KR102554508B1 - Oral beauty care agent - Google Patents

Abstract

An object of the present invention is to provide an oral cosmetic agent for improving skin dullness, skin texture, and skin quality. The above problems are solved by providing an oral cosmetic agent for improving skin dullness, skin texture, and skin quality, which contains glycosylhesperetin as an active ingredient.

Description

Oral beauty agent {ORAL BEAUTY CARE AGENT}

The present invention relates to an oral cosmetic agent, and more particularly, to an oral cosmetic agent for improving dull yellowish skin, skin texture and skin quality.

In recent years, in this field, in contrast to external skin preparations that beautify the skin from the outside of the body represented by skin care, etc., nutrients and functional ingredients that tend to be lacking in daily diet are simply and conveniently aimed at beautifying the skin from the inside. In order to effectively supplement, foods that can be consumed orally (hereinafter simply referred to as 'beauty foods') are in the limelight.

Beauty food has similarities with general food products in that it can be consumed orally, but is different from general food products in that specific nutrients or functional components are fortified to achieve a desired purpose. In addition, beauty food is not aimed at expecting an immediate effect like medicine or treating a specific disease, and it is difficult to consume a sufficient amount just by consuming normal food, and specific nutrients or functionalities helpful for beauty. It is also different from pharmaceuticals in that it is for supplementing ingredients. Examples of beauty foods include, for example, oral compositions containing nutrients and functional ingredients useful for beauty, such as chondroitin sulfate, coenzyme Q10, hyaluronic acid, and glucosamine, which are described in Patent Documents 1 and 2. In addition, Patent Document 3 discloses a melanin-lowering agent containing α-glycosylhesperidin, an inhibitor for lowering skin brightness, and the like, which are used as food, beverages or oral preparations. It is intended to suppress (suppressing the decrease in skin brightness by paying attention to the so-called melanin), which is a completely different index from skin brightness, the dull yellowness of the skin (for example, see Non-Patent Documents 1 and 2), skin texture and skin Nothing is disclosed about means for improving quality, means for improving discomfort in the case of orally ingesting α-glycosylhesperidin, and the like. In addition, Patent Document 4 discloses a method for improving skin color using α-glycosylhesperidin, which is based on an external skin preparation comprising α-glycosylhesperidin blended. are clearly different in terms of dosage form or use form.

Under these circumstances, there is a demand for beauty foods for improving the dull yellowness of the skin, skin texture and skin quality in this field, but for this purpose, it can be safely and easily taken orally without discomfort on a daily basis, and furthermore What can be provided industrially inexpensively has not yet been provided.

Japanese Patent Laid-Open No. 2002-223726 Japanese Patent Laid-Open No. 2008-99562 Japanese Patent Laid-Open No. 2009-7336 Japanese Patent Laid-Open No. 2002-255827

Yashiki Keiko, "FRAGRANCE JOURNAL", Vol. 40, No. 4, pp. 80-82, 2012 Masuda Yuji, "Coloring Materials", Vol. 76, No. 2, pp. 78-83, 2003

In view of the above-mentioned prior art, an object of the present invention is to provide an oral cosmetic agent capable of effectively improving the dull yellow color of the skin, skin texture and skin quality. In addition, the oral cosmetic agent according to the present invention includes those in the form of health food, nutritional functional food, health functional food, and specific health food for the purpose of cosmetic improvement, as well as orally ingested cosmetic food.

In order to solve the above problems, the present inventors have made diligent research efforts and, as a result, when glycosylhesperetin is routinely and continuously taken orally by humans, it effectively improves the dull yellow color of the skin, skin texture and skin quality It newly discovered that it could be done, established its use, and completed the present invention.

That is, the present invention is to solve the above problems by providing an oral cosmetic agent for improving the dull yellow color of the skin, skin texture and skin quality using glycosylhesperetin as an active ingredient.

Glycosylhesperetin as used herein refers to all compounds in which a saccharide is bonded to hesperetin, that is, all compounds having a hesperetin skeleton. 7-O-β-glucosylhesperetin having a structure in which , and a saccharide (for example, a saccharide such as D-glucose, D-fructose, or D-galactose) is α-linked to hesperidin by equimolar or more α-glycosylhesperidin; and the like.

More specifically, hesperidin, also called vitamin P, is a compound represented by the structural formula shown in Formula 1 below, having a structure in which rutinose composed of rhamnose and glucose is bound to hesperetin. It is an ingredient made up of

Formula 1:

Further, 7-O-β-glucosylhesperetin is a compound represented by the structural formula shown in the following formula (2), and has a higher water solubility than hesperidin. As shown in Patent Document 1, for example, 7-O-β-glucosylhesperetin is prepared by adding α-L-rhamnosidase (EC 3.2.1.40) to a solution containing α-glucosylhesperidin and hesperidin. It can be made by working.

Formula 2:

In addition, α-glycosylhesperidin is a compound in which a saccharide (for example, a saccharide such as D-glucose, D-fructose, or D-galactose) is α-linked to hesperidin by equimolar or more. A representative example of α-glycosylhesperidin is α-glucosylhesperidin represented by the structural formula shown in the following formula (3) in which one molecule of glucose is α-linked to glucose in the rutinose structure of hesperidin (aka: Enzymatically modified hesperidin, sugar Hesperidin, water-soluble hesperidin, or sugar transfer vitamin P). As an α-glucosylhesperidin-containing product, for example, a trade name of "Hayashiba Hesperidin (registered trademark) S" (available from Hayashibara Co., Ltd.) is commercially available.

Formula 3:

As described above, glycosylhesperetin itself is a safe and versatile compound that has conventionally been widely used as a material for various foods, cosmetics, pharmaceuticals, and quasi-drugs. Among the glycosyl hesperetins, α-glycosylhesperidin has higher water solubility and superior handling properties compared to hesperidin or 7-O-β-glucosyl hesperetin. Like hesperetin, it is hydrolyzed to hesperetin under the action of enzymes in vivo, and exhibits the original physiological activity of hesperetin.

The oral cosmetic agent of the present invention is an oral cosmetic agent containing glycosylhesperetin as an active ingredient, and it can be taken orally by humans continuously, safely and easily, and without discomfort, and is industrially inexpensive. can provide According to the oral cosmetic agent of the present invention, it is possible to effectively improve the dull yellow color of the skin, skin texture and skin quality. In particular, the oral cosmetic agent of the present invention, when applied to women in their 40s or older, who are so-called working women and begin to worry about dull yellow skin, roughness of skin texture, or deterioration of skin quality, has a desired effect compared to other subjects. has excellent characteristics that are more remarkably exhibited.

1 is a diagram showing changes over time in a* (redness) values obtained by measuring the color difference of the subject's left face, the center connecting the lower part of the ear lobe and the tip of the lips with a spectrophotometer.
FIG. 2 is a diagram showing changes over time in b* (yellowish) values obtained by measuring the color difference of the subject's left face, the center connecting the lower part of the ear lobe and the tip of the lips with a spectrophotometer.
FIG. 3 is a diagram illustrating changes over time in score values obtained by visually evaluating a subject's skin texture by a doctor using an auxiliary light and a microscope.
4 is a diagram showing changes over time in score values obtained by a doctor visually evaluating the dry state of the entire face of the test subject using auxiliary light and a microscope, and also by interviewing each test subject.
5 is a diagram showing changes over time in score values obtained by interviewing each subject as well as visually evaluating the erythema state of the entire face of the subject by a doctor using auxiliary light and a microscope.
Fig. 6 is a diagram showing changes over time in score values obtained by a physician visually evaluating the sensation of stimulation of the subject's entire face using auxiliary light and a microscope, and also by interviewing each subject.
FIG. 7 is a diagram showing changes over time in score values obtained by visually examining the itchiness of the subject's entire face by a doctor using auxiliary light and a microscope, and also by interviewing each subject.

Hereinafter, the embodiments of the present invention will be described, but these are only examples of preferred embodiments in carrying out the present invention, and the present invention is not limited to these embodiments at all.

Glycosylhesperetin, which is included as an active ingredient in the oral cosmetic agent of the present invention, means that humans can take it orally safely, easily, and without discomfort on a daily basis, and can also be provided industrially at low cost, As long as the desired action and effect of the present invention are exhibited, its origin, manufacturing method, purity, etc. can be used without particular limitation.

More specifically, glycosylhesperetin as used herein refers to all compounds in which a saccharide is bound to hesperetin, as described above, and more specifically, hesperetin is produced by the action of enzymes in vivo. It refers to hesperidin, 7-O-β-glucosylhesperetin and α-glycosylhesperidin. Among these glycosylhesperetins, if it is safe and easy for humans and can be taken orally without discomfort with significantly or significantly reduced off-taste, coloration, odor, etc., and can be provided industrially at low cost , Even if it is a commercially available product or one obtained by a conventionally known manufacturing method, it can be used more preferably in the present invention. In addition, since the present invention is not an invention related to a method for producing glycosylhesperetin itself, details of the method for producing it are omitted in the present specification, but an overview thereof is as follows.

Among the glycosyl hesperetins used in the present invention, hesperidin is industrially obtained by extracting hesperidin-containing plants, such as fruits, peels, seeds, and immature fruits of citrus fruits using appropriate solvents such as water or alcohol. Any amount can be prepared. Among the glycosylhesperetins used in the present invention, α-glycosylhesperidin, as disclosed in, for example, Japanese Patent Laid-Open No. 11-346792, etc., is dissolved in a solution containing hesperidin and an α-glucosylsaccharide compound. By reacting glycosyltransferase to produce α-glycosylhesperidin and collecting it, it can be industrially produced in a desired amount at low cost. Among the glycosyl hesperetins used in the present invention, 7-O-β-glucosyl hesperetin is, for example, as disclosed in Patent Document 1 and the like, α-glycosylhesperetin obtained by the action of a glycosyltransferase and By reacting α-L-rhamnosidase with an enzyme reaction solution containing hesperidin to produce 7-O-β-glucosylhesperetin, and collecting this, the desired amount can be produced industrially at low cost. .

In addition, as the glycosyl hesperetin used in the present invention, among commercially available products and glycosyl hesperetin obtained by conventionally known production methods, high-purity products with fewer impurities are preferably used. That is, conventionally known glycosylhesperetin, apart from reagent-grade glycosylhesperetin obtained through a crystallization process, together with glycosylhesperetin, impurities derived from the manufacturing material, unreacted raw materials, and It is a glycosylhesperetin-containing composition containing a physiologically acceptable ionic compound secondaryly produced in the manufacturing process, irrespective of the amount, whether glycosylhesperetin in this form. This is because the present inventors have newly discovered that it contains a plurality of components that are causative substances such as odor and smell, and that interfere with oral intake of glycosylhesperetin. In addition, in the specification of the present application, unless otherwise specified, glycosylhesperetin as a main component, impurities derived from the manufacturing raw material, unreacted raw materials, or physiologically acceptable ionic substances secondaryly generated in the manufacturing process A glycosylhesperetin-containing composition comprising the compound is simply referred to as glycosylhesperetin. In addition, as a matter of course, the glycosyl hesperetin used in the present invention includes high-purity glycosyl hesperetin obtained through a crystallization process.

In addition, the inventors of the present invention improved some of the conventional methods in order to reduce the content of contaminants contained in conventional glycosylhesperetin for the purpose of solving the disadvantages of conventionally known glycosylhesperetin, such as flavoring and coloring. Established glycosylhesperetin with reduced color and odor (hereinafter referred to collectively as "flavor, color and odor", "flavor, etc.") and its manufacturing method, and applied for a patent in Japan 2014- 41066 specification and International Patent Application No. PCT/JP2015/056230 pamphlet. Glycosylhesperetin with reduced flavors and the like has excellent advantages in that humans can take it orally on a daily basis, continuously, safely and easily, and without discomfort, and at the same time, it can be provided industrially at low cost. Therefore, glycosyl hesperetin with reduced buckwheat can be advantageously used as the most suitable glycosyl hesperetin in the practice of the present invention.

Hereinafter, a method for producing glycosylhesperetin with reduced chaff etc. and its physical properties will be described.

Glycosylhesperetin with reduced side taste is obtained by (a) preparing an aqueous solution containing hesperidin and partially degraded starch, (b) applying a glycosyltransferase to the obtained aqueous solution to obtain α-glucosylhesperetin-containing glycosyl hesperetin One or two or more steps (a) to (c) above in a manufacturing method comprising a step of producing a sylhesperetin-containing composition, and (c) a step of collecting the resulting glycosylhesperetin-containing composition. It can be prepared by carrying out in the presence of a reducing agent, or by adding a reducing agent to the starting raw material before one or two or more steps of (a) to (c) and / or to the result after the process. Hereinafter, raw materials and enzymes for glycosyl hesperetin obtained by the manufacturing method using the above reducing agent (hereinafter, glycosyl hesperetin prepared through the above reducing agent treatment step may be referred to as a 'reducing agent treated product'). The reaction (saccharide transfer reaction, etc.), reducing agent treatment, and purification method are sequentially described.

(manufacturing raw material)

As hesperidin, which is a raw material for manufacturing products treated with a reducing agent, all hesperidin used in conventional glycosylhesperetin production can be used, and high-purity hesperidin as well as relatively low-purity hesperidin-containing plant-derived extracts, squeezed juices, or parts thereof can be used. You may use 1 type, such as a purified product, or combining 2 or more types suitably.

Specifically, the hesperidin-containing plant may be exemplified by citrus fruits belonging to the genus Rutaceae and Tangerine, such as wheat tangerines, oranges, aromatic citrus fruits, miscellaneous citrus fruits, tangerines, tangelo fruits, mundans, kumquats, etc. , Fruits, peels, seeds, immature fruits and the like of these citrus fruits can be exemplified as hesperidin-containing sites.

As the starch partial decomposition product of the manufacturing raw material, any material capable of generating α-glycosylhesperidin as glycosylhesperetin by glycosyltransfer to hesperidin when a glycosyltransferase described later is acted on may be used. For example, amylose, dextrin, Partial decomposition products of starch, such as cyclodextrin and maltooligosaccharide, and one or more partially decomposed starch selected from liquefied starch, gelatinized starch, and the like are appropriately selected.

In addition, the amount of starch partial decomposition product used in the enzymatic reaction described later is usually about 0.1 to 150 times, preferably about 1 to about 100 times, more preferably about 2 to about 50 times the mass of hesperidin as a raw material. An amount selected from the range of is used. In the enzymatic reaction, sugar derived from partial starch degradation products is transferred to hesperidin to efficiently produce α-glycosylhesperidin, and an excessive amount of partial starch degradation products relative to hesperidin is added so that unreacted hesperidin remains as little as possible in the enzymatic reaction system. It is preferable to use The reason for this is that, in the purification process described later, partial starch degradation products and sugars derived therefrom can be separated relatively easily from α-glycosylhesperidin, whereas hesperidin behaves the same as α-glycosylhesperidin, and α- This is because, since it is difficult to separate from glycosylhesperetin, if the remaining amount of unreacted hesperidin, which has very low water solubility, is large, the water solubility of the resulting glycosylhesperetin is lowered as a whole.

(Enzyme reaction)

The enzyme reaction as used herein refers to an enzyme reaction in which α-glycosylhesperidin is produced by activating a glycosyltransferase on hesperidin as a manufacturing raw material and partial starch degradation product.

