KR20120097385A - 3,5-dihydroxy-2-menthenyl stilbene, plant extract containing same, method for collecting same, and application for same - Google Patents

Abstract

Provided are 3,5-dihydroxy-2-mentenylstilbene, plant extracts comprising the same, antimicrobial agents, and methods for collecting the same and applications thereof. 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1), ginger plant extract containing 1% by mass or more thereof, applications such as antimicrobial agents containing the active ingredient, and ginger plant Method of collecting the active ingredient. A mixture consisting of a substance of formula (1) and 3,5-dihydroxystilbene of formula (2), an extract of ginger plant containing 1% by mass or more thereof, and an odor producing inhibitor including the same as an active ingredient.

Description

3,5-dihydroxy-2-mentenylstilbene, plant extracts containing the same, and methods for collecting the same and its application {3,5-DIHYDROXY-2-MENTHENYL STILBENE, PLANT EXTRACT CONTAINING SAME, METHOD FOR COLLECTING SAME, AND APPLICATION FOR SAME}

The present invention provides a novel 3,5-dihydroxy-2-mentenylstilbene, a plant extract containing the same, an application of an antimicrobial agent and the like, and a method for collecting an active ingredient of a genus lindera plant. . Moreover, this invention relates to the application of the mixture which consists of 3, 5- dihydroxy- 2-mentenyl stilbene and 3, 5- dihydroxy stilbene, an odor production inhibitor containing the same, etc.

The proliferation of microorganisms such as bacteria causes unfavorable conditions for living organisms and the environment, such as causing disease and expanding pollution, and conventionally, antimicrobial agents and bactericides have been used in various fields for the purpose of improving them. In recent years, substances derived from natural products have been attracting attention due to problems such as load on the environment, but in the current state, there is little that is better than synthetic fungicides in terms of efficacy. For this reason, it is desired to develop an antimicrobial agent having high effectiveness derived from natural products.

It is known that the camphor family belonging to the genus Ginger has a lot of essential oil components, and cinnamon, laurel and the like contain essential oils having antibacterial properties. Ginger tree also contains a lot of essential oils rich in fragrance, the essential oil is used as cosmetic oil, cosmetics, soap, eggplant toothpicks and the like. Further, as a technique to be blended into an oral composition, an oral humectant comprising an oral composition (Patent Document 1) containing an organic solvent extract of a plant containing an ancestor, and an essential oil extracted from an ancestor tree (patent document) 2) is proposed.

That is, in Patent Document 1, it is described that the hibiscus extract inhibits the formation of plaque by inhibiting glucosyltransferase of Streptococcus mutans. It is described that the denture candidiasis is improved. As described above, the antibacterial and antifungal action of the gingko tree is known from the prior art. In addition, as a technique which described the antimicrobial effect of an ancestor tree, an anti-helicobacter Philolyze (patent document 3) and an anti-influenza virus agent (patent document 4) are mentioned.

In addition to antimicrobial activity, cosmetics for preventing acne, rough skin and dandruff (Patent Document 5), external preparations for inhibiting melanin production (Patent Document 6), ultraviolet absorbers (Patent Document 7), and protease inhibitors (Patent Document 8). ), And various functions of ancestor trees have begun.

The extraction method of these hollyhock components can be generally divided into the technique (patent document 2) using the essential oil component obtained by the technique of vacuum-concentrating after extraction of an organic solvent (patent document 1, 3-8), steam distillation, etc.

However, the organic solvent extract usually has a dark brown color, and when blended with a formulation or the like, there is a problem that not only coloration but also discoloration occurs with time. In addition, although it is also possible to fractionate a component by chromatography etc. and fractionate the fraction excellent in coloring discoloration, the detailed fractionation method is still not proposed.

Moreover, although there are reports of flavonoids, chalcones and alkaloids (non-patent documents 1 to 3) as components in the gingko tree, it is the present state that their functions are not sufficiently explained.

Patent Document 1: Japanese Patent Application Laid-Open No. 57-58610 Patent Document 2: Japanese Patent Application Laid-Open No. 2008-036343 Patent Document 3: Japanese Patent Application Laid-Open No. 11-1429 Patent Document 4: Japanese Patent Application Laid-Open No. 2004-59463 Patent Document 5: Japanese Patent Application Laid-Open No. 62-238207 Patent Document 6: Japanese Patent Application Laid-Open No. 7-277941 Patent Document 7: Japanese Patent Application Laid-Open No. 7-285841 Patent Document 8: Japanese Patent Application Laid-Open No. 2001-122728

Non Patent Literature 1: Chem. Pharm. Bull 37 (4) 944-947 (1989) Non-Patent Document 2: Phytochemistry 27 (12) 3937-3939 (1988) Non-Patent Document 3: Pharmaceutical Magazine 89 (5) 737-740 (1969)

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors fractionate and refine | extract the extract extracted with the hydrophilic solvent from the bark of LINDERA UMBELLATA, and suppresses high antimicrobial activity and odor production. It was confirmed that the activity could be obtained, and further, fractionation and purification were carried out, whereby the active body was 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1) and the following structural formula (2 It was specified that it is 3,5-dihydroxystilbene represented by). In addition, it was confirmed that by increasing the content of these active bodies, i.e., removing impurities, it is possible to provide an extract of the ginger tree plant which is also excellent in storage stability.

It is clear by the present inventors that 3,5-dihydroxy-2-mentenyl stilbene according to the present invention is a novel compound which has not been reported so far, which has high antibacterial and bactericidal activity against a wide range of bacterial species. Done In addition, 3,5-dihydroxystilbene inhibits the production of volatile fatty acids, odorous substances such as methyl mercaptan, hydrogen sulfide, and the like by inhibiting branched amino acid aminotransferase and methionine γase, which are bacterial metabolizing enzymes. It was made by the present inventors, and it became clear that the effect is remarkably improved by using together with 3,5-dihydroxy-2-mentenyl stilbene. Therefore, it was confirmed that these active ingredients are effective as active ingredients of an antimicrobial agent and a malodor producing inhibitor.

These compounds are components that are hardly included in essential oil components obtained by steam distillation or the like of the plants known in the art, and are extracted with an organic solvent or a hydrous organic solvent, particularly a hydrophilic organic solvent such as ethanol at an appropriate concentration described later. It became clear. In addition, in the case of extracting only the hydrophilic solvent extract from the hydrophilic solvent, there is not enough content to express the activity of these compounds, and when the amount of extract of the extract of the extract is blended with the formulation, the color of the formulation is changed, as well as discoloration. It became clear that the problem of formulation stability, such as these, may arise. The present inventors conducted further studies for the purpose of solving these problems. As a result, the extracts were further fractionated and purified by partition extraction with a solvent, or by combining various chromatographs. By increasing the contents of dihydroxy-2-mentenyl stilbene and 3,5-dihydroxystilbene, it is possible to express a sufficient effect and to obtain an extract of Gingko plant excellent in formulation stability.

Therefore, this invention provides the following matters.

Claim 1: 3, 5- dihydroxy- 2-mentenyl stilbene represented by following structural formula (1).

Claim 2: LINDERA UMBELLATA or its subspecies whose content of 3,5-dihydroxy-2-mentenyl stilbene represented by following structural formula (1) is 1 mass% or more of solid content Extract from iii).

3: An antimicrobial agent comprising 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) as an active ingredient.

Claim 4: An extract from LINDERA UMBELLATA or its subspecies of a Ginger plant containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) at least 1% by mass of solids: Antimicrobial agent.

5: The composition for oral cavity containing 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1).

Claim 6: Extract from the Lingera umbellata or its subspecies of a Ginger plant containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) at least 1% by mass of solids: Oral composition containing a.

Claim | item 7: The cosmetics for skin or hair containing 3, 5- dihydroxy- 2-mentenyl stilbene represented by following structural formula (1).

Claim 8: Extract from LINDERA UMBELLATA or its subspecies of the Ginger plant containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1): 1 mass% or more of solid content Cosmetics for skin or hair containing the.

9. The cleaning composition containing 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1).

Claim 10: An extract from Lingera umbellata or its subspecies of a Ginger plant containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) at least 1% by mass of solids: Cleaning composition containing a.

Claim 11: The food-drinks containing 3, 5- dihydroxy- 2-mentenyl stilbene represented by following formula (1).

12. An extract from LINDERA UMBELLATA or subspecies of a Ginger plant containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1): 1 mass% or more of solid content Food and drink containing the.

13. A mixture comprising 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) and 3,5-dihydroxystilbene represented by the following structural formula (2).

Claim 14: 3,5-di represented by the following structural formula (2) while containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) at least 1 mass% of solid content An extract from LINDERA UMBELLATA or its subspecies of a Ginger plant containing 1% by mass or more of hydroxystilbene.

15. An extract from Lingera umbellata or its subspecies of a Gingko plant, containing 1,% by mass or more of 3,5-dihydroxystilbene represented by the following structural formula (2).

16. An odor producing inhibitor comprising the mixture of claim 13 as an active ingredient.

17. Odor production inhibitor comprising the extract of claim 14 or 15.

18. An oral composition comprising the mixture of claim 13.

19. A composition for oral cavity containing the extract of claim 14 or 15.

20. A cosmetic for skin or hair containing the mixture of claim 13.

21. A cosmetic for skin or hair containing the extract of claim 14 or 15.

22. A cleaning composition comprising the mixture of claim 13.

23. A cleaning composition comprising the extract of claim 14 or 15.

24: A food and drink containing a mixture according to claim 13.

25. A food or drink containing the extract of claim 14 or 15.

26. A solution in which a ginger plant is extracted with an aqueous 40-100% by mass ethanol solution, the extract is concentrated under reduced pressure at 50 占 폚 or lower, and the alcohol concentration is adjusted to 10-30% (V / V). Adsorbed to a spherical crosslinked polymer having, removed the fraction eluted with less than 40% by mass of ethanol aqueous solution, followed by elution to 40 to 70% by mass ethanol aqueous solution, and / Alternatively, the elution treatment is carried out to an excess of 70% by mass to 100% by mass of ethanol, and 3,5-dihydroxystilbene is collected from the elution by 40% by mass to 70% by mass of ethanol, and / or 70 A 3,5-dihydroxy-2-mentenyl stilbene is collected from an eluate with an aqueous solution of excess to 100% by mass of ethanol.

27. A carrier in which an eluate with an aqueous 40 to 70 mass% ethanol solution was concentrated under reduced pressure at 50 占 폚 or lower, and the concentrated extract was chemically bonded to an octadecyl group on a totally porous spherical or crushed silica gel. The collecting method according to claim 26, which is adsorbed on (iii) and eluted with 50 to 80 mass% methanol aqueous solution to obtain 3,5-dihydroxystilbene.

28: The eluate with an aqueous solution exceeding 70 to 100% by mass of ethanol was developed by silica gel chromatography, and the ratio of the mixture of n-hexane and acetone (V / V) 18: 1 to the final fraction of 8: 1 was used. The extraction method of Claim 26 which collects the eluted fraction between the eluted fractions to obtain 3,5-dihydroxy-2-mentenyl stilbene.

