JP2011168527A - Oil-in-water type emulsified composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-in-water type emulsified composition that comprises solid fat, being hard to stably compound, together with liquid oil, is stable with the lapse of time, exhibits excellent safety and is useful particularly for a cosmetic. <P>SOLUTION: The oil-in-water type emulsified composition comprises the following components (A), (B), (C) and (D): (A) a hydrophilic polyglycerol fatty acid ester; (B) a biosurfactant (MEL is preferable in particular); (C) liquid oil having a melting point of lower than 30°C; and (D) an aqueous medium. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to an oil-in-water emulsion composition, and more specifically, a solid fat which is generally difficult to be stably blended can be blended with a liquid oil in the form of a stable oil-in-water emulsion, and particularly useful as a cosmetic. Type emulsion composition.

Conventionally, it has been known that the moisture in the stratum corneum is important for imparting moisture to the skin and making the skin soft. And, the retention of the water is said to be due to water-soluble components contained in the stratum corneum, that is, free amino acids, organic acids, urea or inorganic ions, and these substances are used alone or in combination as a medicinal oil-in-water type. It is blended in an emulsion composition or an oil-in-water emulsion composition and used for the purpose of improving or preventing skin roughness.

  Apart from this, many moisturizing substances having high affinity with water have been developed and used for the same purpose.

Furthermore, in recent years, it has been found that lipids present between keratinocytes have a high moisturizing ability, and the artificial intercellular lipid composed of a similar structural substance of the keratinocyte lipid component gives moisture to the skin. Softening is performed, and a relatively high effect is obtained.

In recent years, amphiphiles have been used in various fields. An amphiphilic substance is a substance having two different properties of hydrophilicity and lipophilicity, and a substance having such a property is called a surfactant. For example, a glycolipid has two properties of hydrophilicity derived from the property of sugar and lipophilicity derived from the property of lipid, and is an example of a surfactant.

Synthetic surfactants have been developed as a result of the development of the petrochemical industry, and the production of synthetic surfactants has increased dramatically compared to surfactants derived from biological components, and now they are indispensable for daily life. It was.

However, since synthetic surfactants have low biodegradability, environmental pollution is becoming a serious problem as the amount of synthetic surfactants used increases. Therefore, in order to reduce the burden on the environment, biosurfactants with high safety and high biodegradability have been reviewed again, and development of various types of biosurfactants has been desired.

Examples of the biosurfactant include five types of biosurfactants of glycolipid type, acyl peptide type, phospholipid type, fatty acid type and polymer compound type.

Among the biosurfactants, lecithin, which is a phospholipid biosurfactant, has been used as an emulsifier for a long time. When suspended in water, the phospholipid associates to form a double membrane. It is known to form vesicles with confined phases. These vesicles are also called liposomes, and are used as models of biological membranes or as carriers for cosmetics and drugs. In addition, the present condition is that little is known about what forms a vesicle in biosurfactants other than a phospholipid type.

On the other hand, many types of biosurfactants produced by bacteria or yeast have been reported as glycolipid biosurfactants. Glycolipid biosurfactants are not only highly biodegradable, have low toxicity and are environmentally friendly, but also have excellent physiological functions. For example, glycolipid-based biosurfactants are known to have a high moisturizing effect and are expected to be used as ingredients in cosmetics and the like.

One typical glycolipid biosurfactant is mannosyl erythritol lipid (hereinafter sometimes referred to as “MEL”). MEL is a substance discovered from Ustilago nuda and Shizonella melanogramma (see Non-Patent Documents 1 and 2). Thereafter, yeasts of the genus Candida that are mutants of itaconic acid production (see Patent Document 2 and Non-patent Document 3), Candida antarctica (currently Pseudozyma antarctica) (Non-Patent Documents 4 and 5) It is reported that the yeast is also produced by yeasts of the genus Kurtzmanomyces (see Non-Patent Document 6). At present, production of 100 g / L or more is possible by continuous culture and production for a long time.

MEL has 4-O-β-D-mannopyranosyl-meso-erythritol structure and 1-O-β-D-mannopyranosyl-form as shown in the following general formula (1) as optical isomers of erythritol having a sugar skeleton. A meso-erythritol structure (the following general formula (2)) exists.

By synthesizing one kind of MEL having this 1-O-β-D-mannopyranosyl-meso-erythritol structure, it is proved that the sugar skeleton of the conventional MEL has the structure of the above general formula (1). (Non-Patent Document 7). Most recently, the MEL having a conventional 4-O-β-D-mannopyranosyl-meso-erythritol structure is an optical isomer of 1-O-β-D-mannopyranosyl-meso of the above general formula (2). -It has been found that mass production can be achieved by producing MEL having an erythritol structure using microorganisms such as Pseudozyma tsukubaensis (Patent Document 3).

MEL having a conventional 4-O-β-D-mannopyranosyl-meso-erythritol structure has been reported to have various physiological activities including antibacterial properties, antitumor properties, glycoprotein binding ability (non- Patent Document 8). In addition, this conventional MEL exhibits extremely unique self-assembly characteristics, and not only a slight difference in molecular structure greatly affects the formation of self-assemblies, but also dilute solutions (6 3 × 10 ⁻² wt% or less) (non-patent document 9). Furthermore, a liquid crystal emulsification technique (Patent Document 4) using a conventional MEL bicontinuous sponge structure is also reported.