As the glycosyltransferase used in the enzymatic reaction, α-glucosidase (EC 3.2.1.20), cyclomaltodextrin glucanotransferase (EC 2.4.1.19, hereinafter referred to as 'CGTase'), α-amylase (EC 3.2.1.1) and the like can be exemplified. Examples of the α-glucosidase include enzymes derived from animal and plant tissues such as pork liver and buckwheat seeds, or aspergyl species such as Mhucor, Penicillium, and Aspergillus niger. Those derived from fungal cultures belonging to the genus Aspergillus, or those derived from cultures obtained by culturing microorganisms such as yeast belonging to the genus Saccharomyces in a nutrient medium, for example, as CGTase, Bacillus ), Geobacillus, Klebsiella, Paenibacillus, Thermococcus, Thermoanaerobacter, Brevibacterium ), Pyrococcus, Brevibacillus, and Saccharomyces. As the α-amylase, one or two or more kinds derived from bacteria belonging to the genus Geobacillus or the like or fungal cultures belonging to the genus Aspergillus such as Aspergillus niger can be used in appropriate combination. can As these glycosyltransferases, either natural or genetically recombinant types can be employed as long as they can achieve the object of the present invention, and when commercially available products are available, they can also be used appropriately. In addition, it is not necessary to purify and use any of the above glycosyltransferases, and generally, any crude enzyme may be used as long as it can achieve the object of the present invention.

In addition, when using the natural or genetically recombinant glycosyltransferases, the production rate of α-glycosylhesperidin can be increased by employing starch partial decomposition products suitable for these glycosyltransferases.

When the α-glucosidase is used, malto-oligosaccharides such as maltose, maltotriose, and maltotetraose, or starch partial decomposition products having a DE (Dextrose equivalent) of about 10 to about 70 may be preferably used. In the case of using CGTase, α-, β- or γ-cyclodextrin or starch gelatinized product of DE1 or less to partially decomposed starch of DE 60 may be preferably used, and in the case of using α-amylase, DE1 or less Partial decomposition products of starch, such as starch gelatinization of DE about 30 and dextrin, may be preferably used.

As a solution containing hesperidin during the enzymatic reaction, it is preferable to contain hesperidin at a high concentration as much as possible. For example, a suspension containing hesperidin in a suspended form or dissolved in a solvent such as water at a high temperature of room temperature or higher, or using an alkali agent. A solution containing hesperidin in high concentration, dissolved at an alkaline side pH above pH 7.0, is preferably used. As the alkali agent, one or two or more strong alkaline aqueous solutions such as sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, calcium hydroxide aqueous solution, and ammonia water in an amount of about 0.1 to about 1.0 N may be suitably used.

When hesperidin is used in the form of a solution using an alkaline agent, the concentration of hesperidin is usually about 0.005 w/v% or more, preferably about 0.05 to about 10 w/v%, more preferably about 0.5 to about 10 w/v%. , and even more preferably from about 1 to about 10 w/v%.

On the other hand, when hesperidin is used in suspension without using an alkali agent, hesperidin is suspended in a solvent such as water to obtain hesperidin in suspension, and the concentration of hesperidin at that time is usually about 0.1 to about 2 w/v%, more preferably. Preferably from about 0.2 to about 2 w / v%, more preferably from about 0.3 to about 2 w / v%.

The temperature and time for the action of the glycosyltransferase on hesperidin and partial starch degradation products vary depending on the concentrations of hesperidin and starch partial degradation products used in the enzymatic reaction, the type of glycosyltransferase, the optimum temperature, the optimum pH, or the amount of action. , usually about 50 to about 100 ° C, preferably about 60 to about 90 ° C, more preferably about 70 to about 90 ° C, and about 5 to about 100 hours, preferably about 10 to about 80 hours, more It is preferably in the range of about 20 to about 70 hours.

In addition, the pH and temperature when the glycosyltransferase is reacted with an alkaline solution containing hesperidin at a high concentration vary depending on the type of glycosyltransferase, optimum pH, optimum temperature, or amount of action, concentration of hesperidin, etc. As high as possible pH, high temperature, specifically pH about 7.5 to about 10, preferably pH about 8 to about 10, and about 40 to about 80 ° C, more preferably in the range of about 50 to about 80 ° C. do it with In addition, since hesperidin in an alkaline solution easily causes decomposition, in order to prevent this, it is preferable to maintain hesperidin under light blocking and anaerobic conditions as much as possible.

In addition, the pH when the glycosyltransferase acts on the hesperidin in suspension form varies depending on the type of glycosyltransferase, the optimum temperature, the optimum pH, or the amount of action, and the concentration of hesperidin in the suspension form. 7, preferably in the range of pH about 4.5 to about 6.5.

In addition, if additionally necessary, in order to increase the solubility of hesperidin before the enzymatic reaction and to facilitate the sugar transfer reaction to hesperidin, an organic solvent having high compatibility with water is used in a solution containing high hesperidin, in particular, an aqueous solution containing high hesperidin, e.g. For example, one or two or more of methanol, ethanol, n-propanol, iso-propanol, n-butanol, lower alcohols such as acetol and acetone, and lower ketones may coexist in an appropriate amount.

The amount of enzyme and the reaction time are closely related, and usually, from the viewpoint of economy, the enzyme reaction is completed in about 5 to about 150 hours, preferably about 10 to about 100 hours, more preferably about 20 to about 80 hours. What is necessary is just to set the enzyme amount suitably according to the kind of glycosyltransferase used. In addition, it is also possible to carry out repeated reactions in a batch manner or in a continuous manner using an immobilized glycosyltransferase.

The enzyme reaction solution containing α-glycosylhesperidin and hesperidin obtained after the glycosyltransferase reaction is, if necessary, as is or after purification with a porous synthetic adsorption resin, glucoamylase (EC 3.2.1.3) or β-amylase ( The number of α-D-glucosyl groups of α-glycosylhesperidin can be reduced by partial hydrolysis with an amylase such as EC 3.2.1.2). For example, when glucoamylase acts, a polymer higher than α-maltosylhesperidin can be hydrolyzed to produce glucose, while α-glucosylhesperidin can be produced and accumulated. Further, when β-amylase acts, a polymer higher than α-maltotriosylhesperidin is hydrolyzed to produce maltose, and a mixture containing α-glucosylhesperidin and α-maltosylhesperidin can be produced and accumulated. there is.

On the other hand, by allowing glucoamylase and α-L-rhamnosidase to act simultaneously or sequentially with either of them first in the enzyme reaction solution containing α-glycosylhesperidin and hesperidin obtained after the glycosyltransferase reaction, α -Leaving glucose bound to α-linked glucose by equimolar or more to glucose in the rutinose structure of glycosylhesperidin, and converting α-glycosylhesperidin to α-glucosylhesperidin to increase α-glucosylhesperidin content and at the same time, water-soluble By replacing this low hesperidin with 7-O-β-monoglucosyl hesperetin with high water solubility, it can be made into glycosyl hesperetin with high water solubility as a whole.

As with glycosyltransferase, for glucoamylase and α-L-rhamnosidase, the amount of enzyme and the enzyme reaction time are closely related, and usually from the viewpoint of economy, about 5 to about 150 hours, preferably about 10 to about 100 hours, more preferably about 20 to about 80 hours, the amount of enzyme that completes the enzyme reaction may be appropriately set according to the type of enzyme. In addition, repeated reactions in a batch manner using immobilized α-L-rhamnosidase or continuous reactions in a continuous manner can be suitably carried out.

(reducing agent treatment)

Reducing agent treatment as used herein refers to significantly or remarkably reducing the flavor and coloration of glycosylhesperetin (hereinafter, sometimes abbreviated as “flavor/coloration”) and odor by using a predetermined reducing agent. (a) preparing an aqueous solution containing hesperidin and partially decomposed starch, (b) applying a glycosyltransferase to the resulting aqueous solution to obtain a reducing agent, which will be described later, containing α-glucosylhesperidin It is used in one or two or more steps of the process of producing a glycosylhesperetin-containing composition and (c) the process of collecting the produced glycosylhesperetin-containing composition, or one or more of the above (a) to (c) It means adding a predetermined amount to the starting raw material before two or more processes and/or the result after the above process.

The reducing agent used in the method for producing glycosylhesperetin with reduced chaff is not particularly limited as long as the desired object of the present invention can be achieved, and any inorganic or organic reducing agent that is general in this field can be used. there is. However, since glycosylhesperetin or high-purity glycosylhesperetin used in the present invention, including reducing agent-treated products, is mainly applied to humans, reducing agents with high safety, stability, and handling are required. It is preferable to use

Specific examples of reducing agents suitably used in the present invention include, for example, hydroxylamines, chlorine dioxide, hydrogen, hydrogen compounds (hydrogen sulfide, sodium borohydride, lithium aluminum hydride, potassium aluminum hydride, etc.), sulfur compounds (sulfur dioxide, thiourea dioxide , thiosulfate, sulfite, iron sulfate, sodium persulfate, potassium persulfate, ammonium persulfate, calcium sulfite, etc.), nitrite, tin chloride, iron chloride, potassium iodide, hydrogen peroxide, diluted benzoyl peroxide, hydroperoxide, sodium chlorite, etc. inorganic reducing agents such as chlorite; And phenols, amines, quinones, polyamines, formic acid and its salts, oxalic acid and its salts, citric acid and its salts, thiourea dioxide, hydrazine-based compounds, reducing sugars, benzoyl peroxide, benzoyl persulfate, diisobutylaluminum hydride, Organic reducing agents such as catechin, quercetin, tocopherol, gallic acid and its esters, ethylenediaminetetraacetic acid (EDTA), dithiothreitol, reduced glutathione, and polyphenols can be exemplified. The inorganic and organic reducing agents may be used alone or in combination of two or more of them.

Among the inorganic and organic reducing agents, the former reducing agent can more significantly reduce the flavor of glycosyl hesperetin prepared without treatment with a reducing agent, and the coloration or off-odor is significantly reduced. Since sylhesperetin can be provided, it can be used more preferably in the present invention. In addition, although the reason is not certain, it is estimated as follows. That is, when used for the purpose of the present invention, the organic reducing agent has a lower effect of reducing flavor/coloring than the inorganic reducing agent, or since the organic reducing agent is an organic substance, it may itself cause flavor or coloration. In addition, if decomposition products or modifiers of the organic reducing agent remain without being completely removed in the purification process of the reducing agent-treated product, it is thought that this is because they negatively affect the quality of glycosylhesperetin in the final product.

Among inorganic reducing agents, so-called sulfites (also called sulfites) composed of SO ₂ ^- ion, HSO ₃ ^- ion, SO ₃ ^2- ion, S ₂ O ₄ ^{2 -} ion, or S ₂ O ₇ ^2- ion and metal ion .) is a reducing agent that can be used more preferably in the present invention because it is excellent in terms of safety, stability and handling. In particular, sulfites such as inorganic reducing agents such as sodium sulfite, potassium sulfite, sodium hydrogen sulfite, sodium hyposulfite, potassium hyposulfite, sodium pyrosulfite, potassium pyrosulfite, sodium metasulfite, potassium metasulfite, sodium metabisulfite, and potassium metabisulfite can be most preferably used in the present invention.

In addition, the reducing agent is applied to one step in the manufacturing process of glycosylhesperetin with reduced chaff, or the starting raw material before the process and/or the result after the process, and two or more processes, or the starting raw material before those processes. And / or when an appropriate amount is properly subdivided and used in the resultant product after the process, the desired object of the present invention can be efficiently achieved with a smaller amount of reducing agent.

The amount of the reducing agent added is the total, in each step of (a) to (c) above, after the above (b) enzyme reaction (in the case of using enzymes other than glycosyltransferase, it means after completion of all the enzyme reactions) An amount selected from the range equivalent to 0.001% or more, preferably 0.01 to 3%, more preferably 0.01 to 1%, and even more preferably 0.01 to 0.5% is used, based on the mass of the enzyme reaction solution obtained in do. In addition, when a reducing agent is added before the step (c) above, usually, the remaining reducing agent is substantially removed in the purification step, so it is substantially not detected The amount of reducing agent added in the entire process is usually 0.001% or more in total, preferably 0.01% or more, more preferably 0.01 to 1%, based on the mass of the enzyme reaction solution obtained after the enzyme reaction, once or a plurality of times. added in circuit. The temperature at the time of addition is usually the temperature employed in the above steps (a) to (c), but it is also possible to separately set it to a temperature higher than that temperature. Specifically, a temperature of room temperature or higher, preferably 50°C or higher, more preferably 70°C or higher, more preferably 80°C or higher, still more preferably 90 to 120°C can be exemplified.

(purification method)

The enzymatic reaction solution obtained in this way can be used as it is as glycosylhesperetin, which is suitably used in the present invention and has reduced flavors and the like. However, in general, the enzyme reaction solution is obtained by appropriately combining one or two or more means such as a fractionation method, a filtration method, a purification method using a porous synthetic resin, a concentration method, a spray method, and a drying method known in the field. , liquid, solid, powdery, etc. reducing agent treated products.

The porous synthetic resin refers to a synthetic resin that is porous, has a large adsorption surface area, and is nonionic, such as a styrene-divinylbenzene polymer, a phenol-formalin resin, an acrylate resin, or a methacrylate resin. Trade names manufactured by Rohm & Haas: Amberlite XAD-1, Amberlite XAD-2, Amberlite XAD-4, Amberlite XAD-7, Amberlite XAD-8, Amberlite XAD-11, and Amberlite XAD-12, etc. of resin; Product names manufactured by Mitsubishi Chemical Corporation: Diaion HP-10, Diaion HP-20, Diaion HP-30, Diaion HP-40, Diaion HP-50, Diaion HP-2MG, Sepa Beads SP70, Sepa Beads SP207 Resins, such as Sepa beads SP700 and Sepa beads SP800; and resins such as Imacti Syn-42, Imacti Syn-44, and Imacti Syn-46, trade names manufactured by IMACTI.

In the case of the purification method using the porous synthetic adsorbent, when the enzyme reaction solution is passed through a column filled with the porous synthetic adsorbent, glycosylhesperetin is adsorbed to the porous synthetic adsorbent, whereas the remaining starch partial decomposition products or water-soluble sugars Etc. is not adsorbed and flows out of the column as it is. At this time, hesperidin, 7-O-β-glucosylhesperetin, and α-glycosylhesperetin, which are glycosylhesperetin, usually behave the same, so it is not possible to separate them individually by a porous synthetic adsorbent. does not exist. However, although the operation is cumbersome and the yield is reduced, the glycosylhesperetin selectively adsorbed on the column filled with the porous synthetic adsorbent is washed with a solvent such as dilute alkali or water, and then washed with a relatively small amount of an organic solvent or organic solvent. When a mixed solution of a solvent and water, for example, an aqueous methanol solution or an aqueous ethanol solution, is passed through, α-glycosylhesperidin is first eluted from the column, and then unreacted hesperidin is eluted by increasing the passing amount or increasing the concentration of the organic solvent. . When the eluate containing glycosylhesperetin thus obtained is subjected to distillation to remove the organic solvent by distillation and then concentrated to a desired concentration, glycosylhesperetin in which the content of hesperidin is reduced and flavors and the like are reduced is obtained. In addition, since the process of eluting glycosylhesperetin with the organic solvent is also an operation of regenerating the synthetic porous adsorbent at the same time, there is an advantage in enabling repeated use of the synthetic porous adsorbent.

In addition, after the end of the enzyme reaction, between the time the enzyme reaction solution is brought into contact with the porous synthetic adsorbent, for example, insoluble matters generated by heating the reaction solution are removed by filtration, magnesium aluminate silicate, magnesium aluminate, etc. By treating with a combination of purification methods such as adsorbing and removing protein substances in the reaction solution, desalting by treatment with strong acid ion exchange resin (H type), medium basic or weak basic ion exchange resin (OH type), etc. A liquid reducing agent-treated product with increased glycosylhesperetin purity can be produced.

It is also possible to obtain powdery glycosylhesperetin suitably used in the present invention by drying the liquid glycosyl hesperetin with reduced flavorings and the like by a known drying method and pulverizing the glycosyl hesperetin.

