Water-soluble additive composition

Abstract

To provide a new composition including cyclic carboxylic acid.SOLUTION: A water soluble additive composition is provided, which includes cyclic carboxylic acid and satisfies one or more of the following conditions 1-4: (condition 1) the water soluble additive composition includes a component (A) of cyclic carboxylic acid excluding the following component (B1), and one or more kinds selected from the group consisting of the component (B1) gallic acid and its ester; (condition 2) the total amount of contents of Na+ and NH4+ is 100 ppm or more and 5,000 ppm or less based on the cyclic carboxylic acid;(condition 3) a total inorganic ion content (excluding hydrogen ion and hydroxy group ion) is 300 ppm or more and 5,000 ppm or less based on the cyclic carboxylic acid; and (condition 4) the component (A) cyclic carboxylic acid excluding the following component (B2), and the component (B2) of amino acid are included.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a water-soluble additive composition.

[0002] Patent Documents 6 and 7 describe techniques relating to compositions containing cyclic carboxylic acids. Patent Document 6 (JP 2014-31347 A) describes a composition containing a cyclic hydroxy acid or a derivative thereof having a specific structure and a sterol ester. According to this document, this composition has an excellent free radical scavenging effect and is also excellent in terms of irritation, feel during use, odor, and storage stability, and is said to be able to prevent or improve aging phenomena such as wrinkle formation, loss of skin elasticity, and hair loss.

[0003] Patent Document 7 (WO 2016 / 039407) describes a composition containing an acylproline or a salt thereof having a specific structure and a zinc salt of pyrrolidone carboxylic acid, as a technique for providing a composition that reduces the peculiar odor of acylproline or a salt thereof, has a moist feeling, and is highly stable, and also describes that such a composition may contain a hydroxycarboxylic acid. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-35440 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-155158 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-215266 [Patent Document 4] Japanese Patent Application Publication No. 7-126135 [Patent Document 5] Japanese Patent Application Laid-Open No. 2018-150288 [Patent Document 6] Japanese Patent Application Laid-Open No. 2014-31347 [Patent Document 7] International Publication No. 2016 / 039407 [Patent Document 8] Japanese Patent Application Laid-Open No. 2007-238469 [Patent Document 9] Japanese Patent Application Publication No. 8-92589 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides novel compositions comprising cyclic carboxylic acids. [Means for solving the problem]

[0006] According to the present invention, There is provided a water-soluble additive composition containing a cyclic carboxylic acid, which satisfies at least one of the following conditions 1 to 4. (Condition 1) Contains the following components (A) and (B1). (A) The cyclic carboxylic acid other than the following component (B1): (B1) One or more selected from the group consisting of gallic acid and its esters (Condition 2) Na + and NH4 + The total content of the above is 100 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid. (Condition 3) The total inorganic ion content (excluding hydrogen ions and hydroxyl ions) is 300 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid. (Condition 4) Contains the following components (A) and (B2). (A) The cyclic carboxylic acid other than the following component (B2): (B2) Amino acids

[0007] According to the present invention, A food or flavoring material is provided which contains a plant-derived sugar and at least one of a cyclic compound and a derivative thereof derived from a microorganism.

[0008] According to the present invention, A food additive is provided which contains a plant-derived sugar and at least one of a cyclic compound derived from a microorganism and a derivative thereof.

[0009] According to the present invention, A method for producing a cyclic compound or a derivative thereof for use as a food, a food additive, or a flavoring, comprising the steps of: preparing a culture solution containing plant-derived sugars and a microorganism so as to produce at least one of the cyclic compound and its derivatives; Concentrating the culture solution to obtain a concentrate; recovering at least one of the cyclic compound and its derivative from the concentrated solution by crystallization, precipitation, extraction, sublimation purification, or distillation;

[0013] A method for producing a cyclic compound or a derivative thereof is provided, comprising: [Effects of the Invention]

[0010] According to the present invention, a novel composition containing a cyclic carboxylic acid can be provided. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a diagram showing the evaluation results of antibacterial compositions. [Figure 2] FIG. 1 is a diagram showing the evaluation results of antibacterial compositions. [Figure 3] FIG. 1 is a diagram showing the evaluation results of antibacterial compositions. [Figure 4] FIG. 1 is a diagram showing the evaluation results of antibacterial compositions. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, specific examples of embodiments of the present invention will be described. In the embodiments, the composition may contain each component alone or in combination of two or more. Furthermore, the symbol "to" indicating a numerical range indicates from above to below, and both end values ​​are included.

[0013] (First embodiment) The present embodiment relates to an antibacterial composition.

[0014] Patent Documents 1 to 3 describe techniques relating to compositions containing antibacterial components. Patent Document 1 (JP 2004-35440 A) describes a dullness inhibitor containing a specific melanin production inhibitor, a specific fibroblast proliferation promoter, and a specific blood circulation promoter, and also describes that such an agent may be used in combination with an antibacterial agent such as shikimic acid as an additive.

[0015] Patent Document 2 (JP 2013-155158 A) describes an antibacterial composition containing an onion skin extract and acting against one or more bacteria selected from the group consisting of bacteria that cause acne vulgaris and bacteria that cause dental caries, and specifically describes the acquisition of an antibacterial composition containing specific amounts of quercetin, quercetin-4' glucoside, and protocatechuic acid.

[0016] Patent Document 3 (JP 2009-215266 A) describes a melanin production inhibitor containing one or more compounds selected from shikimic acid and its salts as an active ingredient, and describes that the use of such an agent does not include use as a chelating agent or antibacterial agent, or use on hair.

[0017] Although it is in a different technical field, Patent Document 4 describes a composition containing polyphenols. Patent Document 4 (JP Patent Publication No. 7-126135) describes an external preparation for skin in which at least one type of alcohol and / or polyphenol is added to an external preparation containing kojic acid and / or its derivatives and an ultraviolet absorber, and lists a number of examples of polyphenols including gallic acid, gallic acid esters, and shikimic acid.

[0018] The inventors have examined the techniques described in the above-mentioned patent documents and found that there is room for improvement in terms of improving antibacterial properties. Therefore, the present embodiment provides a composition having excellent antibacterial properties.

[0019] According to this embodiment, The following components (A) and (B1): (A) Cyclic carboxylic acids (excluding component (B1) below) (B1) One or more selected from the group consisting of gallic acid and its esters An antimicrobial composition is provided comprising:

[0020] Furthermore, according to this embodiment, for example, daily necessities or cosmetics containing the antibacterial composition of this embodiment can also be obtained.

[0021] According to this embodiment, a composition having excellent antibacterial properties can be provided.

[0022] The embodiment will be described in more detail below. In the embodiment, the composition may contain each component alone or in combination of two or more types.

[0023] In this embodiment, the antibacterial composition contains the following components (A) and (B1). (A) Cyclic carboxylic acids (excluding component (B1) below) (B1) One or more selected from the group consisting of gallic acid and its esters

[0024] (Component (A)) Component (A) is a cyclic carboxylic acid and is a component other than component (B1) described below. Specific examples of component (A) include cyclic carboxylic acids having one or more hydroxy groups, and cyclic carboxylic acids having one or more amino groups, and preferably cyclic polyhydroxycarboxylic acids having two or more hydroxy groups.

