is repeated twice. Here, the upper layer is composed mainly of monoester, and the precipitate (lower layer) is composed mainly of diester and triester. The upper layer obtained in and was concentrated to obtain sucrose oleic acid monoester. The purity of sucrose oleate monoester was about 95%, and the yield was about 65% based on the raw material sucrose oleate. The lower layer obtained in and is dissolved in a 97% methanol solution, and the mixture is allowed to stand at room temperature to separate the upper layer. The upper layer obtained in step 1 was concentrated and dried to obtain sucrose oleic acid diester. The purity of sucrose oleate diester was 65% or more, and the yield based on the raw material sucrose oleate was about 25%.

Production Example 3 Sucrose stearic acid diester
Purified by column chromatography (2) Using 200 ml of chloroform as a solvent, 200 g of silica gel for commercial column chromatography is swollen and packed in a column chromatography tube, and about 10 g of the sucrose stearate obtained by the production method 1 is added. The following solvents are sequentially used to perform stepwise elution. i) Methanol: chloroform = 8: 92 (volume ratio) 1 L ii) Methanol: chloroform = 15: 85 (volume ratio)
1 L iii) Methanol: chloroform = 25: 75 (volume ratio) 1 L of the eluate was fractionated by 70 ml, and sucrose stearate diester was confirmed by gas chromatography and TLC for each fraction. When the diester fraction was concentrated, about 4 g of sucrose stearic acid diester could be collected.

Production Example 4 of sucrose oleic acid diester
Purification by column chromatography Using 400 ml of chloroform as a solvent, 200 g of a commercially available silica gel for column chromatography is swollen and packed in a column chromatography tube, and about 10 g of sucrose oleate obtained by the production method 2 is added. Perform stepwise elution using the following solvents in sequence. i) Methanol: chloroform = 6: 94 (volume ratio) 1 L ii) Methanol: chloroform = 12: 88 (volume ratio)
1 L iii) Methanol: chloroform = 20: 80 (volume ratio) 1 L of the eluent was fractionated by 70 ml, and sucrose oleic acid 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 could be collected.

Production Example 5 Sucrose stearic acid diester
100 g of commercially available sucrose stearate ester, which is said to contain about 30% of monoester, is weighed in a purified 1 L beaker of the above, and 800 ml of methanol and 100 ml of water are added, and the sample is once solvated at a temperature near the solvent. .. Then, a precipitate is generated at 35 ° C., and the precipitate is collected,
A composition containing about 40% sucrose stearate diester and 50% sucrose stearate triester could be obtained. The contents other than sucrose stearate diester and sucrose stearate triester were sucrose stearate monoester, stearic acid, and sodium stearate. The yield based on the raw material sucrose fatty acid ester was about 75%. Next, a thickening gelling agent using the sucrose fatty acid diester produced as described above will be described.

Example 1 A gel having the following composition was prepared using the sucrose stearate diester obtained in Production Example 1, and the hardness of the gel at 25 ° C. was measured by a card tension meter. ──────────────────────────────────── Sucrose stearate diester 1.0% 3.0 5. 0 ──────────────────────────────────── Water 99.0% 97.0 95.0 ── ────────────────────────────────── Gel hardness Immediately after 1 9 17 1 month later 1 10 14 ──── ──────────────────────────────── As is clear from the above results, both gels were tested immediately after production and A good product was obtained in which the hardness did not change even after a lapse of one month and the separation was not caused.

Example 2 2 g of sucrose stearate diester obtained in Production Example 5 was added with 98.0 g of purified water, heated to 60 ° C., sufficiently swelled, and allowed to stand at room temperature to obtain a gel. It was Example 3 To 2 g of sucrose stearate diester obtained in Preparation Example 3, 0.04 g of stearyltrimethylammonium chloride (STAC) and stearyl alcohol were prepared.
0.06 g was added, dissolved in chloroform and evaporated to dryness. To the dried sample, 97.9 g of purified water was added, heated to 60 ° C., and allowed to stand at room temperature to obtain a gel.

Example 4 To 1.72 g of sucrose stearate diester obtained in Preparation Example 3, 0.06 g of sodium hexadecyl sulphate (SODS) and 0.22 g of palmitic acid were added.
Was added, the solution was dissolved in chloroform and evaporated to dryness. 98 g of purified water was added to the dried sample and heated to 60 ° C. to uniformly disperse the sample, and the mixture was allowed to stand at room temperature to obtain a gel. Example 5 To 2 g of sucrose stearate diester obtained in Production Example 3, 0.04 g of sodium stearate and 0.14 g of cholesterol were added and dissolved in chloroform.
Evaporated to dryness. Purified water 97.
After adding 88 g and heating at 60 ° C. to uniformly disperse the sample, the mixture was allowed to stand at room temperature to obtain a gel.

Example 6 Gel whitening cosmetic composition <Gel treatment> Sucrose stearic acid diester 3% Arbutin 3 Glycerin 15 Methylparaben 0.1 Purified water balance sucrose stearic acid diester was obtained according to Preparation Example 1. It has been done. The above composition was heated to 60 ° C. and uniformly dispersed, and then allowed to stand at room temperature to obtain a gel whitening cosmetic composition.