In this way, the characteristic off-flavor, which was a drawback of glycosylhesperetin prepared without going through the reducing agent treatment step (hereinafter sometimes referred to as "product not treated with a reducing agent"), is significantly reduced, and coloration and odor are also reduced. An effectively reduced reducing agent treated product can be produced. In addition, according to what the inventors of the present invention have confirmed, the peculiar taste/coloration or odor of products not treated with a reducing agent is substantially unchanged by simply applying the above purification method. That is, the purification method using, for example, the porous synthetic adsorbent, which is widely used in the manufacturing process of non-reducing agent-treated products, has the advantage of being able to simultaneously remove not only starch partially decomposed products and water-soluble sugars, but also impurities such as water-soluble salts. However, no matter how these purification methods are used, it is difficult to significantly or remarkably reduce the characteristic flavor/coloring or smell of products not treated with a reducing agent. As an expected reason, the causative substances such as miscellaneous rice contained in glycosyl hesperetin have the same adsorption/desorption behavior to the porous synthetic adsorbent as glycosyl hesperetin and cannot be separated from glycosyl hesperetin. I think it might be.

In addition, the glycosylhesperetin suitably used in the present invention, particularly the product treated with a reducing agent, has a significantly reduced taste, electrical conductivity is low, and the content of ionic compounds involved in electrical conductivity is reduced. Further, examples of the ionic compound include compounds such as narirutin, diosmin, and neoponsyrin, which are inherently contained in hesperidin as a raw material, or glucosyl narirutin and glucosyl neophonsyrin, which are enzymatic reaction products; Including furfural as an index in the present invention, which is thought to be derived from a decomposition product, or a compound closely related to the decomposition product, and furthermore, derived from the manufacturing raw material of glycosylhesperetin or produced incidentally in the manufacturing process thereof. , furfurals such as furfuryl alcohol and hydroxymethyl furfural and their salts, as well as compounds that release metal cations such as calcium, potassium, magnesium and sodium in solution. In addition, components such as narirutin, diosmin, neophonsyrin, glucosylnarirutin, and glucosylneophonsyrin are usually included in the reducing agent-treated products suitably used in the present invention, although in small amounts.

In the method for producing a reducing agent-treated product described above, the mechanism by which a reducing agent is used to obtain glycosylhesperetin with significantly reduced flavor and coloring, in particular, flavor is not clear, but it is estimated as follows.

(1) In manufacturing a reducing agent-treated product, there are substances that cause buckwheat derived from the raw material, and the reducing agent acts on them to mask, decompose or modify the causative substance, thereby significantly reducing buckwheat Glycosylhesperetin is obtained.

(2) In the manufacturing process of products treated with a reducing agent, the reducing agent reduces or suppresses the formation of the causative substances of buckwheat, or masks, decomposes or modifies the produced causative substances of buckwheat, so that buckwheat is significantly reduced. ferretin is obtained.

(3) The causative substances of buckwheat shown in (1) and (2) above are modified by a reducing agent, and are easily separated from glycosylhesperetin in the purification process using a porous synthetic adsorbent, etc. As a result, buckwheat is significantly A product treated with a reducing agent significantly reduced is obtained.

Moreover, as the glycosyl hesperetin-containing material suitably used in the present invention, those obtained by contacting the glycosyl hesperetin-containing material with a reducing agent to significantly reduce the off-taste of the glycosyl hesperetin-containing material can be exemplified. Such a glycosylhesperetin-containing material is also included in the reducing agent-treated product referred to in the present specification. In addition, when the glycosylhesperetin-containing material is brought into contact with a reducing agent, the off-taste of the glycosylhesperetin-containing material can be significantly reduced, and coloration and smell can also be effectively and remarkably reduced. Contact between the glycosylhesperetin-containing material and the reducing agent is preferably carried out in a solution state or suspension state using an appropriate solvent such as water, rather than in a solid state. In addition, as the glycosyl hesperetin-containing substance contacted with the reducing agent, glycosyl hesperetin containing at least one or two or more selected from hesperidin, α-glycosylhesperidin, and 7-O-β-glucosylhesperetin. Ferretin can be exemplified. As the glycosylhesperetin-containing material, the glycosylhesperetin content is usually 70% by mass or more and less than 100% by mass per dry solid (hereinafter, unless otherwise specified, “mass%” is abbreviated as “%”. ), more preferably 80% or more and less than 100%, still more preferably 90% or more and less than 100% glycosylhesperetin.

In addition, when bringing the glycosylhesperetin-containing material into contact with a reducing agent, the same reducing agent used in the case of producing a reducing agent-treated product can be used. In addition, the amount of the reducing agent is usually 0.00001% or more, preferably 0.0001 to 0.5%, more preferably 0.001 to 0.4%, and still more preferably 0.001 to 0.3%, per dry solid of glycosylhesperetin. by mixing them uniformly and bringing glycosylhesperetin into contact with a reducing agent, even in a non-reducing agent-treated product prepared without undergoing the above-mentioned reducing agent treatment, it is possible to significantly or remarkably reduce its peculiar flavors and the like. .

In addition, the liquid reducing agent-treated product is concentrated by a known concentration method to form a syrup or paste-like reducing agent-treated product, and also dried by a known drying method to produce a solid, granular, or powdery reducing agent-treated product. It is also arbitrary.

As described above, by using the enzyme reaction solution treated with the reducing agent in the purification method, it is possible to obtain a reducing agent-treated product in which the peculiar taste and the like, which were disadvantages of non-reducing agent-treated products, are significantly or remarkably reduced.

In addition, 4-vinylanisole (aka: 4-methoxystyrene), which is a kind of phenol ether (hereinafter referred to as "4-VA Abbreviated as ""), among the glycosylhesperetins used in the present invention, not only the unpleasant taste is more significantly reduced, but also the coloration and odor are more remarkably reduced. is most appropriately used in Further, substantially not containing furfural as used herein means glycosylhesperetin having a significantly lower level of furfural than conventional products. Specifically, the analysis method using a gas chromatograph mass (GC/MS) analyzer (hereinafter abbreviated as "GC/MS analysis method") shown in "(1) Content of furfural" in Experiment 2 described later. Typically less than 200 ppb (and 1 ppb is one billionth), preferably less than 100 ppb, more preferably less than 50 ppb, even more preferably less than 30 ppb, even more preferably less than 20 ppb, even more preferably Preferably it means less than 15 ppb, particularly preferably less than 10 ppb. In addition, among the glycosylhesperetins of the present invention, those in which the furfural content was reduced to below the detection limit of the GC/MS analysis method had significantly reduced off-taste compared to conventional products, as well as significantly reduced coloration. It is a very high quality glycosylhesperetin. However, since the glycosylhesperetin used in the present invention is formulated into a composition for oral use by humans, it is not necessarily of the highest purity, so the furfural content is necessarily reduced to a level below the detection limit. It is not necessary that it is prepared, but it is not necessary that it does not contain furfural. Therefore, the glycosylhesperetin used in the present invention does not have to substantially contain furfural, and as long as the desired object of the present invention can be achieved, it is significantly smaller than conventional products or has a detection limit. It may contain the following degree of furfural. In addition, as the glycosylhesperetin used in the present invention, one that does not substantially contain the above furfural is more preferably used, but the furfural content is less than about 320 ppb, preferably about 310 ppb, among non-reducing agent-treated products. Those less than that can exhibit an effect of improving or reducing the dull yellowness of the skin, so those glycosylhesperetins can also be used in the present invention.

In addition, the 4-VA is a component estimated to be produced due to the manufacturing raw material of glycosyl hesperetin, and the content in the obtained glycosyl hesperetin is usually less than 30 ppb per dry solid, and the 4-VA content is Those with a furfural content of less than 200 ppb usually have a parallel relationship with the furfural content. In addition, substantially not containing 4-VA means that, as in the case of furfural, the 4-VA content is significantly lower than other glycosylhesperetin-containing compositions such as non-reducing agent-treated products other than reducing agent-treated products. means at the level More specifically, when the 4-VA content in the reducing agent-treated product is measured by an analytical method using a GC/MS analyzer shown in '(2) 4-VA content' of Experiment 2 described later, it is usually dry Less than 30 ppb per solids, preferably less than 15 ppb, more preferably less than 10 ppb, even more preferably less than 5 ppb, even more preferably less than 3 ppb, even more preferably less than 2 ppb.

Next, the reducing agent-treated product has an excellent feature that the coloration (hereinafter sometimes referred to as 'coloring degree') is also remarkably reduced compared to the reducing agent-untreated product. The degree of coloration of glycosylhesperetin was measured by the method shown in '(3) Color tone and degree of coloration' of Experiment 2 described later, and the outline thereof is as follows. That is, after heat treatment of an aqueous solution containing a predetermined concentration of glycosylhesperetin in an airtight container, the color tone of the treatment solution was observed with the naked eye, and the absorbance at a wavelength of 420 nm (OD _{420 nm} ) and the wavelength were observed by a spectrophotometer. The absorbance at 720 nm (OD _{720 nm} ) is measured, and the difference in absorbance at both wavelengths (OD _{420 nm} - OD _{720 nm} ) is obtained, and the measured value is used as the degree of coloration. A preferred embodiment of the glycosylhesperetin used in the present invention is one in which the absorbance difference is less than 0.24, preferably 0.20 or less, more preferably 0.17 or less, and even more preferably more than 0 and 0.15 or less. . In addition, in this measurement method, heating the aqueous solution of glycosyl hesperetin has a drawback that the degree of coloration of products not treated with a reducing agent is greatly increased by heating, and coloring by heating glycosyl hesperetin It is set up for the purpose of evaluating in accordance with reality.

The reducing agent-treated product is a glycosyl hesperetin-containing composition containing glycosyl hesperetin and a physiologically acceptable ionic compound, which is made into a 1 w / v% aqueous solution, heated at 100 ° C. for 30 minutes in a sealed container, and then 20 Containing glycosylhesperetin whose electrical conductivity at °C is less than 10 μS/cm, preferably less than 8 μS/cm, more preferably less than 6 μS/cm, and still more preferably more than 0 μS/cm and less than 4.5 μS/cm is a composition

Physiologically acceptable ionic compounds as used herein refer to physiologically acceptable ionic compounds that are safe for oral intake by humans and contained in non-reducing agent-treated products and reducing agent-treated products, regardless of whether the amount is large or small. As such, they refer to physiologically acceptable ionic compounds that are inherently included in manufacturing materials, or are produced as a secondary product in the manufacturing process, and which are safe for oral intake by humans. Specifically, for example, narirutin, diosmin, neophonsyrin, or glucosylnari, which is an enzymatic reaction product, which is presumed to be a causative substance such as buckwheat of the glycosylhesperetin-containing composition, for example, originally included in hesperidin raw materials It refers to decomposition products such as rutin and glucosyl neophonyrin, or compounds closely related to the decomposition products, and compounds that release metal ions such as calcium, potassium, magnesium and sodium, which are cationic metal elements, in solution can

In addition, the reducing agent-treated product obtained by the above production method is a composition mainly containing one or two or more glycosylhesperetins selected from hesperidin, α-glycosylhesperidin, and 7-O-β-glucosylhesperetin. Preferably, the total glycosylhesperetin content per dry solid of the composition is usually 90% or more and less than 100%, preferably 93% or more and less than 100%, more preferably 95% or more and less than 100%. , more preferably 97% or more and less than 100%, still more preferably 98% or more and less than 100%.

The α-glycosylhesperidin content referred to in the present specification is obtained by taking an α-glycosylhesperidin-containing composition as a sample, diluting or dissolving it with purified water to 0.1% (w/v), and filtering through a 0.45 μm membrane filter. After that, it was subjected to high performance liquid chromatography (HPLC) analysis under the following conditions, using the reagent hesperidin (sold by Wako Pure Chemical Industries, Ltd.) as a standard substance, the area of the peak shown in the chromatogram at UV 280 nm, and hesperidin , α-glycosylhesperidin (α-glucosylhesperidin, etc.), etc., calculated based on the molecular weight of each component, and means the content of each component in the composition in terms of anhydride mass. The summary of the quantification of glycosylhesperetin by the HPLC analysis is as shown in (1) to (4) below.

<HPLC analysis conditions>

HPLC device: 『LC-20AD』 (manufactured by Shimadzu Corporation)

Degasser: 『DGU-20A3』 (manufactured by Shimadzu Corporation)

Column : 『CAPCELL PAK C18 UG 120』

(product of Shiseido Co., Ltd.)

Sample Injection Amount: 10μ1

Eluent: water/acetonitrile/acetic acid (80/20/0.01 (volume ratio))

Flow rate: 0.7m1/min

Temperature: 40℃

Detection: UV detector 『SPD-20A』 (manufactured by Shimadzu Corporation)

Measurement wavelength: 280nm

Data processing device: 『Chromato Pack C-R7A』 (manufactured by Shimadzu Corporation)

<Quantification of glycosylhesperetin>

(1) Hesperidin content: Analyzed by HPLC, and calculated based on the ratio of the peak area to the peak area of the reagent hesperidin (sold by Wako Pure Chemical Industries, Ltd.) as a standard material at a predetermined concentration.

(2) α-glucosylhesperidin content: analyzed by HPLC, the ratio between the peak area and the peak area of the standard reagent hesperidin (sold by Wako Pure Chemical Industries, Ltd.) at a predetermined concentration, and α-glycosylhesperidin and hesperidin It is calculated based on the molecular weight ratio of

(3) 7-O-β-glucosylhesperetin content: analyzed by HPLC, the ratio of the peak area to the peak area of the reagent hesperidin (sold by Wako Pure Chemical Industries, Ltd.), which is a standard material at a predetermined concentration, and 7 It is calculated based on the molecular weight ratio of -O-β-glucosylhesperetin and hesperidin.

(4) Other glycosyl hesperetin content: analyzed by HPLC, the ratio of the peak area to the peak area of the reagent hesperidin (sold by Wako Pure Chemical Industries, Ltd.), which is a standard material at a predetermined concentration, and other glycosyl hesperetins It is calculated based on the molecular weight ratio of and hesperidin.

In addition, among the reducing agent-treated products obtained by the above production method, α-glycosylhesperetin, which is α-glucosylhesperidin, has the desired effect in the present invention, that is, dull yellow skin and skin texture It is preferable in that the effect of improving the skin quality and the effect of improving skin quality such as skin dryness, erythema, irritation and itching are more remarkably exhibited. In addition, a suitable content of α-glucosylhesperidin in the glycosylhesperetin is usually 60 to 90%, preferably 70 to 90%, more preferably 75 to 90% per dry solids of the composition, They are preferable at the point where the said action effect is acquired more remarkably.

In addition, among the reducing agent-treated products obtained by the above production method, a 1 w/v% aqueous solution was heated at 100 ° C. for 30 minutes in an airtight container, then adjusted to room temperature, put into a cell with a width of 1 cm, and the wavelength was measured by a spectrophotometer. Absorbance difference (OD _420nm ) at both wavelengths when absorbance at 420nm ( _OD 420nm) and wavelength 720nm (OD _720nm ) - OD _{720 nm} ) is less than 0.24, preferably 0.20 or less, more preferably 0.17 or less, and still more preferably 0 or more and 0.15 or less, the desired action effect in the present invention, that is, dull yellow skin and skin texture It is preferable in that the effect of improving the skin quality and the effect of improving skin quality such as skin dryness, erythema, irritation and itching appear more remarkably. In addition, compared to glycosylhesperetin obtained by a manufacturing method that does not go through a predetermined reducing agent treatment step, it is also excellent in that flavor/coloring and odor are significantly or remarkably reduced.