[0025] Cyclic carboxylic acids include, for example, benzoic acid. Examples of cyclic carboxylic acids having a hydroxy group include aromatic hydroxycarboxylic acids and alicyclic hydroxycarboxylic acids. Aromatic hydroxycarboxylic acids include, for example, salicylic acid, hydroxybenzoic acids such as 4-hydroxybenzoic acid, monohydroxybenzoic acids such as hydroxy(methyl)benzoic acid and hydroxy(methoxy)benzoic acid, and derivatives thereof; dihydroxybenzoic acids such as protocatechuic acid and gentisic acid, dihydroxy(methyl)benzoic acids such as orsellinic acid, and their derivatives; Monohydroxycinnamic acids such as ferulic acid and their derivatives are included. Examples of alicyclic hydroxycarboxylic acids include shikimic acid and quinic acid. The hydroxyl group-containing cyclic carboxylic acid preferably has two or more hydroxyl groups.

[0026] Furthermore, examples of cyclic carboxylic acids having an amino group include monoaminobenzoic acids such as 4-aminobenzoic acid and derivatives thereof, and other aromatic aminocarboxylic acids; and Alicyclic aminocarboxylic acids are included.

[0027] From the viewpoint of improving the antibacterial properties of the antibacterial composition, component (A) is preferably one or more selected from the group consisting of protocatechuic acid, shikimic acid, 4-hydroxybenzoic acid, 4-aminobenzoic acid, and ferulic acid, and more preferably one or more selected from the group consisting of protocatechuic acid and shikimic acid.

[0028] From the viewpoint of improving antibacterial properties, the content of component (A) in the antibacterial composition may be, for example, 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and still more preferably 98% by mass or more, based on the total amount of the antibacterial composition. From the same viewpoint, the content of component (A) in the antibacterial composition is less than 100% by mass, preferably 99.999% by mass or less, more preferably 99.990% by mass or less, even more preferably 99% by mass or less, and even more preferably 98% by mass or less, based on the total mass of the antibacterial composition.

[0029] (Component (B1)) Component (B1) is one or more selected from the group consisting of gallic acid and its esters. Examples of gallic acid esters include esters of linear alkyl groups having 1 to 20 carbon atoms, such as methyl gallate, ethyl gallate, propyl gallate, butyl gallate, pentyl gallate, hexyl gallate, heptyl gallate, octyl gallate, nonyl gallate, decyl gallate, lauryl gallate, and stearyl gallate.

[0030] From the viewpoint of improving the antibacterial properties of the antibacterial composition, the component (B1) is preferably gallic acid.

[0031] From the viewpoint of improving antibacterial properties, the content of component (B1) in the antibacterial composition may be, for example, 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and still more preferably 1% by mass or more, based on the total amount of the antibacterial composition. From the same viewpoint, the content of component (B1) in the antibacterial composition may be, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, based on the total amount of the antibacterial composition.

[0032] Furthermore, the content of component (B1) relative to the content of component (A) in the antibacterial composition ((B1) / (A)) is preferably 0.01 or more, more preferably 0.015 or more, and even more preferably 0.02 or more, in terms of mass ratio, from the viewpoint of improving the antibacterial properties of the antibacterial composition. From the same viewpoint, the mass ratio ((B1) / (A)) is preferably 5 or less, more preferably 1 or less, even more preferably 0.5 or less, and even more preferably 0.1 or less.

[0033] The antibacterial composition may contain components other than the above-mentioned components (A) and (B1). In this embodiment, the antibacterial composition can be obtained, for example, by preparing the above-mentioned components (A) and (B1) and other components as appropriate, and blending and mixing them in predetermined ratios.

[0034] Another method for preparing the antibacterial composition includes, for example, obtaining a culture solution containing a cyclic carboxylic acid by a bioprocess, and then concentrating and purifying the culture solution to obtain a composition containing components (A) and (B1). Hereinafter, a method for obtaining a culture solution containing components (A) and (B1) by a bioprocess will be described. In bioprocesses, the recovery rate of cyclic carboxylic acids and their derivatives can be improved by appropriately selecting the microorganism, culture medium, culture equipment, and culture conditions. The method for obtaining a culture solution containing components (A) and (B1) by bioprocessing includes a raw material liquid preparation step S01, an activated carbon treatment step S02, a crystallization step S03, and a solid-liquid separation step S04.

[0035] (Raw material liquid preparation process S01) First, biomass is prepared. Here, biomass refers to organic resources derived from plants. Specifically, biomass includes materials converted into and stored in forms such as starch and cellulose, the bodies of animals that grow by eating plants, and products made by processing plant or animal bodies.

[0036] More specific examples of biomass include cellulosic crops (pulp, kenaf, wheat straw, rice straw, waste paper, papermaking residues, etc.), wood, charcoal, compost, natural rubber, cotton, sugarcane, soybean pulp refuse, oils and fats (rapeseed oil, cottonseed oil, soybean oil, coconut oil, castor oil, etc.), carbohydrate crops (corn, potatoes, wheat, rice, rice husks, rice bran, used rice, cassava, sago palm, etc.), bagasse, buckwheat, soybeans, essential oils (pine oil, orange oil, eucalyptus oil, etc.), pulp black liquor, food waste, vegetable oil cakes, fishery residues, livestock excrement, food waste, wastewater sludge, etc. Even more specific examples of biomass include sugarcane pomace.

[0037] -Preprocessing- The biomass is then pretreated to obtain a sugar mixture. Such pretreatments include, for example, physical treatments, chemical treatments, physicochemical treatments, biological treatments, etc., and one or a combination of two or more of these treatments may be employed.

[0038] Of these, examples of physical treatments include pulverization treatment using a disk mill or grinder, compression treatment, electromagnetic wave irradiation treatment, electron beam irradiation treatment, and the like.

[0039] Examples of chemical treatments include treatment with ionic liquids such as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and alkali, hydrothermal treatment, subcritical water treatment, supercritical fluid treatment, treatment with a catalyst, treatment with an oxidizing agent, treatment that applies thermal energy, and treatment that applies light energy.

[0040] Examples of physicochemical treatments include steam explosion treatment and ammonia explosion treatment. Biological treatments include, for example, treatments using fungi, bacteria, and the like.

[0041] In this manner, a sugar mixture is obtained. Examples of the resulting sugar mixture include oligosaccharides or polysaccharides having glucose units. Specific examples include monosaccharides such as glucose, fructose, mannose, arabinose, xylose, and galactose, disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, cellobiose, and xylobiose, and polysaccharides such as dextrin and soluble starch.

[0042] In addition to the above, the sugar mixture may also contain molasses or a saccharified liquid obtained by saccharifying materials such as straw (rice straw, barley straw, wheat straw, rye straw, oat straw, etc.), inedible agricultural waste such as bagasse, energy crops such as switchgrass, napier grass, and miscanthus, wood chips, and waste paper using a saccharifying enzyme.

[0043] -Preparation of raw liquid- Next, a raw material liquid is prepared by culturing or reacting a microorganism or a transformant thereof in a reaction liquid containing the sugar mixture.

[0044] Microorganisms or their transformants The microorganism or its transformant is preferably cultured and grown in a medium prior to reaction with the mixed sugar.

