JP2019141825A - Emulsion composition and use therefor - Google Patents

Abstract

To provide an emulsion composition that is made from natural components, has an excellent emulsifying function, and also has an additional function.SOLUTION: An emulsion composition is composed of a compound in which at least one hydroxy group constituting a flavonoid glycoside is alkyl-esterified.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an emulsified composition having an emulsifying function, and in particular, to an emulsified composition having a high emulsifying function derived from nature and its use.

  An emulsified composition is composed of a compound having both a lipophilic group and a hydrophilic group in the molecule, and is an important chemical additive that is widely required for various applications as an emulsifier.

  An example of an application where such an emulsified composition is required is cosmetics. Since cosmetics contain both a water-soluble component and an oily component as active ingredients, an emulsified composition is required in order to mix them uniformly.

  Furthermore, cosmetics are emphasizing not only the original effects of cosmetics, but also excellent spreadability when applied to the skin and less irritation to the skin, and are emulsified compositions with higher quality and superior usability. There is a high need for

  Emulsified compositions include those derived from petroleum, and higher fatty acid salts and alkyl sulfate esters are known. However, since these petroleum-derived products are highly irritating to the skin and easily cause rough skin, a mild emulsion composition with less irritation has been demanded. Therefore, an emulsified composition derived from a natural component, which is considered to have low irritation to the skin, is required.

  As conventional emulsified compositions, for example, those using plant-derived wax (for example, carnauba wax) as one component are known (for example, see Patent Document 1). Moreover, what uses naturally derived ceramide as one component is known (for example, refer patent document 2).

JP 2017-190292 A JP-A-2006-222600

  However, conventional emulsified compositions have a weak emulsifying function only with naturally-derived components, so that various active ingredients (additives) are blended in addition to naturally-derived components in order to obtain a sufficient emulsifying function. In addition, the effect of such additives on the skin cannot be ignored, and it remains highly irritating and easy to use.

  Further, in cosmetics, since emphasis is also placed on suppressing the amount of additives to suppress production costs, the emulsified composition used in cosmetics is itself sufficiently emulsified from the viewpoint of production costs. It is desired to exert its function. If the emulsified composition itself has not only a basic emulsifying function but also an additional function, it is considered that the amount of the additive contained in the cosmetic can be further suppressed. There is currently no excellent emulsion composition.

  The present invention has been made to solve the above-described problems, and provides an emulsified composition derived from natural components, having an excellent emulsifying function, and further having an additional function.

  The present inventors have found that an emulsified composition synthesized using a certain kind of natural raw material has an excellent emulsifying function and an additional function, and has led to a new type of emulsifying composition.

  Thus, according to the present invention, there is provided an emulsified composition comprising a compound in which at least one hydroxyl group constituting the flavonoid glycoside is alkylesterified. Also provided is a cosmetic composition comprising such an emulsified composition.

The emulsification function measurement result (immediately-after 6 hours) of the emulsion composition which concerns on Example 1 of this invention is shown. The measurement result of the antioxidant ability by the DPPH radical method of the emulsion composition which concerns on Example 1 of this invention is shown. The result (15 minutes later, 1 hour later) of the light absorbency measurement by the spectrophotometer of the emulsion composition which concerns on Example 1 of this invention is shown. ¹ H NMR chart (a) obtained from the emulsified composition according to Example 3 of the present invention, and results of measuring the emulsifying function of the emulsified composition (results of confirming phase separation after standing for 1 hour) (B) is shown. The result of the microscope picture (600 time) of the emulsion composition which concerns on Example 3 of this invention is shown. The measurement result of the antioxidant ability by the DPPH radical method of the emulsion composition which concerns on Example 3 of this invention is shown. The measurement result of the emulsification function of the emulsion composition which concerns on Example 4 of this invention is shown.

  The emulsified composition according to the embodiment of the present invention is composed of a compound in which at least one hydroxyl group constituting the flavonoid glycoside is alkylesterified.

  The emulsified composition has an emulsifying function, and indicates that two or more components exist uniformly as a whole and have a property of being grasped as one substance.

  A flavonoid glycoside is a compound in which a flavonoid (organic compound group having a flavan skeleton as a basic skeleton) and a sugar are bonded by a glycosidic bond, and is a naturally occurring organic compound group. In this respect, the emulsified composition according to this embodiment is naturally derived.