In addition, among the reducing agent-treated products obtained by the above manufacturing method, glycosylhesperetin in which calcium, potassium, magnesium, and sodium contents per dry solid of the reducing agent-treated product as measured by high-frequency inductively coupled plasma emission spectrometry are within the following numerical ranges compositions containing, ie, calcium, potassium, magnesium and sodium contents of 1 ppm or less, 0.1 ppm or less, 0.2 ppm or less and 0.4 ppm or less, respectively; More preferably, the content of calcium, potassium, magnesium and sodium is 0.6 ppm or less, 0.06 ppm or less, 0.1 ppm or less and 0.3 ppm or less, respectively; Even more preferably, the content of calcium, potassium, magnesium and sodium, respectively, is 0ppm or more and 0.5ppm or less, 0ppm or more and 0.05ppm or less, 0ppm or more and 0.08ppm or less, and 0ppm or more and 0.2ppm or less, respectively. , It is preferable in that the effect of improving the dull yellow color and skin texture of the skin and the effect of improving skin quality such as skin dryness, erythema, irritation and itching are more remarkably exhibited. In addition, compared to the glycosylhesperetin-containing composition obtained by the conventional production method, it is also excellent in that the flavor/coloration and odor are significantly or remarkably reduced.

Since the reducing agent-treated product has significantly reduced flavor, coloration and odor, and also has excellent thermal stability, even if it is heated at a high temperature of 80 to 100 ° C. for 30 minutes or more, for example, the reducing agent Even if the process of incorporating the treated product or the oral cosmetic agent containing the same is stored at room temperature or a temperature slightly higher than room temperature for several tens of minutes to several months, the unpleasant taste/coloration and odor due to the reducing agent treated product will be reduced compared to immediately after manufacture. It is maintained without change, or their increase is effectively suppressed. In addition, the product treated with a reducing agent also has the advantage of being good in acid resistance and heat resistance.

As described above, the glycosylhesperetin used in the present invention, regardless of whether it is a product treated with a reducing agent or not treated with a reducing agent, is a compound having a hesperetin skeleton (1) α-glycosylhesperidin (α-glucosylhesperidin, etc. ) and (2) a composition containing one or both of hesperidin and 7-O-β-glucosyl hesperetin as main components, that is, a glycosyl hesperetin mixture, and in addition, it is derived from the raw material or It includes (3) flavonoids such as narirutin, diosmin, neoponsyrin, and glucosylnarirutin, which are thought to be produced incidentally in the manufacturing process, and (4) trace components such as salts. Among these glycosyl hesperetins, the glycosyl hesperetin suitably used in the present invention has a total ratio (%) of the components (1) and (2) (= glycosyl hesperetin content). 90% or more and less than 100%, preferably 93% or more and less than 100%, more preferably 95% or more and less than 100%, and further 97% or more and less than 100%, and 98% or more and less than 100%. In addition, the glycosyl hesperetin may contain hesperetin within a range in which the intended action and effect of the present invention are not hindered. In addition, as glycosylhesperetin used in the present invention, hesperetin having improved dispersibility in a solvent such as water by a known physical or chemical method is appropriately added to the extent that the intended action and effect of the present invention are not hindered. Combination is also possible.

The purity of glycosyl hesperetin used in the present invention, that is, the upper limit of the glycosyl hesperetin content per dry solid, is usually 99%, which can be provided in an industrially relatively large amount, cheaply and easily, more cheaply It may be of a low content up to 98% for providing, or 97% or less for providing more inexpensively. However, when the glycosylhesperetin content per dry solid is low, a large amount is inevitably used compared to a high content, and as a result, the operation becomes complicated and the handling property deteriorates. The lower limit of the glycosylhesperetin content is usually 90% or more, preferably 93% or more, more preferably 95% or more, still more preferably 97 mass% or more.

As a more preferred embodiment of the glycosylhesperetin used in the present invention, when the glycosylhesperetin is α-glycosylhesperidin such as α-glucosylhesperidin, the α-glycosylhesperetin content per dry solid is 50% or more. What is less than 100% can be exemplified.

In addition, as the upper limit of the α-glucosylhesperidin content in the glycosylhesperetin used in the present invention, when providing the oral cosmetic agent according to the present invention at a lower cost, it is usually industrially relatively large and inexpensive, and It may be of a low content of 90% or less, which can be easily provided, more inexpensively, 85% or less, and even more inexpensively, 80% or less. Also, the lower limit of the content of α-glucosylhesperidin is usually preferably 60% or more, 65% or more, or 70% or more for the same reason as the glycosylhesperetin content.

The oral cosmetic preparation of the present invention contains various types of glycosylhesperetin as an active ingredient, such as products not treated with a reducing agent and/or products treated with a reducing agent. Details will be described later, but when glycosylhesperetin is taken orally continuously by humans on a daily basis, it acts from the inside of the body to improve the dull yellow color of the skin, skin texture and skin quality, as well as skin dryness, Since it can effectively improve skin quality such as erythema, irritation, and itching, glycosylhesperetin is a so-called beauty food for improving the dull yellow color of the skin, skin texture, and skin quality, which are attracting attention these days, and also , As a health food, nutritive functional food, health functional food, food for specific health use, and furthermore, it can be used advantageously by properly mixing it with other beauty food, health food, nutritive functional food, health functional food, food for specific health use, or food product. there is. In addition, when glycosylhesperetin is used for the above purpose, polyphenols such as resveratrol, quercetin, chlorogenic acid, anthocyanin, curcumin, kaempferol, and flavonoids; plant extracts such as artichoke leaf extract, keiskei gilt extract, strawberry seed extract, ginkgo leaf extract, onju mandarin extract, cassis extract, kiwi seed extract, cranberry extract, acerola extract, amla extract, and aronia extract; carotenoids such as astaxanthin and β-carotene; And when used with one or two or more ingredients such as plant extracts or compounds having a glycosylation inhibitory action, the improvement of the dull yellow color of the skin, skin texture and skin quality to which glycosylhesperetin is effective is more At the same time as being effectively exerted, skin qualities such as dry skin, erythema, irritation, and itching are more effectively improved.

Plant extracts or compounds having the saccharification inhibitory action include eyebright, ramie, barley tree, Agrimony, Agni fruit, Euleum vine, Acai fruit, ashwagandha, Nahanbaek, Ahseonyak ( Alpine tree, Oyster oak, Stone, Anise, American witch hazel, Alistine, Yinyanggwak, Japanese knotweed, Ginkgo tree, Presser foot, Strawberry, Pine cone, Silly grass, Astragalus tree, Ife bark, Maple tree, Wing sky Lily of the valley, fennel, witch hazel, wintergreen, turmeric, plum blossoms, parsley, Epimedium brevicornum, briar fruit, echinacea, cytisus scoparius, broom flower, elcanpure ( hercampure), elder, elba mate, Borassus flabelifer, hwangbyeok tree, yellow lotus, thistle, oat, king sagebrush, transport herb, girl's lily, white lily, yellow lily, oregano, orange, sweet pumpkin Seed, catuaba skin, deer lily, guarana, karkade, foot-leaved lily, kanto, bellflower, champagne, chrysanthemum, kamala, horse lily, walnut, lingonberry, waterwheel, Sagarame (Eisenia arborea) , pomegranate, sweet potato, sarsaparilla, hawthorn, Japanese pepper log, perilla, sareungdu, turd grass, peony, rhubarb, rhubarb, chrysanthemum, pigweed, Aster ageratoides ssp. Leiophyllus, plantain, red snow plant, buckwheat, Silver bellflower, stork, davilla rugosa, tamoto lily, Cordia salicifolia, clove, tinnevelly senna, centella, daisy, dill, devil's croup (devils crow), hairy buttercup, cedar lily, devil's croup root, tencha, peach seed, sambaccho, rosa roxburghii, eucalyptus tea leaves, tomato, formentilla (potentilla), rattlesnake, poppy Tree, nasturtium, Aster microcephalus var. ovatus), mint, Hakata lily, bush clover, Thai giants (Colocasia gigantea), passion flower, passion flower, passion flower fruit, papia root, jackfruit, Taiwanese cherry tree, sunflower, umbrella tree, sky lily, biraco ( birako), betel nut, butterbur, swallow bean, black cohosh, vermilion plant, chinensis, Machilus odoratissima, pine tree, stone oak (Lithocarpus edulis), mate tea, madonna lily, milk thistle ( Western thistle), red pepper tree, mulberry honey, moose, willow tree, daylily, Yamato manlyeoji (Annona montana Macfady), wild lily, gongsimchae, aster, Litchi chinensis seed, Regal lily, Ryugu porridge, blackberry, Immature apples, Linden flowers, rooibos, lettuce, lemon, lemongrass, lemon thyme, lemon barbena, lemon balm, rosehip, pink rose bud, rosemary, rose red, laurel (Laurus nobilis), rosea ( Rosea), logwood, cucumber grass, purple milkweed, persimmon leaf, licorice leaf, black bean seed husk, black rice seed, dandelion leaf, leaf lily, western willow, plant extracts such as leaves of Eucalyptus leaf; extracts of seaweeds such as Arabidopsis, red chrysanthemum, and chrysanthemum; extracts such as green coffee beans, sweet potato soju lees, and Agaricus mycelium; and equol, isoflavone, 1,4-anthraquinone, 1-amino-2-hydroxymethylanthraquinone, 4-aminophenol, 1,3,5-trihydroxybenzene, kojic acid, 3 ,4-dihydroxyphenylacetic acid, caffeic acid, ifenprodil, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid, 6-hydroxyindole, 7-hydroxy-4 ,6-dimethylphthalide, α-lipoic acid, 4-hydroxychalcone, pearl protein hydrolysate, aminoguanidine, sodium erythrosin, ergothioneine, resveratrol, 3,3',5,5'-tetrahydroxystil Hydroxystilbenes such as Ben, oxyindole, carnosine, salicylic acid, salsolinol hydrobromide, cinapic acid, tocopheryl nicotinate, nicotinic acid amide, nordihydroguaiaretin acid, proanthocyanin, mannitol, hydrochloric acid Degraded casein, hydrolysable tannin, catechol, chlorogenic acid, isochlorogenic acid, neochlorogenic acid, cryptochlorogenic acid, chlorogenic acids such as ferulyl caffeoyl quinic acid, leucocyanidin, prunin, procyanidol oligomer, glucosyl rutin, etc. can be heard Among the above components, plant extracts or compounds having a saccharification inhibitory action, which are more preferably used in the present invention, are ashwagandha, rhododendron, ashenyak tree, ginkgo tree, winter green, hwangbyeok tree, orange, and sweet pumpkin seeds. , Catuaba Peel, Beetroot Tree, Glucosyl Rutin, Bilberry, Perilla, Buckwheat Leaf, Davilla Rugosa, Sambakcho, Blackberry, Vermilion Herb, Raisins, Ryugu Juk, Blackberry, Unripe Apple Fruit, Persimmon Leaves , licorice leaf, patterned woldo leaf, Eucommia leaf extract; and equol, isoflavone, ifenprodil, pearl protein hydrolysate, catechol, caffeic acid, and prunin.

The oral cosmetic agent of the present invention can be used in various solid, granular, powdery, suspension, paste, jelly, and liquid forms such as troches, cod liver oil drops, complex vitamins, oral fresheners, oral flavor tablets, oral/intraoral nutrients, and oral medications. It is also optional to mix and use in various compositions in the form.

The compounding amount of glycosylhesperetin in the oral cosmetic agent of the present invention can be appropriately adjusted according to the intake frequency of the oral cosmetic agent or skin condition. However, usually, the oral cosmetic agent of the present invention contains glycosyl hesperetin selected from one or two or more selected from hesperidin, α-glycosylhesperidin, and 7-O-β-glucosylhesperetin. When all are regarded as hesperidin and converted by mass (hereinafter, simply referred to as "Hesperidin conversion" in the present specification), they are more than 10% and less than 100%, preferably more than 15% and less than 100%, more preferably more than 20%. less than 100%, even more preferably greater than 30% and less than 100% blended. In addition, the intake frequency, intake amount, and intake period of the oral cosmetic agent of the present invention include one or two or more glycosyl hesperetins selected from hesperidin, α-glycosylhesperidin, and 7-O-β-glucosylhesperetin. in terms of hesperidin, usually 1 to 5 times a day, preferably 2 to 3 times a day, 10 to 3,000 mg, preferably 20 to 2,000 mg, more preferably 30 to 1,000 mg, even more preferably, per time It is preferably in the range of 50 to 500 mg, and it is preferable to consume it over several weeks, preferably over 6 weeks, and more preferably over 12 weeks. In addition, when the intake amount is below the lower limit, the intended action and effect may be significantly reduced or may not be exhibited, and when the intake amount exceeds the upper limit, the action and effect appropriate for the dose are not exhibited, which is not preferable from the viewpoint of economy. not.

Various solids, granules, powders, suspensions, pastes, jellies, As a method of blending into various compositions in liquid form, in the process until the composition is completed, for example, mixing, kneading, mixing, adding, dissolving, dipping, infiltrating, dispensing, coating, spraying, One or two or more widely known methods such as injection can be appropriately used.

Even when the oral cosmetic agent of the present invention thus obtained is maintained or stored at room temperature or a temperature slightly above room temperature for several tens of minutes to several months, as well as in various compositions formulated with it, Not to mention coloration, there is no odor at all or it is remarkably reduced to an imperceptible level. In addition, the oral cosmetic agent of the present invention also functions as a highly safe natural antioxidant, stabilizer, quality improver, vitamin P enhancer, etc., food and beverage, beauty food, health food, nutritional functional food, health functional food, specific health It is also optional to blend and use in various compositions such as food, feed, and bait for use.

Hereinafter, the oral cosmetic agent according to the present invention will be described in more detail by experiments.

<Experiment 1: Oral intake test>

(1) Overview

For the purpose of examining the effect of glycosyl hesperetin on the skin, a powdery glycosyl hesperetin-containing composition obtained in Example 1 prepared without using a predetermined reducing agent was used, and the condition of skin quality An oral intake test was conducted with 42 working women between the ages of 35 and 55 who have chronic fatigue symptoms known to adversely affect skin quality, such as skin roughness, as subjects. That is, a subject is orally ingested a predetermined test sample for a predetermined period of time, and at the same time, the dull yellow color of the subject's skin (face) is measured with an instrument, and the skin texture of the skin surface is visually determined by a doctor. In addition, skin quality For , visual determination and interview by a doctor were performed, and the effect of the test sample on the skin was evaluated.

(2) Preparation of test samples

As a test sample used in the oral intake test, in accordance with the known hard gelatin capsule manufacturing method (see Japanese Patent Publication No. 2-51528), hard gelatin capsules (size #1, manufactured by Capsugel Japan) shown in Table 1 below ) was encapsulated with other raw materials except for dextrin to prepare a capsule tablet type test sample containing glycosylhesperetin (hereinafter referred to as 'test sample A'), and as a control, glycosyl hesperetin-containing hard gelatin capsule Ingredients other than sylhesperetin were encapsulated to prepare a test sample (hereinafter referred to as 'test sample B') of a capsule tablet type not containing glycosylhesperetin.

Raw material
Blending amount per 1 tablet of test sample Test sample A Test sample B Composition containing glycosylhesperetin obtained in Example 1 250.0mg - dextrin
(『Finex #1』, manufactured by Matsutani Chemical Industry Co., Ltd.) - 250.0mg pullulan
("Plant Additive Pullulan", manufactured by Hayashibara Co., Ltd.) 2.5 mg 2.5 mg sucrose ester
(『DK Ester F20W』, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) 7.5mg 7.5mg hard gelatin capsules
(Size #1, manufactured by Capsugel Japan) 77.0mg 77.0mg

In the above table, '-' means no addition.