Japanese Patent No. 3095420 Japanese Patent Publication No.57-145896 WO2008 / 018448 JP 2007-181789 A

R. H. R. H. Haskins, Jay. A. Tone (J. A. Thorn), B. Boothroyd, “Can. J. Microbiol.”, Volume 1, p 749-756 (1955). Gee. G. Deml, Tee. T. Anke, F. F. Oberwinkler, B. M. G. Giannetti, W. Steglich, “Phytochemistry”, Vol. 19, p83-87 (1980). Tee. Nakahara, H. Kawasaki, T. T. Sugisawa, Wy. Y. Takamori, Tee. T. Tabuchi, “Journal of Fermentation Technology” (Japan), Japan Fermentation Engineering Society, 61, p19-23 (1983). Di. Kitamoto, S. Akiba, See. C. Hioki, Tee. T. Tabuchi, “Agric. Biol. Chem.”, (Japan), Japan Society for Agricultural Chemistry, Volume 54. p31-36 (1990). H. S. Kim (H.-S. Kim), Bee. Di. Yoon (B.-D. Yoon), Di. H. D.-H. Choung, H. M. Oh (H.-M. Oh), Tee. T. Katsuragi, Wye. Y. Tani "Appl. Microbiol. Biotechnol.", (Germany), Springer-Verlag, 52, p713-721 (1999). K. kakukawa, M. Tamai, K. Imamura, K. Miyamoto, S. Miyoshi, Y. Morinaga, O. Suzuki, Miyagawa (T. Miyakawa) “Bioscience, Biotechnol. Biochem.” (Japan), Japan Society for Agricultural Chemistry, 66, p188-191 (2002). Di. D. Crich, M. A. Mora, Earl. R. Cruz “Tetrahedron” (Netherlands), Elsevier, 58, p35-44 (2002). Dai Kitamoto “Oreoscience” (Japan), Japan Oil Chemists' Society, Volume 3, p663-672 (2003). Tee. T. Imura, N. N. Ohta, K. Inoue, N. N. Yagi, H. H. Negishi, H. H. Yanagishita, Di. Kitamoto “Chemistry European Journal (Chem. Eur. J)” (USA), Wiley, Vol. 12, p 2434-2440 (2006).

An object of the present invention is to provide an oil-in-water emulsified composition which is stable over time and is excellent in safety, which is obtained by blending solid fat which is difficult to be stably blended with liquid oil, and is particularly useful as a cosmetic.

In this situation, the present inventors conducted extensive research focusing on the interaction between keratinocyte lipid molecules in order to solve the above-mentioned problems. As a result, using biosurfactant, for example, the MEL described above, solid fat and It was found that an oil-in-water emulsion composition solves the above problems as a stable and safe cosmetic if emulsified using an oil component containing liquid oil and a hydrophilic polyglycerin fatty acid ester. completed.

That is, the present invention has the following configuration.
(1) An oil-in-water emulsion composition comprising the following components (A), (B), (C) and (D):
(A) Hydrophilic polyglycerin fatty acid ester (B) Biosurfactant (C) Liquid oil having a melting point of less than 30 ° C. (D) Aqueous medium (2) The biosurfactant has a mannose skeleton according to (1) Oil-in-water emulsion composition.
(3) The oil-in-water emulsion composition according to (2), wherein the biosurfactant has a sugar alcohol bonded to the hydroxyl group at the 1-position of the mannose skeleton.
(4) The biosurfactant having a mannose skeleton is selected from the group consisting of mannosyl erythritol lipid (MEL), mannosyl mannitol lipid (MML), mannosyl sorbitol lipid (MSL), mannosyl arabitol lipid (MAraL), and mannosyl ribitol lipid (MRL). The oil-in-water emulsion composition according to (2) or (3), which is one or more selected compounds.
(5) MEL is mannosyl erythritol lipid A (MEL-A), mannosyl erythritol lipid B (MEL-B), mannosyl erythritol lipid C (MEL-C), mannosyl erythritol lipid D (MEL-D), MEL-A (4) Oil-in-water emulsification characterized by being one or more compounds selected from the group consisting of a triacyl body, a triacyl body of MEL-B, a triacyl body of MEL-C and a triacyl body of MEL-D Composition.
(6) The oil-in-water emulsion composition according to any one of (1) to (5), wherein the biosurfactant contains a saturated fatty acid and / or an unsaturated fatty acid.
(7) The oil-in-water emulsion composition according to any one of (1) to (6), wherein the component (A) is a polyglycerin monofatty acid ester.
(8) The oil-in-water emulsion composition according to any one of (1) to (7), wherein the component (A), the component (B), and the component (D) form a thickening structure.
(9) The oil-in-water emulsion composition according to any one of (1) to (8), further comprising (E) an organic acid or a salt thereof.
(10) An oil phase obtained by dissolving component (B) biosurfactant in component (C) liquid oil having a melting point of less than 30 ° C. and dissolving or dispersing component (A) hydrophilic polyglycerin fatty acid ester therein, The manufacturing method of the oil-in-water type emulsion composition added to a component (D) aqueous medium at the temperature more than melting | fusing point of the mixture of a component (B) and a component (C).

Since the oil-in-water emulsion composition of the present invention contains a biosurfactant, the oil phase containing solid fat and liquid oil is stably dispersed for a long period of time as an oil-in-water emulsion, and is particularly useful as a cosmetic. An oil-in-water emulsion composition is provided.

The oil-in-water emulsion composition of the present invention contains a biosurfactant, particularly MEL. Therefore, the oil-in-water emulsion composition of the present invention has an effect of exhibiting excellent characteristics.

The component (A) hydrophilic polyglycerin fatty acid ester used in the present invention is preferably a hydrophilic polyglycerin fatty acid ester having an HLB of 8 or more according to the definition of griffin. In particular, a hydrophilic polyglycerin fatty acid ester in which an aqueous solution of 5% by weight (hereinafter simply referred to as “%”) has fluidity at 25 ° C. is preferable.