  As the flavonoid glycoside, for example, a flavone glycoside, a flavone glycoside, a flavonol glycoside, or a flavanone glycoside can be used, and preferably a quercetin glycoside or an isoquercetin glycoside. Body, rutin glycoside, naringenin glycoside, naringin glycoside, quercitrin glycoside, isoquercitrin glycoside, hyperin glycoside, myricetin glycoside, kaempferol glycoside, luteolin glycoside, Consists of Astragalin Glycoside, Myricitrin Glycoside, Chrysin Glycoside, Apigenin Glycoside, Apiin Glycoside, Eriodictitol Glycoside, Eriocitrin Glycoside, and Neoeriocitrin Glycoside To be selected from a group.

The emulsified composition according to the embodiment of the present invention can be represented by the following general formula (I).

  In the above formula, Fla represents an aglycone of a flavonoid glycoside, Sac represents a glycone of a flavonoid glycoside, and Z represents a straight chain which may be substituted with a substituent and may contain an unsaturated carbon. It is a chain or branched alkyl group, and the subscript k of OZCO is an integer of 1 or more.

  The OZCO group represents a functional group in which at least one hydroxyl group constituting the flavonoid glycoside is alkylesterified. The alkyl esterified hydroxyl group is not particularly limited as long as it is at least one hydroxyl group constituting a flavonoid glycoside. For example, the hydroxyl group constituting the aglycone of the flavonoid glycoside may be used, or the hydroxyl group constituting the glycone of the flavonoid glycoside may be used. It is sufficient that at least one of the hydroxyl groups is alkylesterified.

Therefore, the general formula (I) is also expressed as the following general formula (I ′).

  In the above formula, Fla, Sac, and Z are the same as defined in the general formula (I), and m and n are integers satisfying m + n ≧ 1, m ≧ 0, and n ≧ 0.

  Although carbon number of the alkyl group Z which comprises said OZCO group is not restrict | limited especially, Preferably it is C1-C30, More preferably, it is C8-C22 from the ease of use. The reason for this is that docosahexaenoic acid (carbon number 22) has the largest number of carbon atoms that are practically used, and a certain degree of fat solubility is required to develop an emulsifying function. This is because octanol is used as a standard for measuring fat solubility, and therefore, it preferably has 8 or more carbon atoms.

  More preferably, the carbon number of the alkyl group Z is 15 to 18 carbon atoms, and in this range of carbon number, oleic acid, linoleic acid, palmitic acid can be used as a raw material for the alkyl group used in the alkyl esterification. Therefore, naturally derived camellia oil or olive oil can be used as a raw material, and the safety, usability and reliability as an emulsified composition can be further enhanced.

As the emulsified composition according to the embodiment of the present invention, those represented by the following general formula (II) can be used for ease of use.

In the above formula, p is 0 or 1, q is 0 or 1, and R _{1 to} R ₅ are each independently represented by H, ZCO, or the following general formula (II-1) It represents a glycone of a flavonoid glycoside in which at least one hydroxyl group may be substituted with an alkyl group, and at least one of R _{1 to} R ₅ contains ZCO.

  In the above formula, Sac and Z are the same as defined in the general formula (I).

  Such an emulsified composition is not particularly limited, and for example, quercetin glycoside and naringenin glycoside can be used.

For example, when quercetin glycoside is used as one of the emulsified compositions, an emulsified composition represented by the following general formula (III) is shown.

In the above formula, R _{1 to} R ₄ and R _{11 to} R ₁₆ each independently represent H and ZCO, and at least one of them includes ZCO. Z is the same as defined in the general formula (I).

When using the quercetin glycoside, for example, as represented by the following general formula (III-1), only the hydroxyl group constituting the aglycone of the quercetin glycoside is alkylesterified, The hydroxy group constituting the glycone of the body may be an unsubstituted one that is not alkyl esterified.

In said formula, R < ₁ > -R < ₄ > is the same as the definition of the said general formula (III).

When the quercetin glycoside is used, for example, as represented by the following general formula (III-2), only the hydroxyl group constituting the glycone of the quercetin glycoside is alkylesterified, and quercetin As the hydroxyl group constituting the aglycone of the glycoside, an unsubstituted one that is not alkyl esterified can be used.