29. A ginger plant is extracted with an aqueous 40-100% by mass ethanol solution, the extract is extracted again with an aqueous 20-40% by mass ethanol solution, the insoluble portion is collected, followed by an excess of 40-100% by mass ethanol aqueous solution. A method for producing a mixture of 3,5-dihydroxy-2-mentenyl stilbene and 3,5-dihydroxystilbene, characterized by extracting and extracting the soluble portion thereof.

30. The solution in which the soluble portion is concentrated under reduced pressure at 50 ° C. or lower and the alcohol concentration is adjusted to 10 to 30% (V / V) is adsorbed with a spherical crosslinked polymer having a porous structure, followed by 70% by mass. The elution process is performed with the above ethanol aqueous solution or ethanol, and the eluent is extract | collected, The manufacturing method of Claim 29 characterized by the above-mentioned.

31. A ginger plant is extracted using a mixture of carbon dioxide in a supercritical state with an aqueous 2 to 10% by mass ethanol solution, the soluble part of which is extracted, and 3,5-dihydroxy-2. -Method for collecting active ingredient of Ginger plant, characterized by obtaining mentenylstilbene and / or 3,5-dihydroxystilbene.

32. A ginger plant is extracted with an aqueous 40-100 mass% ethanol solution, and the extract is extracted using a mixture of carbon dioxide in a supercritical state with an aqueous 2-10 mass% ethanol solution, and the extract is collected. And 3,5-dihydroxy-2-mentenylstilbene and / or 3,5-dihydroxystilbene.

According to the antimicrobial agent and malodor production inhibitor of the present invention, the effect of preventing various infectious diseases caused by microorganisms and the malodor production derived from microorganisms can be expected. In other words, in the intraoral region, the present invention not only provides a means for preventing and treating caries and periodontal disease, a prophylactic and therapeutic means for purulent diseases, etc. in the skin region, and also provides an effective preventive and therapeutic means for bacterial infections outside the oral and dermatological fields. In addition, antiseptic effect can also be expected by blending in various products. In addition, it is possible to provide effective means for producing malodors, such as suppressing body odors such as bad breath caused by microorganisms, liquid odors, and foot odors, washing clothes, suppressing damp odors of clothing, and decaying odors of food waste.

Since the antimicrobial agent and odor producing inhibitor of the present invention are derived from a naturally occurring ginger plant, and do not put a load on the human body, animals, or the environment, it is applicable to various foods, beverages, pharmaceuticals, quasi-drugs, cosmetics, and sundries. It is possible to expect that it is possible and can contribute not only to the improvement of the health of the people but also to a pleasant life.

According to the production or harvesting method of the present invention, it is possible to industrially advantageously obtain a ginger plant extract that can be blended into the formulations and compositions.

1 is a flow chart of the fraction-purification method of the biloba extract.
FIG. 2 is a diagram showing a ¹ H-NMR (500 MHz, heavy methanol) spectrum of Preparation Example 7. FIG.
3 shows a ¹³ C-NMR (125 MHz, biethanol) spectrum of Preparation Example 7. FIG.
4 is a diagram showing an ESIMS (neg) spectrum of Preparation Example 7. FIG.
5 is a diagram showing an EIMS (pos, TMS derivative) spectrum of Preparation Example 7. FIG.
FIG. 6 is a diagram showing a UV spectrum of Preparation Example 7. FIG.
7 is a diagram showing an IR spectrum of Preparation Example 7. FIG.
FIG. 8 is a diagram showing a ¹ H-NMR (500 MHz, ethanol) spectrum of Preparation Example 6. FIG.
9 is a diagram showing a ¹³ C-NMR (125 MHz, ethanol) spectrum of Preparation Example 6. FIG.
10 is a diagram showing an ESIMS (neg) spectrum of Preparation Example 6. FIG.
11 is a diagram showing an EIMS (pos, TMS derivative) spectrum of Preparation Example 6. FIG.
12 is a diagram showing a UV spectrum of Preparation Example 6. FIG.
13 is a diagram showing an IR spectrum of Preparation Example 6. FIG.
Fig. 14 is a flow chart for extracting the ivy extract from oyster trees.
Fig. 15 is a flow chart of supercritical extraction of bilberry extract from biloba.

Hereinafter, the present invention will be described in more detail.

3,5-dihydroxy-2-mentenylstilbene of this invention is a novel substance, and is represented by following structural formula (1). The antimicrobial agent of the present invention contains 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) as an active ingredient. In addition, the malodor production inhibitor of the present invention is 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1), and 3,5-dihydroxy steel represented by the following structural formula (2) Ben is an active ingredient. These active ingredients are the active ingredients obtainable by solvent extraction from Gingerbread plants, especially LINDERA UMBELLATA or its subspecies. As these active ingredients, the active ingredient may be used as it is, but an extract of a ginger tree plant containing the active ingredient in a high concentration may be used. As an extract of the Gingko plant which contains a high concentration of an active ingredient, 3,5-dihydroxy-2-mentenyl stilbene of the formula (1) which is an active ingredient especially, or 3,5-dihydride of the formula (1) Gingko plant extract having a content of oxy-2-mentenyl stilbene and 3,5-dihydroxystilbene of formula (2) of 1% by mass or more, particularly 3% by mass or more of solid content is preferable, and is effective for various formulations. Can be combined.

In the present invention, the ginger-tree plant is extracted with 40-100 mass%, preferably 60-90 mass% ethanol aqueous solution, the extract is concentrated under reduced pressure at 50 ° C. or lower, and the alcohol concentration is 10-30% (V / V). The solution adjusted to the above) is adsorbed onto a spherical crosslinked polymer having a porous structure, for example, styrenedivinylbenzene-based synthetic resin, specifically, Dion HP-20 manufactured by Mitsubishi Chemical Co., Ltd., and is less than 40% by mass. Preferably, the fraction eluted with less than 30 mass% ethanol aqueous solution is removed, followed by an elution treatment with 40 to 70 mass%, preferably 50 to 70 mass% ethanol aqueous solution, and / or greater than 70 to 100 mass 3,5-dihydroxystilbene from the eluate with%, preferably 70-90 mass% ethanol aqueous solution, 40-70 mass%, preferably 50-70 mass% ethanol aqueous solution Harvesting And / or, by collecting 3,5-dihydroxy-2-mentenylstilbene from the eluate with an aqueous solution of greater than 70 to 100% by mass, preferably greater than 70 to 90% by mass of ethanol The active ingredient of can be collected.

In this case, the eluate with 40-70 mass%, preferably 50-70 mass% ethanol aqueous solution is concentrated under reduced pressure at 50 degrees C or less, and the concentrated extract is made into chemically octadecyl group on all-porous spherical or crushed silica gel. Adsorbed to a bonded carrier, for example, Cosmosil 75C18-OPN manufactured by Nakaraitesuk Co., Ltd., eluted with 50-80% by mass aqueous methanol solution, developed into three fractions, the central fraction was collected, and 3,5 It is preferable to obtain dihydroxystilbene.

In this case, the eluate from 70% to 100% by mass, preferably 70% to 90% by mass of ethanol aqueous solution, is developed by silica gel chromatography, and the mixing ratio of n-hexane and acetone (V / V) 18: 1 It is preferable to extract an eluting fraction between the eluting fraction by the eluting fraction by 8: 1 volume ratio, and to obtain 3, 5- dihydroxy- 2-mentenyl stilbene.

Furthermore, in the present invention, the ginger-tree plant is extracted with 40-100 mass%, preferably 60-90 mass% ethanol aqueous solution, the extract is further extracted with 20-40 mass% ethanol aqueous solution, and the insoluble part is extract | collected, 3,5-dihydroxy-2-mentenylstilbene and 3,5- by extracting with an aqueous solution of more than 40% to 100% by mass, preferably more than 40% to 60% by mass of ethanol and extracting the soluble part thereof. Mixtures with dihydroxystilbene can be prepared.

In this case, the soluble portion is concentrated under reduced pressure at 50 ° C. or lower, and the solution in which the alcohol concentration is adjusted to 10 to 30% (V / V) is adsorbed with a spherical crosslinked polymer having a porous structure, followed by 70% by mass. As mentioned above, it is preferable to perform an elution process with 90 mass% or more ethanol aqueous solution or ethanol, and to collect the eluent. In addition, as a spherical crosslinked polymer which has a porous structure, the thing similar to the above can be used.

Here, the ginger plant can use the whole plant as a raw material, but a part thereof (branch, stem, root, shoot, leaf, flower, fruit) (果實) etc.) can also be used. It is particularly preferable to use branches, stems, and roots in view of the yield of the target compound. In addition, the plant of origin may be a plant belonging to the genus Ginger. Specifically, Okinawa kobasashi (Lindera communis var. Okinawensis), birch (Lindera erythrocarpa), persimmon (Lindera glauca), ginger (Lindera obtusiloba), ura (Lindera obtusiloba f. Villosa) , Lindera sericea, Linus sericea var.glabrata, Tendai-yaku (Lindera strychnifolia), Elder tree (Lindera umbellata), Kiminooba Lina umbellata var.aurantiaca, Lime umbellata var.lancea, Lina umbellata var.membranacea, Aojiji (Lindera citriodora) ), Oil tree (Lindera praecox), Hosoba oil tree (Paraben oin praecox f. Angustifolium), Kera oil tree (Lindera praecox var. Pubescens), Shiromoji (白 文字) , Marubashiromoji (Paraben oin trilobum f. Integrum), Keshiromoji (毛白文 字), Paraben oin trilobum f. Pilo sum, etc. can be used appropriately, but in particular, the larva (Lindera umbellata) and its subspecies (Lindera umbellata var. aurantiaca) and Hime (姬) lyca (ghkdtldfLindera umbellata var.lancea) and ova lyca (Lindera umbellata var.membranacea) can be used more suitably.

Although the dried tree species plant which becomes these raw materials is preferable in a dry state, it can be used even if it is a wet state.

Extraction from the Ginger plant may include lower alcohols, polyhydric alcohols such as glycerin and propylene glycol, saturated hydrocarbons such as pentane, hexane and heptane, ethyl acetate, acetone, petroleum ether, acidic solutions and alkaline solutions. It can be performed individually or using what mixed 2 or more types. Among these, it can extract efficiently with an organic solvent, and especially a hydrophilic organic solvent is excellent from a viewpoint of extraction efficiency. In particular, lower alcohols having 1 to 4 carbon atoms, that is, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, t-butanol, or a mixture thereof can be more preferably used. Moreover, it is more preferable that these water-soluble organic solvents are water-containing organic solvents, and especially since extraction with the water-containing alcohol of 30-95 mass% concentration can extract a target component more efficiently, it is most preferable.

About 1-50 times is preferable by mass ratio with respect to an extraction raw material, and, as for these extraction solvent, it is especially preferable to use 2-20 times normally.

An extract can remove solid matter by filtration, centrifugation, etc., and can concentrate, and can obtain crude extract fraction. This crude extract fraction also contains 3,5-dihydroxy-2-mentenylstilbene and 3,5-dihydroxystilbene, which are active substances, so the crude extract fraction may be added to the composition as it is. From the viewpoint of securing the stability of the composition, it is preferable to use further fractionated and purified products.