(3) Test procedure

42 subjects were randomly divided into 21 subjects each, group A and group B, and group A took test sample A as a test sample and group B took test sample B 2 tablets once a day for 12 weeks, respectively. . The time to consume the test sample was not specifically designated, but they were instructed to consume it at the same time as possible. Immediately after the end of the oral intake test for 12 weeks, the color difference of each subject's cheeks was measured using a color difference meter, and the dull yellowness of the skin was evaluated (see 'A' below), and the naked eye by a doctor As a judgment, the skin texture of the skin surface of each subject's face (see 'b' below) was evaluated, and furthermore, the skin quality was evaluated through visual examination and medical examination by a doctor (see 'c' below). . In addition, each of the above evaluations was also conducted before the start of oral intake of the test sample (0W) and on the 6th week after the start of oral intake (6W). In addition, since one subject of Group B withdrew from continuing the test in the middle of the test, data analysis of Group B was conducted based on the data of 20 subjects.

<A. Evaluation of dull yellowness of skin by color difference measurement>

·Measurement items: The color difference of the skin was measured based on the L*a*b* indicator.

· Device used: As a color difference meter, 『Konica Minolta Spectrophotometer CM-2600d』, product of Konica Minolta, was used to analyze skin color.

·Measurement location: The center of the left face, below the ear lobe and the tip of the lip, was measured (however, if there were age spots or inflammation at the measurement location, they were avoided).

·Analysis target in color difference measurement: values of a* (red) and b* (yellow), which are coordinate axes in the L*a*b* display system.

The a* value represents the degree of redness of the skin, and the 'b* value' represents the degree of yellowness of the skin. In addition, skin dullness, which is a higher level concept of dull yellow skin, occurs on the entire face or around the eyes or cheeks, and the redness of the skin decreases and the yellowness increases, and the gloss or transparency of the skin decreases, or the skin surface changes. While it is a technical term indicating a state in which the brightness is lowered by shadows caused by irregularities and the like, and it looks dark, the dull yellow color is changed to yellow (yellow color) by denaturation (carbonylation) of proteins in the dermis in the deep part of the skin by peroxides, etc. It is believed that fire) may be the main cause. Based on these technical backgrounds, in this test, the a* value and b* value, which are coordinate axes in the L*a*b* display system, were measured and used as indicators to evaluate the dull yellowness of the skin.

Adopted value: The measured values (n = 3) were averaged.

<I. Skin texture evaluation by a doctor: Comprehensive skin evaluation including crista cutis and sulcus cutis>

· Evaluation site: Evaluation was conducted on the left face, centered on the central part connecting the lower ear lobe and the tip of the lip.

· Evaluation method: According to the following criterion, the doctor visually judged the evaluation site using an auxiliary light and a microscope, and obtained a score value.

<Judgment Criteria>

Good: score is 2

Moderately good: score is 1

Normal: score is 0

Slightly bad: Score value is -1

Poor: The score is -2

<C. Evaluation of skin quality by a physician: evaluation of dryness, erythema, irritation and itching>

Evaluation area: entire face skin

· Evaluation method: According to the following criterion, the doctor visually judged the evaluation site using auxiliary light and a microscope, and questioned each subject to obtain a score value.

<Judgment Criteria>

None: No symptom identified (score value is 0)

Minor: Very few symptoms are seen (score value is 1)

Mild: slightly symptomatic (score value is 2)

· Moderate: obvious symptoms are seen (score value is 3)

· Severity: Significant symptoms are seen (score value is 4)

(4) Results and discussion

(4-1) Results and consideration of color difference measurement

Measured values obtained by measuring the color difference with the analysis target in the color difference measurement shown in 'A' of (3) above as an index for each subject in groups A and B who orally ingested test samples A and B, respectively. An average value ± standard error is obtained based on , and drawings created based on the numerical values are shown in FIGS. 1 and 2, respectively.

As shown in FIG. 1, in group B in which test sample B was orally ingested, the a* value significantly decreased at the 6th week (6W) after initiation of oral ingestion, and as shown in FIG. 2, after initiation of oral ingestion Over 6 to 12 weeks (6 to 12 W), the b* value of Group B hardly changed. In contrast, in group A, in which test sample A was orally ingested, as shown in FIG. In addition, as shown in FIG. 2, the b* (yellow period) value of group A significantly decreased over time over 6 to 12 weeks (6 to 12 W) after oral intake was initiated. In addition, as described in Non-Patent Document 1, even though it is known that the dull yellow color of the skin is improved when the b* value (yellow color) is lowered, the test sample A is judged to have an action to improve or reduce the dull yellow color of the skin It became.

Further, according to Non-Patent Document 1, regarding the L* value and the b* value, the L* value becomes an index of skin brightness and the b* value becomes an index of yellowness, and they are independent values that do not interlock with each other. In addition, regarding the L* value and the b* value, according to Non-Patent Document 2, the degree of pigmentation (melanin) of the skin is well divided using the angle when the L* value and the b* value are configured as a plane as an index. While there are reports that the b* value is affected by factors other than melanin, including the a* value, the L* value and the b* value are values for describing color and are not melanin-specific values. When comprehensively judged according to what is being reported, it cannot be said that the L* value and the b* value are in an interlocking relationship with each other, and the b* value is predicted based on the L* value, or, on the contrary, based on the b* value It cannot be said that there is a relationship in which the L* value can be predicted or made. Therefore, the view that the dull yellow color of the skin is improved or reduced by oral intake of the composition containing glycosylhesperetin, which was revealed in this test, can be said to be a new view that cannot be predicted from the prior art.

From the above, when glycosylhesperetin is orally ingested by humans, glycosylhesperetin generates hesperetin under the action of enzymes in vivo, and this hesperetin improves or reduces the dull yellowness of the skin. Since hesperidin, 7-O-β-glucosyl hesperetin, and α-glycosyl hesperetin or a composition containing the same is orally ingested by a human, the dull yellow color of the skin is improved. It is judged that the mitigating action is exhibited.

(4-2) Results and consideration of skin texture evaluation

The skin texture of the subject is visually evaluated by a doctor using an auxiliary light and a microscope, and the change in the obtained score value over time is shown in FIG. 3 . As can be seen in FIG. 3, in group B, which orally ingested test sample B, there was almost no change at the 6th week (6W) after the start of oral intake, and the score value at the 12th week (12W) after the start of oral intake. was slightly increased, whereas in group A, which orally ingested test sample A, the score value increased over time, and a significant increase in the score value was confirmed at the 12th week (12W) after the start of oral intake. In addition, according to the doctor's opinion, in the comprehensive evaluation of the skin including evaluation of skin ridges and skin furrows as skin texture indicators, the effect was not confirmed in group B orally ingested test sample B, whereas test sample A was In group A, which received oral intake, the size and height of the skin ridges became more uniform at the 12th week (12W) after the start of oral intake compared to before the start of oral intake (0W), and the skin furrows tended to become thinner and shallower This was confirmed, and the effect of improving skin texture was recognized.

From the above results, it can be considered that when glycosylhesperetin is orally ingested by humans, hesperetin is produced by the action of enzymes in vivo, and this hesperetin exerts an action to improve skin texture. , 7-O-β-glucosyl hesperetin, and α-glycosyl hesperetin or a composition containing the glycosyl hesperetin such as α-glycosyl hesperetin orally ingested by humans, it is believed that the skin texture improvement action will be exerted.

(4-3) Evaluation results and consideration of skin quality [dryness, erythema, irritation and itching]

4 to 7 show the changes over time in the score values obtained by visually examining the condition of the skin quality of the entire face of the subject by a doctor using an auxiliary light and a microscope, and also by interviewing each subject. As can be seen from this figure, compared to the subjects in Group B who orally ingested the test sample B, the subjects in the group A who orally ingested the test sample A started oral intake for any of skin dryness, erythema, irritation and itchiness. Compared to before (0W), significant improvement was confirmed at the 6th week (6W) and 12th week (12W) after the start of oral intake, so test sample A effectively improved any of skin dryness, erythema, irritation and itching. It has been found to have the effect of

From the results of this test, it is judged that glycosylhesperetin has an effect of effectively improving all of the skin qualities such as skin dryness, erythema, irritation and itching, as well as effectively improving the dull yellow color and skin texture of the skin. Considering that both of the glycosylhesperetin and reducing agent-treated products used in this test are compositions mainly composed of glycosylhesperetin, the test sample A used in this test was treated with a reducing agent instead of the glycosylhesperetin. In the case of using the product, the same action and effect as in this test result is exhibited, and at the same time, the reduction agent-treated product has a significant or remarkably reduced or improved taste, coloration, odor, etc. compared to the non-reducing agent-treated product, so oral intake without discomfort. There are advantages to doing so. That is, compared to test sample A used in this test, i.e., glycosylhesperetin (non-reducing agent-treated product) prepared without using a predetermined reducing agent, the product treated with a reducing agent was significantly reduced in flavor, as well as discolored or Since the unpleasant odor is also remarkably reduced, for example, oral cosmetics containing as an active ingredient the products treated with a reducing agent shown in Examples 2 to 8 described later are safe and easy to use for humans on a daily basis, and are easily administered without discomfort. Because it can be ingested, the desired action and effect are effectively exhibited, and therefore, the reducing agent-treated product is glycosylhesperetin most suitable for carrying out the present invention.

<Experiment 2: Physical properties of glycosylhesperetin>

As glycosylhesperetin, in the methods of Examples 2, 4, 5, and 6 described later, four types of powdery glycosylhesperetin prepared by the same methods as those described in those Examples except that a reducing agent was not used. (Test samples 1 to 4) and the method of Example 2, except for using 0.1, 0.09, 0.07 or 0.04% by mass of sodium pyrosulfite as a reducing agent, four types of powdery glycolysis prepared in the same manner as in Example 2. Sylhesperetin (test samples 5 to 8) was used. In addition, test sample 1 was prepared without using a predetermined reducing agent, and the contents of α-glucosylhesperidin, hesperidin, and other components were almost equivalent to those of the powdery glycosylhesperetin obtained in Example 1. It is equivalent to the powdery glycosylhesperetin obtained in 1.

(1) Content of furfural

For each of the test samples 1 to 8, the furfural content was determined using the following steps and equipment.

<A. Sample Preparation>

(A) Collect 0.5g of glycosylhesperetin as a test sample in a 50mL conical conical flask.

(B) Subsequently, 5.0 mL of deionized water was added to dissolve glycosylhesperetin, and as a surrogate material (an indicator for examining the recovery rate of the test sample at the time of analysis), cyclohexanol at a concentration of 0.0025% 20 μL is added.

(c) Further, 1.5 g of sodium chloride is added and dissolved, 3 mL of diethyl ether is added, and the mixture is stirred at 700 rpm for 10 minutes.

(D) The entire amount was transferred to a separatory funnel, allowed to stand for 10 minutes, and the diethyl ether phase was recovered, dehydrated with sodium sulfate, and concentrated to about 200 μL under a stream of nitrogen.

(E) Collect 1 μL of the concentrated solution and provide it to the GC/MS analyzer.

(f) As a control, the treatments (a) to (e) were carried out in the same way as the test sample, except that reagent grade furfural was used instead of glycosylhesperetin.

<GC/MS analysis conditions>

GC/MS analyzer: 『Clarus 680 GC』 and 『Clarus SQ8T』 (both manufactured by PerkinElmer)

Column: VF-WAXms [30 m (column length) × 0.25 mm (inner diameter), film thickness 0.25 μm] (manufactured by AGILENT J&W)

Detector: Mass spectrometer

Carrier: Helium gas

Line speed: 35 cm/sec

Heating conditions: Maintain at 40℃ for 3 minutes, raise the temperature from 40℃ to 80℃ at a rate of 5℃/min, raise the temperature from 80℃ to 200℃ at a rate of 10℃/min, and maintain at 200℃ for 7 minutes , The temperature is raised at a rate of 10 ° C / min from 200 ° C to 220 ° C, and further maintained at 220 ° C for 8 minutes.

Substitute: Cyclohexanol

Internal standard substance: Heneikosan

Extraction solvent: diethyl ether

<B. Quantification of furfural in the sample>

A calibration curve was prepared based on the measurement data for the control reagent, high-grade furfural (manufactured by Wako Pure Chemical Industries, Ltd.) obtained by the GC/MS analysis method, and based on this, the furfural content of the test sample was determined.

(2) 4-VA content

For each of Tests 1 to 8, the 4-VA content was determined using the following reagents, procedures and equipment. In addition, the measurement was carried out in accordance with the notice from the Ministry of Health, Labor and Welfare Ministry of Health, Labor and Welfare Ministry of Health, Labor and Welfare Ministry of Food and Drug Safety Standards Standards Examination Division No. 0728008 dated July 28, 2006, 『Regarding Benzene in Soft Drinks』.

<A. Preparation of reagents and various solutions>

(A) Sodium chloride (for water quality testing, sold by Wako Pure Chemical Industries, Ltd.)

(B) Preparation of cyclohexanol standard stock solution

Cyclohexanol (reagent grade 1, sold by Katayama Chemical Industry Co., Ltd.) was dissolved in methanol (for general test methods of the Pharmacy Department) to prepare a 0.01% by mass cyclohexanol solution (hereinafter referred to as 'cyclohexanol standard stock solution').

(C) Internal standard solution 0.0004% by mass cyclohexanol solution (hereinafter referred to as 'internal standard solution 1') and 0.00004 mass% cyclohexanol solution (hereinafter referred to as 'internal standard solution 2') using the cyclohexanol standard stock solution and methanol It is called.) was prepared.

(D) Preparation of standard stock solution

4-VA (sold by Wako Pure Chemical Industries, Ltd.) was dissolved in methanol, and a 0.0005 mass% 4-VA solution (hereinafter referred to as 'standard solution A') and a 0.00005 mass% 4-VA solution (hereinafter referred to as 'standard solution B') were obtained. ) were prepared respectively.

(E) Preparation of standard stock solution for preparation of calibration curve

Using standard solutions A and B, internal standard solution 1 and methanol, 5 types of mixed standard stock solutions with 4-VA concentrations of 0.05, 0.1, 0.2, 0.5 or 1.0 μg/mL were prepared for calibration curve preparation.

(F) Preparation of standard solution for preparation of calibration curve

10 mL of ultrapure water was added to each of 5 20 mL head space vials, and 10 μL of any one of the 5 types of mixed standard stock solutions for calibration curve preparation was added, and 3.0 g of sodium chloride was added, immediately sealed and dissolved by stirring, Five types of standard solutions for preparing a calibration curve were prepared.

<B. Preparation of test sample>

In eight 20 mL head space vials, 0.20 g of any of the test samples 1 to 8 was precisely weighed in terms of dry solid, and ultrapure water was added thereto to make the total amount 10.0 g, followed by stirring and dissolution. 8 types of test samples including any one of test samples 1 to 8 were prepared by adding 10 μL of the internal standard solution 2 to the obtained aqueous solution, further adding 3.0 g of sodium chloride, and immediately sealing and dissolving with stirring.

<C. Quantification method of 4-VA>

(A) Measurement conditions

<GC/MS analysis conditions>

GC/MS analysis equipment: 『Clarus SQ8T GC/MS』 (manufactured by PerkinElmer)

Head space sampler: 『TurboMatrix Trap 40』 (manufactured by PerkinElmer)

Column: VF-WAXms [Column length 30 m × inner diameter 0.25 mm, film thickness 0.25 μm) (manufactured by AGILENT J&W)

Detector: Mass spectrometer

Carrier: Helium gas

Line speed: 35cm/sec

Column inlet temperature: 200℃

Heating conditions: Maintain at 40℃ for 3 minutes, raise the temperature from 40℃ to 80℃ at a rate of 5℃/min, raise the temperature from 80℃ to 200℃ at a rate of 10℃/min, and maintain at 200℃ for 7 minutes And, the temperature is raised at a rate of 10 ° C / min from 200 ° C to 220 ° C, and further maintained at 220 ° C for 8 minutes.