[0045] Culture medium The medium to be used may be a natural medium or a synthetic medium containing a carbon source, a nitrogen source, inorganic salts, other nutrients, etc. A specific example of the medium is LB medium.

[0046] The concentration of the nitrogen source in the medium varies depending on the nitrogen source used, but is, for example, 0.1 to 10 (mass / v%).

[0047] The concentration of inorganic salts in the medium varies depending on the inorganic salts used, but is, for example, 0.01 to 1 (mass / v%).

[0048] The concentration of nutrients in the medium varies depending on the nutrients used, but is, for example, 0.1 to 10 (mass / v%).

[0049] Furthermore, vitamins can be added as needed.

[0050] The pH of the medium is preferably 6-8.

[0051] Reaction solution The reaction liquid may be a natural or synthetic reaction liquid containing a carbon source, a nitrogen source, inorganic salts, etc.

[0052] The carbon source used is the aforementioned mixed sugar. The concentration of the mixed sugar in the reaction solution is preferably 1 to 20 (mass / v%), more preferably 2 to 10 (mass / v%), and even more preferably 2 to 5 (mass / v%).

[0053] In addition, other carbon sources may be used that are appropriately selected from the above-mentioned carbon sources. The concentration of the total carbon source including the mixed sugar is preferably 2 to 5 (mass / v%).

[0054] The nitrogen source is selected from the above-mentioned nitrogen sources. The concentration of the nitrogen source in the reaction solution varies depending on the concentration of the nitrogen source used, but is, for example, 0.01 to 1 (mass / v%).

[0055] The inorganic salts used may be selected from the inorganic salts listed above. The concentration of the nutrient in the reaction solution may vary depending on the concentration of the nutrient used, but is typically 0.1 to 10 (mass / v%). Furthermore, vitamins appropriately selected from the above-mentioned vitamins may be used as needed.

[0056] Reaction conditions The reaction temperature between the sugar mixture and the microorganism or its transformant, i.e., the survival temperature of the microorganism or its transformant, is preferably 20 to 50°C, more preferably 25 to 47°C, from the viewpoint of efficiently producing a cyclic carboxylic acid.

[0057] The reaction time is preferably 1 to 7 days, more preferably 1 to 3 days.

[0058] The culture may be performed by any of batch, fed-batch, and continuous methods, with the batch method being preferred. The reaction may be carried out under aerobic conditions or under reducing conditions.

[0059] A reaction solution under reducing conditions can be prepared by any known method without limitation. For example, an aqueous solution for a reaction solution under reducing conditions can be obtained by removing dissolved gases through heat treatment or reduced pressure treatment. In this case, dissolved gases (more specifically, dissolved oxygen) can be removed by treatment under reduced pressure of preferably 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 3 mmHg or less for preferably about 1 to 60 minutes, more preferably about 5 to 40 minutes, thereby producing an aqueous solution for a reaction solution under reducing conditions.

[0060] Alternatively, an appropriate reducing agent (for example, thioglycolic acid, ascorbic acid, cysteine ​​hydrochloride, mercaptoacetic acid, thiolacetic acid, glutathione, sodium sulfide) may be added to prepare an aqueous solution for the reaction under reducing conditions. Furthermore, these methods may be combined as appropriate.

[0061] When the reaction is carried out under reducing conditions, it is preferable to maintain the reaction solution under reducing conditions during the reaction. In order to maintain reducing conditions during the reaction, it is preferable to prevent oxygen contamination from outside the reaction system as much as possible. Specifically, a method of sealing the reaction system under an inert gas such as nitrogen gas or carbon dioxide gas can be mentioned. As a method for more effectively preventing oxygen contamination, it may be necessary to add a pH maintenance adjusting solution to the reaction system or various nutrient solutions appropriately to efficiently function the metabolic functions within the aerobic bacteria during the reaction. In such cases, it is preferable to remove oxygen from the solution to be added in advance.

[0062] After preparing the raw material liquid, the microorganism or its transformant is separated and removed by, for example, sedimentation, centrifugation, filtration, or a combination of these methods.

[0063] This step may be provided as needed, and may be replaced with a step of preparing a liquid containing a cyclic carboxylic acid produced by recycling or the like.

[0064] -Concentration treatment- The obtained raw material liquid may be concentrated as needed. Concentration methods include, for example, distillation, adsorption, extraction, membrane separation, dialysis, reverse osmosis, etc., and one or more of these may be used in combination.

[0065] Among these, the concentration process is a process in which the raw liquid is brought into contact with a heated heat transfer surface to evaporate the solvent contained in the raw liquid, and is preferably a process in which the raw liquid is repeatedly brought into contact with the heat transfer surface. According to such a process, the heat transfer surface can be constantly wetted with the raw liquid when evaporating the solvent contained in the raw liquid, thereby preventing scorching.

[0066] Specifically, the raw liquid is placed in a stirring tank whose inner wall surface is a heat transfer surface, and the raw liquid that has accumulated at the bottom is pumped up and sprayed onto the inner wall surface while being stirred, and then concentrated. This maximizes the effective area of ​​the heat transfer surface, thereby increasing the concentration efficiency. Furthermore, the occurrence of scorching due to drying of the heat transfer surface is suppressed, and the coloring of the precipitated solid can be suppressed.

[0067] The heating temperature in the concentration treatment is not limited, but is preferably about 15 to 120° C., and more preferably about 20 to 90° C. This can increase the efficiency of concentration while suppressing the occurrence of scorching and denaturation of solutes.

[0068] The raw solution in the concentration treatment may be placed under reduced pressure. This promotes evaporation of the solvent and increases the concentration efficiency. The pressure of the environment in which the raw solution is placed is not limited, but is preferably 80 kPa or less, and more preferably 0.1 to 50 kPa.

[0069] For the concentration, a salt of the cyclic carboxylic acid may be prepared using a basic substance and then dissolved in the aqueous medium. The concentration treatment may be carried out as needed, or may be omitted.

[0070] Concentrating the raw liquid can increase the ratio (yield) of the amount of solids that can be recovered from a unit amount of raw liquid, which can reduce the time and energy required for the steps described below and increase the solid production efficiency (solid production capacity per unit time).

[0071] (Activated carbon treatment process S02) Next, the raw material liquid is treated with activated carbon. Specifically, activated carbon is added to the raw material liquid and the mixture is stirred. This process can decolorize the solutes in the raw material liquid.

[0072] Examples of activated carbon include, but are not limited to, powdered activated carbon, granular activated carbon, fibrous activated carbon, sheet-like activated carbon, and honeycomb-like activated carbon.

[0073] The temperature for the activated carbon treatment is preferably about 10 to 150° C. The time for the activated carbon treatment is not limited, but is preferably about 10 minutes to 40 hours.

[0074] Furthermore, the amount of activated carbon added per 100 g of raw liquid is not limited, but from the viewpoint of achieving sufficient decolorization while preventing the solute from being adsorbed by the activated carbon, it is preferably 0.01 to 10 g, and more preferably 0.1 to 5 g.

[0075] The activated carbon treatment may be performed as needed and may be omitted. The order of the activated carbon treatment step is not limited to that of this embodiment, and may be performed after the elution step, for example. After the treatment, the activated carbon is removed by solid-liquid separation such as filtration.