In this case, fractionation and purification can be performed by combining partition extraction with a solvent and various chromatography. In consideration of the molecular weight and physicochemical properties of the target substance, the conditions for the carrier and the elution solvent can appropriately select a method corresponding to various chromatography.

In addition, in order to change the amount ratio of the antimicrobial agent and malodor production inhibitor in the extract according to the purpose of use, these two active ingredients, 3,5-dihydroxy-2-mentenylstilbene and 3,5- The method of fractionating dihydroxystilbene can be performed according to the following method, for example.

That is, as a 1st method, the method containing the adsorption process and the elution process by an adsorbent, ie, extracting the bark of crushed lumber with hydrophilic organic solvents, such as hydrous ethanol, removes solids with a glass filter, The concentrated crude extract was subjected to adsorption column chromatography using a spherical cross-linked polymer having a porous structure such as activated carbon or Dion HP-20 (Mitsubishi Chemical Co., Ltd.) as a carrier, and the target component was adsorbed. Fractionation may be carried out by eluting sequentially with an eluting solvent such as hydrous ethanol or ethanol. In this case, 3,5-dihydroxystilbene is largely eluted with a highly polar solvent, for example, about 30 to 60 mass% ethanol (hereinafter referred to as elution portion (A)), 3,5 Since dihydroxy-2-mentenyl stilbene is eluted a lot (hereinafter, referred to as elution section B) by a solvent having a lower polarity, for example, about 60 to 90 mass% ethanol, these 2 The active substance of the species can be separated. After separation, decolorization can be carried out with acidic clay, diatomaceous earth or the like.

By carrying out such a process, 3,5-dihydroxy-2-mentenyl stilbene and 3,5-dihydroxystilbene are 1 mass% or more, especially 5 mass% or more of extract solid content, respectively, What contains 7 mass% or more and 20 mass% or less can be prepared, and this can be used as an extract of the ginger tree plant which contains the active ingredient of Formula (1) and / or Formula (2) in high concentration.

The eluting unit (A) and the eluting unit (B) are further subjected to reverse phase chromatography using an ODS carrier (carrier to which the octadecylsilyl group is chemically bonded) and to normal phase chromatography using a silica gel carrier. The desired component can be purified.

Moreover, in addition to the manufacturing method including the adsorption process and elution process by the said adsorbent described as a 1st method, as a 2nd method, the supercritical extraction method by contacting with carbon dioxide in a supercritical state is also effective. From the standpoint of stability and stability, it can be suitably employed as a method of obtaining an extract of the preferred ginger plant. In this case, the desired component can be extracted by supercritical extraction of the pulverized product of the ginger tree plant with an organic solvent such as ethanol, for example, and the extract prepared by the adsorption step and the elution step is again extracted. Critical extraction is also possible, and at this time, the extract may be dispersed and adsorbed onto cellulose powder or the like for the purpose of decolorization before supercritical extraction.

That is, in the present invention, by extracting a ginger plant using a mixture of carbon dioxide in a supercritical state and an aqueous 2 to 10% by mass ethanol solution, extracting the soluble part and collecting the active ingredient of the ginger tree plant , 3,5-dihydroxy-2-mentenylstilbene and / or 3,5-dihydroxystilbene can also be obtained.

In addition, the ginger-tree plant is extracted with 40-100 mass%, preferably 60-90 mass% ethanol aqueous solution, and the extract is prepared using a mixture of carbon dioxide in a supercritical state and an aqueous 2-10 mass% ethanol aqueous solution. It is also possible to obtain 3,5-dihydroxy-2-mentenyl stilbene and / or 3,5-dihydroxystilbene by extracting and extracting the extract and collecting the active ingredient of the ginger plant. .

In addition, although the conditions of supercritical extraction are not specifically limited, It is preferable to extract on conditions of the temperature of 40-80 degreeC, the pressure of 15-45 Mpa, and extraction time of 1 to 6 hours.

By performing such a supercritical extraction process, a mixture of 3,5-dihydroxy-2-mentenyl stilbene and 3,5-dihydroxystilbene can usually be obtained. By adjusting, 3,5-dihydroxy-2-mentenyl stilbene or 3,5-dihydroxystilbene can also be obtained independently. If necessary, 3,5-dihydroxy-2-mentenyl stilbene or 3,5-dihydroxystilbene can also be isolated from the obtained mixture. In this case, 3,5-dihydroxy-2-mentenyl stilbene and 3,5-dihydroxystilbene, as a mixture thereof or alone, are at least 1% by mass, particularly 3% by mass, of the extract solids, respectively. What is contained 20 mass% or more can be prepared, and this can be used as a ginger tree plant extract containing the active ingredient of Formula (1) and / or Formula (2) in high concentration.

It is evident that the 3,5-dihydroxy-2-mentenyl stilbene or the extract of Ginger plant containing it at a high concentration represented by the formula (1) thus obtained has an extremely high antimicrobial activity. It can be used effectively as an antimicrobial agent. In addition, the extract of 3,5-dihydroxystilbene represented by the said Formula (2), or the Gingko plant containing high density | concentration has recognized the odor production inhibitory activity, and also by using these in combination It is also apparent that the malodor production inhibitory activity is greatly increased and can be effectively used as the malodor production inhibitor.

The antimicrobial active agent and odor production inhibitor of the present invention can be blended for the above-mentioned purposes in compositions for oral cavity, skin, hair cosmetics, cleaning compositions, food and drink, and the like.

When the antimicrobial agent and odor producing inhibitor according to the present invention are blended into the composition, the compounding amount is converted into the amount of 3,5-dihydroxy-2-mentenyl stilbene and the amount of 3,5-dihydroxystilbene (net content conversion). Is determined.

When antimicrobial effect is anticipated, mix | blending 0.00001-3 mass%, especially 0.0005-1 mass% with respect to the whole composition converted into 3, 5- dihydroxy- 2-mentenyl stilbene amount, expresses effect And from the viewpoint of ensuring the usability and usability of the composition. When the amount is less than 0.00001% by mass, sufficient antimicrobial activity is not expressed, and when blended in excess of 3% by mass, problems in the usability and usability of the composition may occur, such as discomfort in taste, smell, dissolution, etc. This may occur.

In addition, when expecting a malodor production suppression effect, it is 0.0001-3 mass in total in conversion of the amount of 3, 5- dihydroxy- 2-mentenyl stilbene and the amount of 3, 5- dihydroxystilbene with respect to the whole composition. It is preferable to mix | blend%, especially 0.0005-1 mass%, especially 0.001-0.8 mass% from a viewpoint of effect expression, the usability of a composition, and ensuring usability. When the total of 3,5-dihydroxy-2-mentenyl stilbene amount and 3,5-dihydroxystilbene amount is less than 0.0001 mass%, sufficient malodor production inhibitory activity is not expressed and exceeds 3 mass% When it mix | blends and mix | blends, a problem arises in the usability and usability of a composition, the discomfort, such as a taste and an smell, a poor dissolution, etc. may arise.

Moreover, it is suitable that the amount of 3, 5- dihydroxystilbenes is 0.0001-2 mass%, especially 0.001-1 mass% of the whole composition.

In addition, when using the extract of the extract which performed fractionation purification as an active ingredient of said Formula (1) and (2), when mix | blending with a composition at high concentration, the composition may be colored, discolored, etc. by the impurity in an extract. May cause problems. In this case, the compounding quantity of an extract is preferable from a viewpoint that less than 10 mass% of the whole composition prevents discoloration, and a minimum is 0.001 mass% or more, especially 0.01 mass% or more is preferable.

In addition to the antimicrobial agent and odor production inhibitor, in addition to the antimicrobial agent and odor production inhibitor, the composition for oral cavity, the composition for oral cavity, the skin or hair cosmetic, the cleaning composition, The well-known component used for food-drinks etc. can be mix | blended.

The antimicrobial agent and malodor production inhibitor of the present invention can be used in combination with various formulations, and can be used, for example, in products applied to humans or animals such as external preparations for skin, skin or hair cosmetics, oral compositions. Specifically, the external skin preparations or skin cosmetics include creams, hand creams, emulsions, lotions, lotions, soaps, hand soaps, body soaps, limiting agents, athlete's foot medicines, acne treatments, disinfectants, and bleaches. , Adhesives, packs, eye drops and the like. As a hair cosmetic, it can be mix | blended with shampoo, rinse, treatment, tonic, hair restorer, hair gel, hair wax, hair cream, hair foam, hair spray, hair water, etc. As a composition for oral cavity, it can be mix | blended with a dentifrice, a mouthwash, gum massage cream, etc.

Moreover, the antimicrobial agent and odor production inhibitor of this invention can be used also for cleaning compositions, such as a medical composition, a kitchen composition, and a residential composition. For example, as a cleaning composition for medical use, it can be mix | blended with a detergent for clothes, a detergent detergent for clothing, a detergent for sports shoes, a softener, a bleach, a rinse agent, a water repellent agent, an antistatic agent. As a washing | cleaning composition for kitchens, it can be mix | blended with the detergent for dishes, the detergent for vegetables, the detergent for microwave ovens, the detergent for automatic dishwashers, etc. As a cleaning composition for residential use, it can be mix | blended with the detergent for a toilet, the detergent for a bathroom bath, the detergent for a window, the detergent for furniture, the floor, the room, a room deodorant, the cleaning deodorant for air conditioners, etc.

In addition, the antimicrobial agent and malodor production inhibitor of the present invention can be used for all functional foods including various food compositions, for example, specific health foods, nutritional functional foods, and the like.

These compositions concerning this invention can select suitably the well-known compounding component suited to the purpose of use, the kind, formulation, etc. of a composition, and mix | blend it, and can be prepared by a daily method. For example, surfactants, oils, alcohols, humectants, thickeners, chelating agents, pH adjusting agents, flavoring agents, pigments, ultraviolet absorbing and scattering agents, vitamins, water and the like can be appropriately blended as necessary. In addition, arbitrary components are not limited to these and can be mix | blended in the range which does not prevent the effect of this invention.

The composition for oral cavity of the present invention can be in the form of a solid, solid, liquid, liquid, gel, paste, gum, or the like, a skirting agent such as a blouse, a liquid skirt, a liquid skirt, a lubricated skirt, a mouthwash, Gum massage creams, oral pastes, mouse washes, troches, chewing gums and the like are possible in various formulations. The manufacturing method can also employ | adopt the routine method according to a dosage form.

In the composition for oral cavity, other arbitrary components can be mix | blended suitably other than the essential component mentioned above according to the objective, the formulation of a composition, etc. For example, in the case of a toothbrush, a well-known abrasive, a viscous agent, a caking additive, surfactant In addition, a sweetener, preservative, an active ingredient, a coloring matter, a fragrance | flavor, etc. can be mix | blended as needed, It can manufacture by mixing these components and water.

Specifically, in the case of skirts, as the abrasive, one or two or more kinds of dihydrogen phosphate dihydrate and dihydrate, calcium carbonate, aluminum hydroxide, alumina, silicic anhydride and other synthetic resins can be blended. (The compounding quantity is 5-60 mass% normally, in the case of a training skirt, 10-55 mass%).

