JPH07187947A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain a cosmetic, containing a polyglycerol ester of a fatty acid, excellent in emulsifying, solubilizing or dispersing functions blended therein and capable of maintaining the stable emulsified, solubilized or dispersed state for a long period. CONSTITUTION:This cosmetic contains an ester of a linear polyglycerol which is a polyglycerol composition having 3-15 average polymerization degree and <=5wt.% total content of >=2C branched structural and cyclic structural substances produced by the condensation of a linear polyglycerol without preferably containing the branched and cyclic structural substances with a fatty acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fatty acid ester of a linear polyglycerin composition containing a trace amount of a branched structure and a cyclic structure produced as a result of polycondensation of glycerin, or containing none at all. The present invention relates to cosmetics contained.

[0002]

2. Description of the Related Art Various cosmetics, such as creams and emulsions, generally consist of two or more substances that are not mixed with each other in a uniform state, in which case a surfactant is used. For example, an emulsifier or a solubilizer is used when mixing an oil phase containing a hydrophobic substance with an aqueous phase containing water and / or a hydrophilic substance. A dispersant may be used when the powders are dispersed in the oil phase or the water phase. Thus, a surfactant having an emulsifying, solubilizing or dispersing function,
It is used in various cosmetic products. Such surfactants include various kinds such as polyhydric alcohol ester derivatives, ether compounds, fatty acid soaps, alkylphosphoric acid derivatives, alkylsulfonic acid derivatives, amino acid derivatives.

Of these, polyglycerin fatty acid esters have good biodegradability and are not toxic, so that they have been used not only in the cosmetic field but also in the food field, pharmaceutical field and the like, and have been used as a nonionic emulsifier. In particular, it is possible to prepare an emulsifier having a desired HLB by appropriately changing the distribution of the degree of polymerization of glycerin or the degree of esterification of fatty acid, and the range of its application is wide.

The polyglycerin fatty acid ester used as a surfactant is usually an esterification product of polyglycerin and a fatty acid obtained by heating glycerin, epihalohydrin or the like to cause polycondensation reaction, and has an average degree of polymerization. 2 to 12, and the average degree of esterification is 1 to 3. Therefore, the conventional polyglycerin fatty acid ester is a complicated composition having a polymerization degree distribution and an esterification degree distribution.

Moreover, since the raw material polyglycerin itself is produced by the polycondensation reaction, its molecular structure is not only a complete linear structure but also a branched structure and a cyclic structure associated with the polycondensation of glycerin units. The polyglycerin fatty acid ester commercially available as a surfactant also contained a branched structure and a cyclic structure. In general, polyglycerin fatty acid ester commercially available as a surfactant has about 10 to 10 parts of the branched and cyclic structures described above.
70% by weight is contained.

[0006]

Polyglycerin fatty acid ester is a good surfactant and is often used.
Even if it is used alone, it is difficult to obtain a stable emulsified, solubilized or dispersed system for a long period of time. For this reason, other types of surfactants are used in combination. Therefore, an object of the present invention is to provide a cosmetic having excellent emulsifiability, solubilization or dispersibility in a wide range of mixed systems.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a stable emulsification, solubilization or dispersion system can be realized in a wide range of mixed systems by using an improved polyglycerin fatty acid ester. . The present invention has been completed based on such findings, and has an average degree of polymerization of 3 to 1
5, wherein the total content of the branched structure having 2 or more carbon atoms and the cyclic structure formed by polycondensation of glycerin is 5% by weight or less. A cosmetic containing an ester of a fatty acid and a fatty acid.

In the present invention, the fatty acid ester of the specific polyglycerin composition described below is an essential component. That is, the polyglycerin composition according to the present invention has an average degree of polymerization of 3 to 15 and the total content of a branched structure having 2 or more carbon atoms and a cyclic structure produced by the polycondensation reaction of glycerin. Is 5% by weight or less, and is a polyglycerin composition having a linear structure. In such a polyglycerin composition, the chain of the glycerin skeleton has a linear structure represented by the following general formula (1) or (2), and the number of carbon atoms produced as a by-product along with the polycondensation reaction of the glycerin skeleton unit. The total content of the branched structure and the cyclic structure of 2 or more is 5% by weight or less of the entire polyglycerin composition.