As the structure of the hydrophilic polyglycerin fatty acid ester of the present invention, the polyglycerin part is condensed with 2 to 10 glycerin, and the fatty acid part is composed of saturated or unsaturated fatty acid residues having 8 to 24 carbon atoms. Are preferred. Specific examples of preferable polyglycerin moieties include diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin and the like. Examples of the fatty acid residue include residues such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, oleic acid, linoleic acid, and ricinoleic acid. These hydrophilic polyglycerol fatty acid esters are often obtained as a mixture, and are composed of components having different degrees of glycerol polymerization and esterification.

Component (A) hydrophilic polyglycerin fatty acid ester of the present invention is a polyglycerin monofatty acid ester, polyglycerin difatty acid ester, or from the viewpoint of stability of oil-in-water emulsion and usability and effect as a cosmetic. A mixture thereof is preferred, and polyglycerin monofatty acid ester is particularly preferred. Specifically, mono- or diesters such as myristic acid such as triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, and decaglycerin, stearic acid, isostearic acid, and oleic acid are preferable. As commercial products, Sunsoft Q-18S (decaglyceryl monostearate, HLB12.0), Sunsoft Q-18F (hexaglyceryl monostearate, HLB10.5), Sunsoft Q-182S (decaglyceryl distearate, HLB11.0), Sunsoft Q-17S (decaglyceryl monooleate, HLB14.5), Sunsoft A-181E (pentaglyceryl monostearate, HLB13.0), Sunsoft A-171C (triglyceryl monooleate) , HLB10.0), Sunsoft A-141C (triglyceryl monomyristate, HLB12.0), (Sunsoft M-12J (polyglyceryl monolaurate, HLB16.0) (above solar chemistry), etc .; SY Glister MSW-750 (Monostearic acid de Glyceryl), SY glister SS-500 (hexaglyceryl sesquistearate), S face IS-401 (tetraglyceryl monoisostearate), S face M-1001 (decaglyceryl monomyristate), S face O-1001 (monoolein) Acid decaglyceryl) (above Sakamoto Pharmaceutical).

In the present invention, the component (A) can be used in combination of two or more, and is preferably 0.1 to 20%, particularly preferably 0.5 to 10% from the viewpoint of emulsion stability, feel and texture.

(Biosurfactant)
The (B) biosurfactant used as a part of solid fat in the cosmetic of the present invention is a general term for substances having surface activity ability and emulsification ability produced by living organisms, and has excellent surface activity and high biodegradation. In addition to exhibiting properties, it has various physiological actions and therefore may exhibit behaviors and functions different from those of synthetic surfactants.

Examples of the biosurfactant include mannosyl erythritol lipid (MEL), and mannosyl alditol lipid (MAL) other than MEL include mannosyl mannitol lipid (MML), mannosyl sorbitol lipid (MSL), mannosyl arabitol lipid (MAraL), mannosyl rib Examples include tall lipid (MRL), and among these, biosurfactants that form lamella structures or / and vesicles are preferably used, and MEL is particularly preferable.

(MEL)
The structure of MEL is shown in general formula (3). In general formula (3), substituent R1 is a C4-C24 aliphatic acyl group which may be the same or different. MEL is classified into four types, MEL-A, MEL-B, MEL-C, and MEL-D, based on the presence or absence of acetyl groups at the 4th and 6th positions of mannose.

Specifically, in MEL-A, in the general formula (3), the substituents R2 and R3 are both acetyl groups. In MEL-B, in the general formula (3), the substituent R2 is an acetyl group, and the substituent R3 is hydrogen. In MEL-C, in general formula (3), substituent R2 is hydrogen, and substituent R3 is an acetyl group. In MEL-D, in general formula (3), substituents R2 and R3 are both hydrogen.

The carbon number of the substituent R1 in the above MEL-A to MEL-D is the carbon number of the fatty acid constituting the triglyceride that is an oil or fat to be contained in the MEL production medium, and the degree of utilization of the fatty acid of the MEL-producing bacterium to be used It depends on. In addition, when the triglyceride has an unsaturated fatty acid residue, it is possible to include an unsaturated fatty acid residue as the substituent R1 unless the MEL-producing bacterium assimilates up to the double bond portion of the unsaturated fatty acid. is there. As apparent from the above description, the obtained MEL is usually in the form of a mixture of compounds having different fatty acid residue portions of the substituent R1.

The composition of the present invention contains mannosyl erythritol lipid having the structure represented by the general formula (4) or the general formula (5). In the general formula (4), the substituent R1 is the same or different aliphatic acyl group having 4 to 24 carbon atoms, and the substituent R2 is the same or different hydrogen or acetyl group. The substituent R3 is hydrogen or an aliphatic acyl group having 2 to 24 carbon atoms. In the general formula (5), the substituent R1 is an aliphatic acyl group having 4 to 24 carbon atoms which may be the same or different, and the substituent R2 is a hydrogen or acetyl group which may be the same or different. The substituent R3 is hydrogen or an aliphatic acyl group having 2 to 24 carbon atoms.

The substituent R1 in the general formula (4) and the general formula (5) is an aliphatic acyl group having 4 to 24 carbon atoms which may be the same or different. The number of carbon atoms of the substituent R1 is not particularly limited as long as it is within the above range, but it is more preferably 8 to 14.

The substituent R1 in the general formulas (4) and (5) may be a saturated aliphatic acyl group or an unsaturated aliphatic acyl group, and is not particularly limited. When it has an unsaturated bond, you may have a some double bond, for example. The carbon chain may be linear or branched. In the case of an oxygen atom-containing hydrocarbon group, the number and position of oxygen atoms contained are not particularly limited.