In the case of pasty compositions such as batters, alginate derivatives such as carrageenan, sodium carboxymethyl cellulose and hydroxyethyl cellulose, gums such as xanthan rubber, synthetic binders such as polyvinyl alcohol, silica gel, etc. 1 type, or 2 or more types, such as the inorganic caking additive, can be mix | blended (a compounding quantity is normally 0.3-10 mass%).

As a viscous agent, 1 type (s) or 2 or more types, such as sugar alcohols, such as polyhydric alcohols, such as glycerin and a propylene glycol, sorbitol, xylitol, maltitol, and erythritol, can be mix | blended (the compounding quantity is 5-70 mass% normally).

As surfactant, the well-known nonionic surfactant, anionic surfactant, amphoteric surfactant, and cationic surfactant which are normally mix | blended can be mix | blended.

The compounding quantity of surfactant is suitably selected according to the form, purpose of use, etc. of a composition. For example, 0 to 10 mass%, especially 0.1 to 5 mass%, can be mix | blended with a batter skirt 0-5 mass% in a liquid skirt and a mouthwash.

As a sweetening agent, saccharin sodium etc. can be mix | blended.

Flavoring agents are natural fragrances such as peppermint oil and spearmint oil, and fragrances obtained by processing such natural fragrances (current cut, wake cut, identification, liquid extract, essence, powder flavor, etc.), and menthol , Single flavors such as carbon, anethol, combination flavors such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc. The well-known perfume material used for the composition for oral cavity can be used, It is not limited to the perfume of an Example.

Moreover, although a compounding quantity is not specifically limited, either, It is preferable to use 0.000001-1 mass% of said fragrance | flavor raw materials in a formulation composition. Moreover, it is preferable to use 0.001-2.0 mass% in fragrance | flavor fragrance | flavor as a fragrance | flavor for fragrance using the said fragrance | flavor raw material.

In the oral composition of the present invention, in addition to the compounds of the formulas (1) and (2), as other active ingredients, for example, one kind of known active ingredients such as enzymes, fluorides, vitamins and derivatives thereof, or 2 or more types can be mix | blended. In addition, a compounding quantity can be made an effective amount in the range which does not prevent the effect of this invention (The compounding quantity is 0.0001-5.0 mass% normally).

The composition for oral cavity of this invention can be used in predetermined containers, such as a laminated tube, a plastic tube, or a bottle-shaped container, an aerosol container, etc. which laminated both surfaces of an aluminum tube and aluminum foil with plastics.

In addition, the skin or hair cosmetic of the present invention, formulations such as aqueous solution, solubilization system, emulsification system, emulsion system, gel system, paste system, ointment system, aerosol system, water-oil 2-layer, water-oil-powder 3-layer You can do That is, if the skin or hair external preparation such as cosmetics, body soap, face wash, lotion, shampoo, conditioner, hair conditioner, hair tonic, latex, cream, gel, pack, mask, mist, spray, impregnated sheet, mascara, foundation, Various formulations, such as an adhesive, a dispersing agent, an aerosol spray, and a stick type, can be used, and the manufacturing method can also employ | adopt the routine method according to a formulation.

In this case, skin or hair cosmetics can be mix | blended suitably other well-known arbitrary components as needed other than the component mentioned above according to the objective, the formulation of a composition, etc. as needed. For example, in order to enhance the deodorizing or deodorizing effect, inorganic particles having a deodorizing function, a limiting agent, a chelating agent and the like can be suitably blended.

Here, as an inorganic particle which has a deodorizing function, For example, silicic acid, silicic acid anhydride, zinc oxide, aluminum oxide, etc., these composite materials; Natural products, such as talc, can be mentioned, These can be used individually by 1 type or in mixture of 2 or more types (the compounding quantity is 0.01-60 mass% normally).

Although the shape of the said inorganic particle is not specifically limited, such as spherical shape, plate shape, a granular shape, needle shape, etc., A spherical thing is preferable from the usability at the time of apply | coating to skin. In addition, the particle diameter of the particles is preferably 0.1 to 50 µm, more preferably 0.3 to 20 µm, in terms of usability.

Examples of the limiting component include a single salt having a convergence effect such as aluminum chloride, a glycol complex or an amino acid complex containing these single salts, and these may be used alone or in combination of two or more. It can be used as a mixture (a compounding quantity is 1.0-50.0 mass% normally).

Citric acid, tartaric acid or its sodium salt, potassium salt, etc. can be mentioned as a chelating agent, These can be used individually by 1 type or in mixture of 2 or more types (a compounding quantity is normally 0.01-5 mass%).

The skin or hair cosmetics further include oils and fats such as liquid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicones, various surfactants, water, polymer compounds, Pharmacological components, such as a thickener, a vitamin agent, and a hormonal agent, a fragrance | flavor, a pigment | dye, an emulsion stabilizer, a pH adjuster, astringent, a refreshing agent, etc. can be mix | blended, and the composition according to the objective can be manufactured.

In addition, these arbitrary components are not limited, A compounding quantity can also be made a normal amount in the range which does not prevent the effect of this invention.

As surfactant, a well-known nonionic surfactant etc. which are normally used for these formulations can be mix | blended, There is no restriction | limiting in particular and it can select suitably according to the objective.

It is preferable to use the compounding quantity of surfactant in the range of 0-20 mass% normally.

In addition, these compositions can also be prepared as an aerosol composition, and in this case, the composition and the propellant can be filled into an aerosol container, for example, an aerosol composition containing a limited diodorant agent or the like. You can do

There is no restriction | limiting in particular as a propellant, According to the objective, it can select suitably, For example, ethane, propane, ethylene, isobutane, normal butane, propylene, isopentane, neopentane, normal pentane, cyclopentane, 2,3 -Dimethylbutane, dimethyl ether, compressed gas (carbon dioxide, nitrogen, air, or a mixed gas thereof), and one or two or more thereof can be used (the amount of the mixture is usually 80 to 99% by mass). ).

Moreover, there is no restriction | limiting in particular as said aerosol container, According to the objective, it can select suitably, For example, what consists of a container main body, the valve which adheres to the opening part of the container main body, and the button for injection are mentioned.

In this case, as a material of a container main body, metal, such as aluminum and stainless steel, resin, such as polyethylene terephthalate, pressure-resistant glass, etc. are mentioned, for example.

In addition, the aerosol composition containing the limited diorant agent is filled into the aerosol container by a known method, and examples of the filling method include a cooling filling method, a pressure filling method, an undercup filling method, and the like.

In addition, in the case of the cleaning composition which concerns on this invention, the well-known additive normally added etc. can be used. Specifically, a surfactant, a solvent, and a fragrance | flavor, a pH adjuster, another well-known water-soluble polymer, a stabilizer, a natural extract, a pigment, etc. can be mix | blended arbitrarily as needed.

Surfactant can be mix | blended suitably for the purpose of washing | cleaning, foam | bubble, etc.

As surfactant, what is normally used, such as anionic surfactant, an amphoteric surfactant, and a nonionic surfactant, can be used (a compounding quantity is 5-70 mass% normally).

Moreover, a solvent can be mix | blended suitably for the purpose of dissolution of a component. As a specific example of a solvent, polyhydric alcohols, such as lower monohydric alcohols, such as methanol and ethanol, ethylene glycol, propylene glycol, etc. are mentioned besides water. As content of a solvent, 5-60 mass% is preferable, and 10-30 mass% is preferable. You may use a solvent individually or 2 types or more.

Moreover, a fragrance | flavor can be mix | blended suitably for the purpose of fragrance | flavor etc. A fragrance component is not specifically limited, A well-known fragrance can be mix | blended. Specific examples include synthetic perfumes such as hydrocarbons such as aliphatic hydrocarbons, ethers such as aliphatic alcohols, oxides, aldehydes, ketones, acids, lactones, esters, nitrogen-containing compounds, and natural fragrances from plants. Can be. A fragrance component may use individual or 2 types or more, and a plurality is used normally.

Although the pH adjuster which can be added suitably for the purpose of pH adjustment etc. is not specifically limited, As a specific example, sodium hydroxide, potassium hydroxide, citric acid and its salt, benzoic acid and its salt, malic acid and its salt, hydrochloric acid, sulfuric acid And salts thereof, phosphoric acid and salts thereof.

Moreover, as food-drinks which concern on this invention, candy, candy, chewing gum, gummi jelly, fruit, etc. are mentioned, for example. The food-drinks can be added the well-known component normally added. Specifically, sugars, organic acids, proteins, fats and oils, and also flavors, amino acids, vitamins, and the like may be optionally blended.

Example

Hereinafter, although the preparation example, the experiment example, the Example, the comparative example, and the prescription example are shown and this invention is demonstrated concretely, this invention is not limited to a following example. Also,

All percentages shown in the following examples are% by mass. In addition, Me is a methyl group and Et is an ethyl group.

[Preparation Example]

<Preparation of antimicrobial fraction>

For the specific purpose, the active ingredient present in the bilberry extract is fractionated from the dried branches of the biloba by the method shown below, and the compound obtained by the flow chart of FIG. 1 is identified to identify the obtained compound. It was.

The dried branches of lychee tree, 500 g, were extracted with 2.5 L of 70% ethanol heated to 50 ° C., and after cooling, the solids were removed by filtration, and the filtrate was concentrated under reduced pressure at 50 ° C. or lower, and the lychee tree extract was extracted. About 26 g was obtained (comparative preparation example 1). This was adsorbed onto Diion HP-20, eluted with 100 ml of 30% ethanol, followed by 100 ml of 60% ethanol, and finally eluted with 100 ml of 80% ethanol. Each eluted fraction obtained 10 g (comparative example 2), 6g (formulation example 1), and 8g (formulation example 2) as extract by concentration under reduced pressure, respectively. When the antimicrobial activity and the enzyme inhibitory activity were measured by the method described below, it was recognized that the antimicrobial activity was present in the fraction of Preparation Example 2, and the enzyme inhibitory activity was present in the fraction of Preparation Example 1. Was further purified and its components were specified.

That is, 2 g of the extract of Preparation Example 1 was applied to liquid column chromatography (Cosmosil 75C18-OPN (Nakarai Tesuku Co., Ltd.)) and fractionated into three portions with 50% methanol (Comparative Preparation Example 3, Preparation). Example 3, Comparative Preparation Example 4). Among them, the main peak of the fraction (Preparation Example 3) having the highest enzyme inhibitory activity was fractionated by HPLC to obtain 600 mg of purified product having a purity of 100% (Preparation Example 6).

On the other hand, the fraction of Preparation Example 2 was applied to silica gel chromatography, and eluted sequentially in a capacity ratio of n-hexane: acetone mixture 20: 1, 15: 1, 10: 1, 7: 1, 5: 1, It fractionated into five fractions (comparative example 5, preparation example 4, preparation example 5, comparative preparation example 6, comparative preparation example 7). The most active n-hexane: acetone eluted with 10: 1 fraction and 15: 1 fraction, and the main peak fraction was fractionated by 50% acetonitrile using Cosmosil 75C18-OPN. , 650 mg of pure products having a purity of 98% were obtained (Preparation Example 7).

