JPH09216813A - Gelled emulsion cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a gelled emulsion cosmetic having high stability at high temperature, giving excellent feeling to the skin and having a proper viscosity by using a specific polyglycerol monofatty acid ester in combination with a liquid oil, glycerol and a polyhydric alcohol. SOLUTION: A polyglycerol monofatty acid ester synthesized from a fatty acid and glycidol and having high monoester content (especially preferably decaglyceryl monolaurate, etc.) is compounded with a liquid oil, glycerol and a polyhydric alcohol (excluding glycerol). The amount of the monofatty acid ester is about 1-6wt.% based on the total composition. The liquid oil is e.g. a liquid paraffin or octanoic acid. The polyhydric alcohol other than glycerol is e.g. propylene glycol or 1,3-butylene glycol and its amount is about 1-5wt.%. The compounding amount of glycerol is about 30-60wt.%. The cosmetic is good for cleansing, massaging, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gel-like emulsified cosmetic composition which has good stability at high temperatures, has an excellent feeling of use, and has an appropriate viscosity.

[0002]

2. Description of the Related Art Conventionally, gelled emulsion cosmetics have been applied as cleansing agents, pine surge agents, etc., but due to their properties, stable formulations are difficult to obtain, and gels themselves have to be highly stable in order to make stable formulations. It was also found that the viscosity was used to sacrifice the functionality and feel of the preparation. Also, with the development of hydrophilic polyglycerin fatty acid ester, there have been many studies on application in gel emulsions, but due to the adhesiveness derived from polyglycerin fatty acid ester, there is a problem in feeling during use such as poor elongation during use. was there.

For this purpose, nonionic surfactants other than hydrophilic polyglycerin fatty acid ester are utilized. For example, polyoxyethylene sorbit fatty acid ester and polyoxyethylene glycerin fatty acid ester are used in combination with diglycerin fatty acid ester. No. 4-224507), or examples using a naturally occurring surface-active substance (JP-A-5-491 and JP-A-5-4912).

[0004]

However, from the viewpoint of safety, the development of a gel emulsion cosmetic containing a polyglycerin fatty acid ester having good stability and excellent usability and functionality is earnestly desired. It is a thing.

On the other hand, as a conventional method for producing polyglycerin fatty acid ester, it is produced by esterification reaction of polyglycerin and fatty acid. In this method, in general, the produced polyglycerin fatty acid ester has a purpose. In addition to the monoesters of the above, unreacted polyglycerin, diesters, triesters, tetraesters, and other polysubstituted ester compounds remain, which causes various problems.

[0006]

In view of these problems, the present inventors have diligently studied the disease, a gel emulsion composition of moderate viscosity which is easy to use and contains a hydrophilic polyglycerin fatty acid ester, The inventors have found that the stability can be improved by using a polyglycerin monofatty acid ester having a high monoester content, which is synthesized from fatty acid and glycidol, and finally completed the present invention.

That is, the present invention relates to "one or more polyglycerin monofatty acid esters synthesized from fatty acids and glycidol and having a high monoester content.
It is a gel emulsion cosmetic characterized by containing liquid oil, glycerin and polyhydric alcohol (excluding glycerin).

The present invention will be described in more detail below.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Conventionally, as a method for producing a polyglycerin fatty acid ester, (1) an esterification reaction between polyglycerin and fatty acids [JAOCS (Journal of Ameri
can Oil Chemists' Society) 58, 878 (1981
, JP-A-6-41007, etc.], (2) transesterification reaction of polyglycerin with fatty acid esters, (3)
Transesterification reaction between polyglycerin and oils and fats, (4) Addition polymerization reaction between glycidol and fatty acid monoglycerides [see US Patent 4,515,775], (5) Addition polymerization reaction between glycidol and fatty acids (JP-A-51) -65705 gazette) etc. are known. That is, the polyglycerin fatty acid ester used in the present invention is a polyglycerin monofatty acid ester having a high monoester content, and specifically, methanol is used as an eluent and ODS is used.
A polyglycerin monofatty acid ester having a monoester content of 70% or more in terms of peak area ratio, which is based on a high performance liquid chromatographic analysis method using a UV absorptiometry to separate by column, and is manufactured. The method is a method obtained by reacting glycidol with a fatty acid. The “polyglycerin monofatty acid ester synthesized from fatty acid and glycidol with a high monoester content” in the present invention is produced by the method (5).