In said formula, R < ₁₁ > -R < ₁₆ > is the same as the definition of the said general formula (III).

  When using a quercetin glycoside, although it does not specifically limit, For example, it can extract from the skin of an onion. Since the onion skin is discarded as industrial waste in the onion processing process, it can be manufactured at low cost and is excellent from the viewpoint of resource reuse.

For example, when naringenin glycoside is used as one of the emulsion compositions, an emulsion composition represented by the following general formula (IV) is shown.

In the above formula, R _{1 to} R ₃ and R _{11 to} R ₁₆ each independently represent H or ZCO, and at least one of them includes ZCO. Z is the same as defined in the general formula (I).

In the case of using the above-mentioned naringenin glycoside, for example, as represented by the following general formula (IV-1), only the hydroxyl group constituting the aglycone of the naringenin glycoside is alkylesterified to form the naringenin glycoside. The hydroxy group constituting the glycone of the body may be an unsubstituted one that is not alkyl esterified.

In the above formula, R _{1 to} R ₃ are the same as defined in the general formula (IV).

When the above-mentioned naringenin glycoside is used, for example, as represented by the following general formula (IV-2), only the hydroxyl group constituting the glycone of the naringenin glycoside is alkylesterified, and naringenin As the hydroxyl group constituting the aglycone of the glycoside, an unsubstituted one that is not alkyl esterified can be used.

In the above formula, R _{11 to} R ₁₆ are the same as defined in the general formula (IV).

  Although it does not specifically limit as a raw material of a naringenin glycoside, For example, it can extract from the citrus peel. Citrus peels, like the onion shells described above, are generally discarded as non-edible parts, so that they can be produced at low cost and are excellent from the viewpoint of resource reuse. Although it does not specifically limit as a citrus, Grapefruit can be used, for example, Sagan ruby (registered trademark) which Saga University has registered as a variety can be used.

  The emulsified composition according to this embodiment can be synthesized by causing esterification using flavonoid glycoside and alkylcarboxylic acid as raw materials. For example, a quercetin derivative is used as a flavonoid glycoside, an oleic acid derivative is used as an alkyl carboxylic acid, and an aprotic solvent (for example, dioxane) is present in the presence of an amine (for example, triethylamine) at about 0 ° C. to room temperature. The synthesis can be performed in about 20 hours.

  That is, both the flavonoid glycoside and the alkyl carboxylic acid derivative, which are raw materials, are produced by extraction from naturally derived components. For example, rutin, a quercetin derivative, can be extracted from the onion skin. For example, naringin, a naringenin glycoside, can be extracted from citrus peel. As the alkylcarboxylic acid derivative, for example, derivatives such as oleic acid, linoleic acid, and palmitic acid can be used. For example, when oleic acid is used, it can be extracted from camellia and olives, both of which are known. (For example, Hyogo Prefectural Agriculture, Forestry and Fisheries Technology Center, Takuya Ogawa, Agricultural Research Institute for Agriculture and Food Industry, 2005 Kinki Chugoku Shikoku Agricultural Research Results Information, Food Distribution Promotion Subcommittee " (See “Development of Extraction Method for Quercetins from Onion Skin”).

  It has been confirmed that the novel emulsion composition thus obtained exhibits an excellent emulsifying action. In addition, it has been confirmed that it has an anti-oxidation effect and prevents ultraviolet rays by absorbing ultraviolet rays. Furthermore, after use of an emulsified composition such as after being applied to human skin, it has also been confirmed that it exhibits a safe and excellent resolution of being naturally decomposed into a naturally derived substance (see Examples below). . In addition, whitening action can be achieved by expressing tyrosinase inhibitory action.

  The emulsified composition thus obtained is composed of an alkyl esterified compound of a flavonoid glycoside, and such a compound has excellent emulsifying action and natural decomposition action. Having the action is not conventionally known, but is based on knowledge obtained for the first time by the inventors' diligent research.

  From such excellent properties, the emulsion composition according to the present embodiment can be used for various applications, but more preferably, it is used for cosmetics (cosmetic compositions) used by applying to human skin. In addition to being excellent in safety, excellent cosmetics (cosmetic compositions) having not only a high emulsifying action but also various additional functions can be obtained.