The structure of MAL (mannosylalditol lipid) other than MEL is shown in the general formula (6) (wherein the substituents R2 are hydrogen or acetyl groups which may be the same or different). Mannitol, arabitol, ribitol, and sorbitol are added as sugar alcohols (alditol) other than erythritol (n = 4: mannitol, sorbitol, n = 2: arabitol, ribitol). According to the general formula (6), MAL is a saturated or unsaturated straight chain having 2 to 20 carbon atoms, preferably 4 to 18 carbon atoms, more preferably 6 to 14 carbon atoms at the 2nd and 3rd positions of mannose. Having an alkanoyl group having a chain or a branch (wherein the substituent R 2 is hydrogen or acetyl group which may be the same or different)

(In the formula, the substituents R1 may be the same or different and each has a saturated or unsaturated straight or branched chain having 2 to 20 carbon atoms, preferably 4 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. (In the formula, the substituent R2 is a hydrogen atom or an acetyl group, which may be the same or different, and is preferably a compound in which both of the substituents R2 are acetyl groups.)

(Triacyl derivative)
The biosurfactant used in the present invention may be a MEL triacyl and a MAL triacyl other than MEL. The triacyl biosurfactant is a biosurfactant having higher hydrophobicity than MEL or MAL other than MEL. For example, it also exists in the culture solution of MEL-producing bacteria, and when it is obtained in a large amount, it can be produced by reacting MEL with various vegetable oils using enzymes.

The triacyl form of MEL, that is, triacyl mannosyl erythritol lipid (sometimes referred to as triacyl MEL), is that if the substituents R1 and R3 are both aliphatic acyl groups in the general formula (4) or the general formula (5), Triacyl MEL, and the substituent R2 is hydrogen or acetyl group which may be the same or different. Similarly to MEL, triacyl MEL is classified into four types of triacyl MEL-A, triacyl MEL-B, triacyl MEL-C, and triacyl MEL-D based on the presence or absence of acetyl groups at the 4th and 6th positions of mannose.

Triacyl MEL exhibits different properties from diacyl MEL. Specifically, since it has high hydrophobicity, it is excellent as an emollient agent in that it can be easily adapted to various oil components as compared with conventional MEL.

The biosurfactant preferably used in the present invention is MEL-B having a structure represented by the general formula (7) or the general formula (8).

(In the general formula (7) and the general formula (8), the substituent R1 is the same or different aliphatic acyl group having 4 to 24 carbon atoms)

In addition, although the said biosurfactant may be used independently, 2 or more types of biosurfactants can also be used together.

(Biosurfactant production method)
The method for producing the biosurfactant is not particularly limited, and a fermentation method using microorganisms may be arbitrarily selected. For example, culture production of MEL (MEL-A, MEL-B, MEL-C) can be produced by Pseudozyma antarctica (NBRC 1073) according to a conventional method, and Pseudozyma antarctica, Pseudozyma sp. it can. It is a well-known fact that an MEL mixture can be easily obtained with any microorganism. The MEL mixture can be purified using silica gel column chromatography to isolate MEL-A, MEL-B and MEL-C. Moreover, as bacteria which produce MEL-B, Pseudozyma antarctica and Pseudozyma tsukubaensis are known, and these bacteria may be used. Pseudozyma hubeiensis, Pseudozyma graminicola, etc. are known as bacteria that produce MEL-C, and these bacteria may be used. The microorganism having the ability to produce MEL is not particularly limited, and can be appropriately used depending on the purpose.

Fermentation medium for producing biosurfactant includes N sources such as yeast extract and peptone, C sources such as glucose, glycerol and fructose, and inorganic salts such as sodium nitrate, dipotassium hydrogen phosphate and magnesium sulfate heptahydrate. A medium having a general composition can be used, and oil and fats such as olive oil, soybean oil, sunflower oil, corn oil, canola oil and coconut oil, and water-insoluble such as hydrocarbons such as liquid paraffin and tetradecane can be used. Sexual substrates can be used alone or added with two or more.

Fermentation conditions such as pH and temperature, culture time, and the like can be arbitrarily set, and the culture solution after fermentation can be used as it is as the biosurfactant of the present invention. In addition, it is possible to appropriately add any operation such as filtration, centrifugation, extraction, purification, sterilization and the like to the culture solution after fermentation, and the obtained extract can be diluted, concentrated and dried. .

As oils and fats used as raw materials, vegetable oils and fats are preferable. Vegetable fats and oils are not particularly limited, and can be appropriately selected according to the purpose. For example, soybean oil, rapeseed oil, corn oil, peanut oil, cottonseed oil, safflower oil, sesame oil, olive oil, palm oil, etc. Among them, soybean oil and olive oil are biosurfactants (especially MEL) production efficiency (production amount) , Production rate, and yield) are particularly preferable. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as an inorganic nitrogen source, Although it can select suitably according to the objective, For example, ammonium nitrate, urea, sodium nitrate, ammonium chloride, ammonium sulfate, etc. are mentioned.

There are no particular limitations on the method for recovering and purifying the biosurfactant, and it can be appropriately selected according to the purpose. For example, the culture solution can be collected by centrifuging to recover the oil, and extracting and concentrating with an organic solvent such as ethyl acetate.

Examples of the extraction solvent include water, alcohols (for example, lower alcohols such as methanol, absolute ethanol, and ethanol, or polyhydric alcohols such as propylene glycol and 1,3-butylene glycol), ketones such as acetone, diethyl ether, and dioxane. , Esters such as acetonitrile and ethyl acetate, and organic solvents such as xylene, benzene, and chloroform can be used alone or in any combination of two or more kinds, and each solvent extract is combined. Can also be used.

