Beautifying foods and drinks and peroral beautifying preparations

专利摘要:
The present invention relates to a foodstuff containing one or two or more selected from five-membered triter pans and their physiologically acceptable salts, or derivatives thereof. The present invention also relates to an oral whitening agent comprising, as an active ingredient, one or two or more selected from five-membered triterpanes and their physiologically acceptable salts or derivatives thereof.
公开号:KR20030064799A
申请号:KR10-2003-7007177
申请日:2001-11-30
公开日:2003-08-02
发明作者:시노하라고우；구노노리야스
申请人:닛신 오일리오 가부시키가이샤；
IPC主号:

专利说明:

Beautifying foods and drinks and peroral beautifying preparations
[2] In terms of beauty, especially for women, dark skin, blemishes, freckles, and dark circles are mentioned, and skin whitening is more important than ever before. In general, dark skin, blemishes, freckles, and dark circles are thought to be caused by melanocytes being stimulated by ultraviolet rays, hormonal balance abnormalities, genetic factors, etc., and biosynthetic melanin pigments are deposited on the skin. . Conventionally, for such dark skin, blemishes, freckles and dark circles, melanin production inhibitors such as L-ascorbic acid or its derivatives, hydroquinone derivatives and placental extracts are formulated into cosmetics and treated and applied to the skin for treatment and improvement. The method has been mainly used. However, in the case of such cosmetics, the active ingredient is erased over time due to sweating and the like, the effect cannot be maintained, the whitening effect is insufficient, and there is a problem such that the effect is exerted only on the coated part. That is, when used as a cosmetic, it is necessary to re-apply several times a day, or to apply the cosmetics to the whole body against darkening or blemishes, freckles, and dark circles of the whole body. In addition, some active ingredients are irritating to the skin and have limited use or unusual odors. They may cause precipitation flocculation and lack stability, and they may be decomposed by external stimuli such as changes in the pH of the skin surface caused by light, heat or sweat. In addition, problems such as deterioration and deterioration have been pointed out. From the reasons of improving the problems with such cosmetics, whitening foods or whitening medicines for oral ingestion have also been developed. For example, there is a combination of vitamin C in this kind of food, vitamin C has a problem that can not be enough to satisfy the whitening effect is poor stability. In addition, whitening foods (Japanese Patent Publication No. Hei 6-16685) made with the addition of koji acids, cosmetics, foods and bathing agents (Japanese Patent Laid-Open Publication No. Hei 10-287525) containing isotonic rice extract, and isofurabons Oral whitening agents and whitening foods (Japanese Patent Laid-Open Publication No. Hei 11-269066), whitening foods containing proanthocyanidins and glutathione as active ingredients (Japanese Patent Laid-Open Publication No. 2000-60482), and the like. They have not been able to expect a sufficient whitening effect so far, and depending on the component has the problem that there are concerns about unpredictable side effects due to oral intake. From such circumstances, food or oral whitening agents having a sufficient whitening effect and high stability are expected.
[1] The present invention relates to a food and oral whitening agent having a skin whitening effect, which expresses a whitening effect on the skin by oral ingestion.
[3] The present invention has a very good whitening effect that can prevent or recover dark skin, blemishes, freckles, dark circles and the like, continuously and also in the form that can enjoy without effort, such as cosmetics, skin whitening food and oral The task is to provide a whitening agent.
[4] The present inventors have diligently studied to achieve the above problems, and as a result, they found that five-ring triter pans and their physiologically acceptable salts, or derivatives thereof had excellent whitening effects, and the whitening effect was simplified by oral ingestion thereof. The present inventors have found that the present invention can be fully enjoyed, and have completed the present invention.
[5] That is, the present invention relates to a whitening food or oral whitening agent containing one or two or more selected from five-membered triter pans and their physiologically acceptable salts, or derivatives thereof. The food of the present invention has various effects, in particular, the skin lightening effect. Since it is food, it is possible to easily continue eating, and as a result, a suitable effect can be expected. In addition, the oral whitening agent of the present invention may be taken orally as it is, or may be blended in foods as a raw material.
[6] The present invention also relates to the above-mentioned foodstuff, wherein the 5-ring triter pans and their physiologically acceptable salts are isolated from natural products.
[7] The present invention also relates to the above-mentioned food or oral whitening agent, wherein the content of five-membered triterpanes and their physiologically acceptable salts or derivatives thereof is 0.04% by mass or more based on the total mass of the food or oral whitening agent.
[8] The present invention also relates to the above-mentioned food or oral whitening agent, wherein the five-membered triter pan is a compound selected from the group consisting of olean-based triter pans, Ulsan-based triter pans, and lupine-based triter pans.
[9] The present invention also relates to the above-mentioned food or oral whitening agent wherein the five-ring triter pan is selected from the group consisting of maslinic acid, erythrodiol, ursolic acid, uvaol, betulinic acid and betulin.
[10] The present invention also relates to the above-mentioned food or oral whitening agent, wherein the derivatives of the five-ring triterpanes are derivatives having an alcohol ester group or a fatty acid ester group.
[11] The present invention also relates to the above-mentioned food, wherein the food is processed food.
[12] The present invention also relates to the above food matter wherein the processed food is an oil and fat preparation or a processed milk fat.
[13] The present invention also relates to the above food matter wherein the fat or oil processed product is margarine, shortening, mayonnaise or dressing.
[14] The present invention also relates to the above food, wherein the food is a soft drink.
[15] The present invention also relates to the above-mentioned foodstuff, in which part or all of the five-membered triterfane is present in the state of its physiologically acceptable salts and / or derivatives thereof.
[16] The present invention also relates to an edible combination oil and fat containing olive degreasing with an ethanol solution, concentrated by drying, and then containing masrininic acid purified by chromatography in an amount of 1 mass or more.
[17] The present invention also relates to a dressing containing 1% by mass or more of the milking residue obtained by milking olives, extracted with ethanol, concentrated to dryness, and then purified by chromatography.
[18] The present invention also relates to a tablet-like sweet containing an amount of 2.5% by mass or more of maslininic acid, which is extracted by extracting an olive skim with an ethanol solution, concentrated by drying, and then purified by chromatography.
[19] The present invention also relates to a food and beverage made by combining the oral whitening agent.
[20] The present invention also relates to an oral whitening agent in the form of a tablet containing maslininic acid which is extracted by degreasing the olive with an ethanol solution, concentrated by drying and then purified by chromatography.
[21] The present invention also relates to an oral whitening agent in powder form containing maslininic acid which is obtained by extracting the milking residue obtained by milking the olive with an ethanol solution, drying and concentrating by chromatography.
[22] The present invention also relates to a method for using a compound selected from the group consisting of maslinic acid, erythrodiol, ursolic acid, uvaol, betulinic acid, betulin and their physiologically acceptable salts, or derivatives thereof as oral whitening agent. .
[23] The present invention also relates to the use of the oral whitening agent as a prophylactic and / or therapeutic agent for dark skin, blemishes, freckles, dark circles and dullness.
[24] The present invention relates to a food or oral whitening agent for skin whitening containing a compound selected from the group consisting of five ring triterpanes and their physiologically acceptable salts or derivatives thereof.
[25] Examples of the food and drink of the present invention include various foods such as sweets, processed foods, combination fats and oils, dairy products, and beverages. The shape and properties of the food and drink of the present invention are not particularly limited, and may be any shape such as a solid shape, a semisolid shape, a gel shape, a liquid shape, or a powder shape.
[26] Oral whitening agents of the present invention are typically provided in the form of a solid or liquid formulation. Specifically, oral whitening agents of the present invention include tablets such as uncoated tablets, sugar coated tablets, coated tablets, enteric tablets, chewed tablets, buccal tablets, sublingual tablets, troche tablets, and adhesive tablets; Powder; Capsules such as hard capsules and soft capsules; Granules, solvents, shake mixtures, suspensions, emulsions, syrups, dry, such as coated, pills, troches, liquid preparations, or their pharmaceutically acceptable sustained release preparations Although it is provided in the form of liquid preparations, such as a syrup, elixir, aggression, agitation, limonade, etc., it is not specifically limited to these forms.
[27] Since the food of the present invention contains five-ring triter pans and the like, they have various effects they have, and in particular, have a skin whitening effect. Since it is food, it can be easily and continuously ingested, and an appropriate effect can be expected. In the present invention, the five-ring triter pan is a compound of five rings among triter pans composed of six isoprene units, and is a group of substances present in many plants in nature. These are naturally obtained by extracting them from plants, and some of them are artificially synthesized and already sold as reagents, and both can be suitably used.
[28] As the whitening effect, among the five-ring triter pans, olean-based triter pans, Ulsan-based triter pans, and lupan-based triter pans are preferable, and the present invention is one or two selected from these. Foodstuffs containing more than one species are also preferred. For the oleanan-based triterpans, maslininic acid and / or erythrodiol are preferred, and in particular, maslininic acid is preferable. For the Ulsan-based triter pans, the case of ursolic acid and / or ubaol is preferable. For lupine-based triter pans, betulinic acid and / or betulin are preferable.
[29] They mainly have a whitening effect on the skin, and the whitening effect can be evaluated by continuous ingestion, but the effect can also be evaluated by a test with cultured pigment cells. According to this evaluation method, compared with vitamin C and its derivatives known as conventional oral whitening agents, it has a whitening effect of several tens to hundreds of times and has an excellent whitening effect.
[30] With respect to the food of the present invention, the content of one or two or more selected from five-ring triter pans and their physiologically acceptable salts, or derivatives thereof depends on the frequency, intake, and other conditions of ingestion of the food. Therefore, what is necessary is just to adjust it suitably, Although it does not restrict | limit especially, For example, it can adjust to the range of 0.00001-50 mass%.
[31] Here, as the food, various foods such as confectionery, processed food, combination fat, dairy products, beverages, and the like are mentioned, and the shape and properties are not particularly limited, and the solid, semi-solid, gel, liquid, powder It may be any shape. The five-membered triter pans and / or specific derivatives thereof are generally useful, so that the food is a particularly preferred form when the food is a combination fat and / or oil and fat processed product. Although there is no restriction | limiting in particular, For example, the combined fats and oils with a high content of maslininic acid etc. are mentioned. Moreover, the foodstuff obtained by using the said combined fats and / or fats and oils processed material as a raw material, or using it as frying or roasting is also preferable.
[32] In addition, an aqueous food such as a beverage, for example a soft drink, can be obtained as the food of the present invention. Particularly, it is preferable that some or all of the five-circuit triterpanes are brought into the state of their physiologically acceptable salts and / or specific derivatives thereof, so that the water solubility of the five-circuit triterfans, which is inherently useful, can be improved. Although it does not specifically limit, For example, Aqueous drinks, such as a soft drink which mix | blended the physiologically acceptable salt and derivative of maslininic acid which are oil-soluble in nature, etc. are mentioned.
[33] In addition, the present invention relates to an oral whitening agent comprising one or two or more selected from five-membered triterpanes and their physiologically acceptable salts, or derivatives thereof as an active ingredient. The oral whitening agent of the present invention may be taken orally as it is, or may be blended in food as a raw material.
[34] The five-membered triter pans relates to an oral whitening agent of one or two or more selected from olean-based triter pans, Ulsan-based triter pans, and lupine-based triter pans. For the oleanan-based triter pans, maslininic acid and / or erythrodiol are preferable, and in particular, masurinic acid is preferable. For the Ulsan-based triter pans, the case of ursolic acid and / or ubaol is preferable. For lupine-based triter pans, betulinic acid and / or betulin are preferable.
[35] Here, the content as an active ingredient means that it is contained to such an extent that it exhibits its whitening effect and the like, but the content thereof is not particularly limited and may be appropriately adjusted according to the frequency of intake, the intake amount, and the purpose of use. For example, relatively low concentration is good when taken directly orally, and high concentration is preferable when used for raw materials of food.
[36] As mentioned above, the oral whitening agent of this invention can be mix | blended with a foodstuff as a raw material, and the foodstuff which has a skin whitening effect can be obtained.
[37] The present invention also provides masolinic acid, erythrodiol, oleanic triterfans, ursolic acid of Ulsan-based triterfans, betulinic acid of Ubaol, lupan-based triterfans, betulin, and their physiologically acceptable salts, or A method of using one or two or more of their derivatives as an oral whitening agent.
[38] The present invention relates to a food or oral whitening agent for skin whitening containing a compound selected from the group consisting of five ring triterpanes and their physiologically acceptable salts or derivatives thereof. Here, the five-ring triter pan is a kind of triter pan, and is a five-ring compound composed of six isoprene units, which have 30 carbon atoms, but are transitioned, oxidized, desorption, or alkylated in the process of biosynthesis. It includes about 30 pieces. The five-membered triterpanes in the present invention include the five-membered triterpanes, their physiologically acceptable salts, and / or derivatives in which their hydroxyl or carboxyl groups are substituted.
[39] These can be obtained from natural plants or artificially. Moreover, a commercial item can also be used suitably.
[40] Five-loop triter pans are generally classified according to their skeleton. Although there is no restriction | limiting in particular in this invention, For example, an olean type triter pan, Ulsan type triter pan, Lupan type triter pan, Arcane type triter pan, Ceratan type triter pan, Friedelan type triter pan, Fallen Seran-type triter pans, taraxanthan-based triter pans, multifloran-based triter pans, jamanacan-based triter pans, and the like.
[41] Here, the physiologically acceptable salt is a salt derived from a carboxyl group of a five-ring triterfan (particular structure: -COOX; X represents any cationic substance), and is isolated from the natural product in the present invention. It also includes what is inherently included in water. In the present invention, any salt that is commonly used in food or pharmaceutical compositions is not particularly limited. Examples thereof include alkali metal salts such as sodium, potassium and lithium, alkaline earth metal salts such as calcium, magnesium, barium and zinc, ammonia and methyl. Alkylamine salts, such as amine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, tetrabutylamine, pentylamine, hexylamine, ethanolamine, diethanolamine, triethanolamine, Salts such as alkanolamine salts such as propanolamine, dipropanolamine, isopropanolamine, diisopropanolamine, other organic amine salts such as piperadine and piperidine, and basic amino acid salts such as lidine, arginine, histidine, and tryptophan Can be. Among these, alkali metal salts, alkylamine salts, alkanolamine salts and basic amino acid salts are preferable. In general, these salts are more water-soluble than the specific five-ring triter pans on which they are based, and therefore, in the present invention, these salts are particularly preferable when applied to foods of water system.
[42] In addition, the derivative is a biochemically or artificially formed derivative, and is not particularly limited as long as it is a derivative which can be formed in the present invention. Derivatives, glycosides, and the like. Among these, especially derivatives having an alcohol ester group, derivatives having a fatty acid ester group, derivatives having an alkoxy group, and derivatives having an alkoxymethyl group are particularly useful in the present invention because they are more useful than the specific five-ring triterpans that are the basis. It is preferable in the case of applying to an oil-based food, and since glycoside is more water-soluble than the five-ring triter pan which is the base, it is especially preferable in the case of applying to an aqueous food.
[43] Some of these derivatives exist in nature, and can be obtained by artificially forming as described above. It is also possible to derivatize the derivatives of the present invention to use their salts.
[44] In this manner, the five-membered triter pans can be improved in water solubility or usefulness in the form of physiologically acceptable salts or derivatives. Therefore, the product which improved the handleability, quality, and the whitening effect can be set.
[45] The alcohol ester group represents a functional group formed as a result of the dehydration reaction between the general carboxyl group and alcohols (partial structure: -COOR; R represents an arbitrary hydrocarbon-based functional group). That is, the derivative | guide_body which has an alcohol ester group of the 5-ring triter pan in this invention shows the derivative which can be formed especially with the carboxyl group and alcohol. Although there is no restriction | limiting in particular in alcohol at this time, For example, methanol, ethanol, n-propanol, isopropanol, allyl alcohol, n-butanol, sec-butanol, tert-butanol, ethylene glycol, trimethylsilyl alcohol, triethylsilyl alcohol, Phenol, benzyl alcohol, sugars and the like. Among them, derivatives formed of ethanol, triethylsilyl alcohol, methanol, n-propanol, isopropanol and trimethylsilyl alcohol are preferred.
[46] Fatty acid ester group represents the functional group formed as a result of dehydration reaction of general hydroxyl group and fatty acids (partial structure: -OCOR; R represents arbitrary hydrocarbon type functional group). That is, the derivative | guide_body which has a fatty acid ester group of the 5-ring triter pan in this invention shows the derivative which can be formed especially with this hydroxyl group and fatty acids. There is no restriction | limiting in particular in fatty acids at this time, For example, acetic acid, acetic anhydride, propionic acid, butyric acid, isobutyric acid, gil acetic acid, isogil acetic acid, pivalic acid, caproic acid, caprylic acid, capric acid, undecanoic acid, Lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, oleic acid, vaccenic acid, linoleic acid, linoleic acid, linolenic acid, γ-linolenic acid, arachidonic acid, arachidonic acid And eicosapentaenoic acid, behenic acid, docosahexaenoic acid, lignoseric acid, serotonic acid, montanic acid and melicinic acid. Among these, acetic acid, acetic anhydride, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elideic acid, linoleic acid, linoleic acid And derivatives formed of linolenic acid, γ-linolenic acid, arachidonic acid, arachidonic acid, eicosapentaenoic acid, behenic acid, and docosahexaenoic acid are preferred.
[47] The alkoxy group represents a functional group formed as a result of the dehydration reaction between a general hydroxyl group and an alcohol (partial structure: -OR; R represents an arbitrary hydrocarbon-based functional group). That is, in the five-ring triterfans in the present invention, The derivative which has an alkoxy group shows the derivative which can be formed especially from this hydroxyl group and alcohol. Although there is no restriction | limiting in particular in alcohol at this time, For example, methanol, ethanol, n-propanol, isopropanol, allyl alcohol, n-butanol, sec-butanol, tert-butanol, ethylene glycol, trimethylsilyl alcohol, triethylsilyl alcohol, Phenol, benzyl alcohol, sugars and the like. Among them, derivatives formed of ethanol, triethylsilyl alcohol, methanol, n-propanol, isopropanol and trimethylsilyl alcohol are preferred.
[48] The alkoxymethyl group represents a functional group formed as a result of the dehydration reaction between a general hydroxymethyl group and alcohols (partial structure: -CH ₂ OR; R represents an arbitrary hydrocarbon-based functional group). That is, the derivative | guide_body which has an alkoxy methyl group of the five-ring triter pans in this invention especially shows the derivative which can be formed from this hydroxymethyl group and alcohol. Although there is no restriction | limiting in particular in alcohol at this time, For example, methanol, ethanol, n-propanol, isopropanol, allyl alcohol, n-butanol, sec-butanol, tert-butanol, ethylene glycol, trimethylsilyl alcohol, triethylsilyl alcohol, Phenol, benzyl alcohol, sugars and the like. Among them, derivatives formed of ethanol, triethylsilyl alcohol, methanol, n-propanol, isopropanol and trimethylsilyl alcohol are preferred.