¹ H-NMR (500 MHz, Heavy Methanol), ¹³ C-NMR (125 MHz, Heavy Methanol), ESIMS (neg), EIMS pos, TMS derivatives), UV and IR spectra were measured. The results are as follows. Each spectrum and the chemical structure analysis result of the preparation example 7 are shown to FIGS. From the results, Preparation Example 7 was identified as 3,5-dihydroxy-2-mentenylstilbene. Moreover, each spectrum and the chemical structure analysis result of the preparation example 6 are shown to FIGS. 8-13. From the results, Preparation Example 6 was identified as pinocylbin (3,5-dihydroxystilbene).

Formulation Example 6

¹ H-NMR (500 MHz, Methanol): δ = 6.15-6.25 (1H, t), 6.45-6.55 (2H, d), 6.9-7.1 (2H, dd), 7.15-7.25 (1H, t), 7.3 -7.4 (2H, t), 7.45-7.55 (2H, d)

¹³ C-NMR (125 MHz, Methanol): δ = 103.0-103.5, 105.8-106.4, 127.3-127.6, 128.4-128.6, 129.4-129.6, 129.5-129.8, 129.8-130.1, 138.7-138.9, 140.6-140.9, 159.6 -159.9

ESIMS (neg): m / z = 211.0820 [MH] − (Calcd. For C ₁₄ H ₁₁ O ₂ 211.0759), m / z = 225.0439 [M-H + CH ₂ ] ⁻ ,

EIMS (pos, TMS derivative): m / z = 356.1616 [M + 2 (C ₃ H ₈ Si)] ⁺ (Calc. For C ₂₀ H ₂₈ O ₂ Si ₂ 356.1628),

m / z = 341.1391 [M + 2 (C ₃ H ₈ Si) -CH ₃ ] ⁺ ,

UV: λ _Max (MeOH) 306nm (logε 4.44)

IR: (KBr) ν _Max 3350 cm ^-1 (OH), 1650 cm ^-1 , 1450 cm ^-1 , 830 cm ^-1 (C = C)

Formulation Example 7

¹ H-NMR (500 MHz, Methanol): δ = 0.6-0.75 (3H, d), 0.75-0.8 (3H, d), 1.35-1.65 (2H), 1.7-1.85 (5H), 2.0-2.3 (3H ), 5.3-5.4 (1H, s), 6.2-6.3 (1H, s), 6.5-6.6 (1H, s), 6.7-6.8 (1H, d), 7.1-7.25 (1H), 7.25-7.35 (2H) , d), 7.35-7.45 (2H, d), 7.65-7.85 (1H)

¹³ C-NMR (125 MHz, Methanol): δ = 16.7-17.3, 21.7-22.3, 23.6-24.0, 24.0-24.5, 28.8-30.3, 32.2-32.6, 37.6-38.3, 102.6-103.1, 105.4-105.9, 122.1 -122.6, 127.0-127.5, 128.0-128.4, 128.4-128.7, 129.2-129.5, 129.5-129.8, 129.9-130.2, 133.2-133.8, 139.3-139.8, 139.8-140.3, 156.6-157.0, 157.8-158.2

ESIMS (neg): m / z = 347.2000 [M−H] ⁻ (Calcd. For C ₂₄ H ₂₇ O ₂ 347.2011), m / z = 333.1841 [M−CH ₃ ] ⁻ ,

m / z = 361.1790 [M-H + CH ₂ ] ^- ,

EIMS (pos, TMS derivative): m / z = 492.2836 [M + 2 (C ₃ H ₈ Si)] ⁺ ( ^Calcd . For C ₃₀ H ₄₄ O ₂ Si ₂ 492.2880),

m / z = 422.2025 [M + 2 (C ₃ H ₈ Si) -C ₅ H ₁₀ ] ⁺ ,

UV: λ _Max (MeOH) 306nm (logε 4.31)

_{IR: (KBr) ν Max 3350㎝} -1 (OH), 1650㎝ -1, 1450㎝ -1, 830㎝ -1 (C = C)

<Preparation of berry extract>

The dry branches of the biloba were extracted and fractionated by the extraction method shown below according to the flowchart shown in FIG.

5 kg of dried branches of Chinese banyan tree were heat-extracted twice with 25 L of 80% ethanol heated at 50 ° C. for 2 hours, and after cooling, the solids were removed by filtration and the filtrate was kept at 50 ° C. or lower. It concentrated under reduced pressure and obtained about 300 g (yield 25% of moisture content: comparative preparation example 8) of an extract of a pear tree.

1,000 ml of 30% ethanol was added to 300 g of the obtained berry extract, and after stirring for 1 hour while heating at 50 ° C, the 30% ethanol soluble portion (Comparative Preparation Example 9) was discarded by standing overnight for 1,3,5-dihydroxy. 300 g of bottle-shaped extracts containing 8.0% of 2-mentenylstilbene and 7.3% of 3,5-dihydroxystilbene were obtained (Preparation Example 8).

1,500 ml of 50% ethanol was added to 300 g of the bottle-shaped extract obtained here, and stirring extraction was repeated twice for 1 hour, the insoluble portion (Comparative Preparation Example 10) was discarded, and the soluble portion was previously diated with 50% ethanol. Was adsorbed by circulating three times, and eluted with 1,500 ml of 99.5% ethanol. Again, the adsorbent was washed with 1,000 ml of 99.5% ethanol, and combined with the above-mentioned eluent to carry out concentration under reduced pressure at 50 ° C or lower, thereby obtaining 9.56%, 3,5-di, 3,5-dihydroxy-2-mentenylstilbene. 180 g of lead extract containing 15.19% of hydroxystilbene was obtained (Preparation Example 9). Furthermore, by treating this lead extract with acidic clay and diatomaceous earth, a lead extract containing 14.1% of 3,5-dihydroxy-2-mentenylstilbene and 16.6% of 3,5-dihydroxystilbene 150g was obtained (Preparation Example 10).

<Preparation of bilberry extract by supercritical extraction-1>

The dried branches of the gingko tree were used, and the components were extracted and fractionated by the supercritical extraction method shown below according to the flowchart shown in FIG.

1 kg of dried Chinese (chip-shaped) branches of Chinese biloba branches are placed in an extractor, 5% mass of ethanol is added to 100 times of carbon dioxide, and supercritical extraction is performed under conditions of 40 ° C and 45MPa for 2 hours. It was. When the ethanol was distilled off under reduced pressure from the obtained berry extract, a brown lead extract containing 7.5% of 3,5-dihydroxy-2-mentenylstilbene and 5.3% of 3,5-hydroxystilbene 37.2 g was obtained.

Furthermore, 1,000 ml of 70% ethanol (EtOH) was added to this lead extract, heating and refluxing were performed for 1 hour, and it left to stand overnight and insoluble.

The oily substance was filtered off to obtain 30.1 g of brown extract containing 9.6% of 3,5-dihydroxy-2-mentenylstilbene and 6.7% of 3,5-hydroxystilbene ( Formulation Example 11).

<Preparation of Forage Extract by Supercritical Extraction-2>

In the same manner as above, 1 kg of dried Chinese dried paper was extracted with 10 L of 70% ethanol heated to 40 ° C., and concentrated under reduced pressure to obtain 70 g of dried extract. To uniformly disperse and adsorb to 700 g of cellulose powder for the purpose of decolorization, 5% ethanol was added to 100 times the amount of carbon dioxide, and supercritical extraction was performed under conditions of 40 ° C and 45 MPa for 2 hours. When ethanol was distilled off under reduced pressure from the obtained berry extract, 42 g of brown lead extract containing 10.6% of 3,5-dihydroxy-2-mentenyl stilbene and 3.0% of 3,5-hydroxystilbene was obtained (preparation) Example 12).

[Experimental Example]

The fractions (Preparation Examples 1 to 12, Comparative Preparation Examples 1 to 10) obtained by the fractionation method shown in FIGS. 1, 14 and 15 were evaluated for the following antibacterial activity, lower fatty acid production inhibition evaluation, and volatile sulfur compound production inhibition evaluation. The activity was evaluated using the formulation stability evaluation. In addition, some of these fractions were formulated into the tooth wear composition to evaluate formulation stability. The results are shown in Tables 1 and 2.

Antimicrobial Evaluation

The microorganism used for the test was precultured by the following method using the thing purchased from American type culture collection (ATCC).

Actinomyces viscosus ATCC43146, Fusobacterium nucleatum ATCC10953, Porphyromonas gingⅳalis ATCC33277, Prevotella intermedia (Prevotella intermedia) Streptococcus mutans ATCC25175 is a Tod-Hewitt-Bros (Becton and Dickinson) culture solution containing 5 mg / L hemin (manufactured by Sigma) and 1 mg / L vitamin K (manufactured by Wako Pure Chemical Industries, Ltd.), respectively. Cultured by [THBHM]. The culture was performed for 24 hours at 37 ° C. under anaerobic conditions (80 vol% nitrogen, 10 vol% carbon dioxide, 10 vol% hydrogen).

Escherichia coli ATCC8739, Pseudomonas aeruginosa ATCC9027, Staphylococcus aureus ATCC6538, Bacillus subtilis ATCC6633, Candida alida albicans) ATCC10231 and Aspergillus niger ATCC16404 were each cultured under aerobic conditions at 37 ° C. for 24 hours using a Muller-Hinton II liquid medium (manufactured by Becton and Dickinson). Was performed.

The ethanol solution of the test sample was prepared, 1/100 amount was added to 4 ml of the above-mentioned liquid medium so that it might become the density | concentration shown in Table 1, 2, and it stirred well. The microorganisms described above were inoculated to be 10 ⁵ to 10 ⁶ cfu (Colony Forming Unit), incubated for 24 to 48 hours under the same conditions as the preculture, and absorbance at 550 nm and optical microscopic observation. The presence or absence of microbial growth was determined, and the minimum growth inhibition concentration (MIC) was determined.

<Lower fatty acid production inhibition evaluation>

Preparation of Cell Coenzyme Solution:

Porphyromonas gingivalis ATCC33277, and Prevotella intermedia ATCC25611 were likewise cultured in THBHM liquid medium to steady state. After 10 minutes of centrifugation at 8,000 rpm, the bacterial solution was suspended in phosphate buffered saline (PBS) so that the turbidity at 550 nm was 2.0, and the protease inhibitor cocktail set 2 (Kalbiochem) was used at a standard concentration. The cells were crushed by ultrasonic waves for 3 minutes while being added and ice-cooled. The cell lysate was collected by cooling centrifugation at 14,000 rpm for 20 minutes at 4 ° C to obtain supernatant to obtain a crude enzyme solution.

Inhibition test of isogyl acetate production by bacterial enzyme inhibition:

In 1 ml of the coenzyme solution, a PBS solution of L-leucine (Wako Pure Chemical Industry Co., Ltd.) and α-ketoglutaric acid (Wako Pure Chemical Industry Co., Ltd.) serving as a substrate of isogil acetic acid was species. To each of the concentrations of 2.5 mM, the test sample was added to a final concentration of 500 µg / ml, and reacted at 37 ° C for 6 hours in a 2 ml reaction system.

After 1 ml of the reaction solution was extracted with 2 ml of ethyl acetate under acidic sulfuric acid, 1 µl of an ethyl acetate layer was analyzed by gas chromatography under the following conditions, and the percentage of isogyl acetate production inhibition relative to the control was calculated. In addition, it describes in VFA production suppression rate in a table | surface. The control is the amount of isogyl acetate produced with no test sample.