There are no particular limitations on the extraction method, but usually it may be in the range of the boiling point of the solvent from room temperature to normal pressure. , Paste, gel, and powder. In many cases, it can be used as it is, but if necessary, further purification treatment such as deodorization and decolorization may be added as long as the effect is not affected. As a purification treatment means such as deodorization and decolorization, an activated carbon column or the like may be used, and a normal means generally applied depending on the extracted substance may be arbitrarily selected. If necessary, a high-purity biosurfactant can be obtained by purification using a silica gel column.

(Triacyl production method)
A method for obtaining a biosurfactant triacyl form will be described by taking a method for producing a MEL triacyl form as an example, but the biosurfactant triacyl form used in the present invention is not limited to a triacyl MEL.

For example, in order to obtain a triacyl MEL, a triacyl MEL fraction can be purified from a culture solution produced by fermenting a microorganism as described above. In order to obtain a large amount, MEL is dissolved in an organic solvent, a fatty acid derivative such as vegetable oil is added, and esterification or transesterification is performed in the presence of a hydrolase.

The fatty acid introduced into the erythritol part of MEL may be a long-chain hydrocarbon monovalent carboxylic acid. Further, it may be a saturated fatty acid or an unsaturated fatty acid. In the case of an unsaturated fatty acid, it may have a plurality of double bonds. The carbon chain may be linear or branched. Furthermore, a fatty acid derivative that is a derivative of a fatty acid may be used in the present invention, or a mixture of a fatty acid and a fatty acid derivative may be used in the present invention. The fatty acid or fatty acid derivative introduced into the erythritol part of MEL is preferably derived from oils, higher fatty acids, and synthetic esters.

The “oils” may be vegetable oil, animal oil, mineral oil, and hardened oil thereof. Specifically, avocado oil, olive oil, sesame oil, camellia oil, evening primrose oil, turtle oil, macadamian nut oil, corn oil, mink oil, rapeseed oil, egg yolk oil, persic oil, wheat germ oil, sasanqua oil, castor oil , Linseed oil, safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, kiri oil, jojoba oil, cacao butter, palm oil, horse oil, palm oil, palm kernel oil Animal and vegetable oils such as beef tallow, sheep fat, pork tallow, lanolin, whale wax, beeswax, carnauba wax, molasses, candelilla wax, squalane, and hardened oils thereof. Examples thereof include mineral oil such as liquid paraffin and petrolatum, and synthetic triglycerin such as glycerin tripalmitate. Preferably avocado oil, olive oil, sesame oil, camellia oil, evening primrose oil, turtle oil, macadamia nut oil, corn oil, mink oil, rapeseed oil, egg yolk oil, persic oil, wheat germ oil, southern oil, castor oil, flaxseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, and more preferably olive oil and soybean oil.

Examples of the “higher fatty acid” include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, stearic acid, behenic acid, 12-hydroxystearic acid, isostearic acid, Examples include undecic acid, tolic acid, eicosapentaenoic acid, docosahexaenoic acid, and the like. Preferred are lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, stearic acid and undecylenic acid, and more preferred are oleic acid, linoleic acid and undecylenic acid.

Examples of the “synthetic ester” include methyl caproate, methyl caprylate, methyl caprate, methyl laurate, methyl myristate, methyl palmitate, methyl oleate, methyl linoleate, methyl linolenate, methyl stearate, undecine. Methyl acid, ethyl caproate, ethyl caprylate, ethyl caprate, ethyl laurate, ethyl myristate, ethyl palmitate, ethyl oleate, ethyl linoleate, ethyl linolenate, ethyl stearate, ethyl undecinate, vinyl caproate , Vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl oleate, vinyl linoleate, vinyl linolenate, vinyl stearate, vinyl undecinate, cetyl octanoate , Octyldodecyl myristate, isopropyl myristate, myristyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, Oren'i acid decyl dimethyl octanoate, cetyl lactate, myristyl lactate, and the like. Preferred are methyl laurate, methyl myristate, methyl palmitate, methyl oleate, methyl linoleate, methyl linolenate, methyl stearate, methyl undecylate, more preferably methyl oleate, methyl linoleate, and methyl undecylate. .

Triacyl MEL can be produced by dissolving MEL in an organic solvent and reacting as described above. The organic solvent is not limited as long as it can solubilize MEL. What is necessary is just to be able to solubilize a part even if not all can be solubilized. The organic solvent may be a mixture of a plurality of organic solvents. Specifically, for example, methanol, ethanol, propanol, butanol, acetone, propanone, butanone, pentan-2-one, 1,2-ethanediol, 2,3-butanediol, dioxane, acetonitrile, 2-methyl-butane -2-ol, tertiary butanol, 2-methylpropanol, 4-hydroxy-2-methylpentanone, tetrahydrofuran, hexane, DMF, DMSO, pyridine, methyl ethyl ketone and the like. Acetone, tetrahydrofuran, tertiary butanol, acetonitrile and dioxane are preferable, and acetone is more preferable.

Examples of hydrolases include lipases, proteases, and esterases. It is preferable to use at least one selected from these, and a plurality of hydrolases may be used. Lipase and esterase are preferable, and lipase is more preferable.

Specifically, for example, MEL purified from the culture solution of MEL-producing microorganisms is dissolved in an organic solvent (for example, acetone), and commercially available lipase (for example, Novozyme 435 (manufactured by Novozymes) etc.) and vegetable oils and fats are dissolved therein. Added.

In the case of this production method, the reaction temperature is 10 to 100 ° C., preferably 20 to 50 ° C., more preferably 25 to 40 ° C., and stirring may be performed for 1 to 7 days. Further, molecular sieves may be added to the reaction solution. By this manufacturing method, MEL added as a material becomes a triacyl body almost quantitatively.

The purification of triacyl MEL can be performed according to the above-described purification of MEL.