[49] In addition, the glycoside in the present invention refers to derivatives having an alcohol ester group, derivatives having an alkoxy group, and derivatives having an alkoxymethyl group, particularly derivatives which can be formed from carboxyl groups, hydroxyl groups, hydroxymethyl groups and saccharides of five-membered triterpanes. (Partial structure: -COOR, -OR, -CH ₂ OR; R represents an arbitrary saccharide). There is no restriction | limiting in particular in the sugar at this time, For example, glucose, mannose, galactose, fructose, xylose, arabinose, fucose, rhamnose, glucosamine, galactosamine, glucuronic acid, etc. are mentioned, In either case, α-body or β-body may be used. These glycosides may be monosaccharides or oligosaccharides of various combinations of two or more sugars. Some of these are usually present in nature and are known by the generic name saponin, but any of these may be used in the present invention.
[50] In the present invention, the five-ring triter pan and the like are as described above, but in view of the particularly high whitening effect, olean-based triter pans, Ulsan-based triter pans, lupine-based triter pans and their physiologically acceptable salts, Or derivatives thereof. Each of the five-ring triterpanes having a skeleton represented by the formula (1) for oleanic triterpanes, (2) for the Ulsan-based triterpanes, and (3) for the lupanite triterpanes and their physiologically acceptable Salts, or derivatives thereof. In addition, about the functional group in each formula, it is the same as the above.
[51]
[52] (Wherein, R _1, R ₂ is a hydrogen atom (-H), hydroxy (-OH), alkoxy group (-OR) or an alcohol ester group (-OCOR), R ₃ is a methyl group (-CH _3), Hydroxymethyl group (-CH ₂ OH), alkoxymethyl group (-CH ₂ OR), carboxyl group (-COOH), fatty acid ester group (-COOR) or carbonate (-COOX).)
[53]
[54] (Wherein R ₁ represents a hydrogen atom (-H), a hydroxyl group (-OH), an alkoxy group (-OR) or an alcohol ester group (-OCOR), and R ₂ represents a methyl group (-CH ₃ ), a hydroxymethyl group (-CH ₂ OH), represents an alkoxy group (-CH ₂ oR), carboxyl group (-COOH), a fatty acid ester group (-COOR) or carboxylic acid salt (-COOX).)
[55]
[56] (Wherein R ₁ represents a hydrogen atom (-H), a hydroxyl group (-OH), an alkoxy group (-OR) or an alcohol ester group (-OCOR), and R ₂ represents a methyl group (-CH ₃ ), a hydroxymethyl group (-CH ₂ OH), represents an alkoxy group (-CH ₂ oR), carboxyl group (-COOH), a fatty acid ester group (-COOR) or carboxylic acid salt (-COOX).)
[57] Although there is no restriction | limiting in particular in this invention, For example, maslininic acid, an oleanoic acid, an erythrodiol, (beta) -amylin, hederagenine, a glycyrtine acid, etc. are mentioned as oleanan-type triter pan, Examples of the pans include ursolic acid, ubaol, α-amyline, chinoboic acid, talaxasterol, α-hydroxyursolic acid, and the like. Betulinic acid, betulin, rufeol, etc. have. In addition, their physiologically acceptable salts and derivatives are the same as described above. When using their physiologically acceptable salts, or derivatives thereof, the origin of olean-based triterpanes, Ulsan-based triterpanes, lupan-based triterpanes and their physiologically acceptable salts, or their derivatives is limited. It is possible to use any of those obtained from nature, artificially synthesized, commercially available products and the like, but considering the oral use, it is preferable to use natural products.
[58] As described above, in the present invention, among the five-ring triter pans, olean-based triter pans (I), Ulsan-based triter pans (II), lupan-based triter pans (III), and their physiologically acceptable salts, Or derivatives thereof are preferable, but in view of high whitening effect, maslininic acid and erythrodiol are preferable as oleanan-based triterpans, ursolic acid and ubaol are preferable as ulsan-based triterpans, and lupan-based triterpanes Betulinic acid and betulin are preferable, and of course, their physiologically acceptable salts, or derivatives thereof are preferable.
[59] Maslinic acid and erythrodiol are both oleanan triterfans and are known to exist in various plants. In addition, the physiologically acceptable salts and derivatives thereof are the same as described above. In the food and oral whitening agent of the present invention, when maslinic acid, erythrodiol, their physiologically acceptable salts, or derivatives thereof are used, the origin of these substances is not limited, and they are obtained from nature or artificially synthesized. Although both commercially available products and the like can be used, it is preferable to use natural products in consideration of their oral use.
[60] In the present invention, maslininic acid and / or its physiologically acceptable salt are most preferred in view of high whitening effect and stable supply. Maslinic acid (maslinic acid) is a kind of oleanan-based triterpanes, and has the structure shown in the formula (4), and is known to have anti-inflammatory action and antihistamine action. In nature, it is known to exist in olives, hops, peppermint, pomegranate, cloves, sage, jujube. In the food and oral whitening agent of the present invention, the origin of maslininic acid and its physiologically acceptable salts is not limited, and any of those obtained from nature, artificially synthesized, commercially available products, and the like can be used. For example, it is preferable to obtain naturally from, for example, olives, hops, peppermint, pomegranate, cloves, sage, jujube, and the like. In particular, maslinic acid and / or its physiologically acceptable salts obtained from olives are very different in terms of raw material supply and content. desirable. From these raw materials, in particular from the product obtained in the olive plant and / or olive oil manufacturing process, it can be obtained by extracting with water and / or an organic solvent, and further concentrated and purified to obtain a high concentration of naturally occurring maslininic acid and / or its physiological Acceptable salts can be obtained simply in bulk.
[61] In addition, in the present specification, 'olive' refers to a product obtained in the olive plant and / or olive oil and / or olive oil manufacturing process.
[62]
[63] In the present invention, the physiologically acceptable salts and derivatives of maslinic acid are the same as those described above. That is, the physiologically acceptable salt is derived from -COOH in the general formula (4), and the type of salt is not particularly limited as long as it is usually used in food or pharmaceutical compositions. Specifically, sodium maslininate, potassium maslininate, ammonium masrinate, dimethyl ammonium maslinate, calcium maslininate, magnesium maslininate, etc. are mentioned. Of these, sodium masrinanate and potassium masrinanate are preferred.
[64] In addition, as a derivative of maslininic acid, for example, any one part is derivatized, and methyllinic acid methyl ester, maslinic acid ethyl ester, maslininic acid n-propyl ester, maslininic acid isopropyl ester, and maslininic acid n-butyl Ester, maslininic acid trimethylsilyl ester, maslininic acid triethylsilyl ester, maslininic acid-β-D-glucopyranosyl ester, maslininic acid-β-D-galactopyranosyl ester, 3-O-acetyl-maslininic acid, 3 -O-propionyl-maslininic acid, 3-O-butyryl-maslininic acid, 3-O-valeryl-maslininic acid, 3-O-capryl-maslininic acid, 3-O-lauryl-maslininic acid, 3 -O-myristyl-maslininic acid, 3-O-palmityl-maslininic acid, 3-O-palmitoleyl-maslininic acid, 3-O-stearyl-maslininic acid, 3-O-stearoyl-maslininic acid , 3-O-oleyl-maslininic acid, 3-O-vacenyl-maslininic acid, 3-O-linoleyl-maslininic acid, 3-O-linorenyl-mar Lininic acid, 3-O-arachidyl-maslininic acid, 3-O-arachidonyl-maslininic acid, 3-O-behenyl-maslininic acid, 2-O-acetyl-maslininic acid, 2-O-propionyl- Maslininic acid, 2-O-butyryl-maslininic acid, 2-O-valeryl-maslininic acid, 2-O-capryl-maslininic acid, 2-O-lauryl-maslininic acid, 2-O-myristyl- Maslininic acid, 2-O-palmityl-maslininic acid, 2-O-palmitoleyl-maslininic acid, 2-O-stearyl-maslininic acid, 2-O-stearoyl-maslininic acid, 2-O-ole Mono-masrininic acid, 2-O-vacenyl-maslininic acid, 2-O-linoleyl-maslininic acid, 2-O-linorenyl-maslininic acid, 2-O-arachidyl-maslininic acid, 2-O-araki Donyl-Masrininic Acid, 2-O-Behenyl-Maslininic Acid, 3-O-Methyl-Maslininic Acid, 3-O-Ethyl-Maslininic Acid, 3-Ot-Butyl-Maslininic Acid, 3-O-triethylsilyl Maslininic acid, 3-O-β-D-glucopyranosyl-maslininic acid, 3-O-β-D-galactopyranosyl-maslininic acid, 3-O-β-D-glucuronopyranosyl- Maslinic acid, 2-O-methyl- Srinic acid, 2-O-ethyl-maslininic acid, 2-Ot-butyl-maslininic acid, 2-O-triethylsilyl-maslininic acid, 2-O-β-D-glucopyranosyl-maslininic acid, 2-O -(beta) -D-galactopyranosyl-maslininic acid, 2-O- (beta) -D-glucurono pyranosyl- maslininic acid, etc. are mentioned. Among these, maslininic acid ethyl ester, maslininic acid triethylsilyl ester, 3-O-acetyl-maslininic acid, 2-O-acetyl-maslininic acid, 2-O-triethylsilyl-maslininic acid and 3-O-stearo Preference is given to mono-maslininic acid and 2-O-stearoyl-maslininic acid. As mentioned above, although only one group was derivatized as a derivative, two or more groups which can be induced | guided | derived and the kind in which these may be derived may be derivatized. For example, 2,3-O-diacetyl body, 2,3-O-ditriethylsilyl body, and 2,3-distearoyl body of maslininic acid or the above-mentioned preferable maslininic acid ester are mentioned as a preferable thing. . The glycosides were only monosaccharides, but of course, oligosaccharides of two or more sugars selected from various sugars may be used.
[65] Erythrodiol (erythrodiol) is a type of oleanane-based triterpan, has the same structure as formula (5), and has an anti-inflammatory action (Planta. Med. VOL. 61, No. 2, 182-185, 1995) and the like. Known. In nature, it is known to exist in olives, sunflowers, marigolds, gum arabic trees, Pterocarpus Santaranus, and Nagabakako trees. In the food and oral whitening agent of the present invention, the origin of erythrodiol or derivatives thereof is not limited, and any of those obtained from nature, artificially synthesized, commercially available products, and the like can be used. It is preferable to obtain in nature, such as an olive, a sunflower, a marigold, an arabic rubber tree, a pterocarpus Santa Lanus, and a Nagabakako tree. In particular, olives are preferred, and specifically those obtained from the products obtained in the olive plant and / or olive oil manufacturing process.
[66]
[67] As for erythrodiol, the physiologically acceptable salts and derivatives thereof are the same as described above.
[68] Here, although not limited to the derivatives as follows, for example, any one portion is derivatized, and 3-O-acetyl-erythrodiol, 3-O-propionyl-erythrodiol, 3-O-buty Reyl-erythrodiol, 3-O-valeryl-erythrodiol, 3-O-capryl-erythrodiol, 3-O-lauryl-erythrodiol, 3-O-myristyl-erythrodiol, 3-O-palmi Tyl-erythrodiol, 3-O-palmitoleyl-erythrodiol, 3-O-stearoyl-erythrodiol, 3-O-oleyl-erythrodiol, 3-O-vacenyl-erythrodiol, 3-O -Linoleyl-erythrodiol, 3-O-linorenyl-erythrodiol, 3-O-arachidyl-erythrodiol, 3-O-arakydonyl-erythrodiol, 3-O-behenyl-erythrodiol, 28- O-acetyl-erythrodiol, 28-O-propionyl-erythrodiol, 28-O-butyryl-erythrodiol, 28-O-valeryl-erythrodiol, 28-O-capryl-erythrodiol, 28-O Lauryl-erythrodiol, 28-O-myristyl Erythrodiol, 28-O-palmityl-erythrodiol, 28-O-palmitoleyl-erythrodiol, 28-O-stearoyl-erythrodiol, 28-O-oleyl-erythrodiol, 28-O- Baxenyl-erythrodiol, 28-O-linoleyl-erythrodiol, 28-O-linorenyl-erythrodiol, 28-O-arachidyl-erythrodiol, 28-O-arachidonyl-erythrodiol, 28-O -Behenyl-erythrodiol, 3-O-methyl-erythrodiol, 3-O-ethyl-erythrodiol, 3-Ot-butyl-erythrodiol, 3-O-triethylsilyl-erythrodiol, 28-O-methyl Erythrodiol, 28-O-ethyl-erythrodiol, 28-Ot-butyl-erythrodiol, 28-O-triethylsilyl-erythrodiol, 3-O-β-D-glucopyranosyl-erythrodiol, 3- O-β-D-galactopyranosyl-erythrodiol, 3-O-β-D-glucuronopyranosyl-erythrodiol, 28-O-β-D-glucopyranosyl-erythrodiol, 28-O -β-D-galactopyranosyl-erythrodiol, 28-O-β-D-glucuronopyranosyl-erythrodiol It can be given. Among these, 3-O-acetyl-erythrodiol and 28-O-acetyl-erythrodiol are preferable. As mentioned above, although only one group was derivatized as a derivative | guide_body, two or more groups which can be induced | guided | derived and the kind in which these may be derived may be derivatized. For example, 3,28-O-diacetyl-erythrodiol can be mentioned. In addition, although only a monosaccharide was heard about the glycoside, the oligosaccharide more than 2 sugars chosen from various sugars may be sufficient.
[69] Ursolic acid and ubaol are both kinds of Ulsan-based triter pans and are known to exist in various plants. In addition, the salt and derivative which are physiologically acceptable among these are the same as the above-mentioned. In the food and oral whitening agent of the present invention, when ursolic acid, ubaol, their physiologically acceptable salts, or derivatives thereof are used, the origin of these substances is not limited, and those obtained from nature or artificially synthesized. Although both commercially available products and the like can be used, it is preferable to use natural products in consideration of their oral use.
[70] Ursolic acid (ursolic acid) is a kind of Ulsan-based triter pan, a compound having the structure represented by the formula (6). It is known to have anti-inflammatory action, anti-arteriosclerosis action, antidiabetic action, antihyperlipidemic action (Jie Liu, Journal of Ethnopharmacology, 49, 57-68, 1995) and the like. It is known to be widely distributed in fruits and leaves such as apples, cherries and bilberry leaves. In the food and oral whitening agent of the present invention, the origin of ursolic acid, their physiologically acceptable salts, or derivatives thereof is not limited, and any of those obtained from nature, artificially synthesized, commercially available products, and the like can be used. In view of this, it is preferable to obtain in nature such as apples, cherries, and bilberry leaves.
[71]
[72] The physiologically acceptable salts and derivatives of ursolic acid are the same as described above.
[73] Here, the physiologically acceptable salts thereof are not limited to the following, but for example, as a salt of ursolic acid, sodium ursolate, potassium ursolate, ammonium ursolate, dimethylammonium urethane, calcium ursolate, magnesium ursolate Etc. can be mentioned.
[74] As the derivative of ursolic acid, for example, any one portion is derivatized, and methyl urethane acid, ursolic acid ethyl ester, ursolic acid n-propyl ester, ursolic acid isopropyl ester, ursolic acid n-butyl ester and ursol Acid trimethylsilyl ester, ursolic acid triethylsilyl ester, ursolic acid-β-D-glucopyranosyl ester, ursolic acid-β-D-galactopyranosyl ester, 3-O-acetyl-ursolic acid, 3-O- Propionyl-ursolic acid, 3-O-butyryl-ursolic acid, 3-O-valeryl-ursolic acid, 3-O-capryl-ursolic acid, 3-O-lauryl-ursolic acid, 3-O- Myristyl-ursolic acid, 3-O-palmityl-ursolic acid, 3-O-palmitoleyl-ursolic acid, 3-O-stearyl-ursolic acid, 3-O-oleyl-ursolic acid, 3-O -Vacenyl-ursolic acid, 3-O-linoleyl-ursolic acid, 3-O-linorenyl-ursolic acid, 3-O-arachidyl-ursolic acid, 3-O-arachidonyl-ursolic acid, 3- O-behenyl-ursolic acid, 3-O-methyl- Ursolic acid, 3-O-ethyl-ursolic acid, 3-Ot-butyl-ursolic acid, 3-O-triethylsilyl-ursolic acid, 3-O-β-D-glucopyranosyl-ursolic acid, 3-O -(beta) -D-galactopyranosyl-ursolic acid, 3-O- (beta) -D-glucurono pyranosyl-ursolic acid, etc. are mentioned. As mentioned above, although only one group was derivatized as a derivative, two or more groups which can be induced | guided | derived and the kind in which these may be derived may be derivatized. The glycosides were only monosaccharides, and of course, oligosaccharides of two or more sugars selected from various sugars may be used.
[75] Uvaol (Uvaol) is a kind of Ulsan-based triter pan, and has the same structure as in formula (7), and has an anti-inflammatory action (Planta. Med. VOL. 61, No. 2, 182-185, 1995), glycerophosphate It is known to have a dehydrogenase inhibitory effect (Japanese Patent Laid-Open No. 9-67249) and the like. In nature, it is known to exist in olives, bilberry leaves, sage, gum arabic, kayupote. In the food and oral whitening agent of the present invention, the origin of the ubaol or its derivatives is not limited, and any of those obtained from nature, artificially synthesized, commercially available products and the like can be used. For example, olives, bilberry leaves, sage It is preferable that it is obtained from nature, such as gum arabic and kayupute. In particular, olives are preferred, and specifically those obtained from the products obtained in the olive plant and / or olive oil manufacturing process.
[76]
[77] For ubaol, the physiologically acceptable salts and derivatives thereof are the same as described above.
[78] Here, the derivatives are not limited as follows, but for example, any one portion is derivatized, and 3-O-acetyl-ubaol, 3-O-propionyl-ubaol, 3-O-buty Reel-Ubaol, 3-O-Valeryl-Ubaol, 3-O-Capryl-Ubaol, 3-O-Lauryl-Ubaol, 3-O-Mistyl-Ubaol, 3-O-Palmi Tyl-Ubaol, 3-O-palmitoleyl-Ubaol, 3-O-stearyl-Ubaol, 3-O-Oleyl-Ubaol, 3-O-Vacenyl-Ubaol, 3-O- Linoleyl-ubaol, 3-O-linorenyl-ubaol, 3-O-arachidyl-ubaol, 3-O-arakydonyl-ubaol, 3-O-behenyl-ubaol, 28-O -Acetyl-ubaol, 28-O-propionyl-ubaol, 28-O-butyryl-ubaol, 28-O-valeryl-ubaol, 28-O-capryl-ubaol, 28-O- Lauryl-ubaol, 28-O-myristyl-ubaol, 28-O-palmityl-ubaol, 28-O-palmitoleyl-ubaol, 28-O-stearyl-ubaol, 28-O -Oleyl-ubaol, 28-O-vacenyl-ubaol, 28-O-linoleyl-ubaol, 28-O-linorenyl-ubaol, 2 8-O-Arachidyl-Ubaol, 28-O-Arachidyl-Ubaol, 28-O-Behenyl-Ubaol, 3-O-Methyl-Ubaol, 3-O-Ethyl-Ubaol, 3 -Ot-butyl-ubaol, 3-O-triethylsilyl-ubaol, 28-O-methyl-ubaol, 28-O-ethyl-ubaol, 28-Ot-butyl-ubaol, 28-O- Triethylsilyl-Ubaol, 3-O-β-D-Glucopyyranosyl-Ubaol, 3-O-β-D-Galactopyranosyl-Ubaol, 3-O-β-D-Glucurono Pyranosyl-Ubaol, 28-O-β-D-Glucopyyranosyl-Ubaol, 28-O-β-D-Galactopyranosyl-Ubaol, 28-O-β-D-Glucuronopyra Nosil-Ubaol etc. are mentioned. Among them, 3-O-acetyl-ubaol and 28-O-acetyl-ubaol are preferable. As mentioned above, although only one group was derivatized as a derivative | guide_body, two or more groups which can be induced | guided | derived and the kind in which these may be derived may be derivatized. For example, 3,28-O-diacetyl-ubaol can be mentioned. In addition, although only a monosaccharide was heard about the glycoside, the oligosaccharide more than 2 sugars chosen from various sugars may be sufficient.
[79] Betulinic acid and betulin are both lupine-based triterpanes and are known to exist in various plants. In addition, the physiologically acceptable salts and derivatives thereof are the same as described above. In the food and oral whitening agent of the present invention, when betulinic acid, betulin, their physiologically acceptable salts, or derivatives thereof are used, the origin of these substances is not limited, and those obtained from nature are artificially synthesized. It can use all, a commercial item, etc., It is preferable to use a natural product in consideration of the oral use.
[80] Betulinic acid (betulinic acid) is a kind of lupine-based triter pan, and has the same structure as in formula (8). As a function, anti-cancer action, anti-inflammatory action, wound healing promoting action (Japanese Patent Publication No. 4-26623), alcohol absorption It is known to have an inhibitory effect (Japanese Patent Laid-Open Publication No. Hei 7-53385), a hair growth promoting effect (Japanese Patent Laid-Open Publication No. Hei 9-157139), and the like. It is known to exist naturally in bitter grass, cloves, grape skins, olives, etc., and to exist as saponin in bamboo shoots, carrots, and beets. In the food and oral whitening agent of the present invention, the origin of betulinic acid, their physiologically acceptable salts, or derivatives thereof is not limited, and any one obtained from nature, artificially synthesized, commercially available products, and the like can be used. In view of this, it is preferable that it is obtained from nature, such as bitter grass, cloves, grapes, olives, bamboo shoot ginseng, carrots, and beets. In particular, what is obtained from olive is preferable, and what is obtained from the product obtained by the olive plant and / or olive oil manufacturing process specifically, is preferable.
[81]
[82] As for betulinic acid, the physiologically acceptable salts and derivatives thereof are the same as described above.
[83] Here, the physiologically acceptable salts thereof are not limited as follows, but, for example, as the salt of betulinic acid, sodium betulinate, potassium betulinate, ammonium betulinate, dimethylammonium betulinate, calcium betulinate, betulinic acid Magnesium etc. are mentioned. Among these, sodium betulinate and potassium betulinate are preferable.
[84] As the derivative of betulinic acid, for example, any part is derivatized, and methyl betulinic acid, betulinic acid ethyl ester, betulinic acid n-propyl ester, betulinic acid isopropyl ester, betulinic acid n-butyl ester, Betulinic acid trimethylsilyl ester, betulinic acid triethylsilyl ester, betulinic acid -β-D-glucopyranosyl ester, betulinic acid -β-D-galactopyranosyl ester, 3-O-acetyl-butulinic acid, 3-O -Propionyl-betulinic acid, 3-O-butyryl-betulinic acid, 3-O-valeryl-betulinic acid, 3-O-capryl-betulinic acid, 3-O-lauryl-betulinic acid, 3-O -Myristyl-betulinic acid, 3-O-palmityl-betulinic acid, 3-O-palmitoleyl-betulinic acid, 3-O-stearyl-betulinic acid, 3-O-oleyl-betulinic acid, 3- O-Baxenyl-Betulinic Acid, 3-O-linoleyl-Betulinic Acid, 3-O-linorenyl-Betulinic Acid, 3-O-Arachidyl-Betulinic Acid, 3-O-Arachidyl-Betulinic Acid, 3 -O-behenyl-betulinic acid, 3-O-meth Betulinic acid, 3-O-ethyl-betulinic acid, 3-Ot-butyl-betulinic acid, 3-O-triethylsilyl-betulinic acid, 3-O-β-D-glucopyranosyl-betulinic acid, 3- O-β-D-galactopyranosyl-butulinic acid, 3-O-β-D-glucuronopyranosyl-butulic acid, etc. are mentioned. Among these, betulinic acid ethyl ester is preferable. As mentioned above, although only one group was derivatized as a derivative | guide_body, two or more groups which can be induced | guided | derived and the kind in which these may be derived may be derivatized. The glycosides were only monosaccharides, but of course, two or more oligosaccharides selected from various sugars may be used.
[85] Betulin is a lupine-based triterpan and has the same structure as Formula 9, and has been described as a biological protein denaturation inhibitor (Japanese Patent Laid-Open No. 9-67253) and glycerophosphate dehydrogenase inhibitory action (Japan). Japanese Patent Laid-Open Publication No. Hei 9-67249), lipase inhibitory action (Japanese Patent Laid-Open Publication No. Hei 10-265328), liver disease prevention action (Japanese Patent Laid-Open Publication No. Hei 11-209275) and the like. It is known to exist in bark of birch in nature. In the food and oral whitening agent of the present invention, the origin of betulin or its derivatives is not limited, and any of those obtained from nature, artificially synthesized, commercially available products, and the like can be used. It is preferable to use what is obtained from natural products, such as bark of a birch.