Gas Chromatography Conditions:

Column: FFAP + H ₃ PO ₄ Column (Shinkazu Chemical Co., Ltd.)

Column temperature: temperature rise from 130 ° C to 210 ° C

Detector: FID, 230 ° C (Shimazu Corporation)

Carrier gas: nitrogen (50 ml / min)

<Evaluation of Production of Volatile Sulfur Compounds>

1 ml of L-cysteine and L-methionine were respectively added to a final concentration of the coenzyme solution of Porphyromonas jinjivalis, and the test sample was added to a predetermined concentration, and the total amount was 3 ml with PBS. This was put into a 33 ml sterile test tube, tightly sealed with a silicone stopper, and reacted at 37 ° C for 1 hour. After the reaction, 5 ml of gas phase in the test tube was analyzed by gas chromatography under the following conditions, and methyl mercaptan and hydrogen sulfide inhibition rate (%) for the control were calculated. In the table, the VSC production inhibition rate is described. The control is the respective VSC production amount in the test sample no addition.

Gas Chromatography Conditions:

Filler: DNP 20% Chromosorb WAW DMCS (GL Science)

Column temperature: 70 ℃

Detector: FPD, 130 ℃ (Shimazu Corporation)

Carrier gas: nitrogen (50 ml / min)

<Formulation stability evaluation>

Tooth abrasion composition comprising 0.1% of the biloba extract in the model skirt composition shown below was prepared by a routine method, and stored for 1 month at -5 ° C and 60 ° C, then extruded on paper and visually viewed, -5 ° C Using the skirt composition stored for one month in a thermostat as a control, the discoloration of the skirt composition stored for one month at 60 ° C was evaluated by the following criteria.

Criteria for determination of discoloration:

(Double-circle): A change of color is not recognized compared with a control.

(Circle): A change of color is hardly recognized compared with a control.

(Triangle | delta): The change of color is recognized slightly compared with a control.

X: The change of color is recognized compared with a control.

The composition of the model skirt composition:

Carboxymethylcellulose Sodium 1.4

Propylene Glycol 3.0

Sodium Lauryl Sulfate 1.8

Saccharin Sodium 0.15

Methylparaben 0.1

Butyl Paraben 0.01

Silicic anhydride 25.0

70% Sorbit Liquid 35.0

Spices 1.0

Green tree extract 0.1 to display in table 1, two

Purified water                                            balance

100.0% in total

*: About formulation stability, it measures about Formulation Examples 1, 2, 8-12.

*: About formulation stability, it measures about Comparative Preparation Examples 1, 2, and 8-10.

As shown in Tables 1 and 2, some of the antibacterial activity and the odor production inhibitory activity are recognized by the extract of the biloba extract (Comparative Preparation Examples 1 and 8) without performing the fractionation or purification, but the discoloration of the blended formulation Since this was remarkable, practical use was difficult. On the other hand, it was recognized that not only these activities were increased but also the stability in the preparations was remarkably improved by fractionating and purifying the lychee tree extract by the fractionation method of the present invention (Preparation Examples 1 to 12).

[Example, Comparative Example]

(i) Evaluation of biloba extract blending mouthwash composition

The berry extract obtained by the fractionation method shown in FIG. 14 was mix | blended with the mouthwash composition of the composition shown in Tables 3-5, and it prepared by the routine method. Odor production inhibition evaluation and proliferation inhibition evaluation of oral bacteria shown below were performed by the following method. At the same time, the feeling of use and formulation stability of the mouthwash composition was evaluated. The results are shown in Tables 3-5.

<Evaluation of odor inhibitory effect and proliferation inhibitory effect of oral bacteria>

Porphyromonas gingivalis ATCC33277 strain, Prevotella intermedia ATCC25611 strain, after anaerobic incubation to the normal state in THBHM medium used for the above-mentioned antimicrobial activity, 9,000 g, The cells were collected by centrifugation for 10 minutes and resuspended in 2 x THBHM medium so that the absorbance at 550 nm was 0.5. The same mixture of this bacteria solution (mixed bacteria solution) was used for the experiment.

1.5 ml of mixed bacterial solution and 1.5 ml of mouthwash (washing composition) of the composition shown in Tables 3 to 5 were added to a 33 ml glass sterile test tube, and a silicone stopper was placed in an anaerobic chamber (Hirasawa ANX-3 type). After sealing by, incubation at 37 ° C. for 18 hours. The odor in the test tube after the culture was collected in a syringe, and sensory evaluation was performed by three expert panelists on the following evaluation criteria. In addition, it was made to control that sterilized distilled water was added instead of washing | cleaning liquid. In the table, the odor suppression effect is described.

In addition, the proliferation inhibitory effect on these two types of oral bacteria was evaluated by the method shown below. That is, a 10-fold step dilution of the bacterial solution in a test tube after 18-hour incubation with trypticase soy broth (manufactured by Becton and Dickinson), and the blood agar of the composition shown below using a spiral plater (Gunje Industrial Co., Ltd.) Plates were plated, incubated for 2 weeks under anaerobic conditions (Aneropak anaerobic: Mitsubishi Gas Chemical), and the number of grown colonies was counted and the number of viable cells in the bacterial solution was calculated. Similarly, the number of bacteria added at the beginning of the experiment was calculated, and the proliferation inhibitory effect was determined based on the following evaluation criteria for the number of bacteria in the bacterial solution after culturing with respect to the number of live bacteria at the beginning of the experiment. In the table, it describes as a proliferation inhibitory effect.

Composition of blood agar plate: expressed in mass in 1 liter.

Todd-Hewitt-Bros (Becton and Dickinson): 30g

Agar (Becton and Dickinson): 15g

Hemin (manufactured by Sigma): 5 mg

Vitamin K (made by Wako Pure Chemical Industries, Ltd.): 1 mg

Rabbit de-fiber blood (manufactured by Nippon Bio Testing Laboratory): 100 g

Distilled Water: Rest

(The volume was made up so that the total quantity was 1 liter.)

Evaluation criteria of sensory evaluation of odor suppression effect:

4 points | pieces: It smells very mild compared with the test tube of a control.

3 points | pieces: It smells lightly compared with the test tube of a control.

2 points | pieces: It smells slightly weak compared with the test tube of a control.

1 point | piece: It smells like the test tube of a control.

The average value of three professional panelists was computed, and the inhibitory effect of generation | occurrence | production of an odor was evaluated by the following evaluation criteria.

Evaluation standard :

◎: 3.5 or more points

○: 3.0 or more and less than 3.5

△: 2.0 or more and less than 3.0 points

×: 1.0 or more and less than 2.0 points

Criteria for evaluating the proliferation inhibitory effect of oral bacteria:

◎: The number of viable cells of bacteria solution is 1/10 or less compared to the control

(Circle): The viable cell count of the bacterial solution exceeds 1/10 compared with the control and 1 times or less

(Triangle | delta): More than 1 time and 10 times or less the viable cell count of a bacterial liquid compared with the start of an experiment.

X: The viable cell count of the bacterial solution exceeds 10 times compared with the beginning of the experiment

<Formulation stability evaluation>

Stability Test of the Formulation

After storing the mouthwash compositions shown in Tables 3 to 5 at -5 ° C and 60 ° C for one month, the -5 ° C preservation product was used as a control, and the discoloration state of the 60 ° C preservation product was visually evaluated by the following criteria. It was. In addition, in a table | surface, it described as discoloration and showed the result.

Evaluation criteria of discoloration:

(Double-circle): A change of color is not recognized compared with a control.

(Circle): A change of color is hardly recognized compared with a control.

(Triangle | delta): The change of color is recognized slightly compared with a control.

X: The change of color is recognized compared with a control.

<Evaluation of feeling>

10 ml of the mouthwash composition shown in Tables 3 to 5 was held in the mouth, and the stimulation after brushing for 30 seconds was evaluated in four stages by comparison with the control product (Comparative Example 1), and the average of five judges was taken. It judged by the following evaluation criteria.

Evaluation criteria of feeling:

4: The stimulus is weak compared to the stimulus of the control product.

3: Only the equivalent stimulus is recognized compared with the stimulus of a control product.

2: A slight stimulus is recognized compared with the stimulus of a control product.

1: Clear stimulus is recognized compared with the stimulus of a control product.

Evaluation standard :

◎: average score 3.5 or more

(Circle): Average score is 3.0 or more and less than 3.5 points

(Triangle | delta): An average score is 2.0 or more and less than 3.0 points

×: average score is 1.0 or more and less than 2.0

(Ii) Evaluation of bilberry extract compounding candy

The berry extract obtained by the fractionation method shown in FIG. 14, FIG. 15 was mix | blended and the candy of the composition shown in Table 6 was prepared by a daily method. The effect on the number of black pigment-producing bacteria in saliva and formulation stability were evaluated by the following method. The results are shown in Table 6.

Effect of Candice Extract Blended Candy on Black Pigment-Producing Bacteria in Saliva

One subject (about 2.5 g) of the candy shown in Table 6 was applied to three subjects three times a day without chewing for three days, and the number of bacteria in the oral cavity was measured.

After application of the test candy and after 3 days of application (3 hours after the final application), the solution obtained by brushing for 10 seconds with 3 ml of sterile saline solution was subjected to 10-fold dilution with trypticase soy broth (Becton and Dickinson). Using a spiral plater (Gunje Industrial Co., Ltd.), spread on a kanamycin-containing blood agar plate of the composition shown below, incubated for 2 weeks under anaerobic conditions (Aneropak anaerobic: Mitsubishi gas chemistry), By counting the number of grown black colonies, the number of viable bacteria in physiological saline gargled was calculated. The decrease in the number of growth colonies after application of test candy compared to the value before the test start was determined based on the following evaluation criteria. The results are shown in Table 6 as a decrease in the number of black pigment producing bacteria. In addition, it carried out for the minimum period of 2 weeks of coolin off of each test.

Evaluation standard :

(Circle): The number of growth colonies after a test is 1/100 or less compared with before a test

(Triangle | delta): The number of growth colonies after a test exceeds 1/100 compared with the test before 1/10 or less

X: The number of growth colonies after a test exceeds 1/10 compared with before a test

Composition of kanamycin-containing blood agar plate: Shown as mass in 1 liter.

Todd-Hewitt-Bros (Becton and Dickinson): 30g

Agar (Becton and Dickinson): 15g

Hemin (manufactured by Sigma): 5 mg

Vitamin K (made by Wako Pure Chemical Industries, Ltd.): 1 mg

Rabbit defiber blood (product made by Nippon Bio Testing Laboratory): 100 g

Kanamycin Sulfate (200mg / ml): 1ml

Distilled Water: Rest

(The volume was made up so that the total quantity was 1 liter.)

<Formulation stability evaluation>

After the test candy was stored at −5 ° C. and 60 ° C. for one month, the degree of discoloration was visually determined and evaluated with respect to the 60 ° C. storage product as the control product. In addition, the judgment was based on the criterion of the formulation stability evaluation mentioned above. In addition, in a table | surface, it described as discoloration and showed the result.