  In particular, the emulsified composition according to this embodiment has been confirmed to be 8% spontaneously decomposed in 30 minutes with an acid having a pH of 1 and decomposed under acidic conditions. Later, decomposition proceeds naturally. Furthermore, since resident bacteria exist in human skin and esterase (lipase) is also present, the emulsified composition of the present invention is also composed of an ester structure, so that it is degraded by lipase. That is, it can be naturally decomposed after application to human skin.

  Thus, the cosmetic composition comprised from the emulsion composition which concerns on this embodiment has the outstanding effect that it decomposes | disassembles naturally after apply | coating to human skin. Furthermore, after being naturally decomposed in this way, only natural substances such as oleic acid and flavonoid glycosides remain on the human skin, and there is no effect of irritation on the human skin. This is an excellent feature that cannot be obtained in the past because it can be enjoyed not only at the time of coating but also after coating.

  Examples are shown below, but these examples are merely illustrative and do not limit the present invention.

(Example 1)
As shown in the following synthesis scheme, a 100 mL two-necked eggplant flask is used as a reaction vessel, and quercetin derivative (rutin as a representative flavonoid contained in onion shell, obtained from Tokyo Chemical Industry Co., Ltd.) 1.5 mmol (916 mg) is used as a flavonoid glycoside. In addition, 10 mL of dioxane (obtained from Wako Pure Chemical Industries, Ltd.) and 5 mL of triethylamine (Nacalai Tesque) were used as alkyl carboxylic acids using 4.5 mmol (1.35 g) of oleic acid derivative (oleic acid chloride, obtained from Tokyo Chemical Industry Co., Ltd.). When it was stirred with a magnetic stirrer at 0 ° C. to room temperature for 20 hours in the presence, 1.859 g of a flavonoid glycoside ester as an emulsified composition (hereinafter sometimes referred to as an emulsifier) was obtained. The obtained flavonoid glycoside ester was confirmed by spectral data of ¹ H NMR and mass spectrometry, and the same result as the data described in Example 2 described later was obtained. It was confirmed to be a mixture.

(1) Measurement of emulsification function Oleic acid was selected as an oil component that could actually be used, and its function as an emulsifier was confirmed by visual observation. Experimental procedure: 5 mL of oleic acid and 0.5 mL of purified water were added to two sample tubes, and a red water-soluble colorant (Amaranth) was added and mixed well to improve visibility. Next, 80 mg of the emulsifier synthesized only on one side was added (each left side of FIGS. 1 (a) to (g)). In FIG. 1, each lower white layer represents an aqueous layer. From the obtained results, the person who added the emulsified composition of this example was not separated even after 6 hours.

(2) Measurement of antioxidant capacity by DPPH radical method
Preparation of DPPH (2,2-diphenyl-1-picrylhydrazy) in 100 μM in methanol and emulsification of this example composed of flavonoid glycoside ester obtained above using vitaminE as a positive control by colorimetric method The antioxidant ability of the composition (hereinafter also referred to as R / O emulsifier (rutin oleic acid emulsifier)) (crude) was measured. The state of colorimetric measurement by the obtained DPPH radical method is shown in FIG. In order from the left in FIG. 2, there were a negative control (without additives), a positive control vitaminE 100 μM, 50 μM, 25 μM, 12.5 μM, R / O emulsifier (crude) 250 μM, 125 μM, 62.5 μM.

The raw data obtained as a result of measuring the absorbance with a spectrophotometer (515 nm) is shown below, and the graph is shown in FIG.

The antioxidant ability of the obtained R / O emulsifier is shown in the following table.

  From the obtained results, it was revealed that the R / O emulsifier exhibits antioxidant ability. From the results of the VitaminE plot, the R / O emulsifier showed the antioxidant ability shown in the above table in terms of the antioxidant ability of VitaminE. In addition, compared with Vitamin E, the antioxidant ability of the R / O emulsifier was slow-acting, and the results of gradually removing radicals were observed. (Comparison between 15 minutes and 1 hour later) The thinner, the higher the antioxidant capacity in terms of VitaminE. As a control experiment, the antioxidant ability of oleic acid was measured, but DPPH radical was not removed at all.