[0076] (Crystallization process S03) Next, the raw material liquid is subjected to a crystallization treatment to precipitate the solute of the raw material liquid as a solid. This crystallization treatment involves a process in which the solubility of the solute in the solution is reduced to precipitate a solid, and a subsequent solid-liquid separation step can be carried out to recover a highly pure solid substance. This makes it possible to easily produce a cyclic carboxylic acid that is useful as a raw material for daily necessities, cosmetics, pharmaceuticals, food, etc.

[0077] The crystallization treatment may be any method that allows a solute to be precipitated as a solid from a raw material liquid. Specifically, examples of such processes include a process in which the temperature of the raw liquid is changed to utilize the temperature dependency of solubility for crystallization; a process in which the solvent is evaporated from the raw liquid by heating or reducing pressure to cause crystallization; a process in which a solvent in which the solute has low solubility is added to utilize the solvent-type dependency of solubility for crystallization; and a process in which the pH of the raw solution is changed to utilize the pH-responsiveness of solubility for crystallization. One or more of these processes can be used in combination.

[0078] For example, when using a pH-responsive crystallization process, the solubility of the cyclic carboxylic acid contained in the solute in water generally decreases at low pH levels. Therefore, by lowering the pH to, for example, about 1 to 4 in the crystallization process, the solubility can be reduced and the solute can be precipitated.

[0079] The temperature at this time is not limited, but is preferably about 15 to 80° C., and more preferably about 20 to 60° C. This makes it possible to achieve both high crystallization treatment capacity and high yield.

[0080] The crystallization process may be a batch process or a continuous process. For the crystallization operation, a known stirring tank is used.

[0081] Furthermore, in order to promote crystallization, seed crystals containing the solid components to be precipitated may be added as necessary, whereby the seed crystals act as nuclei to promote crystallization, thereby increasing the crystallization efficiency and facilitating high purity.

[0082] (Solid-liquid separation process S04) Next, the solid cyclic carboxylic acid is recovered from the feed liquid. Examples of solid-liquid separation include filtration, sedimentation, dehydration under reduced pressure, and dehydration under pressure. From the viewpoint of ease of operation and accuracy of separation, filtration is preferably used. Specifically, a centrifugal filter can be used. The solid-liquid separation operation may be a batch operation or a continuous operation.

[0083] Thereafter, washing is carried out using a poor solvent as appropriate, and then drying is carried out as appropriate. In this manner, a solid or other antibacterial composition containing components (A) and (B1) can be recovered.

[0084] The obtained antibacterial composition may be used to obtain an antibacterial composition liquid blend containing a medium such as water, ethanol, etc. In this case, the content of the medium in the liquid blend may be, for example, the remainder after excluding components other than the medium in the liquid blend. The concentration of component (A) in the above-mentioned blended liquid may be, for example, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.15% by mass or more, even more preferably 0.25% by mass or more, and even more preferably 0.4% by mass or more, and may be, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0085] There are no limitations on the form of the antibacterial composition obtained in this embodiment, and it can be in the form of a solid such as powder or granules, or in a liquid form. Furthermore, the antibacterial composition obtained in this embodiment can be used in daily necessities, cosmetics, pharmaceuticals, foods, etc., and is particularly suitable for use in daily necessities and cosmetics. Specific examples of daily necessities include antibacterial agents, antifungal agents, deodorants, detergents, hygiene products, bath products, household chemical products, and oral care products. Cosmetics also include emulsions, creams, foundations, eye shadows, lipsticks, blushers, hair cosmetics, emollient creams, emollient lotions, cream rinses, cold creams, vanishing creams, lotions, packs, gels, face packs, soaps, body soaps, shampoos, conditioners, rinses, bath additives, bath additives, facial cleansers, shaving creams, hair creams, hair lotions, hair treatments, hair packs, glosses, and lip balms.

[0086] Furthermore, the antibacterial composition of this embodiment can be suitably used to inhibit the growth of one or more species selected from the group consisting of bacteria such as Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa, yeasts such as Candida, and molds such as Aspergillus niger.

[0087] The present embodiment includes the following aspects. I-1. The following components (A) and (B1): (A) Cyclic carboxylic acids (excluding component (B1) below) (B1) One or more selected from the group consisting of gallic acid and its esters An antibacterial composition comprising: I-2. The antibacterial composition according to I-1, wherein the component (A) is one or more selected from the group consisting of protocatechuic acid, shikimic acid, 4-hydroxybenzoic acid, 4-aminobenzoic acid, and ferulic acid. I-3. The antibacterial composition according to I-1 or I-2, wherein the content of component (B1) relative to the content of component (A) in the antibacterial composition ((B1) / (A)) is in a mass ratio of 0.01 or more to 5 or less.

[0088] (Second embodiment) The present embodiment relates to a water-soluble additive composition.

[0089] Patent Document 5 (JP 2018-150288 A) describes a technology for improving the solubility of cyclic carboxylic acids. This document describes a technology for providing crystals of protocatechuic acid (PCA) cationic salt that are highly soluble and stable under high-humidity conditions, as well as a method for producing the same. The technology includes a step of precipitating crystals of PCA cationic salt by dropping or adding an alcohol solution or a nitrile solution to an alcohol solution of PCA in which a cation-containing compound has been dissolved, and a step of collecting the crystals of PCA cationic salt from the solution.

[0090] The inventors have examined the technology described in the aforementioned Patent Document 5 and found that there is still room for improvement in terms of obtaining a composition having a high purity of a cyclic carboxylic acid and excellent water solubility of the cyclic carboxylic acid.

[0091] According to this embodiment, A water-soluble additive composition comprising a cyclic carboxylic acid, Na +and NH4 + The water-soluble additive composition has a total content of 100 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid.

[0092] Furthermore, according to this embodiment, A water-soluble additive composition comprising a cyclic carboxylic acid, A water-soluble additive composition is provided having a total inorganic ion content (excluding hydrogen ions and hydroxyl ions) of 300 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid.

[0093] Furthermore, according to this embodiment, for example, daily necessities or cosmetics containing the water-soluble additive composition of this embodiment can also be obtained.

[0094] According to this embodiment, a composition containing a cyclic carboxylic acid with high purity and excellent water solubility can be provided.

[0095] The embodiment will be described in more detail below. In the embodiment, the composition may contain each component alone or in combination of two or more types.

[0096] (Embodiment 2-1) In this embodiment, the water-soluble additive composition contains a cyclic carboxylic acid. + and NH4 + The total content of the above is 100 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid.

[0097] (Embodiment 2-2) In this embodiment, the water-soluble additive composition contains a cyclic carboxylic acid, and the total inorganic ion content (excluding hydrogen ions and hydroxyl ions) in the water-soluble additive composition is 300 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid.

[0098] The components of the water-soluble additive composition will be described in more detail below. The following components can be used in each of the above-mentioned embodiments. In addition, the components described in each of the above-mentioned embodiments can be used in combination with other embodiments.

[0099] (cyclic carboxylic acid) Specific examples of the cyclic carboxylic acid include cyclic carboxylic acids having one or more hydroxy groups and cyclic carboxylic acids having one or more amino groups.