[0009]

Embedded image CH ₂ (OH)-CH (OH)-CH ₂ --O--X _n --H (1)

Embedded image CH ₂ (OH)-CH (CH ₂ OH)-O--X _n --H (2) [In the formulas (1) and (2), X is —CH ₂
─CH (OH) ─CH ₂ ─O- or -CH ₂ CH (C
H ₂ OH) ─O- be either, n represents 2 to 14. ]

On the other hand, the fatty acid according to the present invention is a saturated or unsaturated linear or branched fatty acid having 2 to 22 carbon atoms. Specific examples thereof include acetic acid, lactic acid, caproic acid, caprylic acid, capric acid, 2-ethylhexanoic acid, nonanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitooleic acid, stearic acid, oleic acid, Elaidic acid, linoleic acid, α- and γ-linolenic acid, 2-heptylundecanoic acid, isostearic acid, ricinoleic acid, 10-hydroxystearic acid, 10-ketostearic acid, 12-hydroxystearic acid, behenic acid, erucic acid, Examples include arachidonic acid, eicosapentaenoic acid and docosahexaenoic acid.

Further, palm oil, cacao butter, palm oil, soybean oil, rapeseed oil, cottonseed oil, corn oil, linseed oil, castor oil, safflower oil, sunflower oil, sesame oil, peanut oil,
Olive oil, lard, beef tallow, fish oil and the like, and hydrolyzed mixed fatty acids of these fractionated oils and fats and hydrogenated oils can also be used. Among these fatty acids, caprylic acid, capric acid, 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, isostearic acid, ricinoleic acid, 12-hydroxystearic acid, behenic acid and palm. Preference is given to hydrolyzed mixed fatty acids of oil, soybean oil, rapeseed oil, linseed oil, beef tallow, hydrogenated fish oil.

The polyglycerin fatty acid ester used in the present invention has a branched and cyclic polyglycerin structure after ester synthesis of a polyglycerin composition containing a branched and cyclic structure together with a linear structure and a fatty acid. It can be obtained by removing fatty acid ester or by synthesizing a fatty acid ester using a polyglycerin composition having a linear structure that does not contain polyglycerin having a branched or cyclic structure as a raw material.

The polyglycerin composition is obtained, for example, by heating glycerin or glycidol or epichlorohydrin for polycondensation reaction, and the fatty acid ester thereof is subjected to an esterification reaction with a free fatty acid in the presence of an acidic or metal catalyst, or a fatty acid anhydride. Substance or fatty acid chloride, or may be transesterified with fatty acid methyl ester in the presence of metal alcoholate or lipase. The purification method for removing the molecular and cyclic polyglycerin components may be distillation and / or chromatography, but distillation is not suitable for purification of a high degree of polymerization. Examples of chromatography include gel filtration, partitioning, adsorption, ion exchange and other techniques.

The thus-obtained polyglycerin fatty acid ester used in the present invention is a polyglycerin composition having an average degree of polymerization of 3 to 15, preferably 4 to 10, and a branch having 2 or more carbon atoms accompanying polycondensation of glycerin. The total content of the linear structure and the cyclic structure is 5% by weight or less, preferably 3% or less, and more preferably the linear polyglycerin composition not containing the branched and cyclic structures and the fatty acid are The average degree of esterification is 1-4, preferably 1-3.

In such polyglycerin fatty acid ester, the total content of the branched and cyclic structures is 5
If it exceeds the weight% or if the average degree of esterification is out of the range of 1 to 4, it is not possible to obtain a cosmetic composition having excellent emulsification, solubilization or dispersibility which is the object of the present invention.

Since the polyglycerin fatty acid ester of the present invention has an excellent emulsifying, solubilizing or dispersing function as a surfactant, it can be blended into cosmetics alone. In this case, the addition amount varies depending on the object to be blended, but generally 0.1 to 30% by weight, preferably 0.5 to
It is used in an amount added in the range of 15% by weight. When used in combination with other various surfactants, the total amount of the surfactants to be compounded can be reduced together with the amount of the other surfactants used. As surfactants that can be used together, polyhydric alcohol ester derivatives, ether compounds, fatty acid soaps,
Specific examples thereof include alkylphosphoric acid derivatives, alkylsulfonic acid derivatives, amino acid derivatives and the like.