From the results of Table 6, the candy containing the berry extract of the present invention grows black pigment producing bacteria such as porphyromonas bacteria and prebotella bacteria which are known to produce volatile sulfur compounds and volatile fatty acids. By suppressing or sterilizing, the number can be confirmed to be reduced, and it can be expected that bad breath, periodontal disease or caries can be prevented. Moreover, also regarding the stability, such as discoloration of a preparation, it was also confirmed that the extract of an extract (preparation product) which refined | purified was excellent.

(Iii) Evaluation of holly extract combination tablet

The berry extract obtained by the fractionation method shown in FIG. 14 was blended, and the tablet of the composition shown in Table 7 was prepared by the routine method. The bad breath inhibitory effect was evaluated by the following method. The results are shown in Table 7.

<Front bad breath suppression effect of the extract extract tablet>

In the test, four people without systemic disease were used as subjects, and oral cleaning was stopped 24 hours before the test. On the day of the test, the oral cleaning after the gas phase and the meal were stopped, and the gas in the oral cavity (mouth) after the mouth was closed for 1 minute was directly analyzed using Proton Transfer Reaction Mass Spectrometry (PTR-MS: manufactured by Ionicon Analytik). Then, the mass peak equivalent to methyl mercaptan, the mass peak equivalent to butyric acid, and the peak equivalent to isogi acetic acid mass were measured. Thereafter, two test tablets (1 g / piece) of the composition shown in Table 7 were dissolved in the oral cavity without chewing, and the components in goji were analyzed likewise immediately after 1 hour and after 2 hours. The data represent the average of four of the inhibition rates relative to the measurements (ppb) before the test and are shown in the table.

PTR-MS measurement conditions:

Measurement molecular weight M49 (methyl mercaptan equivalency)

Accumulation time 0.1 second

Velocity constant 2 × 10 ^-9

The measurement was repeated 6 cycles, the average value of 4 cycles except the first and the last was computed, the relative density | concentration when the initial value was set to 100 was computed, and the average of four was shown in Table 7.

Bad breath is the highest during the day, and it is known that the bad breath decreases by oral cleaning and eating. In addition, since most of the causes are microorganisms in the oral cavity, bad breath occurs by limiting oral cleaning. At this time, the physiological bad breath of healthy people was measured by food restriction from stopping oral cleaning for 24 hours and from the time of waking up to the end of the test. In placebo tablets (Comparative Example 3), bad breath immediately after ingestion decreased by about 20% due to the secretion of saliva, but then returned to the level almost before the test in 1 to 2 hours. On the other hand, it is recognized that the biloba extract blended tablets (Examples 27 to 29) suppress the amount of methyl mercaptan in the goji than immediately after ingestion depending on the blending concentration, and are useful for preventing bad breath.

(Iii) Evaluation of holly extract combination cosmetics

The berry extract obtained by the fractionation method shown in FIG. 14, FIG. 15 was mix | blended and the cosmetics of the composition shown in Table 8 were prepared by a daily method. The body odor inhibitory effect was evaluated by the following method. The results are shown in Table 8.

<Deodorant effect>

The cosmetics of the composition shown in Table 8 were apply | coated under the rectangular armpit of ten subjects, and the shirt which sewed the gauze wash | cleaned previously in both axles was worn. The body odor attached to the gauze after wearing for 8 hours was subjected to sensory evaluation by a professional panelist on the following evaluation criteria. In addition, the subject banned the use of another diorant agent three days before the test, and used the fragrance-free body soap on the day before the test.

Evaluation criteria of sensory evaluation:

4 points | pieces: A smell does not smell at all than an uncoated part.

3 points | pieces: It smells less than an uncoated part.

2 points | pieces: It does not smell a little more than an uncoated part.

1 point | piece: It smells like an unpainted part.

About the result of ten subjects, the following evaluation criteria evaluated the inhibitory effect of generation | occurrence | production of an odor.

Evaluation standard :

(Double-circle): The number of people of three or more points was 8-10 people.

(Circle): The number of people of three or more points was 6-7 people.

(Triangle | delta): The number of people of three or more points was 3-5.

X: The number of people of three or more points was 0-2 people.

In addition, the cosmetics were accommodated by the ratio of the stock solution / liquefied petroleum gas (0.15 Mpa / 20 degreeC) in the table | surface using the following container.

Container used: Aluminum cans made by Toyo Seikan Co., Ltd. / Straight junction valve made by Japan Precision Valve Co., Ltd.

(v) Evaluation of biloba extract blended deodorant composition

The decoction extract obtained by the fractionation method shown in FIG. 14, FIG. 15 was mix | blended, and the deodorizing composition of the composition shown in Table 9 was prepared by the routine method. The food odor inhibitory effect and formulation stability were evaluated by the following method. The results are shown in Table 9.

<Food waste odor suppression effect test>

20 g of cabbage cut into about 2 cm squares were placed in a 450 ml glass jar as food waste and left overnight in an open system, and 1 g of deodorizing composition of the composition shown in Table 9 was sprayed using a spray container. The whole bottle was sprayed to get wet. It was sealed and left at 30 ° C for 2 days, and the odor intensity in the bottle was evaluated by three panelists by a six-stage odor intensity labeling method, and the average was based on the following evaluation criteria for the food odor suppression effect. Evaluated.

Criteria for evaluating the effect of food waste odor:

(Circle): Effective (6 stages of odor intensity average: 2 or less)

(Triangle | delta): There exists a some effect (sixth stage odor intensity average: more than 2 and less than 4)

X: Almost no effect (6 stage odor intensity average: 4 or more)

6-step odor intensity indicator:

0: odorless

1: barely detectable smell

2: weak smell to know what the smell

3: smell that can be detected comfortably

4: strong smell

5: intense smell

<Formulation stability evaluation>

In addition, after deodorizing composition was preserve | saved at -5 degreeC and 60 degreeC for 1 month, the degree of discoloration was visually judged and evaluated about the 60 degreeC preserved product using -5 degreeC preserved product as a control. In addition, the judgment was based on the criterion of the formulation stability evaluation mentioned above. In addition, in a table | surface, it described as discoloration and showed the result.

(Iii) Evaluation of biloba extract compounded liquid detergent composition

The berry extract obtained by the fractionation method shown in FIG. 14, FIG. 15 was mix | blended, and the liquid detergent composition of the composition shown in Table 10 was prepared by a daily method. Eradication effect and formulation stability were evaluated by the following method. The results are shown in Table 10.

<Antibacterial activity evaluation of the detergent for the kitchen>

Liquid detergent compositions of various compositions shown in Table 10 were prepared, and the bactericidal activity of the liquid diluted five times with water was evaluated by the following method. That is, 0.6 ml of the test liquid detergent composition was taken into a sterile test tube, and 2.1 ml of sterile distilled water was added and mixed. To this was added 0.3 ml of Staphylococcus aureus ATCC6538 strain suspended in physiological saline to 1 × 10 ⁹ cfu / ml, and allowed to stand at 20 ° C. for 20 minutes after mixing. Thereafter, 10-fold dilution with sterile physiological saline was carried out, plated on SCDLP agar medium (Nisui Pharmaceutical Co., Ltd.) using a spiral plater (manufactured by Gunge Industries Co., Ltd.), and cultured at 37 ° C for 24 hours. The remaining viable cells were counted by counting the number of colonies grown, and the bactericidal performance was evaluated based on the following criteria. In the table, the results were shown by the bactericidal effect.

Evaluation standard :

○: 1 / 1,000 or less compared to the number of growth colonies treated with water

(Triangle | delta): More than 1 / 1,000 and 1/10 or less compared with the case where the number of growth colonies was treated with water

X: The number of growth colonies exceeds 1/10 compared with the case of treatment with water

<Formulation stability evaluation>

Furthermore, after storing the liquid detergent composition at -5 ° C and 60 ° C for one month, the degree of discoloration was visually determined and evaluated for the 60 ° C stored product using -5 ° C preserved product as a control. In addition, the judgment was based on the criterion of the formulation stability evaluation mentioned above. In addition, in a table | surface, it described as discoloration and showed the result.

Hereinafter, a prescription example is shown. In addition, the composition of the fragrance described in fragrances A-G in a prescription example is as follows.

* Fruit mix flavor FM3000 (combination fragrance)

Strawberry Flavor 40%

Apple Flavor 15

Melon Flavor 17

Banana Flavor 10

Pitch flavor 5

Orange oil 2.5

Raspberry Flavor 2.0

Pineapple Flavor 1.5

Grape Flavor 1.0

Tropical Fruit Flavor 1.5

Milk Flavor 1.0

Grapefruit 0.5

Lemon Oil 0.5

Rose oil 0.2

Solvent rest

100.0% in total

A prescription example is shown below.

[Prescription example 1]

Calcium Carbonate 40.0%

Propylene Glycol 4.0

Glycerin 20.0

Carboxymethyl Cellulose Sodium 1.5

Titanium Oxide 0.5

Sodium Lauryl Sulfate 0.8

Saccharin Sodium 0.1

Paraoxybenzoate ethyl 0.1

Birch Extract of Preparation Example 9 0.05

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0048

(2) 3,5-dihydroxystilbene 0.0076)

Spice A 1.0

Purified water                                             Remainder

100.0% in total

[Prescription 2] Liquid Skirt

Glycerin 25.0%

Sorbite solution (70% aqueous solution) 25.0

Propylene Glycol 5.0

Silicate Anhydride 0.3

Sodium Lauryl Sulfate 1.0

Polyoxyethylene (60) Cured Castor Oil 1.0

Saccharin Sodium 0.2

Sodium benzoate 0.3

Birch extract of preparation example 11 0.05

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0048

(2) 3,5-dihydroxystilbene 0.0034)

Spices B 1.0

Purified water                                             Remainder

100.0% in total

[Example 3] Prescription

Propylene Glycol 4.0%

Glycerin 2.0

Polyoxyethylene (60) Cured Castor Oil 0.3

Saccharin Sodium 0.1

Sodium Lauryl Sulfate 0.1

Spices E 1.0

Crude tree extract of preparation example 12 0.02

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.00212

(2) 3,5-dihydroxystilbene 0.0006)

Purified water                                             Remainder

100.0% in total

Prescription 4 Oral Pasta

Cetanol 10.0%

Squalane 20.0

Precipitated Silica 5.0

Polyoxyethylene (40 mol) hardened castor oil 0.1

Sorbitan Monooleic Acid Ester 1.0

Sodium Lauryl Sulfate 0.2

Saccharin Sodium 0.6

Crude Tree Extract of Formulation 10 `0.2

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0282

(2) 3,5-dihydroxystilbene 0.0332)

Spice C 0.6

Purified water                                             Remainder

100.0% in total

Prescription 5 Oral Troche

Arabian rubber 6.0%

Glucose 36.0

Palatinos 36.0

The lychee tree extract of preparation example 10 which made 10 times distribution with erythritol

                                                  3.0

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0423

(2) 3,5-dihydroxystilbene 0.0498)

Spice D 1.3

Purified water                                             Remainder

100.0% in total

[Prescription 6] Chewing Gum

Gum Base 20.0%

Sugar 15.0

Isomaltose 20.0

Palatinos 10.0

Xylitol 10.0

Corn Syrup 12.0

Birch Extract of Formulation 8 0.3

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.024

(2) 3,5-dihydroxystilbene 0.0219)