[0100] Examples of cyclic carboxylic acids having a hydroxy group include aromatic hydroxycarboxylic acids and alicyclic hydroxycarboxylic acids. Aromatic hydroxycarboxylic acids include, for example, salicylic acid, hydroxybenzoic acids such as 4-hydroxybenzoic acid, monohydroxybenzoic acids such as hydroxy(methyl)benzoic acid and hydroxy(methoxy)benzoic acid, and derivatives thereof; dihydroxybenzoic acids such as protocatechuic acid and gentisic acid, dihydroxy(methyl)benzoic acids such as orsellinic acid, and their derivatives; Monohydroxycinnamic acids such as ferulic acid and their derivatives are included. Examples of alicyclic hydroxycarboxylic acids include shikimic acid and quinic acid.

[0101] Furthermore, examples of cyclic carboxylic acids having an amino group include monoaminobenzoic acids such as 4-aminobenzoic acid and derivatives thereof, and other aromatic aminocarboxylic acids; and Alicyclic aminocarboxylic acids are included.

[0102] From the viewpoint of stably improving the water solubility of the water-soluble additive composition, the cyclic carboxylic acid is preferably one or more selected from the group consisting of protocatechuic acid, shikimic acid, 4-hydroxybenzoic acid, 4-aminobenzoic acid, and ferulic acid, and more preferably one or more selected from the group consisting of protocatechuic acid and shikimic acid.

[0103] From the viewpoint of obtaining a composition with a higher concentration, the content of the cyclic carboxylic acid in the water-soluble additive composition is preferably 95% by mass or more, more preferably 95.3% by mass or more, and even more preferably 95.6% by mass or more, based on the total amount of the water-soluble additive composition. Furthermore, from the viewpoint of improving the water solubility of the water-soluble additive composition, the content of the cyclic carboxylic acid in the water-soluble additive composition is less than 100% by mass, and may be, for example, 99.97% by mass or less, preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and even more preferably 99% by mass or less, based on the total mass of the water-soluble additive composition.

[0104] Na in the water-soluble additive composition + and NH4 + From the viewpoint of stably improving the water solubility of the cyclic carboxylic acid in the water-soluble additive composition, the total content of the above is preferably 100 ppm or more, more preferably 200 ppm or more, and even more preferably 300 ppm or more, relative to the cyclic carboxylic acid. From the same viewpoint, Na in the water-soluble additive composition + and NH4 + The total content of the above is preferably 5000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, and even more preferably 500 ppm or less, based on the cyclic carboxylic acid.

[0105] Na in the water-soluble additive composition + From the viewpoint of stably improving the water solubility of the cyclic carboxylic acid in the water-soluble additive composition, the content of may be, for example, 10 ppm or more, or, for example, 90 ppm or more, preferably 100 ppm or more, more preferably 200 ppm or more, and even more preferably 300 ppm or more, relative to the cyclic carboxylic acid. From the same viewpoint, Na in the water-soluble additive composition +The content of is preferably 5000 ppm or less, more preferably 4500 ppm or less, even more preferably 4000 ppm or less, still more preferably 3000 ppm or less, even more preferably 1000 ppm or less, and still more preferably 500 ppm or less, based on the cyclic carboxylic acid.

[0106] Water-soluble additive composition NH4 + From the viewpoint of stably improving the water solubility of the cyclic carboxylic acid in the water-soluble additive composition, the content of may be, for example, 10 ppm or more, preferably 100 ppm or more, more preferably 200 ppm or more, and even more preferably 300 ppm or more, relative to the cyclic carboxylic acid. From the same viewpoint, the NH4 + The content of is preferably 5000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, and even more preferably 500 ppm or less, based on the cyclic carboxylic acid.

[0107] Here, Na in the water-soluble additive composition + and NH4 + The content of K as described below + , SO4 2- , PO4 3- , NO2 - , NO3 - and Cl - The contents of each of the above are measured by ion chromatography or capillary electrophoresis.

[0108] The total inorganic ion content (excluding hydrogen ions and hydroxyl ions) of the water-soluble additive composition is preferably 300 ppm or more, more preferably 500 ppm or more, even more preferably 800 ppm or more, and still more preferably 1500 ppm or more, relative to the cyclic carboxylic acid, from the viewpoint of stably improving the water solubility of the cyclic carboxylic acid in the water-soluble additive composition. From the same viewpoint, the total inorganic ion content (excluding hydrogen ions and hydroxyl ions) of the water-soluble additive composition is preferably 5000 ppm or less, more preferably 4000 ppm or less, even more preferably 3000 ppm or less, and even more preferably 2000 ppm or less, relative to the cyclic carboxylic acid.

[0109] Here, among the inorganic ions (excluding hydrogen ions and hydroxyl ions) contained in the water-soluble additive composition, the above-mentioned Na + and NH4 + Other than that, for example, K + Cations such as SO4 2- , PO4 3- , NO2 - , NO3 - , Cl - Examples of anions include:

[0110] Water-soluble additive composition K + The content of is 0 ppm or more relative to the cyclic carboxylic acid. In addition, the water-soluble additive composition + When the water-soluble additive composition contains the cyclic carboxylic acid, the content thereof may be, for example, 10 ppm or more, and preferably 50 ppm or more, relative to the cyclic carboxylic acid, from the viewpoint of stably improving the water solubility of the cyclic carboxylic acid in the water-soluble additive composition. From the same viewpoint, the water-soluble additive composition K + The content of is preferably 200 ppm or less, more preferably 100 ppm or less, based on the cyclic carboxylic acid.

[0111] SO4 in water-soluble additive composition 2- The content of is 0 ppm or more relative to the cyclic carboxylic acid. In addition, the water-soluble additive composition contains SO4 2- When it contains, its content is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less, based on the cyclic carboxylic acid. Also, SO4 2- The content may be, for example, 10 ppm or more relative to the cyclic carboxylic acid.

[0112] Water-soluble additive composition PO4 3- The content of may be 0 ppm or more, for example 10 ppm or more, relative to the cyclic carboxylic acid. In addition, the water-soluble additive composition 3- When it contains, its content is preferably 500 ppm or less, more preferably 300 ppm or less, and even more preferably 200 ppm or less, based on the cyclic carboxylic acid.

[0113] Water-soluble additive composition NO2 - The content of may be 0 ppm or more, for example 1 ppm or more, relative to the cyclic carboxylic acid. In addition, the water-soluble additive composition - When it contains, its content is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less, based on the cyclic carboxylic acid.

[0114] Water-soluble additive composition NO3 - The content of may be 0 ppm or more, for example 10 ppm or more, relative to the cyclic carboxylic acid. In addition, the water-soluble additive composition is NO3 - When it contains, its content is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less, based on the cyclic carboxylic acid.

[0115] Cl of the water-soluble additive composition - The content of may be 0 ppm or more, for example 5 ppm or more, relative to the cyclic carboxylic acid. In addition, the water-soluble additive composition - When it contains, its content is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less, based on the cyclic carboxylic acid.

[0116] The water-soluble additive composition may contain components other than the above-mentioned cyclic carboxylic acids. For example, the water-soluble additive composition may contain a medium such as water, ethanol, etc. In this case, the content of the medium in the composition may be, for example, the remainder after excluding components other than the medium in the composition.