(Example 2)
It is known that quercetin and quercetin glycoside can be extracted from the onion skin. Therefore, attention was paid to quercetin glycoside having high hydrophilicity. There are several types of quercetin glycosides at the position of saccharification, but the most inexpensive and easy-to-obtain rutin (the one in which rutinose is bound to the oxygen at position 3 of quercetin). As a model compound, the emulsifier according to this example was synthesized by oleic oxidation.

After separation by silica gel column chromatography, the components obtained were 4-substituted, 3-substituted, 2-substituted, and 1-substituted (2 types), respectively. The results of confirming each structure by NMR and mass spectrometry are shown below. NMR acquired the spectrum using the nuclear magnetic resonance apparatus (Agilent NMR System 400) with respect to the compound obtained above. HRMS: Using a Waters Premier Quadrupole Time-of-Flight (Q-TOF) mass spectrometer (Agilent-6624-TOF-LC / MS spectrometer) equipped with an electrospray ionization source operated in positive ion mode, High resolution mass spectra) data was created.

(4-substitution)

IUPAC name: 4- (5,7-bis (oleoyloxy) -4-oxo-3-(((2S, 3R, 4S, 5S, 6R) -3,4,5-trihydroxy-6-((((2R , 3R, 4R, 5R, 6S) -3,4,5-trihydroxy-6-methyltetrahydro-2H-pyran-2-yl) oxy) methyl) tetrahydro-2H-pyran-2-yl) oxy) -4H-chromen -2-yl) -1,2-phenylene dioleate, spectral data ¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (t, J = 7.3 Hz, 12H), 1.20-1.75 (m, 91H), 1.92-2.10 (m, 16H), 2.30-2.42 (m, 8H), 3.25-3.95 (m, 18H), 5.34 (brs, 8H), 6.51 (s, 1H), 6.81 (s, 1H), 7.27 (d, J = 9.2 Hz, 1H), 8.04 (s, 1H), 8.24 (d, J = 9.2 Hz, 1H)
Shape: yellow oil

(3 substitution products)

IUPAC name: 4- (5-hydroxy-7- (oleoyloxy) -4-oxo-3-(((2S, 3R, 4S, 5S, 6R) -3,4,5-trihydroxy-6-(((( 2R, 3R, 4R, 5R, 6S) -3,4,5-trihydroxy-6-methyltetrahydro-2H-pyran-2-yl) oxy) methyl) tetrahydro-2H-pyran-2-yl) oxy) -4H- chromen-2-yl) -1,2-phenylene dioleate, spectral data ¹ H NMR (400 MHz, CDCl ₃ ) δ 0.88 (t, J = 7.3 Hz, 9H), 1.20-1.75 (m, 69H), 1.92- 2.10 (m, 12H), 2.30-2.42 (m, 6H), 3.25-3.95 (m, 18H), 5.34 (brs, 6H), 6.50 (s, 1H), 6.81 (s, 1H), 7.29 (d, J = 9.2 Hz, 1H), 7.94 (s, 1H), 8.26 (d, J = 9.2 Hz, 1H), 11.87 (brs, 1H)
Mass spectrometry HRMS (ESI +) Calcd for C ₈₁ H ₁₂₇ O ₁₉ [M + H ⁺ ]: 1403.8972, Found: 1403.8947.
Shape: yellow oil

(2 substitutes)

IUPAC name: 4- (5,7-dihydroxy-4-oxo-3-(((2S, 3R, 4S, 5S, 6R) -3,4,5-trihydroxy-6-((((2R, 3R, 4R, 5R, 6S) -3,4,5-trihydroxy-6-methyltetrahydro-2H-pyran-2-yl) oxy) methyl) tetrahydro-2H-pyran-2-yl) oxy) -4H-chromen-2- yl) -1,2-phenylene dioleate, spectral data ¹ H NMR (400 MHz, CD ₃ OD) δ 0.90 (t, J = 7.3 Hz, 6H), 1.12 (d, J = 6.2 Hz, 3H), 1.26- 1.60 (m, 44H), 1.98-2.05 (m, 8H), 2.31 (t, J = 7.4 Hz, 4H), 3.25-3.80 (m, 18H), 5.34 (brs, 4H), 6.2 (d, J = 3.3 Hz, 1H), 6.40 (d, J = 3.3 Hz, 1H), 7.01 (d, J = 8.7 Hz, 1H), 7.88 (d, J = 2.2 Hz, 1H), 8.26 (dd, J = 8.7, 2.2 Hz, 1H).
Mass spectrometry HRMS (ESI +) Calcd for C ₆₃ H ₉₅ O ₁₈ [M + H ⁺ ]: 1139.6518, Found: 1139.6510.
Shape: yellow oil