Example 7 Nutrition cream <Gel formulation> Sucrose stearate diester 5% Methylparaben 0.1 Water balance sucrose stearate diester was obtained according to Production Example 1. The above composition was heated at 60 ° C. and uniformly dispersed, and then left at room temperature to obtain a gel. <Emulsified formulation> Pluronic L-68 4% Liquid paraffin 40 Vitamin E acetate 0.5 Glycerin 25 1,3 BG 10 Methylparaben 0.2 Perfume 0.05 Purified water Residual amount Gel and pre-emulsion formulation respectively The emulsion was adjusted, 80 g of the gel and 20 g of the emulsion were mixed with stirring at 70 ° C., and then cooled to 25 ° C. to obtain a nutrition cream.

Example 8 Preparation of beauty essence <Gel formulation> Sucrose fatty acid diester 7.0% Oleyl alcohol 1.4% Potassium palmitate 0.2% Methylparaben 0.1% Glycerin 5.0% Purified water residue Amount Here, the sucrose oleic acid diester is that obtained according to Production Example 2. Of the above composition, the one obtained by removing glycerin and water is dissolved in chloroform, homogenized and then evaporated to dryness. Glycerin and water were added to the dried sample and uniformly dispersed.
5 parts of a solubilizing solution containing 10% of CO 60, 1% of vitamin E acetate, 60% of ethanol and the remaining amount of purified water was added and stirred to obtain a beauty essence.

Example 9 Hand cream <Gel formulation> Sucrose stearic acid diester 5% Methyl paraben 0.1 Water balance Here, the sucrose stearic acid diester was obtained in Production Example 5. The above composition was heated to 60 ° C., uniformly dispersed, and then left at room temperature to obtain a gel. <Emulsified formulation> Pluronic 4% Liquid paraffin 20 Vaseline 15 Vitamin E acetate 0.5 Glycerin 10 1,3BG 10 Perfume 0.05 Purified water balance A gel and an emulsion are adjusted by the gel formulation and the emulsion formulation, respectively, and 70 ° C. While stirring at 80 g, 20 g of the emulsion was mixed and then cooled to 25 ° C. to obtain a hand cream.

Example 10 Pre-Making 1. Dimethyl polysiloxane 4.5 2.2 Cetyl 2-ethylhexanoate 2.2 3. Paraben 0.1 4. Perfume 0.1 5. Purified water 74.5 6. Sucrose stearate diester ^* 0.6 7. Polyethylene glycol 3.2 8. Butylene glycol 4.9 9. Purified water 7.5 10. Sucrose stearate diester ^* 2.4 (*: Sucrose stearate diester obtained in Production Example 1)

[Production method] (5) to (8) are heated and stirred to make them uniform. (1) to (4) are heated and melted, and (5) to
In addition to (8), a homomixer treatment is performed to emulsify. (9)
~ (10) is heated and stirred to make it uniform, and then (1) ~
Add to the emulsion of (8), stir and mix, cool, and add O /
A W-shaped pre-make lotion was produced. [Property] This lotion was stable at 37 ° C., 25 ° C. and 0 ° C. for 1 month or more. And, the usability was also refreshingly liked. Further, it was confirmed that the composition exhibited higher water repellency as compared with the conventional O / W type pre-make lotion, and that when powdery foundation was repeatedly applied, the makeup lasting property was improved as compared with the case without this lotion.

Example 11 Foundation 1. Dimethyl polysiloxane 4.5 2. Trimethylolpropane tri-2-ethylhexanoate 2.2 3. Paraben 0.1 4. Perfume 0.1 5. Purified water 63.2 6. Sucrose oleic acid diester ^* 0.6 7. Titanium dioxide 5.8 8. Talc 4.2 9. Iron oxide 2.1 10. Polyethylene glycol 3.1 11. Propylene glycol 4.8 12. Purified water 7.4 13. Sucrose oleic acid diester ^* 1.9 (*: Sucrose stearic acid diester obtained in Production Example 2)

[Production method] (5) to (11) are heated and stirred, and homogenized to homogenize them. (1)-(4)
Is melted by heating, added to (5) to (11), and treated with a homomixer to emulsify. (12) to (13) are heated and stirred to make them uniform, and then added to the emulsions (1) to (11),
The mixture was stirred and mixed, and cooled to produce an O / W type foundation. [Property] This foundation is 37 ° C, 25 ° C, 0 ° C.
Has been stable for over a month. It was also confirmed that the product has a high water repellency as compared with the conventional O / W type foundation while having a refreshing feeling of use and is excellent in makeup lasting.

[0029]

As described above, according to the thickening gelling agent of the present invention, the gel containing sucrose fatty acid diester and ionic surfactant as the main components is excellent in safety and usability. You can get

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a gel forming region according to an embodiment of the present invention.

Claims (1)

[Claims] 1. A thickening gelling agent comprising 50% by weight or more of a sucrose fatty acid diester and 0.5% by weight or more of an ionic surfactant.