[0117] Next, a method for producing the water-soluble additive composition will be described. A method for preparing the water-soluble additive composition includes, for example, obtaining a culture solution containing a cyclic carboxylic acid by a bioprocess as described below, and then concentrating and purifying the culture solution to obtain a composition containing the cyclic carboxylic acid. where Na + and N.H. 4+ In order to control the total inorganic ion content or the total inorganic ion content to fall within the above-mentioned specific range, it is important to appropriately select the conditions for producing the cyclic carboxylic acid in the bioprocess and also the purification conditions. For example, the purification conditions include appropriately selecting the conditions for concentration and filtration and the number of washings.

[0118] The water-soluble additive composition obtained in this embodiment contains Na + and NH4 + Since the total content of the above or the total inorganic ion content is within a specific range, the purity of the cyclic carboxylic acid is high and the water solubility of the cyclic carboxylic acid is excellent.

[0119] A method for obtaining a culture solution containing a cyclic carboxylic acid by a bioprocess will be described below. The method for obtaining a culture solution containing a cyclic carboxylic acid by a bioprocess includes a raw material liquid preparation step S01, an activated carbon treatment step S02, a crystallization step S03, and a solid-liquid separation step S04.

[0120] (Raw material liquid preparation process S01) The raw material liquid preparation step S01 can be carried out, for example, in accordance with the raw material liquid preparation step S01 described in the first embodiment. For example, the materials, procedures, methods, conditions, etc. used in the raw material liquid preparation step S01 can be those described in the first embodiment.

[0121] (Activated carbon treatment process S02) The activated carbon treatment step S02 can be appropriately performed, for example, in accordance with the activated carbon treatment step S02 described in the first embodiment. For example, the materials, procedures, methods, conditions, etc. used in the activated carbon treatment step S02 can be the same as those described in the first embodiment.

[0122] (Crystallization process S03) The crystallization step S03 can be carried out, for example, in accordance with the crystallization step S03 described in the first embodiment. For example, the materials, procedures, methods, conditions, etc. used in the crystallization step S03 can be the same as those described in the first embodiment.

[0123] (Solid-liquid separation process S04) The solid-liquid separation step S04 can be carried out, for example, in accordance with the solid-liquid separation step S04 described in the first embodiment. For example, the materials, procedures, methods, conditions, etc. used in the solid-liquid separation step S04 can be the same as those described in the first embodiment.

[0124] Thereafter, washing is carried out using a poor solvent as appropriate, and then drying is carried out as appropriate. In the above, for example, by appropriately selecting the purification conditions, it is possible to recover a water-soluble additive composition in a solid state or the like having an ion content within a specific range.

[0125] There are no limitations on the form of the water-soluble additive composition obtained in this embodiment, and it may be in the form of a solid such as powder or granules, or in liquid form. Furthermore, the water-soluble additive composition obtained in this embodiment can be used in daily necessities, cosmetics, pharmaceuticals, foods, etc., and is particularly suitable for use in daily necessities and cosmetics. Examples of daily necessities include antibacterial agents, antifungal agents, deodorants, detergents, hygiene products, bath products, household chemical products, and oral care products. Cosmetics include emulsions, creams, foundations, eye shadows, lipsticks, blushers, hair cosmetics, emollient creams, emollient lotions, cream rinses, cold creams, vanishing creams, lotions, packs, gels, face packs, soaps, body soaps, shampoos, conditioners, rinses, bath additives, bath additives, facial cleansers, shaving creams, hair creams, hair lotions, hair treatments, hair packs, glosses, lip balms, and the like. In this embodiment, the water-soluble additive composition can be used, for example, as an antibacterial agent or a taste enhancer.

[0126] The present embodiment includes the following aspects. II-1. A water-soluble additive composition containing a cyclic carboxylic acid, Na + and NH4 + The water-soluble additive composition, wherein the total content of the above is 100 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid. II-2. A water-soluble additive composition containing a cyclic carboxylic acid, A water-soluble additive composition having a total inorganic ion content (excluding hydrogen ions and hydroxyl ions) of 300 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid. II-3. The water-soluble additive composition according to II-1 or II-2, wherein the cyclic carboxylic acid is one or more selected from the group consisting of protocatechuic acid, shikimic acid, 4-hydroxybenzoic acid, 4-aminobenzoic acid, and ferulic acid. II-4. The water-soluble additive composition according to any one of II-1 to II-3, wherein the content of the cyclic carboxylic acid in the water-soluble additive composition is 95% by mass or more and 99.9% by mass or less, based on the total mass of the water-soluble additive composition.

[0127] (Third embodiment) The present embodiment relates to a water-soluble additive composition.

[0128] Techniques relating to compositions containing cyclic carboxylic acids include those described in Patent Document 6 (JP 2014-31347 A) and Patent Document 7 (WO 2016 / 039407 A), which were mentioned in the Background Art section.

[0129] The present inventors have examined the techniques described in the above-mentioned Patent Documents 6 and 7 and have found that there is room for improvement in terms of moisturizing properties and antibacterial properties. Therefore, the present embodiment provides a composition that has excellent moisturizing and antibacterial properties.

[0130] According to this embodiment, Components (A) and (B2) below: (A) Cyclic carboxylic acids (excluding component (B2) below) (B2) Amino acids A water-soluble additive composition is provided, comprising:

[0131] Furthermore, according to this embodiment, for example, daily necessities or cosmetics containing the water-soluble additive composition of this embodiment can also be obtained.

[0132] According to this embodiment, a composition having excellent moisturizing properties and antibacterial properties can be provided.

[0133] The embodiment will be described in more detail below. In the embodiment, the composition may contain each component alone or in combination of two or more types.

[0134] In this embodiment, the water-soluble additive composition comprises the following components (A) and (B2). (A) Cyclic carboxylic acids (excluding component (B2) below) (B2) Amino acids

[0135] (Component (A)) Component (A) is a cyclic carboxylic acid and is a component other than component (B2) described below. Specific examples of component (A) include cyclic carboxylic acids having one or more hydroxy groups, and cyclic carboxylic acids having one or more amino groups.

[0136] Examples of cyclic carboxylic acids having a hydroxy group include aromatic hydroxycarboxylic acids and alicyclic hydroxycarboxylic acids. Aromatic hydroxycarboxylic acids include, for example, salicylic acid, hydroxybenzoic acids such as 4-hydroxybenzoic acid, monohydroxybenzoic acids such as hydroxy(methyl)benzoic acid and hydroxy(methoxy)benzoic acid, and derivatives thereof; dihydroxybenzoic acids such as protocatechuic acid and gentisic acid, dihydroxy(methyl)benzoic acids such as orsellinic acid, and their derivatives; Monohydroxycinnamic acids such as ferulic acid and their derivatives are included. Examples of alicyclic hydroxycarboxylic acids include shikimic acid and quinic acid.

[0137] Furthermore, examples of cyclic carboxylic acids having an amino group include monoaminobenzoic acids such as 4-aminobenzoic acid and derivatives thereof, and other aromatic aminocarboxylic acids; and Alicyclic aminocarboxylic acids are included.

[0138] From the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition, component (A) is preferably one or more selected from the group consisting of protocatechuic acid, shikimic acid, 4-hydroxybenzoic acid, 4-aminobenzoic acid, and ferulic acid, and more preferably one or more selected from the group consisting of protocatechuic acid and shikimic acid.