(1 substitute A)

IUPAC name: 4- (5,7-dihydroxy-4-oxo-3-(((2S, 3R, 4S, 5S, 6R) -3,4,5-trihydroxy-6-((((2R, 3R, 4R, 5R, 6S) -3,4,5-trihydroxy-6-methyltetrahydro-2H-pyran-2-yl) oxy) methyl) tetrahydro-2H-pyran-2-yl) oxy) -4H-chromen-2- yl) -2-hydroxyphenyl oleate, spectral data ¹ H NMR (400 MHz, CD ₃ OD) δ 0.90 (t, J = 7.3 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H), 1.26-1.60 ( m, 22H), 1.98-2.05 (m, 4H), 2.31 (t, J = 7.4 Hz, 2H), 3.25-3.80 (m, 18H), 5.34 (brs, 2H), 6.2 (d, J = 3.3 Hz , 1H), 6.40 (d, J = 3.3 Hz, 1H), 6.87 (d, J = 8.5 Hz, 1H), 7.61 (dd, J = 8.5, 2.2 Hz, 1H), 7.65 (d, J = 2.2 Hz , 1H).
Mass spectrometry HRMS (ESI +) Calcd for C ₄₅ H ₆₃ O ₁₇ [M + H ⁺ ]: .875.4065, Found: 875.4059.
Shape: yellow oil

(1 substitute B)

IUPAC name: 5- (5,7-dihydroxy-4-oxo-3-(((2S, 3R, 4S, 5S, 6R) -3,4,5-trihydroxy-6-((((2R, 3R, 4R, 5R, 6S) -3,4,5-trihydroxy-6-methyltetrahydro-2H-pyran-2-yl) oxy) methyl) tetrahydro-2H-pyran-2-yl) oxy) -4H-chromen-2- yl) -2-hydroxyphenyl oleate, mass spectrometry HRMS (ESI +) Calcd for C ₄₅ H ₆₃ O ₁₇ [M + H ⁺ ]: .875.4065, Found: 875.4073.
Shape: yellow oil

(1) Measurement of antioxidant ability by DPPH radical method The antioxidant function of each substitution product was confirmed by DPPH assay in the same manner as in Example 1 above. The results obtained are shown in the table below. The emulsified composition of this example was prepared from a mixture of these 4-substituted product, 3-substituted product, 2-substituted product, and 1-substituted product (two types).

(Example 3)
Extraction was performed to obtain quercetin and its derivatives from onion rind.
Solvent: Methanol (100%) or ethanol (50%): 800 ml each, onion hull: 100 g each, extracted on a rotary shaker (150 rpm) for 60 h, after suction filtration, after flash column chromatography And concentrated on a rotary evaporator.

  The extract yield was methanol extract: 2.497 g (brown solid) and ethanol / water extract: 3.718 g (brown solid). Among them, the content of polyphenol was converted by DPPH assay. The methanol extract (1 g) was 0.34 g, and the ethanol / water extract (1 g) was 0.29 g (both equivalent to quercetin (QE)).

The obtained extract was synthesized into an emulsion composition according to the following synthesis example.

That is, methanol extract 1 g = 0.34 gQE (0.75 mmol) and oleic acid chloride 0.68 g (2.25 mmol) were reacted to obtain an emulsifier with a yield of 1.27 g. The resulting product was a brown solid. Also, 1 g (= 0.29 gQE) of ethanol / water extract was reacted with 0.56 g (1.95 mmol) of oleic acid chloride to obtain an emulsifier with a yield of 1.06 g. The resulting product was a brown solid. When ¹ H NMR was measured on the obtained product in the same manner as in Example 2, the NMR chart shown in FIG. 4A was obtained. From the obtained NMR chart, at least an oleic acid part, a sugar part, and a quercetin part were confirmed, and it was confirmed that various quercetin glycosides including rutin derived from onion hull were contained. That is, it was confirmed to contain a mixture of flavonoid glycoside esters derived from onion hulls. This indicates that the extract derived from onion husk is composed of a collection of various useful substances including various flavonoid glycoside esters. First of all, useful compounds derived from onion hulls exert mutually overlapping effects and complementary effects, and can exhibit many additional functions including an antioxidant function as well as an emulsifying function described later Is.