(Method for producing MEL having saturated fatty acid side chain)
MEL having a saturated side chain can be produced in accordance with the above-described method for producing biosurfactant. At that time, as the fats and oils used as a raw material, it is carried out by adding one or more water-insoluble substrates such as olive oil, saturated fatty acids or esters thereof, hydrocarbons such as liquid paraffin and tetradecane. The MEL having a saturated side chain can be purified according to the above-described MEL purification.

(Manufacturing method of MAL such as MML)
The production of MAL having alditol other than erythritol, such as MML, can be carried out according to the above-described method for producing biosurfactant. In that case, as a raw material, it carries out by adding alditol, such as mannitol, arabitol, ribitol, sorbitol, alone or in combination. Purification of MAL having an alditol other than erythritol such as MML can be performed according to the above-described purification of MEL.

Component (C) The liquid oil having a melting point of 30 ° C. or lower includes horse oil, mink oil, egg yolk oil, lanolin, liver oil, squalene, squalane, soybean oil, olive oil, sunflower oil, safflower oil, jojoba oil, camellia oil, Animal and vegetable oils and their derivatives such as camellia oil and sesame oil; plant essential oils such as lavender oil, chamomile oil and eucalyptus oil; glyceryl mono-, di- or tri-oleate, glyceryl mono-, di- or tri-2-ethylhexanoate Monoacylglycerols such as glyceryl mono-, di- or tri-isostearate, diacylglycerols, triacylglycerols and their derivatives; fatty acids and alcohols such as isotridecyl isononanoate, isopropyl isostearate, octyldodecyl myristate, neopentyl glycol dicaprate, etc. Consist of Steal oil; ester oil composed of organic acid such as diisostearyl malate and octyldodecyl lactate and long chain alcohol; ether oil such as cetyl-1,3-dimethylbutyl ether and cetyl-2-ethylhexyl ether; hydrocarbon oil, petrolatum And mineral oils such as liquid paraffin; silicone oils such as dimethicone, cyclomethicone, alkyl-modified silicone and ethylene oxide-modified silicone; and fluorine oils such as fomblin. These components (C) can also be used in combination of two or more, and considering the application, dosage form, texture, etc., the content in the oil-in-water emulsion composition is 0.05 to 50%, particularly 0.1 to 30% is preferable.

Examples of the aqueous medium for component (D) include pure water, ion-exchanged water, alkaline ionized water, deep layer water, wave water, natural water, and the like; lower alcohols such as ethyl alcohol, propyl alcohol, and isopropyl alcohol; glycerin, 1, Examples thereof include polyhydric alcohols such as 3-butylene glycol, isoprene glycol and dipropylene glycol. In particular, it is preferable to use water from the viewpoints of economy, safety, and feel. The content of the component (D) is preferably 30% or more in consideration of the dosage form and the amount of other components.

The oil-in-water emulsion composition of the present invention may further contain component (E) an organic acid or a salt thereof. Specific examples include hydroxycarboxylic acids such as glycolic acid, lactic acid, malic acid, tartaric acid and citric acid; oxalic acid, malonic acid, succinic acid, adipic acid, glutaric acid, maleic acid, fumaric acid, citraconic acid, aconitic acid, etc. These are used in any form of acid form, neutralized salt, and mixtures thereof. The content of the oil-in-water emulsion composition of these organic acids or salts thereof is appropriately determined according to the product characteristics, but in order to develop sufficient pH adjusting ability, Excluding) is preferably 0.005% or more. The upper limit is preferably 5% or less for the acid type in consideration of crystal precipitation, skin irritation when used as a cosmetic.

The pH of the composition of the present invention is preferably 2 to 7 when used as a cosmetic from the viewpoint of no irritation to the skin.

The composition of the present invention may contain components such as alcohols, polyhydric alcohols, medicinal agents, antioxidants, preservatives, salts, amino acids, saccharides and the like used in normal cosmetics.

The oil-in-water emulsified composition of the present invention is characterized in that it is not an oil-in-water emulsified system as disclosed in JP-A-4-178315 but an oil-in-water type, and is a stable oil-in-water type. In order to form an emulsification system, a solid fat having a melting point of 30 ° C. or higher at a meltable temperature is dissolved in a liquid oil having a melting point of less than 30 ° C. and the component (A) is hydrophilic. The oil phase obtained by dissolving or dispersing the functional polyglycerin fatty acid ester and the component (D) aqueous medium are mixed at a temperature equal to or higher than the melting point of the mixture of the component (B) and the component (C). Is preferred.

The oil-in-water emulsified composition of the present invention thus obtained is a form in which solid fat and liquid oil are stably dispersed in an aqueous phase (aqueous medium), so that the skin care effect of solid fat is effectively exhibited. In addition, it is excellent in use feeling, particularly refreshing feeling, moist feeling, spread, familiarity, etc., and is useful as a cosmetic, particularly as a skin care cosmetic. When used as a cosmetic, it is preferably used as a milky lotion or cream.

Hereinafter, the present invention will be described in more detail based on examples. The present invention is not particularly limited to the examples.