The fatty acid having 6 to 22 carbon atoms is used as the fatty acid used in the production of the polyglycerin monofatty acid ester having a high monoester content, which is synthesized from the fatty acid and glycidol in the present invention by an addition polymerization reaction. May be a saturated fatty acid or an unsaturated fatty acid, a linear fatty acid, a fatty acid having a side chain, or a hydroxyl group-substituted fatty acid. Examples of these fatty acids include caproic acid, caprylic acid, and 2-
Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid,
Examples include linoleic acid, behenic acid, erucic acid, ricinoleic acid and hydroxystearic acid.

The reaction between the fatty acid and glycidol is preferably carried out in the presence of an acidic catalyst. The acidic catalyst that can be used is phosphoric acid or an ester of phosphoric acid, and specifically, phosphoric acid, phosphoric anhydride, polyphosphoric acid, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid. Or a phosphoric acid such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, 2 ethylhexyl acid phosphate, or the like can be used. In addition, as these acidic phosphoric acid esters, any of a monoester body, a diester body, and a mixture thereof can be used, and the above-mentioned these may be used alone or in combination of two or more kinds. May be used.

The amount of the catalyst added is 0.01 to
It is 10% by weight, preferably 0.1 to 5% by weight. 0.
If it is less than 01% by weight, the reaction rate is small, and if it exceeds 10% by weight, the effect cannot be expected to be improved, and depending on the catalyst used, a large amount of glycidol-addition polymer with the catalyst as an initiator is produced, which is not preferable.

The reaction method is to take a fatty acid in a reaction vessel,
The above-mentioned soot is added thereto, and the reaction is carried out while adding glycidol little by little. The reaction temperature is 50 to 180 ° C., preferably 70 to 160 ° C., more preferably 120.
~ 140 ° C. If the temperature is less than 50 ° C, the reaction rate is low, and 1
If the temperature exceeds 80 ° C, coloring becomes severe, and if the temperature exceeds 230 ° C, glycidol is decomposed to cause a side reaction, which is not preferable.

In this case, in order to prevent the reaction temperature from rising, a low boiling point compound which does not react with glycidol may be added. The reaction is preferably carried out in a nitrogen gas atmosphere, and may be pressurized if necessary.

By the above reaction, glycidol is added and polymerized to the fatty acid to produce a polyglycerol monofatty acid ester having a higher degree of polymerization. The product is a polyglycerin monofatty acid ester having a high monoester content.

The polyglycerin monofatty acid ester produced by the above method has an oxirane oxygen content of 500 to 2000 ppm, which is considered to be derived from glycidyl, depending on the production conditions.
May be contained.

Therefore, it is preferable to add water to the product obtained by the above method, heat it, and dehydrate it to obtain a high-purity polyglycerin fatty acid ester in which the detected amount of oxirane oxygen concentration is small.

The amount of water added is 0.1 to 20 relative to the polyglycerin fatty acid ester solution obtained in the first step.
It is preferable to select in the range of weight%. If the amount of water is less than 0.1% by weight, the amount of unreacted glycidol cannot be sufficiently reduced, and if it exceeds 20% by weight, the post-treatment operation becomes complicated, and neither is preferable. A particularly preferable range of the amount of water to be added is 1 to 10% by weight.

Further, in this purification step, water is added to the polyglycerin fatty acid ester solution and then heated,
Unreacted glycidol can be converted to glycerin. The heating temperature at this time is preferably selected in the range of 60 to 200 ° C. If the heating temperature is lower than 60 ° C, the residual oxirane group concentration derived from the oxirane group-containing compound, which is expected to be an unreacted glycidol or a product of a side reaction, cannot be sufficiently reduced. The polyglycerin fatty acid ester that is a product is colored, so that both are not preferable.

Particularly preferably in the above temperature range, 80 to 1
It is in the range of 60 ° C. The heating time depends on the temperature,
It is in the range of 0.5 to 15 hours, particularly preferably 1 to 7 hours. Dehydration can be performed by distillation, azeotropic distillation, vacuum distillation, or the like. The heating temperature for distillation is 100 to 200.
It is preferable to select in the range of ° C. If the heating temperature is lower than 100 ° C., it is not sufficient to remove the water contained in the polyglycerin fatty acid ester of the product.
If the temperature exceeds 0 ° C, the high-purity polyglycerin fatty acid ester of the product will be colored, which is not preferable. Particularly preferable temperature range is 110 to 160 ° C. The dehydration time depends on the temperature and the degree of reduced pressure, but is 1 to 10
Selected in a time range. Among them, the range of 1 to 6 hours is preferable.

The polyglycerin fatty acid ester thus purified is a high-purity polyglycerin fatty acid ester having an oxirane oxygen concentration of less than 100 ppm by the titration method defined by AOCS test method Cd.9-57.