(1) Measurement of emulsification function Four sample bottles were prepared, and distilled water (1 ml) and oleic acid (1 ml) colored with amaranth dyes were added thereto. Then, in order from the left, blank, lecithin 50 mg, emulsifier (methanol extraction) 100 mg, and emulsifier (water / ethanol extraction) 100 mg were added. FIG. 4 (b) shows the result after stirring and stirring for 1 hour to confirm the phase separation.

In FIG.4 (b), the mode of emulsification (time-dependent change) of the emulsification composition (onion extraction emulsifier) of a present Example was confirmed with the comparative example as follows.
Left: Blank Middle left: Lecithin (50 mg)
Middle right: Emulsifier (methanol extraction) (100 mg)
Right: Emulsifier (water / ethanol extraction) (100 mg)

  From the obtained results, since layer separation was not confirmed even after 1 hour, it was confirmed that the emulsified composition of this example had a sufficient emulsifying function.

(2) Micrograph The onion hull-derived emulsifier (methanol extraction) 600 times photograph and the water / oleic acid two-layer system are shown in FIG. 5 (a). From FIG. 5 (a), it was confirmed that the typical micelle size was 4-5 μm, and it took the form of association of Water in Oil (W / O type).

  Moreover, an onion hull-derived emulsifier (water / ethanol extraction) 600 times photograph and a water / oleic acid two-layer system are shown in FIG. 5 (b). From FIG. 5 (b), it was confirmed that the typical micelle size is 30-40 μm and it takes the form of association of Water in Oil (W / O type).

(3) Measurement of antioxidant capacity by DPPH radical method
Antioxidant capacity was measured according to the following protocol using DPPH assay.
protocol
96-well plate solvent: methanol
DPPH final concentration: 100 μM
Vitamin E (VE) (positive control): 200 μM to 3.1 μM
Emulsifier (methanol extraction / ethanol extraction): 1.4 mg / L to 10.9 μg / L
After standing for 50 min, measure the absorbance with a microplate reader (492 nm) Each sample n = 3

A graph of the obtained results is shown in FIG. The half effect concentration EC ₅₀ calculated from this graph was as follows.
Vitamin E: 11.1μg / mL
Emulsifier (methanol extraction): 86.3 μg / mL
Emulsifier (ethanol / water extraction): 60.7 μg / mL
It was shown to have an antioxidant power of about 1/8 to 1/6 in terms of vitamin E.

  Note that the synthesis method is not limited to the above synthesis method, and other synthesis methods (for example, oleic oxidation with sulfuric acid or enzymatic synthesis method) are also possible.

(4) Measurement of stability Under acidic conditions (1N HCl), onion hull-derived 1 hydrolyzed 8% in 30 minutes and converted to rutin and oleic acid. Under basic conditions (1N NaOH), onion husk 1 was hydrolyzed 93% in 30 minutes and converted to rutin and oleic acid. It became clear that it was very easy to decompose compared to natural emulsifier lecithin. Moreover, even if it is decomposed, it is characterized by being converted into rutin and oleic acid which are natural ingredients and healthy ingredients.

Example 4
An emulsifier (naringin emulsifier) based on Sagan Ruby (registered trademark) disposal site was synthesized.
Background: Sagan Ruby (registered trademark) is a grapefruit variety that Saga University has registered for its variety, and is the first grapefruit in Japan. Among various features, Sagan Ruby (registered trademark) is characterized by a large amount of albedo (the inner skin, the white portion between the outer skin and the fruit). Albedo is bitter and not usually suitable for food and is discarded, but it is known to contain a lot of naringin. Naringin is a glycoside of a polyphenol having an antioxidant function, and an object thereof is to develop an emulsifier having an antioxidant function.