(Production of MEL-A and triacyl MEL-A)
Inoculum culture was carried out by inoculating a seed medium (20 ml / 500 ml Sakaguchi flask) with 1 loop of Pseudozyma antarctica NBRC 10736 colonies. Cultured overnight at 30 ° C. The obtained culture broth was used as an inoculum. The seed medium composition was 4% Glucose, 0.3% NaNO ₃ , 0.02% MgSO ₄ .7H ₂ O, 0.02% KH ₂ PO ₄ , 0.1% yeast extract. The culture was performed by inoculating 75 ml of the above inoculum into 1.5 L (5 L-jar) of the production medium and using 5 L-jar under the conditions of 30 ° C., 300 rpm (stirring rotation), and 0.5 L / min (Air). The production medium composition was 3% soybean oil, 0.02% MgSO ₄ .7H ₂ O, 0.02% KH ₂ PO ₄ , 0.1% yeast extract. 250 ml of the culture solution was centrifuged (6500 rpm, 30 min), the supernatant was removed, and the precipitate (bacteria) was collected. 50 ml of ethyl acetate was added to the precipitate, and after sufficient stirring, the mixture was centrifuged (8500 rpm, 30 min), divided into a precipitate and a supernatant, and the supernatant was concentrated with an evaporator. Using silica gel, eluting with chloroform: acetone = 1: 0, chloroform: acetone = 9: 1, chloroform: acetone 1: 1, chloroform: acetone = 3: 7, chloroform: acetone = 0: 1, and MEL-A and A triacyl MEL-A fraction was obtained.

(Production of MEL-B and triacyl MEL-B)
0.2 ml of Pseudozyma tsukubaensis frozen stock was inoculated into a 20 ml YM medium / 500 ml Sakaguchi flask and cultured overnight at 26 ° C., 180 rpm, and used as an inoculum. 0.2 ml of the inoculum was again inoculated into a 20 ml YM seed medium / 500 ml Sakaguchi flask and cultured overnight at 26 ° C., 180 rpm, and used as an inoculum. 20 ml of the inoculum was inoculated into 2 L of YM medium / 5 L Jar and cultured at 26 ° C. and 300 rpm (1/4 VVM, 0.5 L air / min) for 8 days. The culture solution was centrifuged at 7,900 rpm for 60 min at 4 ° C. to separate the cells (including MEL-B) and the supernatant. 80 ml of ethyl acetate was added to each of the bacterial cell fractions, stirred up and down so that the bacterial cells were sufficiently suspended, and then centrifuged at 7,900 rpm for 30 minutes at 4 ° C. An equal amount of saturated saline was added to the obtained supernatant and stirred to obtain an ethyl acetate layer. An appropriate amount of anhydrous sodium sulfate was added to the ethyl acetate layer, and the mixture was allowed to settle for 30 minutes and then evaporated to obtain a crude MEL-B product. The obtained MEL-B crude purified product was eluted with hexane: acetone = 5: 1 and hexane: acetone = 1: 1 using a silica gel column to obtain MEL-B and triacyl MEL-B fraction purified products. .

(Production of MEL-C and triacyl MEL-C)
0.2 ml of Pseudozyma hubeiensis frozen stock was inoculated into a 20 ml YM seed medium / 500 ml Sakaguchi flask and cultured overnight at 26 ° C., 180 rpm, and used as a seed seed. 0.2 ml of the inoculum was again inoculated into a 20 ml YM seed medium / 500 ml Sakaguchi flask and cultured overnight at 26 ° C., 180 rpm, and used as an inoculum. 20 ml of the inoculum was inoculated into 2 L of YM medium / 5 L Jar and cultured at 26 ° C. and 300 rpm (1/4 VVM, 0.5 L air / min) for 8 days. The culture solution was centrifuged at 7,900 rpm for 60 minutes at 4 ° C. to separate the cells (including MEL-C) and the supernatant. 80 ml of ethyl acetate was added to each of the bacterial cell fractions, stirred up and down so that the bacterial cells were sufficiently suspended, and then centrifuged at 7,900 rpm for 30 minutes at 4 ° C. An equal amount of saturated saline was added to the obtained supernatant and stirred to obtain an ethyl acetate layer. An appropriate amount of anhydrous sodium sulfate was added to the ethyl acetate layer, and the mixture was allowed to settle for 30 minutes and then evaporated to obtain a crude MEL-B product. The obtained MEL-C crude product was eluted using a silica gel column with heptane: ethyl acetate = 1: 1, heptane: ethyl acetate = 1: 2, heptane: ethyl acetate = 1: 3, and MEL-C and A triacyl MEL-C fraction purified product was obtained.

(Manufacture of MEL using olive oil)
In the production of MEL in Example 1, soybean oil was used as a raw material for production, but instead, olive oil was used and cultured in the same manner as in Example 1 to isolate MEL-A, MEL-B, and MEL-C. Purify. The MEL fraction obtained at this time is referred to as MEL-A (OL), MEL-B (OL), and MEL-C (OL) in order to distinguish from the MEL of Example 1.

(Manufacturing Mannosyl Mannitol Lipid (MML))
Pseudozyma parantarctica JCM 11752 strain was cultured. That is, Pseudozyma parantarctica JCM 11752 stored in a storage medium (malt extract 3 g / L, yeast extract 3 g / L, peptone 5 g / L, glucose 10 g / L, agar 30 g / L). A test tube containing 2 mL of liquid medium having a composition of glucose 20 g / L, yeast extract 1 g / L, sodium nitrate 3 g / L, potassium dihydrogen phosphate 0.3 g / L, and magnesium sulfate 0.3 g / L 1 platinum ear was inoculated and shake-cultured at 30 ° C. for 1 day. Subsequently, the obtained cell culture broth was mixed with olive oil 50 g / L as vegetable oil, mannitol 100 g / L as sugar alcohol, yeast extract 1 g / L, sodium nitrate 3 g / L, potassium dihydrogen phosphate 0.3 g / Inoculated into a Sakaguchi flask containing 30 mL of a liquid medium having a composition of L and magnesium sulfate 0.3 g / L, and cultured at 34 ° C. for 7 days. Collect the above culture broth, extract mannosyl alditol lipid in the culture broth with ethyl acetate, purify by silica gel chromatography, analyze the structure of the product with ¹³ C-NMR and ¹ H-NMR, and confirm the structure did.