[86]
[87] As for betulin, the physiologically acceptable salts and derivatives thereof are the same as described above.
[88] Here, the derivative is not limited as follows, but for example, any one portion is derivatized, and 3-O-acetyl-vetulin, 3-O-propionyl-vetulin, 3-O-buty Reel-Betulin, 3-O-Valeryl-Betulin, 3-O-Capryl-Betulin, 3-O-Lauryl-Betulin, 3-O-Mistyl-Betulin, 3-O-Palmi Tyl-Betulin, 3-O-palmitoleyl-Betulin, 3-O-stearyl-Betulin, 3-O-Oleyl-Betulin, 3-O-Vaxenyl-Betulin, 3-O- Linoleyl-vetulin, 3-O-linorenyl-vetulin, 3-O-arachidyl-vetulin, 3-O-arachidonyl-vetulin, 3-O-behenyl-vetulin, 28-O -Acetyl-Betulin, 28-O-propionyl-Betulin, 28-O-Butylyl-Betulin, 28-O-Valeryl-Betulin, 28-O-Capryl-Betulin, 28-O- Lauryl-Betulin, 28-O-Mistyl-Betulin, 28-O-Palmityl-Betulin, 28-O-Palmitoleyl-Betulin, 28-O-Stearyl-Betulin, 28-O -Oleyl-vetulin, 28-O-vacenyl-vetulin, 28-O-linoleyl-vetulin, 28-O-linorenyl-vetulin, 2 8-O-Arachidyl-Betulin, 28-O-Arachidyl-Betulin, 28-O-Behenyl-Betulin, 3-O-Methyl-Betulin, 3-O-Ethyl-Betulin, 3 -Ot-Butyl-Betulin, 3-O-triethylsilyl-Betulin, 28-O-Methyl-Betulin, 28-O-Ethyl-Betulin, 28-Ot-Butyl-Betulin, 28-O- Triethylsilyl-Betulin, 3-O-β-D-Glucopyyranosyl-Betulin, 3-O-β-D-Galactopyranosyl-Betulin, 3-O-β-D-Glucurono Pyranosyl-Betulin, 28-O-β-D-Glucopyyranosyl-Betulin, 28-O-β-D-Galactopyranosyl-Betulin, 28-O-β-D-Glucuronopyra Nosyl-betulin and the like. Among these, 3-O-acetyl- betulin and 28-O-acetyl-betulin are preferable. As mentioned above, although only one group was derivatized as a derivative | guide_body, two or more groups which can be induced | guided | derived and the kind in which these may be derived may be derivatized. For example, 3,28-O-diacetyl-vetulin is preferred. In addition, although only a monosaccharide was heard about the glycoside, the oligosaccharide more than 2 sugars chosen from various sugars may be sufficient.
[89] These five-loop triter pans can be obtained by extracting from plants described in nature, specifically extracting with water and / or an organic solvent, followed by concentration and / or fractionation and purification. That is, each plant can be extracted with water and / or an organic solvent, and again, the solvent extraction method, the method using the solubility difference with impurities, fractional precipitation method, recrystallization method, ion exchange resin method, liquid chromatography method, etc. Can be separated or purified alone or in combination as appropriate or by repeated use.
[90] In particular, maslininic acid and / or its physiologically acceptable salts can be extracted from the olive plant with water and / or an organic solvent, and in the extract, solvent extraction method, method using difference in solvent degree with impurities, fractional precipitation The separation, recrystallization, ion exchange resin, liquid chromatography and the like can be separated and purified alone or in combination as appropriate.
[91] Olive plants (Olea europaea L.) can be used regardless of the origin, edible or milking of Japanese and European origin. Maslininic acid and / or its physiologically acceptable salts contained in the food and oral whitening agents of the present invention can be obtained mainly from the olive plant, which is a natural plant, from fruit or seeds, and from skins, seedlings, leaves, stems and shoots thereof. Can be. Furthermore, these can also be suitably obtained from dried products, pulverized products and degreasing products. Among them, degreased fruits (including peels), dried products of peels, and ground products are preferable. In addition, products generated in the production process of olive oil, such as crushed residues, extracted residues, milking residues, crushed milk, extracted oils, degumming oil residues, deoxidized oil residues, dark oil, waste bleaching agents, deodorizing scum ), Milking juice, drainage, and waste filter materials. Of these, milking residues are preferred.
[92] In addition, when a humidification process such as steaming or the like is performed by adding water or the like to the fruit of the olive plant or its defatted substance, or the like, the fruit or the skim of the olive plant or the like is properly swelled. Therefore, extraction effect becomes favorable and it is preferable.
[93] In particular, the degreasing of the olive plant is preferable because maslininic acid and / or its physiologically acceptable salts are present in high concentration, and there is no need to remove oil from the obtained maslinic acid and / or its physiologically acceptable salts.
[94] The degreasing | defatting material can be made into the olive milking residue computed during a food oil refinement | purification process, or the extraction residue by hexane etc. as a raw material.
[95] One or two kinds of known non-aqueous organic solvents such as hydrocarbons such as pentane, hexane and heptane, lower fatty acid alkyl esters such as ethyl acetate and diethyl ester can be used for the lipid component contained in the olive plant or the degreasing product. The degreasing material which extracted and removed above and repeated this washing process as needed can also be used suitably.
[96] By extraction with water and / or an organic solvent from an olive plant, maslininic acid and / or its physiologically acceptable salts contained in the food and oral whitening agent of the present invention can be obtained.
[97] As an organic solvent used for obtaining maslinic acid and / or its physiologically acceptable salt in an olive plant, both a hydrophilic organic solvent and a hydrophobic organic solvent are good. Specifically, as a hydrophilic organic solvent, alcohols such as methyl alcohol, ethyl alcohol, glycerin, propylene glycol, 1,3-butylene glycol, acetone, tetrahydrofuran, acetonitrile, 1,4-dioxane, pyridine, dimethyl sulfoxide Well-known organic solvents, such as a seed, N, N- dimethylformamide, acetic acid, etc. are mentioned, As a hydrophobic organic solvent, hexane, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ester, Known organic solvents, such as ethyl acetate, benzene, and toluene, are mentioned. In addition, these organic solvents can be used 1 type or in combination of 2 or more types.
[98] Industrially, for example, in terms of permeability into plant tissues, extraction efficiency, etc., it is preferable to use a hydrophilic organic solvent, and it is preferable to use a hydrophilic hydrophilic organic solvent. Specifically, alcohols, such as methyl alcohol, ethyl alcohol, glycerin, propylene glycol, 1, 3- butylene glycol, organic solvents, such as acetone, tetrahydrofuran, acetonitrile, and these aqueous solvents are mentioned. By 1 type, or 2 or more types selected from these, the maslininic acid and / or its physiologically acceptable salt contained in the foodstuff and oral whitening agent of this invention can be obtained from an olive plant.
[99] Although extraction conditions are not specifically limited, For example, it can extract suitably also in 5-95 degreeC, Preferably it is 10-90 degreeC, More preferably, it is 15-85 degreeC and normal temperature. The higher temperature tends to increase the extraction efficiency. The pressure can be appropriately extracted even under normal pressure, under pressure, and under reduced pressure by suction or the like. Moreover, in order to improve extraction efficiency, it can also extract with a shaker, the extractor equipped with a stirrer. Although extraction time changes with other extraction conditions, it is several minutes to several hours, and sufficient extraction is performed for a long time, but what is necessary is just to determine suitably according to production conditions, such as a production facility and a yield.
[100] In addition, the solvent used for extraction is preferably 1 to 100 times the amount of the raw material in any case when water is used alone, when an organic solvent is used alone, or when water and an organic solvent are mixed and used. 'Mass / mass', which is the same below), and more preferably 1 to 20 times the amount can be used.
[101] In addition, in consideration of safety to the human body, it is particularly preferable to extract by any one of water, water-containing lower alcohol, anhydrous lower alcohol.
[102] In addition, when taking into account the yield of maslininic acid and / or its physiologically acceptable salts and the strength of the whitening effect, it is preferable to extract the hydrous lower alcohol having a lower alcohol content of 10% by mass or more. In addition, it is preferable to use a hydrous alcohol having a lower alcohol content of 10 to 95% by mass, and most preferably a hydrous lower alcohol having a lower alcohol content of 30 to 95% by mass.
[103] Herein, the alcohol used in the present invention is a primary alcohol such as methyl alcohol, ethyl alcohol, 1-propanol, 1-butanol, secondary alcohol such as 2-propanol, 2-butanol, 2-methyl-2-propanol, or the like. Known solvents, such as liquid polyhydric alcohols, such as the tertiary alcohol, ethylene glycol, propylene glycol, and 1, 3- butylene glycol, are mentioned, These solvent can be used 1 type or in combination of 2 or more types.
[104] Lower alcohols include known alcohols having 1 to 4 carbon atoms, for example, the above-mentioned primary, secondary, tertiary, or liquid polyhydric alcohols, and these may be used alone or in combination of two or more thereof.
[105] The solvent and water are removed from the coarse extract and / or coarse extract obtained in this way to obtain the maslininic acid and / or its physiologically acceptable salt thereof.
[106] Removal of the solvent and water can be carried out by known methods such as vacuum distillation, reduced pressure and vacuum drying, freeze drying and spray drying.
[107] Of course, the solvent and water may be contained, and the state is not particularly limited.
[108] Since the extract from a skim substance does not contain useful components, such as a triglyceride, a sterol, and a tocopherol, since it is not necessary to remove and refine | purify these, it is preferable. In addition, since degreasing products include residues after milking, it is possible to use pressurized residues and extraction residues milked with olive oil, which is a very good effective use method of olives, and is generally used for waste or feed. Therefore, it is an excellent method in terms of production cost.
[109] Further, in order to further bring out the whitening effect of maslininic acid and / or its physiologically acceptable salts extracted from olive plants, it is necessary to concentrate the maslininic acid and / or its physiologically acceptable salts contained in the food or the like of the present invention. desirable.
[110] Although concentration conditions are not specifically limited, For example, the method using the solubility which melt | dissolves in water is mentioned. Maslininic acid and / or its physiologically acceptable salts contained in the food and oral whitening agent of the present invention are relatively low polar, poorly water-soluble compounds. Using this property, the coarse extract from the olive plant can be divided into a component which is difficult to dissolve in water and / or a component which does not dissolve in water, that is, a component such as poor water solubility, and a component which is easily soluble in water. have. The components such as poor water solubility contained in the coarse extract from the olive plant are excellent in whitening effect significantly compared to the whole coarse extract from the olive plant, and the concentration of maslinic acid and / or its physiologically acceptable salts is concentrated. You can see that.
[111] Components such as poor water solubility can be obtained simply by adding and stirring a coarse extract from an olive plant to water, and then collecting the precipitated portion by filtration or the like.
[112] In addition, maslininic acid and / or its physiologically acceptable salt contained in the food or the like of the present invention can be concentrated by liquid-liquid distribution by a combination of general solvents as necessary. Although the combination of solvents is difficult to define uniformly, the combination of water-hydrophobic organic solvent is mentioned, for example, As hydrophobic organic solvent, hexane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, diethyl ether, acetic acid Known organic solvents, such as ethyl, n-butanol, benzene, toluene, are mentioned. Of these, hexane, ethyl acetate and n-butanol are preferable.
[113] Since maslininic acid and / or its physiologically acceptable salt are poorly water-soluble, a hydrophobic organic solvent phase can be fractionated and the unnecessary water-soluble component can be removed. The solvent can be removed to easily concentrate maslininic acid and / or its physiologically acceptable salts.
[114] Moreover, it is preferable to fractionate and refine | purify the maslininic acid and / or its physiologically acceptable salt contained in the foodstuff and oral whitening agent of this invention from the above-mentioned extract and / or concentrate. Thereby, it can concentrate above the said concentration and can isolate the target component.
[115] Advantages of the fractionation and purification treatment include the fact that the whitening effect and the like can be greatly improved, and that impurities can be removed. That is, in the case of the fractionation and purification treatment, since maslininic acid and / or its physiologically acceptable salt can be obtained as white crystals, there is a merit such that it can be suitably blended without adding unnecessary color to food or the like. Do.
[116] Although it is difficult to define uniformly about the method of fractionation and purification, the recrystallization method, the fractionation precipitation method, the method using chromatography, etc. are mentioned, for example. In particular, a method using liquid chromatography is preferred among the chromatography because the yield can be satisfactorily fractionated and purified without degrading the maslinic acid and / or its physiologically acceptable salts contained in the food and oral whitening agent of the present invention. . Specific examples of liquid chromatography include normal phase liquid chromatography, reverse phase liquid chromatography, thin layer chromatography, paper chromatography, high performance liquid chromatography (HPLC), and the like. All the above methods can be used when fractionating and refining the physiologically acceptable salt. In consideration of separation ability, throughput, process water and the like, pure phase liquid chromatography, reverse phase liquid chromatography, and high performance liquid chromatography (HPLC) are preferred.
[117] Here, normal phase liquid chromatography means the following method, for example. That is, for example, a column in which silica gel is used as a fixed phase, a hexane-ethyl acetate mixture, a chloroform-methanol mixture, or the like as a mobile phase is prepared, and a coarse extract or an concentrate thereof from an olive plant is loaded at a loading factor of 0.1. A predetermined fraction is eluted by -5% (wt (mass) / v (volume)) by a continuous elution method using a single mobile phase or a stepwise elution method that sequentially increases the solvent polarity.
[118] Reverse phase liquid chromatography means the following method, for example. That is, for example, a column having a fixed phase, a water-methanol mixture, a water-acenitrile mixture, a water-acetone mixture, and the like, comprising a silica (ODS) bound to octadecylsilane, is prepared, and a coarse extract from an olive plant or The concentrate is represented by a loading ratio of 0.1 to 5% (wt (mass) / v (volume)) and eluted with a predetermined fraction by a continuous elution method with a single solvent or a stepwise elution method in which solvent polarity is sequentially reduced. to be.
[119] High-speed liquid chromatography (HPLC) is, in principle, the same as the above normal phase liquid chromatography or reverse phase liquid chromatography, and is used for fractionation and purification at a faster and higher separation ability.
[120] By combining one or two or more of the above methods, maslininic acid and / or its physiologically acceptable salts can be concentrated, which is preferable in that the impurities are removed.
[121] In addition, by combining one or two or more of the above methods, the purity of maslinic acid and / or its physiologically acceptable salts can be adjusted, and the strength, characteristics, and the like of the whitening effect can be designed as necessary.
[122] About the above-mentioned concentration treatment, Preferably, the concentration treatment can be repeated, and other concentration treatments can be combined. Similarly, the fraction and purification treatment can be preferably repeated and fractionation and purification treatment, and other fraction and purification treatments can be combined. After performing the concentration treatment, fractionation and purification may be performed. After performing the fractionation and purification treatment, fractionation and purification may be performed. After concentration treatment, fractionation and purification may be performed and concentration may be performed again. Naturally, you may perform combinations other than the combination mentioned above.
[123] By various combinations of the aforementioned extraction treatment, concentration treatment, fractionation and / or purification treatment, maslininic acid and / or its physiologically acceptable salts can be appropriately obtained. Although it does not specifically limit about the combination, The following methods are mentioned as a specific example of a series of process.
[124] For example, after extracting and treating the olive plant with water and / or a hydrophilic organic solvent, part or all of the hydrophilic organic solvent is removed from the obtained extract, and if necessary, water is added and stirred to precipitate the water layer. Recover water insoluble and concentrate. Precipitated water insoluble matter can be recovered by filtration, centrifugal separation, or the like. However, in order to improve the recovery efficiency, water can be added to the aqueous solution, stirred or the like as necessary. In addition, the dried state extract from which the water and / or the hydrophilic organic solvent of the extract obtained from an olive plant is removed is subjected to the treatment such as addition and stirring of water in the same manner as above, and the water insoluble content is recovered by filtration or the like and concentrated. can do. According to this concentration method, since it is a process in an aqueous system, it is more preferable than the concentration using a solvent, and the range of the apparatus which can be used is also wide, and it is preferable. Moreover, since it contains little oil, it is preferable because it is excellent in the efficiency of concentration and refining.
[125] By fractionation and purification of these concentrates by normal phase and / or reverse phase chromatography and / or recrystallization, maslininic acid purified from high purity and / or its physiologically acceptable salt can be appropriately obtained.
[126] In addition, the hydrophilic organic solvent was removed from the extract obtained from the olive plant, water was added to the remaining aqueous solution as needed, and then hydrophobic organic solvent was added again, and concentrated by liquid-liquid distribution in the water-hydrophobic organic solvent. Can be processed. In addition, water extracts in the dry state can be added in the same manner as above, followed by addition of hydrophobic organic solvents, and concentrated treatment by liquid-liquid distribution in water-hydrophobic organic solvents. These concentrates are fractionated and purified by normal phase and / or reverse phase chromatography and / or recrystallization, to thereby obtain highly purified maslininic acid and / or its physiologically acceptable salts.
[127] Herein, the amount of water to be added during liquid-liquid distribution is not particularly limited as long as it is an amount that can be dispensed, but is preferably 1 to 100 times by weight of the dried extract, more preferably 5 to 50 times, More preferably, it is about 10-30 times.
[128] In the liquid-liquid distribution in a water-hydrophobic organic solvent, water and a hydrophobic organic solvent are preferably used in a water: hydrophobic organic solvent = 9: 1 to 1: 9 (volume ratio), and 8: 2 to It is more preferable to use at 2: 8.
[129] Further, the total content of maslininic acid and their physiologically acceptable salts in the mixture of maslinic acid and its physiologically acceptable salts obtained from the olive plant and / or the product obtained in the olive oil manufacturing process is preferably 95% or more, more preferably. Preferably 95-99.99%. The content rate can be measured, for example by gas chromatography.
[130] Although the food and oral whitening agent of the present invention contains maslinic acid and / or its physiologically acceptable salts, the food or the like of the present invention may be obtained even when the extract and the concentrate are contained. In addition, the concentration of maslininic acid and / or its physiologically acceptable salts and the like can be adjusted by adjusting the degree of concentration, purification, and the like, and the compound can be appropriately blended with food or the like. That is, when a stronger effect is required, it can be concentrated, and when the weak effect can be diluted, it can also be diluted, and can be made into the form suitable for use at the density | concentration according to a use purpose.
[131] In addition, it is possible to mix and use other whitening substances, and thus, it is possible to design a detailed whitening effect, and also to greatly enhance the whitening effect by synergy with other whitening effect substances. That is, the whitening effect can be designed by appropriately adjusting the strength and efficacy of the whitening effect. The intensity | strength of the whitening effect can be adjusted by diluting and mix | blending when a more powerful effect is needed, and when it may be a weak effect, for example, and it can be set as the intensity according to a use purpose. Or the intensity | strength of the whitening effect can also be adjusted by combining the whitening component other than the five-ring triter pan made into object by this invention, and the maslininic acid made into object by this invention. The effects of the whitening effect include sun protection by blocking ultraviolet rays, prevention of pigmentation occurring after sunburn, and improved effects after pigmentation. Such efficacy can be adjusted by combining the five-ring triter pans targeted by the present invention with other whitening agents other than the five-ring triter pans.