The cosmetic of the present invention can be produced by a known method by substituting a part or all of the conventional polyglycerin fatty acid ester with that of the present invention. As the target cosmetics, in consideration of the emulsifying, solubilizing or dispersing function of the polyglycerin fatty acid ester according to the present invention, creams for skin products, emulsions, lipsticks, shampoos for hair products, rinses, hair conditioners Etc. are suitable, and in addition, they can be blended in bath products, makeup powder products, etc. Reference examples and examples are shown below,
These do not limit the embodiments of the invention.

[0018]

【Example】

Reference Production Example A commercially available polyglycerin composition obtained by a polycondensation reaction using epichlorohydrin as a raw material was subjected to gel filtration chromatography using water as an eluent to fractionate into polyglycerin of each polymerization degree. Further, after acetylating each fraction, 4 by flash chromatography with a hexane eluent.
It was purified twice to obtain cyclic, branched and linear polyglycerol acetates. After saponification with an aqueous sodium hydroxide solution, the alkali was removed with an ion exchange resin, desalting and dehydration drying were performed to obtain the corresponding polyglycerin having a purity of 95% or more. Purified polyglycerin of each type was collected to have an average degree of polymerization of 6 or 10, and 1 mol of each weight equivalent to 1 mol% of lipase as a catalyst for 20 hours at 40 to 50 ° C. for 1 mol of stearic acid or 2 mol of oleic acid. Linear, branched and cyclic hexa or decaglycerin monostearate or its dioleate were prepared by esterification with. Yield of the esterified product: 90 to 95%, acid value: 0.1 to 0.5,
Hydroxyl value: 320-610.

Reference Example 1 Emulsification test: sodium caseinate was dissolved in distilled water to obtain an aqueous phase, and the polyglycerin fatty acid ester obtained in the commercial and production examples was mixed with liquid paraffin to obtain an oil phase. Mix the water and oil phases and use a homogenizer at 1500 rpm for 5
Emulsified for minutes. Shows the changes over time in the emulsified state of each emulsion.
Shown in 1. As is clear from Table 1, the linear polyglycerin fatty acid ester of the present invention exhibits excellent emulsifying ability.

[0020]

[Table 1] Note) Units of compounding ingredients: m for distilled water and liquid paraffin
l, others g

Reference Example 2 Solubilization test: Sucrose monostearate, glycerin and the polyglycerin fatty acid ester obtained in Production Example were added to tocopherol, and these were dissolved in ethanol to obtain a sample. Distilled water was added while stirring this sample, and the amount of water capable of solubilizing the sample was measured. The results are shown in Table-2. The linear polyglycerin fatty acid ester of the present invention exhibits excellent solubilizing ability.

[0022]

[Table 2] Note) Unit of each compounding component: g

Reference Example 3 Dispersibility test: Lecithin and POE in 10 times by weight ether.
(20) A sample was prepared by dissolving sorbitan stearate and the polyglycerin fatty acid ester obtained in the Production Example, dispersing titanium oxide, and then distilling off the ether. This sample was dispersed in liquid paraffin and the time-dependent change in the state was examined. The results are shown in Table-3. Those to which the linear polyglycerin fatty acid ester of the present invention was added maintained a good dispersion state.

[0024]

[Table 3] Note) Unit of each compounding component: g Evaluation of dispersion state: ○ (good), △ (partially separated), × (separated)

Example 1 Linear decaglycerin (average degree of polymerization: 10) having a purity of 98% was obtained according to the method described in Reference Production Example. This 1 molar equivalent weight and stearic acid 2 molar equivalent weight were converted into p-toluenesulfonic acid (0.5% by weight of the total amount of both raw materials).
Was used as a catalyst and heated at 150 to 200 ° C. for 5 hours and stirred to cause an esterification reaction to prepare a linear decaglycerin distearate. Yield of the esterified product: 91%,
The acid value was 0.3 and the hydroxyl value was 436. Using this linear decaglycerin distearate and according to the formulation shown in Table 4, a makeup cream was prepared according to a conventional method.
That is, using a homomixer, add 80 parts of components other than purified water.
The mixture was heated to 0 ° C. and gradually added to purified water heated to the same temperature to emulsify. This product did not show phase separation even after being stored at 30 ° C. for 3 months, and maintained a stable emulsified state.