The liquid oil in the gel emulsion cosmetic of the present invention is liquid at 25 ° C., and examples thereof include hydrocarbon oils such as liquid paraffin and squalane, ester oils such as cetyl octanoate and isopropyl myristate, Further, glycerin trioctanoate, fatty acid triglyceride such as olive oil, and the like are preferable, and liquid oils containing higher alcohols and higher fatty acids as main components are unsuitable because high temperature stability is impaired. The hydrophilic polyglycerin fatty acid ester obtained by the reaction of the above-mentioned fatty acid and glycidol used in the present invention preferably has an HLB value of 11 or more, among which decaglyceryl monolaurate and hexagceryl monolaurate having an HLB value of 11 to 15. Is preferred.

Further, one or more kinds of these hydrophilic polyglycerin fatty acid esters may be blended, and the blending amount thereof is preferably in the range of 1 to 6% by weight based on the total composition. If the amount of hydrophilic polyglycerin fatty acid ester is not within this range,
This results in the separation of oil.

Further, the polyhydric alcohol excluding glycerin used in the present invention is, for example, propylene glycol,
1,3-butylene glycol, maltitol, sorbitol and the like, among which propylene glycol and 1,3-butylene glycol are preferable. These polyhydric alcohols
One or more kinds may be blended, and the blending amount thereof is in the range of 0.5 to 10% by weight, preferably 1 to 5% by weight, based on the entire composition.

Further, the content of glycerin is preferably in the range of 20 to 60% by weight, particularly preferably 30 to 60% by weight. If the amount of glycerin is less than 20% by weight, the feeling of use will be impaired,
If it exceeds 60% by weight, a feeling of warmth will appear during use and the feeling of use will be impaired.

The present invention is used for cosmetics such as cleansing and pine surge, and depending on the purpose, other than the components of the present invention, known components such as ultraviolet absorbers, preservatives and bactericides are used within a range not impairing the present invention. , Antioxidants, pigments, fragrances,
Other medicinal ingredients and the like can be appropriately mixed.

[Examples] The present invention will be described in more detail with reference to the following examples.

The present invention is not limited to the examples, and [%] in the examples means [% by weight] unless otherwise specified.

Reference Example 1 0.5 mol (100.1) of lauric acid was placed in a 1-liter 4-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller, and a dropping cylinder.
6g) and 0.0622g of phosphoric acid (85% product)
Heated to 40 ° C. Then, while maintaining the reaction temperature at 140 ° C., 3.0 mol (222.24 g) of glycidol was added dropwise over 5 hours. The temperature was further maintained, and the reaction was continued for 26 hours.

After cooling, the reaction product was taken out to obtain about 300 g of hexaglycerin monolaurate. When the obtained polyglycerin monolauric acid ester was evaluated under the analysis conditions of the following high performance liquid chromatography (hereinafter abbreviated as HPLC), the monosubstitution rate was 87.7%.

(HPLC analysis conditions) Column: Wakosil 5C18 * 2, developing solvent: MeOH, flow rate: 0.75 ml / min., Column oven temperature: 40 ° C., detection method: ultraviolet absorption method (λ = 210 nm), sample concentration : 10%, Injection amount: 5 μl [Reference Example 2] 4.0 mol of glycidol (296.3)
2 g) The same operation as in Reference Example 1 was performed except that it was used, and after cooling, the reaction product was taken out to obtain about 400 g of octaglycerin monolaurate. When the obtained octaglycerin monolauric acid ester was evaluated by HPLC, the monosubstitution rate was 84.5%.

Reference Example 3 5.0 mol of glycidol
(370.40 g) The same operation as in Reference Example 1 was carried out except that the mixture was used. After cooling, the reaction product was taken out to obtain about 470 g of decaglycerin monolaurate. When the obtained decaglycerin monolaurate was evaluated by HPLC, the monosubstitution rate was 77.2%.

Comparative Reference Example 1 / In the Case of Reaction of Fatty Acid with Polyglycerin Polyglycerin [Daicel] was placed in a 1-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer, a cooling tube, a temperature controller and a dropping cylinder. Chemical industry PG
L06: hexaglycerin, hydroxyl value 960] 175.
3 g (0.5 mol) was taken, heated to 80 ° C., and while maintaining the reaction temperature at 80 ° C., 0.5 mol (10 mol) of lauric acid.
0.16 g) was added and dissolved. Next, 0.75 g of sodium carbonate and 0.25 g of sodium bisulfite were added, and an esterification reaction was performed at 210 ° C.