[132] Since olive oil contains maslininic acid, an appropriate whitening effect and the like are obtained for the food and oral whitening agent of the present invention by using olive oil as an oily component.
[133] Further, when extracting maslininic acid and / or its physiologically acceptable salts from an olive plant, at the same time oleanolic acid and / or its physiologically acceptable salts are extracted, but this oleanolic acid and / or its physiologically acceptable salts is masri Since the compatibility with nitric acid is excellent, these mixture can be mix | blended directly with the foodstuff of this invention. Thereby, a synergistic effect can be expected with respect to the physiological effect which each has, and especially since a synergistic effect can be expected with respect to the whitening effect in this invention of maslinic acid and / or its physiologically acceptable salt, it is preferable. When maslininic acid and / or its physiologically acceptable salts are extracted and fractionated from an olive plant, the conditions may be adjusted to obtain a mixture with oleanolic acid and / or its physiologically acceptable salts, respectively, separately from the olive plant. Separately, maslininic acid and / or its physiologically acceptable salts, oleanolic acid and / or its physiologically acceptable salts can be isolated and subsequently mixed. Moreover, the mixture which mixed maslininic acid and / or its physiologically acceptable salt, and oleanolic acid and / or its physiologically acceptable salt which were respectively obtained from different raw materials may be sufficient.
[134] In addition, five-ring triterpanes other than maslininic acid and / or its physiologically acceptable salts can be isolated from natural products in accordance with the raw materials and methods described for maslininic acid and / or its physiologically acceptable salts.
[135] In the case of using food and oral whitening agents using an isolated material from natural products, the effect of contaminants derived from natural products is eliminated, which is preferable because it is colorless to pale and / or odorless to odorless. Therefore, by isolating the five-loop triter pans and their physiologically acceptable salts or derivatives thereof from natural products, it is possible to cook without affecting the flavor of the dish to be provided. In particular, it can mix | blend with the dish which does not require the flavor of the natural material made from raw materials, such as olive. Therefore, the food or drink of the present invention includes foods that can be cooked or blended without being affected by the kind of natural products used as raw materials.
[136] In addition, when olive or olive oil is ingested as it is, only a small amount of the five-loop triter pans of the present invention can be ingested, but when the food or oral whitening agent containing the five-ring triter pans isolated from natural products is ingested, The five-cycle triter pan can be ingested relatively easily in large quantities.
[137] In addition, since the five-loop triter pans included in olives and the like are generally fat-soluble substances, they are usually present in fats and oils, and therefore, it is difficult to mix them with foods in water, but if the five-loop triter pans isolated from natural products are oils, It can be mix | blended with the food of the system, and the food of an aqueous system. By using water-based foods such as soft drinks, it is possible to easily ingest, for example, several g to several tens of five-ring triter pans to be the object of the present invention.
[138] In addition, the food or oral whitening agent of the present invention containing five-ring triter pans isolated from natural products is free from impurities or contaminants that inhibit the whitening effect of the present invention or absorption into the body of the present invention. It is desirable to obtain a whitening effect of suitable skin.
[139] In addition, the five-ring triterpanes contained in the food and oral whitening agent of the present invention has a function of inhibiting melanogenesis.
[140] Melanin production suppression function is a function which suppresses the biosynthesis of melanin pigment by melanocytes stimulated by ultraviolet exposure, hormonal abnormalities, genetic information and the like. In general, dark skin, blemishes, freckles, and dark circles are thought to be caused by melanocytes being stimulated by ultraviolet rays stimulation or hormonal abnormalities, and thus biosynthetic melanin pigments are deposited on the skin. Therefore, if the production of melanin can be suppressed, it is possible to prevent and improve dark skin, blemishes, freckles and dark circles. That is, the food and oral whitening agent of the present invention can enjoy the melanin production inhibiting function by containing the five-ring triter pan, which is ingested to express the function from the inner surface of the body and to maintain a beautiful and beautiful skin. To contribute.
[141] Melanin production inhibitory function of the five-ring triter pan contained in the food and oral whitening agent of the present invention is shown by a test method using cultured pigment cells. Pigment cells are melanin-producing cells which, when cultured normally, melanin accumulates and becomes black. In contrast, when a substance having a melanin production inhibitory function is present in the culture system, the production of melanin is suppressed and is relatively whitened. From this degree of relative whitening, the melanin production suppressing function can be expected.
[142] According to the evaluation in the above test method, the whitening effect of the five-ring triter pans and their physiologically acceptable salts or derivatives thereof contained in the food and oral whitening agent of the present invention is known as magnesium ascorbate phosphate which is a known oral whitening agent. Compared with, for example, about 100 to 200 times in maslininic acid, about 100 to 200 times in salt of maslininic acid, about 10 to 100 times in erythrodiol, about 100 to 200 times in ursolic acid, about 30 in Ubaol ~ 120 times, about 30 to 120 times with betulinic acid, about 10 to 100 times with betulin, about 100 to 200 times with ethyl ester of maslininic acid, about 50 to 150 times with acetylated maslininic acid, triethylsilylated maslininic acid About 30 to 120 times, about 50 to 150 times with ethyl stearoylated maslininate, about 10 to 100 times with acetylated erythrodiol, about 100 to 200 times with ethyl ursolate, acetylated In approximately 10 to 100 times, betulinic acid ethyl ester in approximately 10 to 100 times, acetylated betulinic the baol of about 5 to 50 times, and has a high melanogenesis inhibitory function. That is, the food and oral whitening agent of the present invention can enjoy a very strong melanin production inhibiting function by containing five-ring triterpanes and their physiologically acceptable salts or derivatives thereof.
[143] Five-ring triterpanes, derivatives having an alcohol ester group thereof, derivatives having a fatty acid ester group, derivatives having an alkoxy group, derivatives having an alkoxymethyl group are generally useful, and thus are suitably formulated for foods or oral whitening agents of oil or emulsion type. can do. Moreover, especially in intake as a combination fat or oil processed product, since it is expected to be absorbed with oil, it is preferable at the point of water absorption.
[144] In addition, since the physiologically acceptable salts or glycosides of the five-membered triter pans are generally water-soluble, they can be suitably blended by uniformly dissolving or dispersing them in foods such as aqueous or emulsifying systems and oral whitening agents. In particular, beverages and the like are often commercialized in an aqueous or emulsified system. In this case, five-ring triter pans can be suitably blended as the physiologically acceptable salts or glycosides as necessary.
[145] In addition, the five-loop triter pans and / or their physiologically acceptable salts have a cost advantage since they can be obtained by mixing with very small amounts of food, oral or whitening agents, and the whitening effect usually required. In view of the above, since there is a margin for blending other components, other functions can be further satisfied, which is preferable.
[146] Naturally, the production of food and oral whitening agents having a very good whitening effect and the like by increasing the compounding amount of the five-loop triter pans and / or their physiologically acceptable salts is possible by the present invention.
[147] The food and oral whitening agent of the present invention is orally ingested to express a whitening effect.
[148] The whitening effect is to improve or prevent dark skin, blemishes, freckles and dark circles caused by various factors such as UV exposure, changes in hormonal balance, genetic programs, etc., making skin beautiful or transparent It aims to maintain beautiful skin and reduce the dullness of the skin to increase the luster and tension. In general, dark skin, blemishes, freckles, and dark circles are known to be caused by melanocytes being stimulated by ultraviolet light stimulation or hormonal balance changes, and thus biosynthetic melanin pigments are deposited on the skin. Therefore, if the production of melanin can be suppressed, it is possible to prevent and improve dark skin, blemishes, freckles and dark circles. In this respect, since the food and oral whitening agent of the present invention contains five-ring triterpanes having melanin production-inhibiting function, the production of melanin pigments can be expected to be minimized. That is, the food and oral whitening agent of the present invention expresses its whitening effect by ingestion, and greatly contributes to improving or preventing dark skin, blemishes, freckles, and dark circles to maintain a beautiful skin with transparency.
[149] The whitening effect as food can be evaluated as an indicator of the degree of improvement of pigmentation of the skin, for example, by ingesting a feed containing five-ring triter pans into the animal.
[150] Specifically, half of the brown guinea pig's back is epilated and irradiated with UV lamps for 2 weeks, and these guinea pigs are irradiated so as not to cause a difference in the degree of melanin pigmentation caused by UV induction. The test foods containing various triter pans were fed to each herd to the low-vitamin C-containing feed, and compared with the control group and the positive control group for the degree of pigmentation of the skin after 4 weeks. have.
[151] From these evaluations, it was found that the five-ring triter pans in the present invention can be orally ingested to reliably improve pigmentation to the skin early and to be inconspicuous.
[152] The whitening effect as a food in humans is an indication of the improvement of pigmentation, blemishes, freckles, dark circles, and dullness of the skin when, for example, a granulated confectionery containing five-ring triter pans is actually ingested. Can be evaluated as.
[153] Specifically, 30 females aged 25 to 50 were randomly divided into two groups of 15 people each, and each group was used as a control group and a test group. Confectionery was served to the control group by equal grain snacks that did not contain five-ringed triterpanes every morning, lunch, and dinner at the same time. After 12 weeks, each subject was allowed to self-evaluate the improvement of pigmentation, blemishes, freckles, dark circles, and dullness of the skin, thereby evaluating the whitening effect.
[154] In this evaluation, the food and oral whitening agent of the present invention reliably prevent and improve skin pigmentation, blemishes, freckles, dark circles, and dullness compared to equivalent foods that do not contain five-ring triter pans. I knew that I could make it beautiful skin.
[155] In addition, the present invention relates to a food containing one or two or more selected from five-ring triter pans and their physiologically acceptable salts, or derivatives thereof. It relates to the food to contain as a component. To contain as a whitening ingredient is to contain in an extent to have a whitening effect of the skin and to produce a whitening effect.
[156] In the food and drink of the present invention, the content of five-ring triter pans and their physiologically acceptable salts, or derivatives thereof is not particularly limited, and the kinds, five kinds of foods, intakes, What is necessary is just to adjust suitably according to the frequency of ingestion, the weight of a person to take, sex, etc., and it is although it does not restrict | limit especially, For example, 0.00001-50 mass%, Preferably it is 0.001-30 mass%, More preferably, it is 0.001-20 mass %, Especially preferably, it is 0.01-15 mass%, More preferably, it is 1-10 mass%, Most preferably, it is 2-10 mass%. When it contains as a whitening component, it does not restrict | limit in particular similarly.
[157] Since the food of the present invention contains the five-membered triter pan and the like, it has various effects that they have, but in particular, has a skin whitening effect. Because it is food, it can be easily and continuously ingested, and a suitable effect can be expected.
[158] In addition, the present invention is preferably one species selected from the olean-based triter pans represented by the formula (1), the Ulsan-based triter pans represented by the formula (2), the lupan-based triter pans represented by the formula (3) Or two or more kinds of food. These are especially preferable because they have a strong whitening effect.
[159] For the oleanan-based triter pans, maslininic acid and / or erythrodiol are preferable, and in particular, masurinic acid is preferable. For the Ulsan-based triter pans, the case of ursolic acid and / or ubaol is preferable. For lupine-based triter pans, betulinic acid and / or betulin are preferable. The content thereof is not particularly limited as described above, but is, for example, 0.00001 to 50% by mass, preferably 0.001 to 30% by mass, more preferably 0.001 to 20% by mass, particularly preferably 0.01 to 15% by mass, More preferably, it is 1-10 mass%, and most preferably 2-10 mass%. When it contains as a whitening component, it does not restrict | limit in particular similarly.
[160] In addition, the food and drink of the present invention can be blended with other physiologically active ingredients for the purpose of improving the function, in particular, synergistically improving the whitening effect, assisting in the whitening effect, and improving the absorbency. There is no particular limitation, but for example, other oral whitening ingredients that can be expected to have a synergistic effect, antioxidants that contribute indirectly to the whitening effect, oily ingredients to enhance the efficiency of the body by improving its absorption, nutritional enhancement Various vitamins, minerals, amino acids and the like can be mentioned.
[161] Other oral whitening ingredients include vitamin C and its derivatives and salts thereof, kojic acid and its derivatives, hydroquinone and its derivatives, pro-anthocyanidins, isofuravonoids and their derivatives, tannins, cysteine and glutathione, and the like. And colloidal sulfur, peptides having a specific amino acid sequence, placental extract, strawberry geranium extract, yokuining extract, golden extract, seaweed extract, wheat extract and the like. Among these oral whitening agents, particularly preferred examples thereof include vitamin C and derivatives thereof, salts thereof, pro-anthocyanidins, isofurabonoids and derivatives thereof, and tannins. These oral whitening agents are preferable because they can expect synergistic effects with the five-ring triter pans in the present invention. When using together with the foodstuff of this invention, it is preferable to use these whitening agents and the foodstuff of this invention in the range of 0: 100-99.99: 0.01 (mass ratio). When the placenta extract and the plant extract are used in the state of extract, it is good to use this range as dry solid content. If it is this range, it will show more excellent whitening effect.
[162] The antioxidant component is not particularly limited as long as it is commonly used in foods and the like, but for example, vitamin C and its derivatives and salts thereof, tocopherol, tocotorienol and derivatives thereof, dibutylhydroxytoluene, butylhydroxyanisol and ethylene Diamine disodium acetate, sodium ethylenediamine dibasic sodium acetate, tannins and derivatives thereof, such as molar assets and erratic acid, sulfuric compounds such as sodium sulfite, sodium hyposulfite and sulfur disulfide, ferulic acid derivatives such as γ-orizanol, and rutin And derivatives thereof, sesamin, episamine, sesaminol, sesamolin, sesamol and other lignans and their glycosides, carotenoids such as β-carotene and derivatives thereof, flavones, catechins, kelcetin, isocelcetin, leucoanthos Cyanidin, Genistin, Genistein, 6 ”-O-acetylgenistin, 6” -O-malonylgenistin, Dydazine, Diyzein , 6 ”-O-acetylidezine, 6” -O-malonyldiazine, glycidine, glycidine, 6 ”-O-acetylglycithin, 6” -O-malonylglycithin, Flavonoids such as puerin, quercetin, camphorol, and labyrol, quinones such as ubiquinone and vitamin K, enzymes such as superoxide dismutase, catarases, and glutathione peroxidase, mallow extracts, and asus Ferguers terreus extract, licorice oil extract, cloves extract, guayac resin, green coffee bean extract, rice bran extract, canna extract, sage extract, buttercup extract, tempe extract, rapeseed oil extract, pimenta extract, blueberry extract, pro Police extract, pepper extract, melaleuca extract, eucalyptus extract, gentian extract, buckwheat extract, red bean extract, rosemary extract, olive extract, soybean extract, soybean germ extract, thiamines and the like , Riboflavin such as riboflavin and riboflavin acetate, pyridoxine such as pyridoxine hydrochloride, pyridoxine dioctanoate, nicotinic acid such as nicotinic acid amide, and nicotinic acid benzyl, bilirubin, mannitol, tryptophan, histidine, nordihydro Guaiaretic acid; and the like. These antioxidants are known to indirectly have a whitening effect, and are also preferable because of their synergistic effect on the skin due to the anti-aging effect and the anti-aging effect on the skin due to the original antioxidant action.
[163] The oily component is not particularly limited in addition to animal fats and oils such as soybean oil, rapeseed oil, sesame oil, olive oil, lard, bee tallow, fish oil, etc. The structure maintenance etc. which designed the structure of MCT, MLCT, diglyceride, monoglyceride, and a fatty acid obtained by the above are mentioned.
[164] Various vitamins, minerals, amino acids and the like for nutritional enhancement are not particularly limited, but those specified in the food additive process sheet are preferred.
[165] In addition, the foodstuff of this invention can mix | blend and use the raw material used for normal foodstuff. Although there is no restriction | limiting in particular, For example, animal fats and oils, such as miso, soy sauce, sauce, ketchup, bouillon, charcoal beef yakiniku sauce, curry, stew premix, soup premix, instant bouillon, various seasonings, lard, Uji, fats and oils, etc. Seafood oils such as whale oil, sardine oil, herring oil, soybean oil, vegetable oil, cottonseed oil, rice oil, corn oil, sesame oil, peanut oil, sunflower oil, safflower oil, camellia oil, olive oil, linseed oil, copper oil, Vegetable oils such as castor oil, coconut oil, palm oil, cacao oil, thickeners such as xanthan gum, sweeteners such as sugar, granulated sugar, lactose, fructose, dextrose, sorbitol, honey and MSG (glutamic acid soda) Edible vinegars such as seasonings, rice vinegar, apple cider vinegar, spirit vinegar, acidifiers such as citric acid, malic acid, lactic acid, tartaric acid, synthetic preservatives such as sodium benzoate, salt, pepper, spices and the like. In particular, olive oil is very preferable because it contains maslinic acid and the like in the present invention.
[166] Each said component can be suitably designed and mix | blended according to a use purpose. According to the kind of water absorbency or effect, the whitening effect can be enhanced or supplemented, or a preferred embodiment can be used. For example, isofurabons and derivatives thereof are excellent in water solubility and act on the body simultaneously with the five-ring triterpans in the present invention, which are generally useful substances, and include tyrosinase inhibitory effect, and include water and lipids. It is anticipated that the synergistic effect through various mediated metabolic pathways will be exerted, and the effect will be synergistic. In addition, the whitening food and the like, which is a combination of the five-ring triter pan and the isoflavonoid in the present invention, can be expected to simultaneously activate synergistically the physiological activity such as the antioxidant and estrogen of the isoflavonoid.
[167] Although the specific example is listed below about the foodstuff of this invention, this invention is not limited to these. Although the foodstuff of this invention does not have a restriction | limiting in particular about the form, etc., For example, in addition to a normal form, it can take the form of liquid food, enteral nutrition, health food, infant food, etc. Specifically, Japanese sweets such as sliced rice cakes, rice cakes, rice cakes, manju and candy, cookies, biscuits, crackers, cereal foods, pies, castella, donuts, puddings, sponge cakes, waffles, butter cream, custard cream, cream puffs, Chocolate, chocolate, caramel, candy, chewing gum, jelly, hot cakes, breads, buns, Western sweets, snacks such as potato chips, ice cream, popsicles, sherbets, ice cream, lactic acid beverages, lactic acid bacteria drinks, rich Soft drinks, such as oily beverages, fruit juices, pulp drinks, functional drinks, carbonated drinks, preference products such as green tea, black tea, coffee, cocoa and their drinks, sake, wine, brandy, whiskey, medicinal liquor, milk , Dairy products such as fermented milk, processed milk, cheese, soybean processed foods such as soy milk, tofu, jams, fruit syrups, flower pastes, peanut pastes, fruit pastes, such as pickles, udon noodles, pasta Products, meat products such as ham, sausages, bacon, dry sausages, beet jockeys, hamburgers, fish products such as fish hams, fish sausages, fish paste, fish paste, hampen, dried fish such as fish, shellfish, bonito, mackerel and tuna Various salted foods such as squids, sea urchins and squids, salted foods such as squids and fish, smoked products such as salmon, seaweed, green fish, shellfish, wild vegetables, shiitake mushrooms, kelp and soy sauce, curry and stew Retort food, miso, soy sauce, sauce, ketchup, bouillon, charcoal grilled yakiniku sauce, curry, stew premix, various types of soup premix, instant bouillon, rice oil, combination oil or margarine, shortening, mayonnaise, dressing And fats and oils such as fats and oils, various ranges containing a combination fat and fat, frozen foods, and the like. In particular, in terms of continuous intake, rice and various seasonings, processed fats and oils such as margarine, shortening, mayonnaise, dressing may be preferred. In addition, the shape and properties are not particularly limited, and any one may be solid, semisolid, gel, liquid, powder, or the like.