The olein oxidation reaction of naringin is represented by the following reaction formula, using a 100 mL 2-necked eggplant flask as a reaction vessel, and using naringin (obtained from Sigma-Aldrich) 1.5 mmol (0.968 mg) as a flavonoid glycoside, Using 4.5 mmol (1.86 ml) of oleic acid derivative (oleic acid chloride, obtained from Tokyo Chemical Industry Co., Ltd.) as the alkylcarboxylic acid, 10 mL of dioxane (obtained from Wako Pure Chemical Industries, Ltd.) and 5 mL of triethylamine (from Nacalai Tesque) Obtained) Stirring with a magnetic stirrer at 0 ° C. to room temperature for 20 hours in the presence gave 1.859 g of oleic oxidized naringin. A mixture with a substitution number of 1-4 was obtained. Preferentially, the aromatic OH group was olein oxidized. When the spectrum data of ¹ H NMR and mass spectrometry were confirmed with respect to the obtained product in the same manner as in Example 2, it was confirmed to be a mixture of flavonoid glycoside esters.

A mixture with a substitution number of 1-4 was obtained. Preferentially, the aromatic OH group was olein oxidized. Hereinafter, representative compounds identified among the compounds obtained as a result of the olein oxidation reaction of naringin from the obtained ¹ H NMR and mass spectral data are shown.

IUPAC name: 7-((4,5-dihydroxy-6- (hydroxymethyl) -3-((3,4,5-trihydroxy-6-methyltetrahydro-2H-pyran-2-yl) oxy) tetrahydro-2H-pyran -2-yl) oxy) -2- (4- (oleoyloxy) phenyl) -4-oxochroman-5-yl oleate, spectral data ¹ H NMR (400 MHz, CDCl ₃ ) δ 0.90 (t, J = 7.3 Hz, 6H), 1.12-1.80 (m, 47H), 1.98-2.05 (m, 8H), 2.28-2.40 (m, 6H), 3.30-4.40 (m, 18H), 4.85-5.13 (m, 1H), 5.34 ( brs, 4H), 6.13 (s, 1H), 6.53 (s, 1H), 7.14 (d, J = 8 Hz, 2H), 7.44 (d, J = 8 Hz, 2H).
Shape: yellow oil

IUPAC name: 4- (7-((4,5-dihydroxy-6- (hydroxymethyl) -3-((3,4,5-trihydroxy-6-methyltetrahydro-2H-pyran-2-yl) oxy) tetrahydro- 2H-pyran-2-yl) oxy) -5-hydroxy-4-oxochroman-2-yl) phenyl oleate, spectral data ¹ H NMR (400 MHz, CDCl ₃ ) δ 0.90 (t, J = 7.3 Hz, 3H) , 1.12-1.80 (m, 25H), 1.98-2.05 (m, 4H), 2.28-2.40 (m, 4H), 3.30-4.40 (m, 18H), 4.85-5.13 (m, 1H), 5.34 (brs, 2H), 6.13 (s, 1H), 6.33 (s, 1H), 7.14 (d, J = 8 Hz, 2H), 7.44 (d, J = 8 Hz, 2H), 11.91 (s, 1H).
Shape: yellow oil

(1) Measurement of emulsification function The results of an emulsification test of the obtained naringin emulsifier (crude) are shown in FIG. In FIG. 7, left: blank, middle: naringin emulsifier, right: lecithin. The emulsified composition according to this example was confirmed to have a high emulsification function equivalent to lecithin.

Claims (5)

An emulsified composition, wherein at least one hydroxyl group constituting the flavonoid glycoside is composed of an alkyl esterified compound. The emulsion composition according to claim 1,
The flavonoid glycoside is quercetin glycoside, isoquercetin glycoside, rutin glycoside, naringenin glycoside, naringin glycoside, quercitrin glycoside, isoquercitrin glycoside, hyperin glycoside, Myricetin glycoside, kaempferol glycoside, luteolin glycoside, astragalin glycoside, myricitrin glycoside, chrysin glycoside, apigenin glycoside, apiin glycoside, eriodictitol glycoside An emulsified composition selected from the group consisting of: eriocitrin glycoside, and neoeriocitrin glycoside. In the emulsion composition according to claim 1 or 2,
The emulsion composition, wherein the alkyl esterification is esterification with an alkyl group having 1 to 30 carbon atoms. In the emulsion composition according to any one of claims 1 to 3,
The emulsified composition, wherein the flavonoid glycoside is obtained from an onion skin or a citrus peel extract. A cosmetic composition comprising the emulsified composition according to any one of claims 1 to 4.