After the reaction for 2 hours, the acid value becomes 0.89,
After cooling to 100 ° C., the reaction product was taken out. The obtained hexaglycerin monolauric acid ester was evaluated by HPLC. As a result, the monosubstitution rate was 55.1%.

[Comparative Reference Examples 2 and 3 / Evaluation Results of Commercially Available Polyglycerin Fatty Acid Ester] As the commercially available polyglycerin fatty acid ester produced by the reaction of polyglycerin and fatty acid, SY Glister (manufactured by Sakamoto Yakuhin Kogyo) (ML-500, ML-750) was selected. When these polyglycerin monolauric acid esters were evaluated by HPLC, the mono-substitution rates of ML-500 and ML-750 were 5 respectively.
It was 2.0% and 44.3%. Moreover, let each be Comparative Reference Examples 2 and 3.

Examples and Comparative Examples shown in Table 1 were prepared by preparing gels in advance with components other than glycerin and then adding glycerin.

The evaluation method is shown below.

Evaluation method 1. Stability: The product of the present invention and the comparative product are placed at a constant temperature of 40 ° C,
After 60 days, the state of separation was judged according to the following criteria.

◯: Separation is not recognized ×: Separation is recognized in the upper layer or the lower layer Viscosity: The Bruchk field viscometer (spindle # 4) of the present invention product and the comparative product, which are kept at a constant temperature of 25 ° C. Feeling of use: The present invention product and the comparative product were used by 5 specialist panels and the feeling of use was evaluated according to the following criteria.

◯: All were evaluated as good.

X: The panel evaluated to be good is 4 or more.

From the results of Table 1, it can be said that the product of the present invention is a gel-like emulsified cosmetic composition which is superior in stability and feeling to use and is easy to use as compared with Comparative Examples.

Table 1 Example Comparative Example 1 2 3 1 2 3 Compounding component (%) A1 3.5 A2 3.5 A3 3.5 A4 3.5 A5 3.5 A6 3.5 Characteristic stability (1 month at 40 ° C.) ○ ○ ○ ○ ○ × Viscosity ( cps × 10 ³ ) 7 7.6 8.1 9 9.5 9.7 Usability ○ ○ ○ × × ○ In Examples 1 to 3 and Comparative Examples 1 to 3, 1,3-
Butylene glycol was 3%, liquid paraffin was 75%, glycerin was 15%, fragrance was 0.5%, and purified water was 3%.

A1: Polyglycerin fatty acid ester obtained in Reference Example 1 A2: Polyglycerin fatty acid ester obtained in Reference Example 2 A3: Polyglycerin fatty acid ester obtained in Reference Example 3 A4: Polyglycerin obtained in Comparative Reference Example 1 Fatty Acid Ester A5: Polyglycerin Fatty Acid Ester Obtained in Comparative Reference Example 2 A6: Polyglycerin Fatty Acid Ester Obtained in Comparative Reference Example 3 As shown by the results in Table 1, the gel emulsion cosmetic of the present invention is a comparative example product. The stability was good and the feeling of use was excellent as compared with.

<Example 4 / Cleansing gel> (Ingredient name) (Blending amount%) Decaglycerin laurate obtained in Reference Example 3.00 1,3-butylene glycol 2.00 Purified water balance Liquid paraffin 56.00 Glycerin 37 .00 Sodium hyaluronate 0.002 Purified water 0.20 Perfume 0.20 Total 100.00 <Example 5 / Massage gel> (ingredient name) (blending amount%) Decaglycerin laurate obtained in Reference Example 3 3.00 1,3- Butylene glycol 2.00 Purified water balance Liquid paraffin 25.00 Glyceryl trioctanoate 25.00 Glycerin 42.00 Sodium hyaluronate 0.002 Perfume 0.50 Total 100.00 <Example 6 / Wipe off make-up> (Ingredient%) Deca Glyceryl monomyristate 1.50 Hexaglyceryl monolaurate 1.50 1,3-Butylene glycol 2.00 Purified water balance Liquid paraffin 40.00 Glycerin 42.00 Sodium hyaluronic acid 0.001 perfume 0.50 Total 100.00

[0046]

EFFECT OF THE INVENTION A gel emulsion cosmetic using a polyglycerin monofatty acid ester of the present invention, which is synthesized from fatty acid and glycidol and has a high monoester content, is excellent in stability and feeling after use. Met. (Below margin)

Claims (1)

[Claims] 1. A polyglycerin monofatty acid ester having a high monoester content, which is synthesized from a fatty acid and glycidol, and one or more kinds thereof, liquid oil, glycerin, and polyhydric alcohol (excluding glycerin) are mainly used. A gel-like emulsified cosmetic characterized by being used as an ingredient.