[168] Since the five-circuit triter pans in the food and drink of the present invention are largely oil-soluble substances, fats and oils, processed foods, and the like are preferable as foods of the present invention in terms of solubility. Although there is no restriction | limiting in particular as such fats and oils, For example, the combination fats and oils which melt | dissolved and contained the five-ring triter pan obtained by natural or artificial in normal fats and oils can also be mentioned. And combination oils and fats containing five-ring triter pans at high concentrations in the compressed and extracted oils, and combination oils and fats remaining in the oil by adjusting the refining conditions. In addition, it is also possible to mix the five-fold triter pan-containing combination fat and other fats and oils, in this case, a synergistic effect with the physiological activity effect of the trace components contained in the other fats and oils can be expected.
[169] Since the five-loop triter pans can be obtained from plants which are oils and fats raw materials, combination fats and oils are preferable in terms of manufacturing, and margarine, shortening, It can be said that fats and oils, such as mayonnaise and dressing, are preferable.
[170] Similarly, the product using the said combination fats and oils of this invention is also favorable. Here, using means using both as a raw material, what is used as what is called combined fats and oils used for frying, roasting, etc.
[171] Here, there are no particular limitations on the use of five-membered triterpanes in food, but five-membered triterpanes, or derivatives having an alcohol ester group, derivatives having an fatty acid ester group, derivatives having an alkoxy group, and alkoxymethyl groups for oil-based foods. Preference is given to derivatives having Since they are relatively useful, they can be suitably applied to oil-based foods. In addition, although it is also possible to mix | blend the physiologically acceptable salt or glycoside of five-ring triter pans, in this case, it is preferable to use an emulsifier.
[172] In addition, for aquatic foods, physiologically acceptable salts or glycosides of 5-ring triter pans are preferable. Since they are relatively water soluble, they can be suitably applied to foods in water. It is also possible to mix | blend other five-ring triter pans or its derivative naturally, of course, In this case, it is preferable to use an emulsifier.
[173] By ingesting the food of the present invention, the effect is obtained by absorbing the five-loop triter pans and their physiologically acceptable salts, or derivatives thereof, which have a skin whitening effect. Since it is a form of food and drink, it does not require effort, such as cosmetics, and since it can be consumed continuously, it is preferable.
[174] The present invention relates to an oral whitening agent comprising one or two or more selected from the group consisting of five ring triterpanes and their physiologically acceptable salts or derivatives thereof.
[175] Oral whitening agent of the one or two or more selected from the olean-based triter pans represented by the formula (1), the Ulsan-based triter pans represented by the formula (2), the lupan-based triter pans represented by the formula (3) will be. For the oleanane-based triter pans, maslinic acid and erythrodiol are preferable, and in particular, maslinic acid is preferable. About Ulsan type | system | group triter pan, ursolic acid and ubaol are preferable. For lupine-based triter fans, betulinic acid and betulin are preferable.
[176] The oral lightening agent of the present invention has a melanin production inhibitory effect, and is particularly used as a prophylactic and / or therapeutic agent for dark skin, blemishes, freckles, dark circles, dullness and the like. The use as a prophylactic agent means that it is used for the purpose of suppressing melanin production and preventing skin blackening, blemishes, freckles, dark circles, and dullness. Use as a therapeutic agent reduces total melanin levels by further inhibiting melanin production or by rapid decomposition of melanin, thereby removing blackening, blemishes, freckles, dark circles, dullness, etc. To use for that purpose.
[177] The oral whitening agent of the present invention may be used in the form of tablets, powders, capsules, granules, pills, solid preparations such as tablets, powders, capsules, granules and pills, or aqueous solutions, suspensions, emulsions, and the like. It is obtained by preparation into a liquid preparation or the like. Specifically, tablets such as uncoated tablets, sugar coated tablets, coated tablets, enteric tablets, chewed tablets, oral tablets, sublingual tablets, troche tablets, and attached tablets; Powder; Capsules such as hard capsules and soft capsules; Granules, solvents, shakers, suspensions, emulsions, syrups, dry syrups, elixirs, acupuncture agents, powders, such as coatings, pills, troches, liquid preparations, or their pharmaceutically acceptable sustained release preparations Although it is provided in the form of liquid materials, such as limonad, etc., it is not specifically limited to these forms. In formulating, excipients, binders, disintegrants, lubricants, coatings, bases, suspending agents, emulsifiers, humectants, preservatives, stabilizers, surfactants, corrigents, etc., which are generally used in oral dosage forms, are added. In addition, it can manufacture according to a conventional method. Among them, uncoated tablets, sugar coated tablets, coated tablets, enteric tablets, chewed tablets, powders, capsules, and granules are preferable.
[178] In addition, the oral whitening agent of the present invention can be used in combination with other physiologically active ingredients for the purpose of improving the function, in particular, synergistically improving the whitening effect, assisting in the whitening effect, and improving the absorbency. There is no particular limitation, but for example, other oral whitening agents that can expect synergistic effects, antioxidants that indirectly contribute to whitening benefits, oily ingredients to enhance the efficiency of the body by improving the absorption efficiency, nutritional enhancement And various vitamins, minerals, amino acids and the like.
[179] Other oral whitening components include vitamin C and derivatives thereof, salts thereof, kojic acid and derivatives thereof, hydroquinone and derivatives thereof, pro-anthocyanidins, isofurabonoids and derivatives thereof, tannins, cysteine and glutathione, and the like. Base agents, colloidal sulfur, peptides having certain specific amino acid sequences, placental extracts, strawberry geranium extracts, yokuining extracts, golden extracts, seaweed extracts, wheat extracts and the like. Among these oral whitening agents, particularly preferred examples thereof include vitamin C and derivatives thereof, salts thereof, pro-anthocyanidins, isofurabonoids and derivatives thereof, and tannins. These oral whitening agents are preferable because they can expect synergistic effects with the five-ring triter pans in the present invention. When using together with the oral whitening agent of this invention, it is preferable to use these whitening agents and the oral whitening agent of this invention in the range of 0: 100-99.99: 0.01 (mass ratio). When the placenta extract and the plant extract are used in the state of extract, it is good to use this range as dry solid content. If it is this range, it will show more excellent whitening effect.
[180] The antioxidant component is not particularly limited as long as it is commonly used in foods and the like, but for example, vitamin C and its derivatives and salts thereof, tocopherol, tocotorienol and derivatives thereof, dibutylhydroxytoluene, butylhydroxyanisol and ethylene Diamine disodium acetate, sodium ethylenediamine dibasic sodium acetate, tannins and derivatives thereof, such as molar assets and erratic acid, sulfuric compounds such as sodium sulfite, sodium hyposulfite and sulfur disulfide, ferulic acid derivatives such as γ-orizanol, and rutin And derivatives thereof, sesamin, episamine, sesaminol, sesamolin, sesamol and other lignans and their glycosides, carotenoids such as β-carotene and derivatives thereof, flavones, catechins, kelcetin, isocelcetin, leucoanthos Cyanidin, Genistin, Genistein, 6 ”-O-acetylgenistin, 6” -O-malonylgenistin, Dydazine, Diyzein , 6 ”-O-acetylidezine, 6” -O-malonyldiazine, glycidine, glycidine, 6 ”-O-acetylglycithin, 6” -O-malonylglycithin, Flavonoids such as puerin, quercetin, camphorol, and labyrol, quinones such as ubiquinone and vitamin K, enzymes such as superoxide dismutase, catarases, and glutathione peroxidase, mallow extracts, and asus Ferguers terreus extract, licorice oil extract, cloves extract, guayac resin, green coffee bean extract, rice bran extract, canna extract, sage extract, buttercup extract, tempe extract, rapeseed oil extract, pimenta extract, blueberry extract, pro Police extract, pepper extract, melaleuca extract, eucalyptus extract, gentian extract, buckwheat extract, red bean extract, rosemary extract, olive extract, soybean extract, soybean germ extract, thiamines and the like , Riboflavin such as riboflavin and riboflavin acetate, pyridoxine such as pyridoxine hydrochloride, pyridoxine dioctanoate, nicotinic acid such as nicotinic acid amide, and nicotinic acid benzyl, bilirubin, mannitol, tryptophan, histidine, nordihydro Guaiaretic acid; and the like. These antioxidants are known to indirectly have a whitening effect, and are also preferable because of their synergistic effect on the skin due to the anti-aging effect and the anti-aging effect on the skin due to the original antioxidant action.
[181] The oily component is not particularly limited in addition to animal fats and oils such as soybean oil, rapeseed oil, sesame oil and olive oil, lard, tallow and fish oil, but is not limited to, for example, MCT, MLCT, Diglyceride, monoglyceride, the structure maintenance which designed the structure of fatty acid, etc. are mentioned.
[182] Various vitamins, minerals, amino acids and the like for nutritional enhancement are not particularly limited, but those specified in the food additive process sheet are preferred.
[183] Each said component can be suitably designed and mix | blended according to a use purpose. According to the kind of water absorbency or effect, the whitening effect can be enhanced or supplemented, or a preferred embodiment can be used. For example, isofurabons and derivatives thereof are excellent in water solubility and act on the body simultaneously with the five-ring triterpans in the present invention, which are generally useful substances, and include tyrosinase inhibitory effect, and include water and lipids. It is anticipated that the synergistic effect through various mediated metabolic pathways will be exerted, and the effect will be synergistic. In addition, oral whitening agents including the five-ring triter pan and the isoflavonoid in combination with the present invention can be expected to synergistically activate the physiological activity such as the antioxidant and estrogen of the isoflavonoid at the same time.
[184] The oral whitening agent of the present invention has the whitening effect as described above. That is, the oral whitening agent of the present invention can be directly or indirectly consumed to enjoy the whitening effect. In addition, more desirable effects can be obtained by continuous ingestion. To contain as an active ingredient means to contain the amount having the effect, the compounding quantity of the five-loop triter pans and their physiologically acceptable salts or derivatives thereof in the oral whitening agent of the present invention is generally defined. Depending on the type, prevention, or improvement of the triter pans, the effect required based on the period, amount, age, gender, weight, direct oral intake or blending as raw materials, etc. What is necessary is just to determine suitably according to the intensity | strength of the. Although not limited to the following, for example, 0.00001 mass% or more, Preferably it is 0.0001 mass% or more, More preferably, it is 0.001 mass%-99.9 mass%, More preferably, it is 0.001 mass%-99.99 mass%, More Preferably it is 0.01 mass%-99.9 mass%, More preferably, it is 0.01 mass%-99.99 mass%, More preferably, it is 0.1 mass%-99.9 mass%, More preferably, 0.01 mass%-99.99 mass%, More preferably, they are 1 mass%-99.99 mass%, More preferably, they are 2 mass%-99.99 mass%, Most preferably, they are 3 mass%-99.99 mass%. The higher the content, the stronger the effect, but in the case of direct oral ingestion, it is necessary to adjust the content in consideration of the effect on the human body, and when used as a raw material, a relatively high concentration is suitable.
[185] When maslininic acid, erythrodiol, ubaol, betulinic acid, betulin and / or their physiologically acceptable salts, or derivatives thereof are used as raw materials for oral whitening agent, preferably 0.1 mass% or more, more preferably 0.1 to 99.99 mass%, More preferably, it is 1-99.99 mass%, More preferably, it is 2-99.99 mass%, More preferably, it is 10-99.99 mass%, More preferably, it is 30-99.99 mass%, More preferably, 50-99. 99.99 mass%, More preferably, it is 70-99.99 mass%, More preferably, it is 80-99.99 mass%, More preferably, 90-99.99 mass% can be contained.
[186] In addition, by ingesting the food, the five-ring triterpanes of the oral whitening agent and their physiologically acceptable salts, or derivatives thereof, the small dose to obtain a whitening effect suitably is determined by the type of intake, sex, weight, condition of the subject. And the like, but are not particularly limited, and for example, 0.0001 g / 1 day or more, preferably 0.001 g / 1 day or more, more preferably 0.01 g / 1 day or more, particularly preferably 0.1 g / 1 day or more More preferably 0.5 g / 1 day or more, even more preferably 1 g / 1 day or more, and most preferably 2 g / 1 day or more.
[187] The oral whitening agent of the present invention is characterized by containing five-ring triter pans, and its use is arbitrary, but can be used in a wide range of fields, such as pharmaceuticals and quasi-drugs. At this time, the amount of the oral whitening agent of the present invention varies depending on conditions such as use, dosage form, type of administration target, age, sex, weight, degree of symptom, health condition, etc., but is not uniformly defined. It is an amount that is effective in preventing and / or treating skin, blemishes, freckles, dark circles, and dullness.
[188] As mentioned above, the oral whitening agent of this invention can be mix | blended with a foodstuff as a raw material, and the foodstuff which has a skin whitening effect can be obtained. The food or drink to which the oral whitening agent of the present invention is applied is as described above. The content of the oral whitening agent may be blended according to the strength of the effect of the oral whitening agent or the whitening effect to be obtained. What is necessary is just to adjust the content in 1 type (s) or 2 or more types of foods chosen from the group which consists of five-loop triter pans, their physiologically acceptable salts, or derivatives thereof, as an index to the content in the above-mentioned foods.
[189] Although the formulation is not specifically limited as a medicine, quasi-drug, beauty and health care products to which the oral whitening agent of the present invention is applied, and examples thereof include oral preparations such as tablets, granules, capsules, and potions. These medicines can take the required unit dosage form with physiologically acceptable vehicles, carriers, excipients, binders, stabilizers, flavors and the like. For example, compositions for tablets and capsules may include binders such as tragacanth, gum arabic, gelatin, hydroxypropyl cellulose and carboxymethyl cellulose, crystalline cellulose, microcrystalline cellulose, sugars (lactose, sucrose, glucose, etc.). And excipients such as starch (corn, potato, flour), swelling agents such as gelatinized starch, alginic acid, lubricants such as magnesium stearate, sweeteners such as sucrose, lactose, saccharin, flavoring agents such as peppermint, rhododendron and cherry Etc. can be mixed together and prescribed by an ordinary method.
[190] Oral whitening agent of this invention may be taken orally as it is, and it can also be mix | blended with oral ingestion of foods, medicines, etc. as a raw material.
[191] The present invention relates to maslininic acid, erythrodiol, oleanic triterpans, ursolic acid of ulsan-based triterpans, betulinic acid of ubaol, lupanic triterpans, betulin and their physiologically acceptable salts, or derivatives thereof. Although one or two or more of the present invention relates to a method of using as an oral whitening agent, the meaning of the use is, as described above, particularly used as a prophylactic and / or therapeutic agent for dark skin, blemishes, freckles, dark circles, dullness, etc. It includes both the use as a raw material and the direct use as an oral agent.
[192] The present invention relates to a food and oral whitening agent comprising five ring triterpanes and their physiologically acceptable salts or derivatives thereof. Since these five-ring triter pans are particularly excellent in skin whitening effects, the food and oral whitening agents of the present invention do not require the burden of time or effort, and are simply and continuously skin whitening effects. In addition, since the five-loop triter pans of the present invention can be obtained from natural plants, they can be used with confidence in daily use, and also have a refreshing feeling for the user. It is preferable for giving.
[193] Next, although an Example is given and this invention is demonstrated, this invention is not limited to these Examples.
[194] As a five-ring triter pan used in the examples, erythrodiol (manufactured by Funakoshi Co., Ltd.), ubaol (manufactured by Funakoshi Co., Ltd.), betulinic acid (manufactured by Funakoshi Co., Ltd.), and betulin (manufactured by Funakoshi Co., Ltd.) are purchased as reagents. It was. HPLC was used as it was, otherwise it was dissolved in ethanol heated to the boiling point until it became saturated, and then cooled and recrystallized, it was used by filtration and drying. Maslininic acid was described as an example below, but extracting and purifying from an olive plant was confirmed to have a purity of 95%.
[195] <Manufacture example 1>
[196] 500 g of dried fruits (including seeds) of Japanese olives (Olea europaea L.) were crushed, and 3 L of hexane was added and extracted for 3 hours. The seed was removed from the degreased fruit, which was repeated four times, pulverized and extracted again with 5 times the amount of hexane for 3 hours to obtain 229 g of degreasing waste, from which oil was completely removed. A hydrous ethanol aqueous solution of 60 mass% of 10-fold amount of ethanol was added to this degreasing waste, and it extracted for 3 hours, stirring vigorously at room temperature. After filtering the whole amount, the filtrate was concentrated to dryness to obtain 112.7 g of extract.
[197] 2 L of water was added to 100 g of this extract, and the mixture was stirred vigorously at room temperature for 1 hour. After the whole amount was treated by centrifugation, the supernatant was removed by decantation and the remaining precipitate was dried to give 10.0 g of concentrate.
[198] This concentrate was then fractionated by silica gel column chromatography using a column packed with about 40 times (400 g) silica gel. First, eluted unnecessary components in a 10-fold (4000 mL) hexane: ethyl acetate = 3: 1 eluent of the gel, and then again in a 2.5-fold (1000 mL) hexane: ethyl acetate = 1: 1 eluent. Unnecessary components were eluted. Subsequently, the target maslininic acid was eluted with a 10-fold (4000 mL) hexane: ethyl acetate = 1: 1 eluent of the filled gel, to obtain a coarse maslininic acid fraction. Hexane and ethyl acetate were removed from this fraction, followed by vacuum drying to obtain 1.96 g of a coarse maslininic acid fraction.
[199] This coarse maslininic acid fraction was purified by OSD column chromatography using a column packed with about 30-fold (60 g) octadecyl silica gel. First, miscellaneous unnecessary components were eluted with an eluent of 10 times (600 mL) methanol: water = 8: 2 of the filled gel. Subsequently, the desired maslininic acid was eluted with a 30-fold (1800 mL) methanol: water = 8: 2 eluent of the filled gel to obtain a purified maslininic acid fraction. After methanol was removed from this fraction, 1.51 g of purified maslininic acid (1) was obtained by vacuum drying.
[200] Here, the analysis of NMR, MS, etc. confirmed that this purified maslininic acid (1) was a part in the state of a sodium salt and a potassium salt, and the remainder was the state of a free acid. In addition, these purity was measured by GC and confirmed that the purity as maslininic acid was 95% or more.
[201] <Manufacture example 2>
[202] To 1 kg of milking residue obtained by milking olives from Italy, an aqueous hydrous ethanol solution containing 65 mass% of 10-fold amount of ethanol was added and extracted for 3 hours with vigorous stirring at room temperature. After filtering the whole amount, the filtrate was concentrated to dryness to obtain 20.2 g of an extract.
[203] 1L of n-butanol and 1L of water were added to this extract, and the mixture was stirred for 10 minutes, and then divided into n-butanol phase and aqueous phase. After removing n-butanol on n-butanol, it was vacuum-dried and 13.3g of concentrates were obtained.
[204] This concentrate was then fractionated by silica gel column chromatography using a column packed with about 40 times (500 g) silica gel. First, eluted unnecessary components were eluted with a 10-fold (5000 mL) hexane: ethyl acetate = 3: 1 eluent of the packed silica gel, followed by a 2.5-fold (1250 mL) hexane: ethyl acetate = 1: 1 eluent. Unnecessary components were eluted. Subsequently, the target maslininic acid was eluted with a 10-fold (5000 mL) hexane: ethyl acetate = 1: 1 eluent of the packed silica gel, to obtain a coarse maslininic acid fraction. Hexane and ethyl acetate were removed from this fraction, followed by vacuum drying to obtain 2.66 g of a coarse maslininic acid fraction.