Vial oven temperature: 60℃

·Needle temperature: 140℃

Transfer line temperature: 205℃

Vial heating time: 30 minutes

<Detection method>

·Ionization [Electron Impact (EI)] method

·SIM Selected Ion Monitoring

m/z 134, 119 (4-VA)

m/z 82, 57 [cyclohexanol (reagent grade 1, sold by Katayama Chemical Industry Co., Ltd.)]

(B) Quantification of 4-VA

Based on the peak height ratio of 4-VA and the internal standard (cyclohexanol) in the above 5 standard solutions for preparation of the calibration curve and the above 8 types of test samples, and the separately prepared 4-VA calibration curve, The 4-VA concentration of was obtained, and the 4-VA content in test samples 1 to 8 was calculated based thereon.

(3) Hue and coloration

The color tone of each of the aqueous solutions of Test Samples 1 to 8 was visually observed, and the degree of coloration was determined according to the following procedure. That is, each of the test samples 1 to 8 was made into a 1 w/w% aqueous solution, 40 mL of the solution was heated in an airtight container (50 mL) at 100 ° C for 30 minutes, then set to 27 ° C, put into a cell with a width of 1 cm, and was measured with a spectrophotometer. (trade name "UV-2600", manufactured by Shimadzu Corporation), absorbance was measured at a wavelength of 420 nm (OD _{420 nm} ) and a wavelength of 720 nm (OD _{720 nm} ), and the difference in absorbance at both wavelengths (OD _{420 nm} - OD _{720 nm} ) was obtained, and the value was used as the degree of coloration. In addition, it means that the coloration degree is low, so that the numerical value of an absorbance difference is small.

(4) Electrical conductivity

Next, each of these test samples 1 to 8 was dissolved in pure water to form a 1 w/v% aqueous solution, heated in an airtight container at 100°C for 30 minutes, and then the obtained aqueous solutions of test samples 1 to 8 were heated to 20°C, respectively. After cooling, the electrical conductivity at 20°C was measured with an electrical conductivity meter (trade name "CM-50AT", manufactured by Donga DK Co., Ltd.).

(5) Content of ionic compounds

Since it is not easy to quantify the ionic compound, as a simple method, the content of the cationic metal element was determined by the following method. That is, about 0.5 g of each of the test samples 1 to 8 was accurately weighed in a 50 mL container (trade name “Falcon Tube”, manufactured by Becton Dickinson Co., Ltd., Japan), dissolved by heating in 20 mL of ultrapure water, and 60 w/ After adding 0.54 mL of an aqueous solution of w% nitric acid, heating at 70 ° C. for 14 hours, cooling to room temperature, the total amount was 50 mL with ultrapure water, and the metal element content was determined under the following analyzer and measurement conditions. In addition, only ultrapure water was used as a control group.

<Apparatus and measurement conditions>

Inductively Coupled Plasma Emission Spectrometer : 『CIROS-120』(Product of Spectro)

·Plasma power: 1,400W

Plasma gas (Ar): 13.0L/min

·Auxiliary gas (Ar): 1.0L/min

Atomizer gas (Ar): 1.0L/min

·Pump action: 1.0mL/min

Calculation method of metal element content (ppm): {(measured value of test sample) - (measured value of control group)} × dilution factor

Table 1 shows the results of (1) to (5) above. In addition, since the composition of glycosylhesperetin in Test Samples 1 to 8 is substantially the same as that shown in Examples 2, 4, 5 or 6, description of these compositions is omitted in Table 2.

* Equivalent to glycosylhesperetin prepared by the method of Example 1

** Lighter color than the light yellow color of test samples 1 to 4, which are non-reducing agent treated products

As can be seen from Table 2, the furfural contents of samples 1 to 4 were all greater than 300 ppb, while samples 5 to 8 were all about 10 ppb. In addition, all of the 4-VA contents of test samples 1 to 4 were over 40 ppb, whereas all of the test samples 5 to 8 were about 2 ppb or less.

In addition, as shown in Table 2, the color tone of the aqueous solutions of test samples 1 to 4 (non-reducing agent treated products) was light yellow (by visual observation), but the aqueous solutions of test samples 5 to 8 (reduced agent treated products) were similar to those of test samples 1 to 4. It was clearly a lighter color than the others. In addition, the coloring degree of the aqueous solutions of test samples 1 to 4 was all 0.24 or more, whereas the aqueous solutions of test samples 5 to 8 were all low values of 0.20 or less. In addition, the coloring degree of the test samples 5 to 8 showed a lower value as the amount of the reducing agent used increased.

In addition, as can be seen from Table 2, the electrical conductivity of the aqueous solutions of test samples 1 to 4 was about 11 to about 12 μS/cm and 10 μS/cm or more, whereas the aqueous solutions of test samples 5 to 8 had about 3 to about 7 μS. /cm and less than 10 μS/cm.

In addition, as can be seen from Table 2, the content of metal elements (calcium, potassium, magnesium, and sodium) in Samples 5 to 8 is obviously lower than that in Samples 1 to 4, and the results are consistent with the measurement results of electrical conductivity. also matched well.

From the above results, it was found that the furfural content of the reducing agent-treated product was significantly reduced compared to the non-reducing agent-treated product, and the 4-VA content, coloring degree, electrical conductivity, and metal element content were also significantly reduced.

<Experiment 3: Relation between flavor and coloring of glycosylhesperetin and content of furfural and 4-VA>

The following test was conducted for the purpose of examining the relationship between the taste and coloring of glycosylhesperetin and the contents of furfural and 4-VA.

(1) Preparation of test samples

In accordance with the methods of Example 5 and Example 1 described later, glycosylhesperetin treated with a reducing agent (hereinafter referred to as 'sample A') and glycosylhesperetin untreated with a reducing agent (hereinafter referred to as 'sample A') B'.) were prepared respectively. Then, for convenience, samples A and B were mixed in an appropriate ratio, and three glycosylhesperetin samples (hereinafter referred to as 'test samples 9 to 11') having different furfural contents in stages were prepared as shown in Table 3. .

(2) Furfural and 4-VA content

The furfural content and 4-VA content of test samples 9 to 11 were measured according to the measurement methods shown in '(1) Content of furfural' and '(2) 4-VA content' of Experiment 2, respectively.

(3) Coloration judgment test

9 healthy men and women aged 28 to 57 years old (2 women, 7 men) were used as a panel to evaluate coloration using test samples 9 to 11 and sample B (hereinafter referred to as 'control group'). did That is, the test samples 9 to 11 and the control group were each dissolved in distilled water to form a 1w/w% aqueous solution at room temperature, and each panel had them visually observed, so that each panel had "reduced coloring" for each test sample compared to the control group. In the case of "yes", "decision A1" was evaluated, and in the case of "coloration was not reduced", "decision B1" was judged, respectively, and the results are shown in Table 3.

(4) sensory test

A sensory test was conducted on test samples 9 to 11 and the mixed rice of the control group with the 9 men and women above as a panel. That is, the test samples 9 to 11 and the control group were each dissolved in distilled water to form a 1w/w% aqueous solution at room temperature, and each panel sampled them, and each panel said that the taste was improved compared to the control group for each test sample. " was judged as 'decision A2', and when evaluated as "the taste was not improved", it was judged as 'decision B2', and the results are shown in Table 3.

test sample
Furfural content
(ppb) 4-VA content
(ppb) number of panels Coloration judgment test sensory test Judgment A1 Judgment B1 Judgment A2 Judgment B2 Sample B
(control group) 330 45.0 9 234 39.4 4 5 4 5 10 171 29.1 9 0 8 One 11 108 10.2 9 0 9 0 Sample A 56 2.0

Note: In the table, 'Judgment A1' refers to what each panel evaluated as "reduced coloration" compared to the control group in the coloration judgment test, and 'Judgment B1' refers to what was evaluated as "not reduced" indicate In addition, 'decision A2' indicates that each panel judged, in the sensory test, that "the taste was improved" compared to the control group, and 'judgment B2' was evaluated that "the taste was not improved."

As can be seen from the results of Table 3, the perfural content of the mixed rice of glycosylhesperetin was significantly and significantly improved around 200 ppb, and the 4-VA content was significantly and significantly improved around 30 ppb. Improved. The same was true for the coloration of glycosyl hesperetin.

From these results, the furfural content and the 4-VA content can be used as indicators for strictly distinguishing glycosylhesperetin with a significant reduction in off-taste and significantly reduced coloring. That is, if the furfural content is 200 ppb or less and the 4-VA content is 30 ppb or less, strictly distinguishing between them, it is possible to obtain glycosylhesperetin with a significantly reduced coloration and a significant reduction in off-flavor compared to products not treated with a reducing agent. there is.

In addition, Table 3 summarizes the relationship between the powdery glycosylhesperetin flavor shown in Table 2 of Experiment 2 and Examples 1 to 8 described later, and the furfural content and 4-VA content. indicate In Table 4, the powdery glycosylhesperetin of test samples 5 to 8 and Examples 2 to 8 (hereinafter, collectively referred to as "reducing agent-treated samples"), which are reducing agent-treated products, had a furfural content of 191 ppb or less, 4- The VA content was 28.7 ppb or less, and the peculiar taste of the non-reducing agent treated product was significantly reduced. On the other hand, the powdery glycosylhesperetin of Test Samples 1 to 5, which are non-reducing agent-treated products (hereinafter collectively referred to as "reducing agent-untreated samples"), had a furfural content of 308 ppb or more and a 4-VA content of 40.0 ppb. This is the above, and it had the peculiar taste of the non-reducing agent-treated product.

The results shown in Table 4 below are in good agreement with the results of Experiment 2, and based on these series of results, the furfural content and/or 4-VA content are used as indicators, and the furfural content is less than 200 ppb and/or 4-VA content. Strictly distinguishing that the VA content is less than 30 ppb, it is judged that it is possible to obtain glycosylhesperetin with significantly reduced flavor compared to products not treated with a reducing agent.

test sample
Furfural content
(ppb) 4-VA content
(ppb) miscellaneous rice

reducing agent
untreated sample

One* 308 40.2 × 2* 322 46.6 × 3* 343 55.1 × 4* 385 63.8 × 5
(Example 1) 310 40.0 ×


reducing agent
processed sample


Example 8 191 28.7 ○ Example 7 180 20.0 ○ 8* 12 2.1 ○ Example 2 12 2.0 ○ 7* 11 1.8 ○ Example 3 11 1.5 ○ Example 4 10 3.0 ○ 6* 10 1.5 ○ Example 6 10 1.5 ○ Example 5 9 2.0 ○ 5* 8 1.2 ○

Note: In the tables, '*' indicates that they are extracted from Table 2 in this specification. In addition, '○' indicates that the peculiar taste of the non-reducing agent-treated product is reduced, and 'x' indicates that the product has a peculiar taste almost equal to that of the non-reducing agent-treated product.

From the results in Table 4, compared to glycosylhesperetin, which is a reducing agent-treated product, the off-flavor is significantly reduced, and coloration and odor are also significantly reduced. It has been found that it can be taken orally on a daily basis, consistently, safely, easily and, moreover, without discomfort.

<Experiment 4: sensory test>

(1) Preparation of test samples

Among the test samples 5 to 8, which are products treated with a reducing agent used in Experiment 2, test sample 6 showing values in the middle of each of the furfural content, coloration, electrical conductivity, and metal element content, and a test sample that is not treated with a reducing agent Among 1 to 4, 8 healthy men and women (2 women, 6 men) aged 28 to 59 years old were selected as a panel using test sample 1, which showed the lowest values in furfural content, coloration, electrical conductivity and metal element content. The sensory test shown in (2) below was conducted. That is, the non-reducing agent treated product (test sample 1) and the reducing agent treated product (test sample 6) were dissolved in RO water (water passed through a reverse osmosis membrane) at room temperature to form 1 w/v% aqueous solutions, respectively, and unheated test samples 1 and 6 and stored in an airtight container until used for the following tests. In addition, unheated test samples 1 and 6 were placed in containers, respectively, sealed, heated in a boiling water bath for 30 minutes, and cooled to room temperature.

(2) sensory test

For each panel, unheated test samples 1 and 6 (10 mL each) and heated test samples 1 and 6 (10 mL each) obtained in (1) above, adjusted to room temperature, before tasting, (a) coloration and (b) odor were evaluated individually. Thereafter, each panelist was asked to rinse their mouths with boiled water before tasting each test sample, and then (c) bitter taste (including bitterness, acrid taste, astringent taste), (d) aftertaste, and (e) tasting Individuals were asked to rate the odor. Evaluation criteria are as shown in Table 5 below. In addition, for the unheated test sample 6, the unheated test sample 1 was used as a control, and for the heated test sample 6, the heated test sample 1 was used as a control, and each panel for each evaluation item of (a) to (e) above to evaluate The results are shown in Table 6 and Table 7, respectively.

(Evaluation standard)

Evaluation score (5-point evaluation)


city
hmm
jeon




(a) coloring



Compared to non-reducing agent treated products

1. Very Low 2. Slightly lower 3. Equivalent 4. Slightly high 5. Very high

(b) smell



Compared to non-reducing agent treated products

1. Very Weak 2. Somewhat weak 3. Equivalent 4. Somewhat strong 5. Very strong





city
hmm
city





(c) bitterness



Compared to non-reducing agent treated products

1. Highly Desirable 2. Slightly Desirable 3. Can't say either way 4. Slightly undesirable 5. Very undesirable

(d) aftertaste



Compared to non-reducing agent treated products

1. Highly Desirable 2. Slightly Desirable 3. Can't say either way 4. Slightly undesirable 5. Very undesirable

(e) smell



Compared to non-reducing agent treated products

1. Very Weak 2. Somewhat weak 3. Equivalent 4. Somewhat strong 5. Very strong

(3) Result of sensory test

number of panels before tasting tasting score (a) coloring (b) smell (c) bitterness (d) aftertaste (e) smell One 4 3 0 3 4 2 4 5 7 4 4 3 0 0 One One 0 4 0 0 0 0 0 5 0 0 0 0 0

(Score distribution of unheated test sample 6)

number of subjects before tasting tasting score (a) coloring (b) smell (c) bitterness (d) aftertaste (e) smell One 6 4 3 4 5 2 2 3 4 One One 3 0 One One 3 2 4 0 0 0 0 0 5 0 0 0 0 0

(Score distribution of heating test sample 6 (product treated with reducing agent))

In addition, the evaluation results shown in Tables 6 and 7 are (a) coloration, (b) odor, (c) bitterness, (c) bitterness, Although the evaluation results of (d) aftertaste and (e) odor are not shown, as shown in the evaluation criteria, the evaluation results shown in Tables 5 and 6 are based on glycosylhesperetin, which is a reducing agent-treated product, reducing agent treatment Since glycosylhesperetin, which is a product, was evaluated, the evaluation result of the reducing agent-treated product itself was an intermediate "3" in terms of the score (5-level evaluation) indicated in the evaluation criteria for each evaluation item.

On the other hand, as can be seen from the evaluation results of Table 6, the unheated test sample 6, that is, the reducing agent-treated product without heat treatment, had (a) coloration, (b) odor, (c) bitter taste, (d) aftertaste, and (e) For each evaluation item of odor, the number of panelists who rated '1', the highest in the 5-step evaluation, was 4, 3, 0, 3, and 4 out of 8, respectively (14 in total). was On the other hand, the heating test sample 6 shown in the evaluation results of Table 6, that is, the heat-treated reducing agent-treated product, was evaluated for (a) coloration, (b) odor, (c) bitterness, (d) aftertaste, and (e) odor. Regarding the item, the number of panelists who rated '1', which is the highest in the 5-step evaluation, was 4, 5, 7, 4, and 4 (total of 24) out of 8, respectively. This result indicates that the reducing agent-treated product is a high-quality glycosylhesperetin in which not only the bitter taste and coloring inherent in the reducing agent-treated product but also the odor are effectively reduced.