[0139] From the viewpoint of improving moisturizing properties and antibacterial properties, the content of component (A) in the water-soluble additive composition is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 98% by mass or more, based on the total mass of the water-soluble additive composition. From the same viewpoint, the content of component (A) in the water-soluble additive composition is less than 100% by mass, for example, 99.999% by mass or less, or for example, 99.98% by mass or less, preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and even more preferably 99% by mass or less, based on the total mass of the water-soluble additive composition.

[0140] (Component (B2)) Component (B2) is an amino acid, such as a neutral amino acid, an acidic amino acid, or a basic amino acid. Neutral amino acids include, for example, aliphatic amino acids such as glycine, alanine, valine, leucine, and isoleucine; oxyamino acids such as serine and threonine; sulfur-containing amino acids such as cysteine, cystine, and methionine; aromatic amino acids such as phenylalanine, tyrosine, and tryptophan; imino acids such as proline; and Examples include acetic acid amino acid amides such as asparagine and glutamine. Acidic amino acids include, for example, aspartic acid and glutamic acid. Basic amino acids include, for example, lysine, histidine, and arginine.

[0141] From the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition, component (B2) is preferably one or more amino acids selected from the group consisting of glutamic acid, alanine, valine, glycine, aspartic acid, serine, histidine, threonine, arginine, tyrosine, cystine, methionine, phenylalanine, isoleucine, leucine, lysine, and proline, more preferably one or more amino acids selected from the group consisting of aspartic acid, glutamic acid, glycine, alanine, valine, isoleucine, lysine, and proline, and even more preferably glutamic acid.

[0142] From the viewpoint of improving moisturizing properties and antibacterial properties, the content of component (B2) in the water-soluble additive composition may be, for example, 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and still more preferably 1% by mass or more, based on the total amount of the water-soluble additive composition. From the same viewpoint, the content of component (B2) in the water-soluble additive composition may be, for example, 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, based on the total amount of the water-soluble additive composition.

[0143] Furthermore, the water-soluble additive composition preferably contains glutamic acid, and the content of glutamic acid in the water-soluble additive composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, based on the total mass of the water-soluble additive composition, from the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition. From the same viewpoint, when the water-soluble additive composition contains glutamic acid, the content of glutamic acid in the water-soluble additive composition is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less, based on the total amount of the water-soluble additive composition.

[0144] When the water-soluble additive composition contains aspartic acid, the content of aspartic acid in the water-soluble additive composition is preferably 1 ppm or more, more preferably 10 ppm or more, and preferably 200 ppm or less, more preferably 50 ppm or less, based on the total amount of the water-soluble additive composition, from the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition.

[0145] When the water-soluble additive composition contains glycine, the content of glycine in the water-soluble additive composition is preferably 1 ppm or more, more preferably 10 ppm or more, and is preferably 200 ppm or less, more preferably 100 ppm or less, based on the total amount of the water-soluble additive composition, from the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition.

[0146] When the water-soluble additive composition contains alanine, the content of alanine in the water-soluble additive composition is preferably 10 ppm or more, more preferably 50 ppm or more, and is preferably 3000 ppm or less, more preferably 1000 ppm or less, based on the entire water-soluble additive composition, from the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition.

[0147] When the water-soluble additive composition contains valine, the content of valine in the water-soluble additive composition is preferably 1 ppm or more, more preferably 10 ppm or more, and is preferably 500 ppm or less, more preferably 200 ppm or less, relative to the entire water-soluble additive composition, from the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition.

[0148] When the water-soluble additive composition contains isoleucine, the content of isoleucine in the water-soluble additive composition is preferably 1 ppm or more, more preferably 2 ppm or more, and is preferably 20 ppm or less, more preferably 10 ppm or less, based on the total amount of the water-soluble additive composition, from the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition.

[0149] When the water-soluble additive composition contains proline, the content of proline in the water-soluble additive composition is preferably 5 ppm or more, more preferably 50 ppm or more, and is preferably 1000 ppm or less, more preferably 500 ppm or less, based on the entire water-soluble additive composition, from the viewpoint of improving the moisturizing properties and antibacterial properties of the water-soluble additive composition.

[0150] The water-soluble additive composition may contain components other than the above-mentioned components (A) and (B2). For example, the water-soluble additive composition may contain a medium such as water, ethanol, etc. In this case, the content of the medium in the composition may be, for example, the remainder after excluding components other than the medium in the composition.

[0151] Next, a method for producing the water-soluble additive composition will be described. In this embodiment, the water-soluble additive composition can be obtained, for example, by preparing the above-mentioned components (A) and (B2) and other components as appropriate, and blending and mixing them in predetermined ratios.

[0152] Another method for preparing the water-soluble additive composition is, for example, to obtain a culture solution containing components (A) and (B2) by a bioprocess, and then to obtain a composition containing components (A) and (B2) by concentrating and purifying the culture solution. Hereinafter, a method for obtaining a culture solution containing a cyclic carboxylic acid by a bioprocess will be described. The method for obtaining a culture solution containing components (A) and (B2) by a bioprocess includes a raw material liquid preparation step S01, an activated carbon treatment step S02, a crystallization step S03, and a solid-liquid separation step S04.

[0153] (Raw material liquid preparation process S01) The raw material liquid preparation step S01 can be carried out, for example, in accordance with the raw material liquid preparation step S01 described in the first embodiment. For example, the materials, procedures, methods, conditions, etc. used in the raw material liquid preparation step S01 can be those described in the first embodiment.

[0154] (Activated carbon treatment process S02) The activated carbon treatment step S02 can be appropriately performed, for example, in accordance with the activated carbon treatment step S02 described in the first embodiment. For example, the materials, procedures, methods, conditions, etc. used in the activated carbon treatment step S02 can be the same as those described in the first embodiment.

[0155] (Crystallization process S03) The crystallization step S03 can be carried out, for example, in accordance with the crystallization step S03 described in the first embodiment. For example, the materials, procedures, methods, conditions, etc. used in the crystallization step S03 can be the same as those described in the first embodiment.

[0156] (Solid-liquid separation process S04) The solid-liquid separation step S04 can be carried out, for example, in accordance with the solid-liquid separation step S04 described in the first embodiment. For example, the materials, procedures, methods, conditions, etc. used in the solid-liquid separation step S04 can be the same as those described in the first embodiment.

[0157] Thereafter, washing is carried out using a poor solvent as appropriate, and then drying is carried out as appropriate. In this manner, a water-soluble additive composition in a solid form or the like containing components (A) and (B2) can be recovered.

[0158] There are no limitations on the form of the water-soluble additive composition obtained in this embodiment, and it may be in the form of a solid such as powder or granules, or in liquid form. Furthermore, the water-soluble additive composition obtained in this embodiment can be used in daily necessities, cosmetics, pharmaceuticals, foods, etc., and is particularly suitable for use in daily necessities and cosmetics. Specific examples of daily necessities include antibacterial agents, antifungal agents, deodorants, detergents, hygiene products, bath products, household chemical products, and oral care products. Cosmetics also include emulsions, creams, foundations, eye shadows, lipsticks, blushers, hair cosmetics, emollient creams, emollient lotions, cream rinses, cold creams, vanishing creams, lotions, packs, gels, face packs, soaps, body soaps, shampoos, conditioners, rinses, bath additives, bath additives, facial cleansers, shaving creams, hair creams, hair lotions, hair treatments, hair packs, glosses, and lip balms. In this embodiment, the water-soluble additive composition can be used, for example, as a moisturizer or an antibacterial agent. Furthermore, according to this embodiment, it is possible to obtain a water-soluble additive composition that is less irritating to the skin, for example.