[205] This coarse maslininic acid fraction was purified by OSD column chromatography using a column packed with about 30-fold (80 g) octadecyl silica gel. First, miscellaneous unnecessary components were eluted with 10 times (800 mL) methanol: water = 8: 2 eluent of the filled gel. Then, 30 times (2400 mL) methanol: water = 8: 2 eluent of the filled gel was eluted. The target maslininic acid was eluted, and the purified maslininic acid fraction was obtained. Methanol was removed from this fraction, followed by vacuum drying to obtain 2.06 g of purified maslininic acid (2).
[206] Here, from the analysis of NMR, MS, etc., it was confirmed that this purified maslininic acid (2) was part of the free acid state, and most of the remaining was the state of sodium and potassium. In addition, these purity was measured by GC and confirmed that the purity as maslininic acid was 97% or more.
[207] <Manufacture example 3>
[208] 10 kg of ethanol was added to 1 kg of milking residue (the skim residue from which the milking residue was processed in the extraction process) of Italian olive obtained at the olive oil manufacturing process, and it heated at 55 degreeC, and extracted for 3 hours, stirring vigorously. It was. After filtering the whole amount, the filtrate was concentrated to dryness to obtain an extract 35g.
[209] This extract was then subjected to silica gel column chromatography using a column packed with about 40 times (1400 g) silica gel. First, eluting unnecessary components in a 10-fold (14 L) hexane: ethyl acetate = 3: 1 eluent of the silica gel, followed by 2.5-fold (3500 mL) hexane: ethyl acetate = 1: 1 eluent Unnecessary components were eluted. Subsequently, the target maslininic acid was eluted with a 10-fold (14 L) hexane: ethyl acetate = 1: 1 eluent of the packed silica gel, to obtain a coarse maslininic acid fraction. Hexane and ethyl acetate were removed from this fraction, followed by vacuum drying to obtain 5.90 g of a coarse maslininic acid fraction.
[210] This coarse maslininic acid fraction was purified by OSD column chromatography using a column packed with about 30-fold (180 g) octadecyl silica gel. First, miscellaneous unnecessary components were eluted with a 10-fold (1800 mL) methanol: water = 8: 2 eluent of the filled gel. Subsequently, the desired maslininic acid was eluted with a 30-fold (5400 mL) methanol: water = 8: 2 eluent of the filled gel to obtain a purified maslininic acid fraction. Methanol was removed from this fraction, and it dried under vacuum to obtain 5.36 g of purified maslininic acid (3).
[211] Here, the analysis of NMR, MS, etc. confirmed that this refined maslininic acid (3) was a part in the state of a sodium salt and a potassium salt, and the remainder was the state of a free acid. In addition, these purity was measured by GC and confirmed that the purity as maslininic acid was 97% or more.
[212] Derivatives of the five-ring triter pans were obtained as follows.
[213] Synthesis Example 1 Ethyl Maslinate
[214] 4.5 g of maslinic acid and 1.0 g of triethylamine were dissolved in 50 mL of chloroform, and 1.1 g of thionyl chloride was dissolved in 10 mL of chloroform, and the mixture was stirred for 1 hour while dropping under ice cooling. Subsequently, 3.2 g of ethanol was added, and what dissolved 1.0 g of triethylamine in 10 mL of chloroform was stirred for 3 hours, dropwise under ice-cooling. After the completion of the reaction, the dissolved chloroform was extracted, and the crude reactant obtained by distilling off chloroform was purified by silica gel column chromatography to obtain 3.5 g of maslinic acid ethyl ester.
[215] Synthesis Example 2 2,3-O-di-acetyl-masrininic acid
[216] 2.0 g of maslinic acid was dissolved in 100 mL of pyridine, 50 mL of acetic anhydride was added, and the mixture was stirred overnight. After pyridine and acetic anhydride were distilled off, the residue was dissolved in ether, and the ether phase was washed once with 1N aqueous hydrochloric acid solution, once with saturated sodium bicarbonate solution and three times with pure water, and then magnesium sulfate Was added and left overnight. Magnesium sulfate was removed by filtration, and the crude reaction product obtained by distilling off ether was purified by silica gel column chromatography to obtain 2.2 g of 2,3-O-di-acetyl-maslininic acid.
[217] Synthesis Example 3 2,3-O-di-triethylsilyl-maslinic acid triethylsilyl ester
[218] 1.0 g of maslininic acid was dissolved in 200 mL of anhydrous dimethylformamide, 144.0 mg of imidazole and 350 μl of triethylsilyl chloride were added at 0 ° C., and the mixture was tightly stirred for 2 hours. After distilling off dimethylformamide, the residue was dissolved in ether, and the ether phase was washed once with 1N aqueous hydrochloric acid solution, once with saturated sodium bicarbonate solution and three times with pure water, and then left overnight by adding magnesium sulfate. It was. Magnesium sulfate was removed by filtration, and the crude reaction product obtained by distilling off ether was purified by silica gel column chromatography to obtain 1.5 g of 2,3-O-di-triethylsilyl-mastrininic triethylsilyl ester.
[219] Synthesis Example 4 2,3-O-di-stearoyl-ethyl maslinate
[220] 1.0 g of ethyl masrinate obtained in Synthesis Example 1 was dissolved in 50 mL of toluene anhydrous, 5.0 g of triethylamine were added, and 6.0 g of stearic acid chloride was gradually added under ice-cooling, stirring for 1 hour, and gradually returned to room temperature for 9 hours. Stirred. A proper amount of 1N aqueous hydrochloric acid solution was added, extracted with ether, and the ether phase was washed once with saturated sodium bicarbonate solution and three times with pure water, and then magnesium sulfate was left to stand overnight. The magnesium sulfate was removed by filtration, and the crude reaction product obtained by distilling off the ether was purified by silica gel column chromatography to obtain 1.2 g of ethyl 2,3-O-di-stearoyl-mastrininate.
[221] Synthesis Example 5 3,28-O-di-acetyl-erythrodiol
[222] 5.0 g of erythrodiol was dissolved in 250 mL of pyridine, 100 mL of acetic anhydride was added, and the mixture was stirred overnight. After pyridine and acetic anhydride were distilled off, the residue was dissolved in ether, and the ether phase was washed once with 1N aqueous hydrochloric acid solution, once with saturated sodium bicarbonate solution, three times with pure water, and then magnesium sulfate was added. It was left overnight. Magnesium sulfate was removed by filtration, and the crude reaction product obtained by distilling off ether was purified by silica gel column chromatography to obtain 5.4 g of 3,28-O-di-acetyl-erythrodiol.
[223] Synthesis Example 6 Ethyl Ursolate
[224] 5.0 g of ursolic acid and 1.1 g of triethylamine were dissolved in 50 mL of chloroform, and 1.2 g of thionyl chloride was dissolved in 10 mL of chloroform, and the mixture was stirred for 1 hour while dropping under ice cooling. Next, 3.5 g of ethanol was added, and the thing which melt | dissolved 1.1 g of triethylamine in 10 mL of chloroform was stirred for 3 hours, dropping under ice-cooling. After completion of the reaction, the dissolved chloroform was extracted, and the crude reaction product obtained by distilling off chloroform was purified by silica gel column chromatography to obtain 3.8 g of ursolic acid ethyl ester.
[225] Synthesis Example 7 3,28-O-di-acetyl-ubaol
[226] 5.0 g of uvaol was dissolved in 250 mL of pyridine, and 100 mL of acetic anhydride was added and stirred overnight. After pyridine and acetic anhydride were distilled off, the residue was dissolved in ether, and the ether phase was washed once with 1N aqueous hydrochloric acid solution, once with saturated sodium bicarbonate solution, three times with pure water, and then magnesium sulfate was added. It was left overnight. Magnesium sulfate was removed by filtration, and the crude reaction product obtained by distilling off ether was purified by silica gel column chromatography to obtain 5.4 g of 3,28-O-di-acetyl-ubaol.
[227] Synthesis Example 8 Ethyl Betudate
[228] 5.0 g of betulinic acid and 1.1 g of triethylamine were dissolved in 50 mL of chloroform, and 1.2 g of thionyl chloride dissolved in 10 mL of chloroform was added dropwise under ice cooling, followed by stirring for 1 hour. Next, 3.5 g of ethanol was added, and the mixture of 1.1 g of triethylamine dissolved in 10 mL of chloroform was stirred for 3 hours while being added dropwise under ice cooling. After the completion of the reaction, the dissolved chloroform was extracted, and the crude reactant obtained by distilling off chloroform was purified by silica gel column chromatography to obtain 3.8 g of betulinic acid ethyl ester.
[229] Synthesis Example 9 3,28-O-di-acetyl-vetulin
[230] 5.0 g of betulinic acid was dissolved in 250 mL of pyridine, and 100 mL of acetic anhydride was added and stirred overnight. After pyridine and acetic anhydride were distilled off, the residue was dissolved in ether, and the ether phase was washed once with 1N aqueous hydrochloric acid solution, once with saturated sodium bicarbonate solution, three times with pure water, and then magnesium sulfate was added. It was left overnight. Magnesium sulfate was removed by filtration, and the crude reaction product obtained by distilling off ether was purified by silica gel column chromatography to obtain 5.4 g of 3,28-O-di-acetyl-butulin.
[231] Example 1
[232] <Evaluation of melanin production inhibitory function>
[233] 2 ml / well of medium is taken into a plate with six holes, and a predetermined amount of B-16 melanomer cells are seeded, and the cells are left to culture at 37 ° C. and a carbon dioxide concentration of 5%. The next day, the sample sample (five triter pan) preparation solution is added and mixed so as to have a predetermined concentration, and the culture is continued. On day 5 of culture, the medium is changed and sample preparation is added again. The next day the medium is removed and the cells are collected, washed with PBS (phosphate buffered saline) and evaluated by the degree of whitening of the cells. In addition, evaluation of melanin production inhibitory function was compared with the whitening degree when 450 ppm (positive control) of vitamin C magnesium phosphate, which is known to be effective instead of the sample preparation, and the whitening level when no sample was added (control). It evaluated by the following references | standards.
[234] (Evaluation standard)
[235] <Evaluation> <contents>
[236] + + Whiter than positive control.
[237] + Whitened to the same extent as positive control.
[238] It's not as positive control, but whiter than control.
[239] － The same degree as the control
[240] The method of inhibiting melanin production was evaluated by the above method. The results are shown in Table 1.
[241] <Melanin production inhibition evaluation result>Concentration (ppm) 246810152550100200300450 Reference productVitamin C Magnesium Phosphate－－－－－±±+ InventionPurified maslinic acid 1±++++ Purified Maslinic Acid 2±++++ Purified Maslinic Acid 3 Erythrodiol±±±±±±++ Ursolic acid Ubaol－－－±++++ Betulinic acid－±±±++++ Betulin－－±±±+++ Compound of Synthesis Example 1±++++ Compound of Synthesis Example 2±±++++ Compound of Synthesis Example 3－±±+++++ Compound of Synthesis Example 4±±++++ Compound of Synthesis Example 5±±±±±±++ Compound of Synthesis Example 6－－－±++++ Compound of Synthesis Example 7－±±±++++ Compound of Synthesis Example 8－－±±±+++ Compound of Synthesis Example 9 Comparative productKojisan－－－±±+++
[242] * Standard is whitening degree when 450 ppm of vitamin C magnesium phosphate is added
[243] From Table 1, the melanin production inhibitory function of the five-ring triter pans and their physiologically acceptable salts or their derivatives was compared with the case of magnesium c-phosphate with a concentration of 450 ppm added as a positive control, respectively. It can be seen that it has a function of inhibiting melanin production from tens to hundreds of magnesium. For example, in the free maslinin (tablet maslininic acid 1), compared to the case where the concentration of vitamin C magnesium phosphate is 450 ppm, the addition concentration showing the same degree of whitening is 4 ppm. It can be seen that maslininic acid 1 and purified maslininic acid 3) have melanin production inhibitory function of about 110 times that of vitamin C magnesium phosphate. Similarly, on the basis of 450 ppm of vitamin C magnesium phosphate, about 110 times in the salt of maslininic acid (refined maslininic acid 2), about 20 times in erythrodiol, about 110 times in ursolic acid, and about 40 times in Ubaol. About 40 times in betulinic acid, about 20 times in betulin, about 110 times in ethyl mastrininic acid, about 75 times in acetylated maslininic acid, about 40 times in triethylsilylated maslininic acid, ethyl stearylated maslininate Inhibits melanin production by about 75 times, about 20 times with acetylated erythrodiol, about 110 times with ethyl ursolate, about 20 times with acetylated ubaol, about 20 times with ethyl betulinate, and about 10 times with acetylated betulin It can be seen that it has a function.
[244] Similarly, from Table 1, the whitening effect of the five-loop triter pans, their physiologically acceptable salts, or derivatives thereof is excellent as compared with koji acid which has been widely used.
[245] As described above, it was found that the five-ring triter pans and their physiologically acceptable salts, or derivatives thereof, have a phenomenal whitening effect of dozens to hundreds of times of the vitamin C magnesium phosphate widely used as a conventional oral whitening agent. . Accordingly, it has been clarified that food and oral whitening agents with very good whitening effects that have never been provided can be provided.
[246] Example 2
[247] <Confirmation test of whitening effect in animal>
[248] Brown guinea pigs (5 weeks old, males) were pre- bred for one week with commercial feed (Crea, Japanese Crea Corporation, CG-7), and then half of the back was shaved. On 5 minutes, on the 2nd and 3rd day, 1.0 mW was irradiated for 5 minutes. Subsequently, after 2 weeks of breeding with a low vitamin C feed (200.0 mg / kg), the guinea pigs were divided into 12 groups (seven in each group) so that there was no difference in the degree of melanin pigmentation induced by UV induction. As the vitamin C feed, the test food to which triter pans were added was freely taken to each group as shown in Table 2 below. However, the control group received low vitamin C feed and the positive control group added vitamin C. The pigmentation degree of the skin 4 weeks after the start of the test was judged based on the following criteria. The results are shown in Table 3.
[249] <Feeding composition> Group No.additiveAddition amount (mg / feed kg) 1 (control)-- 2 (positive control)L-ascorbic acid2500.0 3Purified maslinic acid 1500.0 4Purified maslinic acid 1250.0 5Erythrodiol500.0 6Ursolic acid500.0 7Ubaol500.0 8Betulinic acid500.0 9Betulin500.0 10Purified maslinic acid 2500.0 11Compound of Synthesis Example 1500.0 12Compound of Synthesis Example 2500.0
[250] (Evaluation standard)
[251] <Evaluation> <contents>
[252] Significantly less pigmentation compared to positive control group
[253] Medium pigmentation as medium improvement positive control group
[254] Slightly improved pigmentation between the control and positive control groups
[255] No change in pigmentation to the same degree as the control group
[256] <Whitening evaluation result in guinea pig> Group No.Markedly improvedMedium improvementSlightly improvedNo change 1 (control)0007 2 (positive control)0One42 34300 42320 5222One 642One0 7One4OneOne 824One0 9One32One 1033One0 1123OneOne 1224One0
[257] As shown in Table 3, it became clear that the five-necked triterfans and their physiologically acceptable salts, or derivatives thereof, can be improved orally inconspicuous by early oral ingestion.
[258] Example 3 Edible Combination Oil
[259] 5.0 g of purified maslininic acid 1 of Preparation Example 1
[260] Soybean oil 1000.0 g
[261] Purified maslinic acid 1 was added to the soybean oil in the above mixing ratio, and mixed and dissolved until the whole became clear using a stirrer while maintaining a temperature of 60 ° C to prepare an edible combination fat or oil.
[262] Example 4 Dressing
[263] 46.6 g of water
[264] Xanthan gum 0.1g
[265] Fructose, glucose, liquid sugar 5.0 g
[266] 5.0 g of salt
[267] MSG 0.3g
[268] Rice vinegar (acidity 10%) 10.0g
[269] Pepper quantity
[270] 1.0 g of purified maslininic acid 2 of Preparation Example 2
[271] Soybean Salad Oil 32.0g
[272] At the above mixing ratio, the raw materials except for soybean salad oil are first put into a warmable container with a stirrer, and heated at 100 rpm using a propeller stirrer and heated until the temperature of the mixture reaches 90 ° C, and the temperature of the mixture is increased. Stir for 25 minutes while maintaining at 90 ℃. Thereafter, the mixture was cooled to 20 ° C. and combined with soy salad oil to prepare a dressing. The finished dressing was a savory dressing.
[273] Example 5 Kernels
[274] 1.0 g of citric acid
[275] Skim milk powder 15.5g
[276] Sucrose Fatty Acid Ester 1.0g
[277] Spices
[278] 2.5 g of purified maslininic acid 1 of Preparation Example 1
[279] 20.0 g per granue
[280] 60.0 g of lactose
[281] The said raw material was mixed uniformly, it was made into granules, and it pressed tightly and obtained the grain confectionery which is 500 mg.
[282] Example 6 Cookies
[283] Margarine 70.0g
[284] 40.0 g of sugar
[285] 0.7 g of salt
[286] 20.0 g of eggs
[287] Force 100.0g
[288] 0.1 g of 3,28-O-di-acetyl-ubaol of Synthesis Example 7
[289] Raw materials were mixed by the above formulation, divided into 10 g each, and baked at 180 ° C. for 15 minutes to prepare cookies.
[290] Example 7 Soft Drinks
[291] 0.5 g of 3,28-O-di-acetyl-erythrodiol of Synthesis Example 5
[292] Honey 15.0g
[293] 0.1 g citric acid
[294] 0.1 g of dl-apple acid
[295] 10.0 g of D-sorbitol solution (70%)
[296] 0.1 g sodium benzoate
[297] Spices
[298] Residue to 100 g of purified water
[299] The raw materials were mixed uniformly to obtain a health beverage.
[300] Example 8 Tablets
[301] Purified maslininic acid 1 of Preparation Example 1 250.0 mg
[302] Corn starch 14.5mg
[303] Crystalline Cellulose 25.0mg
[304] Carboxymethyl cellulose calcium 10.5 mg
[305] Each substance was mixed well by the above mixing ratio, and the mixture was pressed tightly to obtain a tablet having 300 mg of tablets.
[306] Example 9 Edible Combination Oil
[307] 10.0 g of purified maslininic acid 3 of Preparation Example 3
[308] EXV. Olive Oil 1000.0g
[309] Add the refined maslinic acid 3 to EXV. Prepared.
[310] Example 10 Margarine
[311] Seed oil 42.0g
[312] Rapeseed oil 42.0g
[313] 14.0 g of water
[314] 0.5 g of salt
[315] 0.5 g of lecithin
[316] 0.4 g of monoglycerine
[317] Purified Maslininic Acid 1 of Preparation Example 1 0.6 g
[318] Spices
[319] Trace amount of carotene
[320] The raw materials were mixed by a conventional method, quenched and kneaded using a bonding machine to obtain margarine.
[321] Example 11 Mayonnaise
[322] Soybean Salad Oil 74.0g
[323] 8.4 g of water
[324] 1.0 g of sugar
[325] 0.3 g sodium glutamate
[326] 0.3g powder mustard
[327] 1.0 g of salt
[328] Rice Vinegar 4.0g
[329] 1.0 g of purified maslininic acid 2 of Preparation Example 2
[330] 10.0 g salted egg yolk
[331] In the blending ratio, the raw materials except for soybean salad oil and egg yolk to which salt was added were first heated to 90 ° C while mixing and stirring, and stirred for 25 minutes while maintaining at 90 ° C. After cooling to 20 ° C, the mixture was combined with soybean salad oil and egg yolk added with salt, followed by stirring under reduced pressure to obtain mayonnaise.
[332] Example 12 Powder
[333] 10.0 mg of purified maslininic acid 2 of Preparation Example 2
[334] Lactose 981.0mg
[335] Hydroxypropylcellulose 4.0mg
[336] Light anhydrous silicic acid 5.0mg
[337] In the above blending ratio, first, purified maslininic acid 2 and lactose are mixed well, and then hydroxypropyl cellulose is added to form granules. This was made into particles after drying, hard silicic anhydride was added and mixed well to obtain a powder.
[338] Example 13 Capsules
[339] 150.0 mg of ethyl ursolate of Synthesis Example 6
[340] Lactose 70.0mg
[341] Corn starch 38.0mg
[342] Magnesium Stearate 2.0mg
[343] In the above blending ratio, the capsules were obtained by filling the capsules with a mixture of each substance well.
[344] Example 14
[345] <Confirmation test of whitening effect in person>
[346] The whitening effect of the granulated confectionery obtained in Example 5 was evaluated as the degree of improvement of dark skin, blemishes, freckles, dark circles, and dullness when this was actually ingested.
[347] (Test Methods)
[348] The test was conducted on 30 women aged 25 to 50 who were suffering from dark skin, blemishes, freckles, dark circles and dull skin. That is, 30 women aged 25 to 50 were randomly divided into two groups of 15 people each, and each group was used as a control group and a test group. One tablet obtained in the same manner as Example 5 was given three tablets of 500 mg tablets equivalent to those of Example 5 containing no five-membered triter pans in the control group. Three tablets of mg confectionary were eaten at the same time every morning, lunch and dinner, that is, 9 tablets (4.5 g) per day in total. The tasting was carried out for 12 weeks, and at this point, each subject was self-evaluated based on the following criteria for improvement in dark skin, blemishes, freckles, dark circles, and dullness. The results are shown in Table 4.
[349] (Evaluation standard)
[350] <Evaluation> <contents>
[351] Significantly improved dark skin, blemishes, freckles, dark circles, and dullness almost visible
[352] It became inconspicuous
[353] Medium improvement Dark skin, blemishes, freckles, dark circles and dullness are quite noticeable
[354] It became inconspicuous
[355] Slightly improved dark skin, blemishes, freckles, dark circles, and dullness
[356] It became inconspicuous
[357] No change Before use and no change
[358] Markedly improvedMedium improvementSlightly improvedNo change Dark skinControl group00213 Trial Group5640 Blemish, freckleControl group00One14 Trial Group7530 Dark circlesControl group0One212 Trial Group374One DullnessControl group0One311 Trial Group4542
[359] As shown in the results of Table 4, the granulated confectionery of Example 5 prevents dark skin, blemishes, freckles and dark circles, prevents and improves the dullness of the skin, making it inconspicuous and beautiful skin. It became clear that
[360] According to the food or oral whitening agent of the present invention, it is possible to simply and continuously ingest five-ring triter pans and their physiologically acceptable salts or derivatives thereof without requiring a burden of time or effort. In particular, the skin whitening effect can be suitably enjoyed. In addition, since the five-circle triter pans in the present invention can be obtained in nature, the use thereof can be assured.