[0026]

[Table 4]

Example 2 The linear decaglycerin described in Example 1 (average degree of polymerization:
10, purity: 98%) 1 mol equivalent weight and oleic acid 1.
Esterification reaction was carried out in the same manner as in Example 1 using 5 mol equivalent weight to prepare a linear decaglycerin sesquioleate. The yield of the esterified product was 94%, the acid value was 0.1, and the hydroxyl value was 518. Using this linear decaglycerin sesquioleate, a lotion was prepared according to a conventional method according to the formulation shown in Table-5. That is, using a homomixer, the oil component and the aqueous component are each heated to 80 ° C.
Then, the oil phase was added to the aqueous phase to emulsify. This product did not show phase separation even after being stored at 30 ° C. for 3 months, and maintained a stable emulsified state.

[0028]

[Table 5]

Example 3 According to the method described in Reference Production Example, straight-chain type triglycerin (average degree of polymerization: 3) containing neither branched nor cyclic structure was obtained. An esterification reaction was performed with 2 mol of isostearic acid (manufactured by Emery Co., Ltd.) by the method of Reference Production Example to prepare a linear triglycerin diisostearate. Yield of the esterified product: 8
It was 5%, the acid value was 0.1, and the hydroxyl value was 221. Using this linear triglycerin diisostearate,
Lipstick was prepared according to the conventional method according to the formulation of 6. That is, all components were heated to 85 ° C. to be melted, and then poured into a mold for molding. This was a lipstick with well dispersed pigment and no sweating phenomenon.

[0030]

[Table 6]

Example 4 According to the method described in Reference Production Example, linear hexaglycerin (average degree of polymerization: 6) having a purity of 95% was obtained. This one
Using a molar equivalent weight and 1 mol of 2-ethylhexanoic acid,
Esterification was carried out in the same manner as in Example 1 to prepare linear hexaglycerin mono-2-ethylhexanoate. Yield of the esterified product: 95%, acid value: 0.
4, the hydroxyl value was 665. Using this linear hexaglycerin 2-ethylhexanoate, a shampoo was prepared according to a conventional method according to the formulation shown in Table-7. That is, all the components were mixed and heated to 80 ° C. to make a uniform state. This was a good lather shampoo.

[0032]

[Table 7]

Comparative Example 1 According to the method described in Reference Production Example, a branched type decaglycerin having a purity of 97% (average degree of polymerization: 10) and a purity of 98%.
The cyclic type decaglycerin (average degree of polymerization: 10) was obtained, and 1 mol of each of these and 2 mol of stearic acid were subjected to an esterification reaction in the same manner as in Example 1 to obtain a branched type and a cyclic type. Decaglycerin distearate was prepared. A makeup cream was prepared in the same manner as in Example 1 (prescription of Table 4) using both esterified products, and the emulsified state was observed. As a result, it was found that the composition containing the branched decaglycerin distearate was 1.5 months. In addition, the mixture containing cyclic decaglycerin distearate phase-separated in one month.

[0034]

According to the present invention, a cosmetic containing polyglycerin fatty acid ester having an excellent emulsifying, solubilizing or dispersing function can be obtained, and the cosmetic of the present invention can be stably emulsified, solubilized or dispersed. Maintain for a long time.

Claims (3)

[Claims] 1. A polyglycerin composition having an average degree of polymerization of 3 to 15, and a total content of a branched structure having 2 or more carbon atoms and a cyclic structure produced by polycondensation of glycerin is 5% by weight. % Or less, a cosmetic containing an ester of a linear polyglycerin composition and a fatty acid. 2. The cosmetic according to claim 1, wherein the linear polyglycerin composition does not contain the branched structure and the cyclic structure. 3. The cosmetic according to claim 1, wherein the ester has an average degree of esterification of 1 to 4.