Similarly, as can be seen from the evaluation results in Table 6, unheated test sample 6 (glycosylhesperetin-containing composition not subjected to heat treatment) had (a) coloration, (b) odor, (c) bitterness, ( For the evaluation items of d) aftertaste and (e) smell, the number of panelists who rated '5', the lowest level, and '4', which is one level higher than the lowest level in the 5-level evaluation, was all 0 (0 persons in total). . On the other hand, as can be seen from the evaluation results in Table 7, the heating test sample 6 (the composition containing glycosylhesperetin that was subjected to heat treatment) had (a) coloration, (b) odor, (c) bitter taste, and (d) aftertaste. and (e) for the evaluation item of smell, the number of panelists who rated '5', the lowest level, and '4', which is one level higher than the lowest level in the 5-level evaluation, was 0 (0 persons in total). These results indicate that the reducing agent-treated product is a high-quality glycosylhesperetin-containing composition in which odors as well as unpleasant taste/coloration are effectively reduced compared to products not treated with a reducing agent.

From these results, compared to non-reducing agent-treated products, regardless of heating/non-heating, (a) coloration, (b) odor, (c) bitter taste, (d) aftertaste, and (e) ) Not only was it remarkably excellent in all evaluation items of odor, but it was also found that the difference in superiority and inferiority appeared in a more significant difference when heated.

In addition, test samples 5, 7 and 8 shown in "(1) Preparation of test sample" of Experiment 3 were also subjected to "(2) Sensory test" of Experiment 4, results almost equivalent to those of test sample 6 is obtained

In this way, it was found that the reducing agent-treated product had significantly reduced bitterness and aftertaste, i.e., off-taste peculiar to the reducing agent-treated product, as well as significantly reduced coloration and odor compared to the reducing agent-untreated product.

As described above, compared to the non-reducing agent-treated product, it was found that the bitterness and aftertaste peculiar to glycosylhesperetin, that is, the aftertaste of the reducing agent-treated product were significantly reduced, as well as the coloration and smell were significantly reduced. It became.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

Example 1

<Oral Cosmetics>

As a raw material, 7 parts by mass of dextrin (DE20) was used with respect to 1 part by mass of hesperidin in the same manner as in the method described in Example A-2 of Japanese Patent Laid-Open No. 11-346792, Bacillus stearothermophilus 20 units of cyclomaltodextrin glucanotransferase (manufactured by Hayashibara Co., Ltd.) derived from dextrin were added per gram of dextrin, maintained at pH 6.0 and 75° C., and reacted for 24 hours to obtain a syrup-like glycosylhesperetin-containing composition, To this, 100 units of glucoamylase (trade name 'Glucocim', manufactured by Nagase Chemtex Co., Ltd.) was added per gram of dry solids of the glycosylhesperetin-containing composition, and reacted at 50°C for 5 hours. Subsequently, the obtained syrupy glycosylhesperetin-containing composition was concentrated under reduced pressure and powdered to obtain a powdery glycosylhesperetin-containing composition in a yield of about 60% based on the mass of hesperidin as a raw material per dry solid. This product contained 77.0% by mass of α-glucosylhesperidin, 15.5% by mass of hesperidin, and 7.5% by mass of other components.

The furfural content of this product was 310 ppb, the 4-VA content was 40.0 ppb, the coloring degree was 0.24, and the electrical conductivity was about 11 μS/cm. In addition, this product contained about 3ppm, about 0.2ppm, about 0.4ppm, and about 1ppm of calcium, potassium, magnesium and sodium, respectively, per dry solid.

By processing this product or beauty food, health food, nutritional functional food, health functional food, or specific health food containing it and ingesting it orally to humans, it improves the dullness of the skin and skin texture, as well as skin dryness and erythema. , It can effectively improve skin quality such as irritation and itchiness, and can be advantageously used as an oral cosmetic agent that humans can safely and easily take orally.

Example 2

<Oral Cosmetics>

4 parts by mass of an aqueous solution of 1 normal sodium hydroxide was heated to 80°C, and 1 part by mass of hesperidin and 7 parts by mass of dextrin (DE20) were added while maintaining this temperature, dissolved while stirring for 30 minutes, the pH was set to 9.0, and geo 30 units of CGTase derived from Bacillus stearomyphilus Tc-91 (Independent Administrative Corporation Industrial Technology Research Institute, Patent Organism Deposit Center, accession number FERM BP-11273, deposit date: July 30, 1973) are added per gram of dextrin. and reacted for 18 hours while maintaining the pH at 6.9 and 50°C to convert about 70% of hesperidin to α-glycosylhesperidin. Subsequently, 0.05% by mass of sodium pyrosulfite as a reducing agent was added to the obtained enzyme reaction solution, heated at 100° C. for 30 minutes, and the remaining enzyme was heat-inactivated, followed by glucoamylase (trade name “Glucocim”, Nagasechem). Tex Co., Ltd.) was added in an amount of 100 units per gram of solid content of the enzyme reaction solution, and reacted for 5 hours while maintaining pH 5.0 and 55 ° C. to produce α-glucosylhesperidin. The obtained enzyme reaction solution was heated to inactivate the remaining enzyme, filtered, and the filtrate was placed in a column packed with a porous synthetic adsorbent, trade name “Diaion HP-10” (sold by Mitsubishi Chemical Corporation) at a space velocity (SV) of 2. Passed. As a result, α-glucosylhesperidin and unreacted hesperidin in the solution were adsorbed to the porous synthetic adsorbent, and D-glucose and salts were not adsorbed but flowed out. Subsequently, purified water was passed through the column, the column was washed, and then the ethanol aqueous solution was passed again while increasing the concentration stepwise, and the α-glucosylhesperidin-containing fraction was collected, concentrated under reduced pressure, powdered, and light yellow powdery glycosyl A composition containing hesperetin was obtained in a yield of about 70% based on the mass of hesperidin as a raw material per dry solid. In addition, the powdery glycosylhesperetin-containing composition obtained in this example contained 80.0% by mass of α-glucosylhesperidin, 12.3% by mass of hesperidin, and 7.7% by mass of other components.

The furfural content of this product was 12 ppb, the 4-VA content was 2 ppb, the coloration was 0.19, and the electrical conductivity was about 6 μS/cm. In addition, this product contained about 0.4 ppm, about 0.05 ppm, about 0.1 ppm and about 0.1 ppm of calcium, potassium, magnesium and sodium, respectively, per dry solid.

In addition, compared to the powdery glycosylhesperetin-containing composition obtained in Example 1, which was prepared without using a predetermined reducing agent, this product significantly reduced flavor and coloration, and significantly reduced odor. , Even after heating for 30 minutes under a relatively high temperature condition of 90 to 100 ° C., odors as well as flavors/coloring were effectively reduced.

Even when processed into this product or beauty food, health food, nutritional functional food, health functional food, or specific health food containing it, and maintained or preserved for several tens of minutes to several months at a temperature within or below the above temperature range, Excellent action and effect of effectively reducing odors as well as flavor/coloration derived from this product are exhibited.

The oral cosmetic agent of this example is an oral cosmetic agent that has excellent storage stability and can be taken orally by humans continuously, safely and easily without discomfort on a daily basis. It has excellent benefits that can effectively improve skin quality such as irritation and itchiness.

Example 3

<Oral Cosmetics>

4 parts by mass of an aqueous solution of 1N sodium hydroxide was heated to 80°C, and while maintaining this temperature, 1 part by mass of hesperidin, 4 parts by mass of dextrin (DE10), and 0.06 part by mass of sodium sulfite were sequentially added thereto, stirring for 30 minutes. After dissolving and neutralizing with 0.01 standard hydrochloric acid solution, CGTase derived from Geobacillus Stear Asomophilus Tc-91 strain (Industrial Research Institute of Industrial Technology, Patent Organism Depository Center, accession number FERM BP-11273) was dextrin gram 20 units of sugar were added, maintained at pH 6.0 and 75°C, and reacted for 24 hours while stirring. As a result of sampling the obtained enzyme reaction solution and analyzing it by high-performance liquid chromatography, it was found that about 69% of hesperidin was converted to α-glycosylhesperidin. Subsequently, sodium pyrosulfite was added as a reducing agent to the obtained enzyme reaction solution so as to be 0.03% by mass, heated at 90 ° C. for 120 minutes, and then glucoamylase (trade name “Glucocim”, manufactured by Nagase ChemteX Co., Ltd.) was added to the intermediate product in grams 50 units of sugar were added and reacted for 10 hours while maintaining the pH at 5.0 and 55°C to produce α-glucosylhesperidin. The obtained enzyme reaction solution was heated to inactivate the remaining enzyme, filtered, and the filtrate was passed through a column packed with a porous synthetic adsorbent, trade name "Diaion HP-10" (sold by Mitsubishi Chemical Corporation) at SV2. As a result, α-glucosylhesperidin and unreacted hesperidin in the solution were adsorbed to the porous synthetic adsorbent, and sugars and salts were not adsorbed but flowed out. Then, purified water was passed through the column to wash the column, and then the aqueous solution of ethanol was passed again while increasing the concentration in stages, and the α-glucosylhesperidin-containing fraction was collected, concentrated under reduced pressure and pulverized to obtain pale yellow powdery glycosylheses The ferretin-containing composition was obtained in a yield of about 68% based on the mass of hesperidin as a raw material per dry solid. In addition, the powdery glycosylhesperetin-containing composition obtained in this example contained 79.0% by mass of α-glucosylhesperidin, 14.0% by mass of hesperidin, and 7.0% by mass of other components.

The furfural content of this product was 11 ppb, the 4-VA content was 1.5 ppb, the coloration was 0.14, and the electrical conductivity was about 4 μS/cm. In addition, this product contained about 0.4 ppm, about 0.06 ppm, about 0.1 ppm and about 0.1 ppm of calcium, potassium, magnesium and sodium, respectively, per dry solid.

Compared to the powdery glycosylhesperetin-containing composition obtained in Example 1, which was prepared without using a predetermined reducing agent, this product has significantly reduced flavor and coloration, and significantly reduced odor, as well as a 90 to 90% Even when heated for 30 minutes under a relatively high temperature condition of 100°C, not only flavor/coloration but also odor were effectively reduced.

Even when processed into this product or a beauty food, health food, nutritional functional food, health functional food, or specific health food containing it, maintained or preserved for several tens of minutes to several months at a temperature within or below the above temperature range, , It exhibits an excellent action effect that effectively reduces odors as well as flavor/coloration derived from this product.

The oral cosmetic agent of this example has excellent storage stability, and is an oral cosmetic agent that can be safely and easily taken orally by humans on a daily basis without discomfort. It has excellent advantages that can effectively improve skin quality such as irritation and itching.

Example 4

<Oral Cosmetics>

4 parts by mass of an aqueous solution of 1N sodium hydroxide was heated to 80° C., and while maintaining this temperature, 0.1 part by mass of sodium sulfite, 1 part by mass of hesperidin, and 4 parts by mass of dextrin (DE10) were sequentially added thereto as a reducing agent, and stirred for 30 minutes. After neutralizing by adding 0.01 standard hydrochloric acid solution, Geobacillus Stear Asomophilus Tc-91 (Independent Administrative Corporation Industrial Technology Research Center, Patent Organism Depository Center, accession number FERM BP-11273) was derived. As a result of adding 20 units of CGTase per gram of dextrin and maintaining the pH at 6.0 and 75° C. and stirring for 24 hours, about 72% of hesperidin was converted to α-glycosylhesperidin. The obtained enzyme reaction solution was heated to inactivate the remaining enzyme, filtered, and the filtrate was passed through a column filled with a porous synthetic adsorbent, trade name "Diaion HP-20" (sold by Mitsubishi Chemical Corporation) at SV2. As a result, α-glycosylhesperidin and unreacted hesperidin in the solution were adsorbed to the porous synthetic adsorbent, and D-glucose and salts were not adsorbed but flowed out. Subsequently, purified water was passed through the column, the column was washed, and the aqueous ethanol solution was passed again while increasing the concentration step by step, and the α-glycosylhesperidin-containing fraction was collected, concentrated under reduced pressure, and pulverized to produce light yellow powdery α-glycosyl The hesperidin-containing composition was obtained in a yield of about 71% per dry solid, based on the mass of hesperidin as a raw material. In addition, the powdery glycosylhesperetin-containing composition obtained in this example contained 76.0% by mass of α-glycosylhesperidin, 18.5% by mass of hesperidin, and 5.5% by mass of other components.

The furfural content of this product was 10 ppb, the 4-VA content was 3.0 ppb, the coloring degree was 0.17, and the electrical conductivity was about 4 μS/cm. In addition, this product contained about 0.3 ppm, about 0.04 ppm, about 0.1 ppm and about 0.05 ppm of calcium, potassium, magnesium and sodium, respectively, per dry solid.

In addition, compared to the powdery glycosylhesperetin-containing composition obtained in Example 1, which was prepared without using a predetermined reducing agent, this product significantly reduced flavor and coloration, and significantly reduced odor. , Even when heated for 30 minutes under a relatively high temperature condition of 90 to 100 ℃, it has excellent characteristics in that it effectively reduces odor as well as flavor and color.

Even if this product or beauty food, health food, nutritional functional food, health functional food, or specific health food containing it is processed and maintained or preserved for several tens of minutes to several months at a temperature in or below the above temperature range, , It exhibits excellent functional effects by effectively reducing odors as well as flavor/coloration derived from this product.

The oral cosmetic agent of this example has excellent storage stability, and is an oral cosmetic agent that can be safely and easily taken orally by humans on a daily basis without discomfort. and it has an excellent advantage of effectively improving skin quality such as itchiness.

Example 5

<Oral Cosmetics>

1 part by mass of hesperidin, 10 parts by mass of dextrin (DE8), and 0.05 part by mass of sodium pyrosulfite as a reducing agent were added to 500 parts by mass of water, heated at pH 9.5 and 90°C for 70 minutes, and then Geobacillus stearothermophilus Tc-91 30 units of CGTase per gram of dextrin were added, maintained at pH 8.2 and 65° C., and maintained for 40 hours while stirring. Immediately before the end of the enzyme reaction, 0.05 part by mass of sodium pyrosulfite was added, heated at 85 ° C. to inactivate the enzyme, and then glucoamylase (trade name “Glucocim”, manufactured by Nagase Chemtex Co., Ltd.) was added to the enzyme reaction solution as a solid 100 units per gram were added and reacted for 5 hours while maintaining pH 5.0 and 55°C to produce α-glucosylhesperidin. The obtained enzyme reaction solution was heated to inactivate the remaining enzyme. Subsequently, 0.5 part by mass of hesperidinase (trade name “Soluble Hesperidinase <Tanabe> No. 2”, manufactured by Tanabe Pharmaceutical Co., Ltd.) as α-L-rhamnosidase was added to the obtained enzyme reaction solution to adjust the pH to 4, After reacting at 55 ° C. for 24 hours, 0.01 part by mass of sodium pyrosulfite was added to the resulting enzyme reaction solution, heated to inactivate the enzyme, filtered, and the filtrate was a porous synthetic adsorbent, trade name “Diaion HP-10” (Mitsubishi Chemical Co., Ltd.) was passed through a column packed with SV2. As a result, α-glucosylhesperidin, 7-O-β-glucosylhesperetin, and unreacted hesperidin in the solution were adsorbed to the porous synthetic adsorbent, but D-glucose and salts were not adsorbed and flowed out. Subsequently, purified water was passed through the column, the column was washed, and then the ethanol aqueous solution was passed again while increasing the concentration in stages, and the α-glucosylhesperidine fraction was collected, concentrated under reduced pressure, and pulverized, and light yellow powdery glycosylhespere The tin-containing composition was obtained in a yield of about 70% based on the mass of hesperidin as a raw material per dry solid. In addition, the powdery glycosylhesperetin-containing composition obtained in this example contains 81.9% by mass of α-glucosylhesperetin, 0.5% by mass of hesperidin, 8.9% by mass of 7-O-β-glucosylhesperetin, and 8.7% by mass of other components. % was contained.