权利要求:
Claims (19)
[1" claim-type="Currently amended] A food or oral whitening agent for skin whitening containing, as an active ingredient, a compound selected from the group consisting of 5-ring triterfans and their physiologically acceptable salts or derivatives thereof.
[2" claim-type="Currently amended] The food or oral whitening agent according to claim 1, wherein the five-loop triterfan and its physiologically acceptable salts are isolated from natural products.
[3" claim-type="Currently amended] The food or oral whitening agent according to claim 1, wherein the content of the five-loop triter pans and their physiologically acceptable salts or derivatives thereof is 0.04% by mass or more based on the total mass of the food or oral whitening agent.
[4" claim-type="Currently amended] The food or oral whitening agent according to claim 1, wherein the five-membered triter pan is a compound selected from the group consisting of olean-based triter pans, Ulsan-based triter pans, and lupine-based triter pans.
[5" claim-type="Currently amended] The food or oral whitening agent according to claim 1, wherein the five-ring triter pan is selected from the group consisting of maslininic acid, erythrodiol, ursolic acid, uvaol, betulinic acid, and betulin.
[6" claim-type="Currently amended] The food or oral whitening agent according to claim 1, wherein the derivative of the five-ring triterpane is a derivative having an alcohol ester group or a fatty acid ester group.
[7" claim-type="Currently amended] The food or drink according to claim 1, wherein the food or drink is processed food.
[8" claim-type="Currently amended] 8. The food or drink according to claim 7, wherein the processed food is a combination fat or oil.
[9" claim-type="Currently amended] 9. The food or drink according to claim 8, wherein the fat or oil processed product is margarine, shortening, mayonnaise or dressing.
[10" claim-type="Currently amended] A food or drink according to claim 1, wherein the food or drink is a soft drink.
[11" claim-type="Currently amended] The food or drink according to claim 1, wherein some or all of the five-membered triterpanes are present in the form of their physiologically acceptable salts and / or their derivatives.
[12" claim-type="Currently amended] The edible debris of olives is extracted with ethanol solution, concentrated by drying and then edible combination fat or oil containing 1% by mass or more of maslininic acid purified by chromatography.
[13" claim-type="Currently amended] A dressing containing 1% by mass or more of the milking residue of olives, extracted with ethanol solution, concentrated by drying and then purified by chromatography.
[14" claim-type="Currently amended] A grain confectionery containing 2.5% by mass or more of the degreasing residue of olives, extracted by drying with ethanol solution, concentrated by drying, and then purified by chromatography.
[15" claim-type="Currently amended] The foodstuff which mix | blended the oral whitening agent of Claim 1.
[16" claim-type="Currently amended] An oral whitening agent in the form of granulated confections containing maslinic acid, which is extracted by degreasing the olive debris with an ethanol solution, concentrated by drying, and then purified by chromatography.
[17" claim-type="Currently amended] The milking residue of olives is extracted with an ethanol solution, concentrated by drying, and then orally whitening agent in powder form containing maslinic acid purified by chromatography.
[18" claim-type="Currently amended] A method using as a oral whitening agent a compound selected from the group consisting of maslinic acid, erythrodiol, ursolic acid, ubaol, betulinic acid, betulin and their physiologically acceptable salts, or derivatives thereof.
[19" claim-type="Currently amended] Use of the oral whitening agent of claim 1 as a prophylactic and / or therapeutic agent for dark skin, blemishes, freckles, dark circles and dullness.