(Production of mannosyl arabitol lipid (MAraL))
MAraL was produced by culturing in the same manner as in Example 5 except that the culture of Example 5 was performed in a medium containing 100 g / L of arabitol as a sugar alcohol.

(Production of mannosyl sorbitol lipid (MSL))
MSL was produced by culturing in the same manner as in Example 5 except that the culture of Example 5 was carried out in a medium containing 100 g / L of sorbitol as a sugar alcohol.

(Production of mannosyl ribitol lipid (MRL))
MRL was produced by culturing in the same manner as in Example 5 except that the culture of Example 5 was performed in a medium containing 100 g / L of ribitol as a sugar alcohol.

(Preparation of oil-in-water emulsion composition)
The oil-in-water emulsion composition shown in Table 1 was prepared, and its storage stability was evaluated.

(Manufacturing method)
After 10, 11, and 14 were uniformly dissolved, 12 was added to adjust the pH to 4.5. After the temperature was raised to 80 ° C., 13 was uniformly dissolved to obtain an aqueous phase. 1 to 8 were uniformly dissolved and dispersed at 80 ° C. to obtain an oil phase. The oil phase and the aqueous phase were mixed at 80 ° C., 9 was added, and emulsification was performed using a homogenizer while maintaining the temperature at 80 ° C. It cooled to 25 degreeC, stirring, and was complete | finished.

(Evaluation methods)
The properties and physical properties of the samples when stored at 5 ° C. and 40 ° C. for 1 month were evaluated according to the following criteria. These results are also shown in Table 1.

(Evaluation criteria)
○ No change is observed △ Some change is observed × Clear change is observed (problem level in product characteristics)

The emulsion according to the present invention was excellent in stability with little change in properties and physical properties even after storage at 5 ° C. and 40 ° C. for 1 month, particularly without precipitation of crystalline substances.

 (Skincare emulsion 1)

The composition shown in Table 2 was used. After 11, 12, and 15 were mixed and uniformly dissolved, 13 was added to adjust the pH to 4.5. After the temperature was raised to 80 ° C., 14 was uniformly dissolved to obtain an aqueous phase. After 1 to 7 and 9 were uniformly dissolved at 80 ° C., 8 was dispersed to obtain an oil phase. The oil phase and the aqueous phase were mixed at 80 ° C. and emulsified using a homogenizer while maintaining at 75 ° C. While stirring, the mixture was cooled to 40 ° C., 10 was added thereto, and the mixture was further cooled to 25 ° C. to complete.

(Skincare emulsion 2)

The composition shown in Table 3 was used. After mixing and dissolving 11 to 13 and 17, 14 was added to adjust the pH to 5.5. After raising the temperature to 75 ° C., 16 was dissolved to obtain an aqueous phase. After dissolving 1 to 5 at 75 ° C., 8 and 9 were dispersed, and 6 and 7 were uniformly dissolved therein to obtain an oil phase. The oil phase and the aqueous phase were mixed at 70 ° C., 10 was added, and emulsification was performed using a homogenizer while maintaining the temperature at 70 ° C. While stirring, the mixture was cooled to 40 ° C., 15 was added thereto, and the mixture was further cooled to 25 ° C. to complete. This skin care cream was excellent in stability with little change in properties and physical properties even after storage at 5 ° C. and 40 ° C. for 1 month.

The oil-in-water emulsion composition of the present invention is an oil-in-water emulsion containing a solid fat and a liquid oil that is stably dispersed for a long period of time, and is particularly useful as a cosmetic. It is expected to make a significant contribution in the cosmetics industry.

Claims (10)

An oil-in-water emulsion composition comprising the following components (A), (B), (C) and (D):
(A) Hydrophilic polyglycerin fatty acid ester (B) Biosurfactant (C) Liquid oil having a melting point of less than 30 ° C. (D) Aqueous medium The oil-in-water emulsion composition according to claim 1, wherein the biosurfactant has a mannose skeleton. 3. The oil-in-water emulsion composition according to claim 2, wherein the biosurfactant has a sugar alcohol glycoside bonded to the hydroxyl group at the 1-position of the mannose skeleton. The biosurfactant having a mannose skeleton was selected from the group consisting of mannosyl erythritol lipid (MEL), mannosyl mannitol lipid (MML), mannosyl sorbitol lipid (MSL), mannosyl arabitol lipid (MAraL) and mannosyl ribitol lipid (MRL). The oil-in-water emulsion composition according to claim 2 or 3, wherein the composition is one or more compounds. MEL is mannosyl erythritol lipid A (MEL-A), mannosyl erythritol lipid B (MEL-B), mannosyl erythritol lipid C (MEL-C), mannosyl erythritol lipid D (MEL-D), a triacyl derivative of MEL-A, 5. The oil-in-water emulsion composition according to claim 4, wherein the composition is one or more compounds selected from the group consisting of a MEL-B triacyl, MEL-C triacyl, and MEL-D triacyl. object. The oil-in-water emulsion composition according to any one of claims 1 to 5, wherein the biosurfactant contains a saturated fatty acid and / or an unsaturated fatty acid. The oil-in-water emulsion composition according to any one of claims 1 to 6, wherein the component (A) is a polyglycerol mono fatty acid ester. Component (A), component (B), and component (D) form a thickening structure, The oil-in-water emulsion composition in any one of Claims 1-7 characterized by the above-mentioned. The oil-in-water emulsion composition according to any one of claims 1 to 8, further comprising (E) an organic acid or a salt thereof. Component (B) Biosurfactant is dissolved in component (C) liquid oil having a melting point of less than 30 ° C., and an oil phase obtained by dissolving or dispersing component (A) hydrophilic polyglycerin fatty acid ester into component (B) ) And a component (C) mixture at a temperature equal to or higher than the melting point of the component (D) aqueous medium.