The furfural content of this product was 9ppb, the 4-VA content was 2.0ppb, the coloration was 0.16, and the electrical conductivity was about 4μS/cm. In addition, this product contained about 0.3 ppm, about 0.03 ppm, about 0.05 ppm, and about 0.05 ppm of calcium, potassium, magnesium and sodium, respectively, per dry solid.

Compared to the powdery glycosylhesperetin-containing composition obtained in Example 1, which was prepared without using a predetermined reducing agent, this product significantly reduced flavor and coloration, and significantly reduced odor, as well as 90 Even when heated for 30 minutes under a relatively high temperature of 100 ° C., it has excellent characteristics in that odors as well as flavor and color are effectively reduced.

Even when processed into this product or beauty food, health food, nutritional functional food, health functional food, or specific health food containing it, and maintained or preserved for several tens of minutes to several months at a temperature in or below the above temperature range, , It exhibits excellent functional effects by effectively reducing odors as well as flavor/coloration derived from this product.

The oral cosmetic agent of this example is an oral cosmetic agent that has excellent storage stability and can be taken orally by humans continuously, safely and easily without discomfort on a daily basis, and has an action to improve dull skin tone and skin texture, and skin dryness, erythema, and irritation. and it has an excellent advantage of effectively improving skin quality such as itchiness.

Example 6

<Oral Cosmetics>

50 parts by mass of Hesperidin and 1 part by mass of sodium hyposulfite were dissolved in 0.9 parts by mass of an aqueous solution of 0.25 normal sodium hydroxide by heating at 80°C, dissolved by adding 150 parts by mass of DE8 dextrin, adjusted to pH 9.0, and then Geobacillus Stearothermophilus 15 units of CGTase derived from Tc-91 strain (Independent Administrative Corporation National Institute of Industrial Technology, Patent Biodepositary Center accession number FERM BP-11273) per 1 part by mass of dextrin were added, and the pH was adjusted to 8.3 while heating to 60°C for 6 hours. reacted Thereafter, the pH was adjusted to 7.0, heated to 68°C, and reacted for 40 hours. After completion of the enzyme reaction, the enzyme was inactivated by heating and then filtered to obtain an enzyme reaction solution. As a result of analyzing the enzyme reaction solution by high-performance liquid chromatography (HPLC), 72% of the hesperidin in the solution before the reaction was converted to α-glucosylhesperidin, and the remaining 28% remained unreacted. To the enzyme reaction solution, 2 parts by mass of hesperidinase (trade name “Soluble Hesperidinase <Tanabe> No. 2”, manufactured by Tanabe Pharmaceutical Co., Ltd.) was added as α-L-rhamnosidase to adjust the pH to 4, and at 55°C. After reacting for 24 hours, 1 part by mass of glucoamylase (trade name "Glucocim", manufactured by Nagase ChemteX Co., Ltd.) was added, and the mixture was further reacted at 55°C for 24 hours. After the end of the enzyme reaction, the obtained enzyme reaction solution was heated to inactivate the enzyme, and then hung on a column filled with mesopolar porous adsorption resin (trade name: 『Amberlite XAD-7』, manufactured by Rohm & Haas), and the column was washed with water. , The resin adsorption component was eluted with an 80 v/v% ethanol aqueous solution. After removing the ethanol in the eluate, freeze-dried to contain 82.0% by weight of α-glucosylhesperidin, 8.0% by weight of 7-O-β-glucosylhesperetin, 1.0% by weight of hesperidin, and 9.0% by weight of other components. A powdery glycosylhesperetin-containing composition was obtained.

The furfural content of this product was 10 ppb, the 4-VA content was 1.5 ppb, the coloration was 0.15, and the electrical conductivity was less than 10 μS/cm. In addition, this product contained about 0.4 ppm, about 0.04 ppm, about 0.1 ppm, and about 0.2 ppm of calcium, potassium, magnesium and sodium, respectively, per dry solid.

Compared to the powdery glycosylhesperetin-containing composition obtained in Example 1, which was prepared without using a predetermined reducing agent, this product significantly reduced flavor and coloration, and significantly reduced odor, as well as 90 Even when heated for 30 minutes under a relatively high temperature of 100 ° C., it has excellent characteristics in that odors as well as flavor and color are effectively reduced.

If this product or beauty food, health food, nutritional functional food, health functional food, or specific health food containing it is processed, maintained or preserved for several tens of minutes to several months at a temperature in or below the above temperature range Even in the case of this product, it exhibits excellent operational effects by effectively reducing odors as well as flavor/coloration derived from this product.

The oral cosmetic agent of this example is an oral cosmetic agent that has excellent storage stability and can be taken orally by humans continuously, safely and easily without discomfort on a daily basis, and has an action to improve dull skin tone and skin texture, and skin dryness, erythema, and irritation. and it has an excellent advantage of effectively improving skin quality such as itchiness.

Example 7

<Oral Cosmetics>

In the same manner as in Example 1 except for adding 0.001% of potassium metasulfite as a reducing agent to the enzyme reaction solution, light yellow powdery glycosylhesperetin was obtained in a yield of about 69% based on the mass of hesperidin as a raw material per dry solid. . In addition, the powdery glycosylhesperetin-containing composition obtained in this example contained 79.5% α-glucosylhesperidin, 13.8% hesperidin, and 6.7% other components.

The furfural content of this product was 180 ppb, the 4-VA content was 20.0 ppb, the coloration was 0.23, and the electrical conductivity was less than 10 μS/cm. In addition, this product contained about 0.5 ppm, about 0.08 ppm, about 0.1 ppm and about 0.3 ppm of calcium, potassium, magnesium and sodium, respectively, per dry solid.

Although this product is inferior to the powdery glycosylhesperetin-containing compositions obtained in Examples 2 to 5, it has a significant reduction in off-taste compared to products not treated with a reducing agent, as well as remarkably reduced coloration and odor. In addition, even after heating for 30 minutes under relatively high temperature conditions of 90 to 100 ° C., it has excellent characteristics that not only the flavor is significantly reduced compared to the non-reducing agent treated product, but also the coloration and odor are effectively and significantly reduced. .

This product or beauty food containing it, health food, nutritional functional food, health functional food, or specific health food, etc. (these are collectively referred to as "oral beauty agents") are processed, and the temperature ranges above or below it. , even when maintained or stored for several tens of minutes to several months, excellent functional effects such as odors as well as flavor/coloration derived from this product are effectively reduced.

The oral cosmetic agent is an oral cosmetic agent that has excellent storage stability and can be safely and easily taken orally by humans on a daily basis without discomfort, and has a dull yellowish color and skin texture improvement action, and skin dryness, erythema, irritation and It can effectively improve skin quality such as itchiness.

Example 8

<Oral Cosmetics>

In the same manner as in Example 7 except for replacing potassium metasulfite with sodium hydrogensulfite, a pale yellow powdery glycosylhesperetin-containing composition was obtained in a yield of about 65% based on the mass of hesperidin as a raw material per dry solid. In addition, the powdery glycosylhesperetin-containing composition obtained in this example contained 77.2% of α-glucosylhesperidin, 16.5% hesperidin, and 6.3% of other components.

The furfural content of this product was 191 ppb, the 4-VA content was 28.7 ppb, the coloration was 0.23, and the electrical conductivity was less than 10 μS/cm. In addition, this product contained about 0.5 ppm, about 0.07 ppm, about 0.09 ppm and about 0.4 ppm of calcium, potassium, magnesium and sodium, respectively, per dry solid.

Although this product is inferior to the physical properties of the powdery glycosylhesperetin-containing compositions obtained in Examples 2 to 6, this product has a significant reduction in off-taste compared to products not treated with a reducing agent, as well as discoloration and odor. Not only is it significantly reduced, even after heating for 30 minutes under a relatively high temperature condition of 90 to 100 ° C., compared to products not treated with a reducing agent, of course, coloration and odor are significantly reduced. It has excellent characteristics.

This product or beauty food containing it, health food, nutritional functional food, health functional food, or specific health food, etc. (hereinafter collectively referred to as "oral beauty agents") are processed, and Even when maintained or stored at the temperature for several tens of minutes to several months, an excellent effect of effectively reducing odor as well as flavor/coloring derived from this product is exhibited.

The oral cosmetic agent is an oral cosmetic agent that has excellent storage stability and can be taken orally by humans on a daily basis, continuously, safely and easily without discomfort. It can effectively improve skin quality such as itchiness.

Example 9

<Oral Cosmetics>

10 parts by mass of calcium acetate monohydrate, 50 parts by mass of magnesium L-lactate trihydrate, 57 parts by mass of maltose, 150 parts by mass of the powdery glycosylhesperetin-containing composition obtained in Example 1, and γ-containing 20% eicosapentaenoic acid 12 parts by mass of the cyclodextrin inclusion compound were uniformly mixed, put into granules in a granulation machine, and sealed in gelatin capsules according to a conventional method to obtain a capsule-type oral cosmetic agent containing 300 mg of the contents per capsule.

By taking 1 to 10 capsules per day orally by humans on a daily basis, this product exhibits the effect of improving the dull yellow color of the skin and skin texture, and effectively treats skin qualities such as skin dryness, erythema, irritation and itching. can be improved

Example 10

<Oral Cosmetics>

10 parts by mass of any one of the glycosylhesperetin-containing compositions obtained in Examples 2 to 8, 0.003 parts by mass of sucralose, 0.01 part by mass of ascorbic acid 2-glucoside (trade name "Asco Fresh" (registered trademark) sold by Hayashibara Co., Ltd.) Part by mass and 20 parts by mass of dextrin were stirred and mixed, and 0.5 g each was accommodated in a stick-shaped light-shielding/moisture-proof packaging container to obtain seven kinds of powdery oral cosmetic agents of the present invention.

This product is substantially free from off-flavors, coloration, and odor, and can be easily orally ingested by humans without discomfort on a daily basis. This product is usually added in 1 to 3 packets per day to various beverages such as water, tea, black tea, coffee, or other food products, and when continuously orally ingested by humans on a daily basis, it improves the dull yellow color of the skin and skin texture. At the same time, it is possible to effectively improve skin qualities such as skin dryness, erythema, irritation and itching.

Example 11

<Oral Cosmetics>

1 part by mass of any one of the 7 types of powdered oral cosmetic agents obtained in Example 10, 0.001 part by mass of anthocyanin, 30 parts by mass of purified water and an appropriate amount of a pH adjuster were added and stirred, the pH was adjusted to 7.0, microfiltration was performed, and sterilization was performed. It was aseptically filled into a container to obtain five types of liquid oral cosmetic preparations of the present invention.

This product is substantially free from off-flavors, coloring, and off-flavors, and can be easily orally ingested by humans without discomfort on a daily basis. By ingesting about 30 to 100mL of this product per day to humans on a daily basis, it can effectively improve skin quality such as skin dryness, erythema, irritation and itching while exhibiting the action of improving the dull yellow color of the skin and skin texture. there is.

Example 12

<Oral Cosmetics>

1 part by mass of the powdery glycosylhesperetin-containing composition obtained in Example 1 was uniformly dissolved in 50 parts by mass of purified water, microfiltered, and filled into a sterile container to obtain various liquid oral cosmetic agents.

This product is substantially free from undesirable flavors, coloring, and off-flavors, and is consumed as it is or by adding about 1 to 5 mL to beverages such as green tea, black tea, coffee, cocoa, and soft drinks. At the same time, it is possible to effectively improve skin qualities such as skin dryness, erythema, irritation and itching.

Example 13

<Oral Cosmetics>

One part selected from sodium sulfite, sodium hyposulfite, potassium pyrosulfite, sodium pyrosulfite, and sulfur dioxide with respect to 1 part by mass of the powdery glycosylhesperetin-containing composition obtained in Example 1, which is produced without using a predetermined reducing agent. Alternatively, a total of 0.0005 parts by mass of two or more reducing agents was added, uniformly dissolved in 50 parts by mass of purified water, microfiltered, and filled into a sterile container to obtain various kinds of liquid oral cosmetic agents.

Even after storage for several tens of minutes to several months in a room temperature or relatively high temperature environment, this product was not substantially confirmed to increase or change in flavor/coloration or odor caused by the product, and had excellent storage stability and thermal stability. This product is substantially free from added flavor, coloration, and off-flavor, and is consumed as it is or by adding about 1 to 5 mL to beverages such as green tea, black tea, coffee, cocoa, and soft drinks to improve dull yellowness and skin texture. At the same time as the action is exhibited, skin qualities such as skin dryness, erythema, irritation and itching can be effectively improved.

According to the oral cosmetic agent of the present invention, it is possible to effectively improve the dull yellow color and skin texture of the skin, as well as effectively improve skin dryness, erythema, irritation and itching. As the glycosyl hesperetin used in the oral cosmetic agent of the present invention, especially when using glycosyl hesperetin prepared using a predetermined reducing agent, glycosyl hesperetin prepared without using a predetermined reducing agent Compared to this, the flavors are significantly reduced, and the discoloration and unpleasant odor are also remarkably reduced, so that humans can take it orally safely, easily, and without discomfort on a daily basis. The effect of improving skin texture is effectively exhibited, and at the same time, the effect of improving skin quality such as skin dryness, erythema, irritation and itching is effectively exhibited. Since the influence of the present invention on this field is so great, the industrial applicability of the present invention is very great.

In Figures 1 to 7, the symbol '●' represents the α-glucosylhesperidin-containing composition administration group, and the symbol 'Δ' represents the control group. In addition, in FIGS. 1 to 7, symbols '#', '##' and '###' indicate the values of the α-glucosylhesperidin-containing composition administration group and the control group, and the corresponding α-glucosylhesperidin-containing composition administration group, respectively. Between the values of and the control group, p (hazard rate) in the statistical hypothesis test, p <0.1, p <0.05 and p <0.01 indicate a significant difference.

Patent Organism Depository Center FERMBP-11273 19730730

Claims (13)

In the glycosylhesperetin composition containing either or both of hesperidin and 7-O-β-glucosylhesperetin together with α-glycosylhesperidin, the glycosylhesperetin is 90 mass% or more per dry solid. A glycosylhesperetin composition containing less than 100% by mass and 90% by mass or less of α-glucosylhesperidin per dry solid, and having a furfural content of less than 200 ppb per dry solid as measured by GC/MS analysis method , An oral cosmetic agent for improving dull yellow skin, characterized in that it lowers the b* value in the L*a*b* indicator in color difference measurement. According to claim 1,
An oral cosmetic agent in a unit dosage form that enables oral intake of 10 to 3,000 mg of a glycosylhesperetin composition in terms of hesperidin, once a day. According to claim 1 or 2,
An oral cosmetic agent comprising a glycosylhesperetin composition having a 4-methoxystyrene content of less than 30 ppb per dry solid as measured by GC/MS analysis. According to claim 1 or 2,
Contains a glycosylhesperetin composition having calcium, potassium, magnesium and sodium content per dry solid of 1 ppm or less, 0.1 ppm or less, 0.2 ppm or less, and 0.4 ppm or less, respectively, as measured by high-frequency inductively coupled plasma emission spectrometry. Oral cosmetic agent consisting of. According to claim 1 or 2,
An oral cosmetic agent in the form of tablets, granules, powders, suspensions, pastes, jellies, or liquids. delete delete delete delete delete delete delete delete

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