类似技术:

---

公开号 | 公开日 | 专利标题

---

EP2156751B1|2018-10-03|Novel sweetener having sugar-like taste and production method and use of the same

---

AU725308B2|2000-10-12|Anti-stress composition

---

JP4644787B2|2011-03-02|Anti-obesity agent having lipase inhibitory activity and antioxidant properties

---

CA2478714C|2012-07-31|Method for producing sdg, and food and drink comprising it

---

JP2018524398A|2018-08-30|Composition for preventing, improving or treating muscle diseases or improving muscle function

---

JP4448266B2|2010-04-07|Chillability improving agent and composition for improving cooling performance

---

TWI254613B|2006-05-11|Method for inhibiting the formation of volatile aldehydes including their related compounds and/or the decomposition of fatty acids including their related compounds, and uses thereof

---

EP1069105B1|2007-09-19|Capsaicinoide-like substances having ester bond

---

KR101262686B1|2013-05-15|Composition for body fat reduction

---

RU2279226C2|2006-07-10|METHOD FOR PRODUCTION OF OIL AND FAT COMPOSITION CONTAINING HYDROPHOBIC COMPONENTS FROM Glycyrrhiza, OIL AND FAT COMPOSITION AND OIL-AND-FAT CONTAINING FOODSTUFF

---

KR101007790B1|2011-01-14|Associates of trehalose or maltitol and metal ion compounds

---

EP1254658B1|2008-09-24|Remedies for the treatment of nerve diorders

---

ES2441570T3|2014-02-05|Use of capsinoids for the treatment of arteriosclerosis

---

JPWO2002022140A1|2004-03-04|Homeostasis

---

US20060193962A1|2006-08-31|Preventive or remedy for arthritis

---

TWI239245B|2005-09-11|Medical composition for oral administration or intravenous administration for a disease requiring enhancement of nerve growth factor production for treatment or prevention

---

JP4432069B2|2010-03-17|Obesity inhibitor

---

EP1210880A1|2002-06-05|Compositions containing sucralose and application thereof

---

KR20040036941A|2004-05-03|Oil composition

---

US20170035725A1|2017-02-09|Muscle atrophy inhibitor

---

WO2004105739A1|2004-12-09|Compositions and foods and drinks contiaing higher fatty acid derivative

---

CN1477962A|2004-02-25|Beautifying foods and drinks and peroral beautifying preparations

---

KR101244586B1|2013-03-25|Sesamin/episesamin compositions

---

JP5686496B2|2015-03-18|Metabolic syndrome improvement / prevention composition

---

JP4375946B2|2009-12-02|Anti-obesity composition comprising peanut astringent skin extract as active ingredient

同族专利:

---

公开号 | 公开日

---

US20040086553A1|2004-05-06|

---

AU2413002A|2002-06-11|

---

EP1340501A4|2004-09-22|

---

WO2002043736A1|2002-06-06|

---

CN1477962A|2004-02-25|

---

EP1340501A1|2003-09-03|

---

CA2430346A1|2002-06-06|

---

JPWO2002043736A1|2004-04-02|

---

JP4398147B2|2010-01-13|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

法律状态:
2000-11-30|Priority to JP2000366139

---

2000-11-30|Priority to JPJP-P-2000-00366139

---

2001-11-30|Application filed by 닛신 오일리오 가부시키가이샤

---

2001-11-30|Priority to PCT/JP2001/010514

---

2003-08-02|Publication of KR20030064799A

优先权:

---

申请号 | 申请日 | 专利标题

---

JP2000366139|2000-11-30|

---

JPJP-P-2000-00366139|2000-11-30|

---

PCT/JP2001/010514|WO2002043736A1|2000-11-30|2001-11-30|Beautifying foods and drinks and peroral beautifying preparations|