Spice F 0.6

Syrup

100.0% in total

[Prescription 7] Candy

50.0% sugar

Starch syrup 33.0

Organic acid 2.0

Spice G 0.2

Elder tree extract of formula 11 0.3

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0288

(2) 3,5-dihydroxystilbene 0.0201)

Purified water                                             Remainder

100.0% in total

[Prescription 8] Deodorizing Spray

Fermented Ethanol 40.0%

Citric Acid 0.03

Crude Extract 0.2 of Formulation Example 10

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0282

(2) 3,5-dihydroxystilbene 0.0332)

Purified water                                             Remainder

100.0% in total

[Prescription 9] Restriction Agent

Icylin 1.0%

Chlorhydroxyaluminum 20.0

Ethanol 35.0

Hydroxyethylcellulose 0.6

PPG5-CETETH-20 2.0

Birch Extract of Formulation 9 0.3

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0287

(2) 3,5-dihydroxystilbene 0.0456)

Spices 0.5

Purified water                                             Remainder

100.0% in total

[Prescription 10] Acne Treatment

Floating paraffin 3.0%

Squalane 10.0

Cetostearyl Alcohol 4.0

Beeswax 2.0

Glycerin Monostearate 2.0

Polyoxyethylene (20) sorbitan monolaurate 2.0

Glycolic acid 0.2

Salicylic Acid 0.1

Japanese Pharmacy Room Sulfur 5.0

Diglycerin 5.0

(1) 3,5-dihydroxy-2-mentenylstilbene 0.05

(2) 3,5-dihydroxystilbene 0.05

Purified water                                             Remainder

100.0% in total

Prescription 11 Soap

Fatty acid sodium 80.0%

Partic acid 4.0

Birch Tree Extract of Preparation 10

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0705

(2) 3,5-dihydroxystilbene 0.083)

Titanium Oxide 0.2

Spices 0.8

Purified water                                            Remainder

100.0% in total

[Prescription 12] Hand Cream

Floating paraffin 10.0%

Vegetable Squalane 5.0

Jojoba You 3.0

Dimethyl Silicone 2.0

Isopropyl myristate 1.5

Decaglycerin Monoisostearate 1.0

Decaglycerin triisostearate 0.5

Glycerin Monostearate 1.0

Stearic Acid 1.5

Polyoxyethylene (20) Glyceryl Monostearate 0.8

Glycerin 3.0

1,3-butylene glycol 5.0

Triisopropanolamine 0.1

Ethanol 2.0

Carboxyvinyl Polymer 0.1

Citric Acid 0.1

Birch Tree Extract of Preparation 11

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.048

(2) 3,5-dihydroxystilbene 0.0335)

Spices 0.05

Purified water                                             Remainder

100.0% in total

[Example 13] Kitchen Detergent

n-hexyl glycoside (glucose average condensation degree 1.3 moles) 5.0%

Palm kernel oil fatty acid diethanolamide 10.0

Sodium Malate 0.5

(1) 3,5-dihydroxy-2-mentenylstilbene 0.02

(2) 3,5-dihydroxystilbene 0.01

Purified water                                             Remainder

100.0% in total

[Prescription 14] Hand Soap

Potassium laurate 8.0%

Mystery Potassium 4.0

Mono-N-laurylperacid amine 1.0

Propylene Glycol 10.0

Palm fatty acid diethanolamine 5.0

Ethylenediaminetetrasodium acetate acetate dihydrate 0.1

Potassium Carbonate 3.0

Spices 0.1

Crude tree extract of formula 12 12

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0106

(2) 3,5-dihydroxystilbene 0.003)

Purified water                                             Remainder

100.0% in total

[Prescription Example 15] Granular Denture Cleaner

Potassium Hydrogen Persulfate 10.0%

Sodium perborate 50.0

Sodium Tripolyphosphate 20.0

Sodium Lauryl Sulfate 1.0

Alcalase 0.5

Carboxymethylcellulose Sodium 4.0

Chondang 2.0

Spices 1.0

Crude Extract of Formulation 8 0.1

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.008

(2) 3,5-dihydroxystilbene 0.0073)

Sodium sulfate rest

100.0% in total

Prescription 16 Tea drink

Kelp 89.5%

Birch Extract of Formulation 8 0.3

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.024

(2) 3,5-dihydroxystilbene 0.022)

L-cysteine 0.2

plum Extract                                       10.0

100.0% in total

[Prescription 17] Tablet for gargle

Sodium bicarbonate 53.0%

Citric Acid 18.0

Anhydrous Sodium Sulfate 12.0

Dibasic Sodium Phosphate 10.0

Polyethylene Glycol 3.0

Spices 2.0

Crude tree extract 2.0 of Formulation Example 10

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.282

(2) 3,5- Dihydroxystilbene                           0.332)

100.0% in total

[Prescription 18] Mouth Cooling Agent

Ethanol 30.0%

Xylitol 10.0

Spices 2.0

Polyoxyethylene (EO60) hardened castor oil 1.5

Birch Extract of Formulation 9 0.3

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0287

(2) 3,5-dihydroxystilbene 0.0456)

Purified water                                             Remainder

100.0% in total

[Prescription 19] Drinks

Glucose 1.35%

Fructose 1.35

Milk Ingredients 0.1

Elder tree extract of formula 11 0.3

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.0288

(2) 3,5-dihydroxystilbene 0.0201)

Sodium chloride 0.029

Vitamin C 0.03

Vitamin B1 0.00022

Citric Acid 0.01

Malic Acid 0.01

Fragrance 0.01

Water rest

100.0% in total

[Prescription 20] Gummy

40.3% sugar

Starch syrup 47.2

Gelatin 8.0

Juicer 2.0

Citric Acid 0.5

Malic Acid 0.5

Spices 0.5

Crude tree extract of formula 10 10

(Net equivalent conversion value:

(1) 3,5-dihydroxy-2-mentenylstilbene 0.141

(2) 3,5- Dihydroxystilbene                           0.166)

100.0% in total

Claims (32)

3,5-dihydroxy-2-mentenylstilbene characterized by the following structural formula (1).

The content of 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) is 1% by mass or more of solid content, from LINDERA UMBELLATA or its subspecies. extract.

An antimicrobial agent comprising 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) as an active ingredient.

Consisting of extracts from Lingera umbellata or subspecies of Gingko plants, containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1): Antimicrobial agent characterized by.

An oral composition comprising 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1).
[Chemical Formula 5]

Containing an extract from Lingera umbellata or its subspecies of 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1) containing 1% by mass or more of solid content Composition for oral cavity, characterized in that.

The cosmetics for skin or hair containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1).

Containing an extract from Lingera umbellata or its subspecies of 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1) containing 1% by mass or more of solid content Cosmetics for skin or hair, characterized in that.

A cleaning composition comprising 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1).

Containing an extract from Lingera umbellata or its subspecies of 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1) containing 1% by mass or more of solid content Cleaning composition, characterized in that.

A food and drink characterized by containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1).

Containing an extract from Lingera umbellata or its subspecies of 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1) containing 1% by mass or more of solid content Gourmet food characterized in that.

A mixture comprising 3,5-dihydroxy-2-mentenylstilbene represented by the following structural formula (1) and 3,5-dihydroxystilbene represented by the following structural formula (2).

3,5-dihydroxysteel represented by the following structural formula (2) while containing 3,5-dihydroxy-2-mentenyl stilbene represented by the following structural formula (1) at least 1 mass% of solid content An extract from LINDERA UMBELLATA or its subspecies of a Ginger plant, characterized by containing 1% by mass or more of ben as solid content.

An extract from Lingera umbellata or a subspecies of a Ginger plant, characterized by containing 3% by mass or more of 3,5-dihydroxystilbene represented by the following structural formula (2).

An odor producing inhibitor comprising the mixture according to claim 13 as an active ingredient. An odor producing inhibitor, comprising the extract according to claim 14 or 15. The composition for oral cavity containing the mixture of Claim 13. The composition for oral cavity containing the extract of Claim 14 or 15. It contains the mixture of Claim 13, The cosmetics for skin or hair characterized by the above-mentioned. The cosmetic for skin or hair containing the extract of Claim 14 or 15. A cleaning composition comprising the mixture according to claim 13. A cleaning composition comprising the extract according to claim 14 or 15. A food and drink comprising the mixture according to claim 13. A food and drink comprising the extract according to claim 14 or 15. A ginger plant was extracted with an aqueous 40-100% by mass ethanol solution, the extract was concentrated under reduced pressure at 50 占 폚 or lower, and the alcohol concentration was adjusted to 10-30% (V / V). Adsorbed to the crosslinked polymer, the fraction eluted with less than 40% by mass of ethanol aqueous solution was removed, followed by elution to 40 to 70% by mass ethanol aqueous solution, and / or elution to more than 70% to 100% by mass ethanol aqueous solution. 3,5-dihydroxystilbene was collected from the elution with 40-70 mass% ethanol aqueous solution, and / or 3,5-di from the elution with more than 70-100 mass% ethanol aqueous solution. A method for collecting an active ingredient of a ginger plant, characterized by collecting hydroxy-2-mentenyl steelbene. 27. The method of claim 26,
The eluate with 40-70 mass% ethanol aqueous solution was concentrated under reduced pressure at 50 degrees C or less, the concentrated extract was adsorb | sucked to the carrier which chemically bonded the octadecyl group to the all porous spherical or crushed silica gel, and 50-80 mass% methanol Elution with aqueous solution to obtain 3,5-dihydroxystilbene. 27. The method of claim 26,
The eluate from 70% to 100% by mass ethanol aqueous solution was developed by silica gel chromatography, and the elution fraction from the elution fraction of n-hexane and acetone (V / V) 18: 1 to the final 8: 1 volume ratio. An elution fraction in between is taken to obtain 3,5-dihydroxy-2-mentenylstilbene. The ginger plant is extracted with an aqueous 40-100% by mass ethanol solution, the extract is extracted again with an aqueous 20-40% by mass ethanol solution, the insoluble portion is collected, followed by extraction with an excess of 40-100% by mass ethanol aqueous solution. A method for producing a mixture of 3,5-dihydroxy-2-mentenylstilbene and 3,5-dihydroxystilbene, characterized by collecting a soluble portion. 30. The method of claim 29,
The soluble portion was concentrated under reduced pressure at 50 ° C. or lower, and the solution in which the alcohol concentration was adjusted to 10 to 30% (V / V) was adsorbed with a spherical crosslinked polymer having a porous structure, followed by 70% by mass or more of an ethanol aqueous solution. Or eluting with ethanol to extract the eluent. The Ginger plant was extracted using a mixture of carbon dioxide in a supercritical state with an aqueous 2 to 10% by mass ethanol solution, and the soluble part was collected to obtain 3,5-dihydroxy-2-mentenylstilbene and / Or 3,5-dihydroxystilbene. Ginger plant was extracted with 40-100 mass% ethanol aqueous solution, the extract was extracted using a mixture of carbon dioxide in a supercritical state and 2-10 mass% ethanol aqueous solution, and the extract was collected, 3, A method for collecting active ingredients of a Ginger plant, characterized by obtaining 5-dihydroxy-2-mentenyl steelbene and / or 3,5-dihydroxystilbene.

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