[0159] The present embodiment includes the following aspects. III-1. The following components (A) and (B2): (A) Cyclic carboxylic acids (excluding component (B2) below) (B) Amino acids 1. A water-soluble additive composition comprising: III-2. The water-soluble additive composition according to III-1, wherein component (A) is one or more selected from the group consisting of protocatechuic acid, shikimic acid, 4-hydroxybenzoic acid, 4-aminobenzoic acid, and ferulic acid. III-3. The water-soluble additive composition according to III-1 or III-2, wherein component (B2) comprises one or more amino acids selected from the group consisting of glutamic acid, alanine, valine, glycine, aspartic acid, serine, histidine, threonine, arginine, tyrosine, cystine, methionine, phenylalanine, isoleucine, leucine, lysine, and proline. III-4. The water-soluble additive composition according to any one of III-1 to III-3, wherein the content of component (A) in the water-soluble additive composition is 95% by mass or more and 99.9% by mass or less. III-5. The water-soluble additive composition according to any one of III-1 to III-4, wherein the content of component (B2) in the water-soluble additive composition is 0.001% by mass or more and 5% by mass or less. III-6. The water-soluble additive composition according to any one of III-1 to III-5, wherein the component (B2) contains glutamic acid, and the content of the glutamic acid in the water-soluble additive composition is 0.001% by mass or more and 1% by mass or less.

[0160] (Fourth embodiment) The present embodiment relates to a method for producing a food, a food additive, and a cyclic compound or a derivative thereof.

[0161] It is known that cyclic compounds having specific structures are used as food additives. For example, Patent Document 8 (JP 2007-238469 A) describes that aromatic hydroxycarboxylic acids are important as food antiseptics and preservatives.

[0162] However, such cyclic compounds are usually obtained from petroleum. In such cases, the petroleum-derived cyclic compounds (chemicals) that can be recovered by fractional distillation and refining of petroleum are so-called backbone compounds with simple chemical structures. On the other hand, high-value-added compounds with more complex chemical structures must be derived from these backbone compounds through a synthetic process. In this case, unless petroleum is fractionally refined to a high degree, regardless of production costs, various isomers derived from the raw materials and synthetic process, as well as trace components, ionic components, mineral components, etc. derived from catalysts, may remain in the petroleum-derived chemicals. These impurities contained in petroleum-derived chemicals are not desirable from the perspective of safety for the human body.

[0163] An object of the present embodiment is to provide safer foods and food additives that do not contain petroleum-derived impurities, and to provide a method for producing a cyclic compound or a derivative thereof that can be used as a food or food additive.

[0164] Such an object can be achieved by the present embodiment described in (VI-1) to (VI-10) below. (VI-1) Foods containing plant-derived sugars and at least one of cyclic compounds and their derivatives derived from microorganisms.

[0165] (VI-2) The food according to (VI-1) above, wherein the cyclic compound is a compound represented by the following general formula (1): [ka] [In the above general formula (1), ring A is a saturated ring, a partially saturated ring, or a five-membered aromatic ring, or a six-membered saturated ring, a partially saturated ring, or an aromatic ring; X is a single bond or a bond containing one or more carbon atoms; Y is a hydrogen atom or an alkyl group; and R 2~R 6 (When ring A is a five-membered ring, R 2 ~R 5 ) are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group.

[0166] (VI-3) The food according to (VI-2) above, wherein the cyclic compound is at least one selected from the group consisting of 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid.

[0167] (VI-4) When ring A of the cyclic compound is a saturated or partially saturated five-membered ring in which all of the ring-constituting atoms are carbon atoms, R 2 ~R 5 and when one or more of the carbon atoms of ring A to which X is bonded is an asymmetric carbon atom, and ring A of the cyclic compound is a saturated or partially saturated six-membered ring in which all of the ring constituent atoms are carbon atoms, R 2 ~R 6 and the food product according to (VI-2) above, wherein one or more of the carbon atoms of ring A to which X is bonded are asymmetric carbon atoms.

[0168] (VI-5) In the cyclic compound, the carbon atom of ring A to which X is bonded is C 1 Let R 2 The carbon atom of ring A to which is attached is C 2 Let R 3 The carbon atom of ring A to which is attached is C 3 Let R 4 The carbon atom of ring A to which is attached is C 4 Let R 5 The carbon atom of ring A to which is attached is C 5 Let R 6 The carbon atom of ring A to which is attached is C 6 The food product according to (VI-4) above, wherein the combination of asymmetric carbon atoms is one selected from the group consisting of the following (a) to (h): (a)C1 (b)C 2 (c)C 3 (d)C 4 (e)C 1 and C 4 (f)C 3 and C 4 (g)C 1 , C 3 and C 4 (h)C 3 , C 4 and C 5

[0169] (VI-6) The food according to (VI-1) above, wherein the cyclic compound or a derivative thereof is 3-dehydroquinate, 3-dehydroshikimic acid, shikimic acid, chorismic acid, or prephenic acid.

[0170] (VI-7) A food according to any one of (VI-1) to (VI-6) above, wherein the microorganism is Escherichia coli, Bacillus subtilis, Staphylococcus aureus, Corynebacterium, Actinomycete, Cyanobacteria, methanogens, halophiles, thermotolerant acidophiles, acid-fast bacteria, mold, yeast, or a transformant thereof.

[0171] (VI-8) The food according to any one of (VI-1) to (VI-7) above, wherein the raw material for the plant-derived sugars is a non-edible biomass resource.

[0172] (VI-9) Food additives containing at least one of plant-derived sugars and cyclic compounds and their derivatives derived from microorganisms.

[0173] (VI-10) A method for producing a cyclic compound or a derivative thereof to be used as a food or a food additive, comprising the steps of: preparing a culture solution containing plant-derived sugars and a microorganism so as to produce at least one of the cyclic compound and its derivatives; Concentrating the culture solution to obtain a concentrate; recovering at least one of the cyclic compound and its derivative from the concentrated solution by crystallization, precipitation, extraction, sublimation purification, or distillation; A method for producing a cyclic compound or a derivative thereof, comprising:

[0174] According to this embodiment, safer foods and food additives that do not contain petroleum-derived impurities can be provided.

[0175] Furthermore, according to this embodiment, safer foods or food additives that do not contain petroleum-derived impurities can be efficiently produced.

[0176] Hereinafter, the food, food additive, and method for producing a cyclic compound or a derivative thereof according to the present embodiment will be described in detail based on preferred embodiments.

[0177] <Food and food additives> As a result of extensive research, the present inventors have found that by including plant-derived sugars and at least one of a cyclic compound and its derivative derived from a microorganism, it is possible to provide a food or food additive that is free from petroleum-derived impurities. In this regard, they have found that it is preferable to produce the cyclic compound or its derivative by a bioprocess using plant-derived sugars (raw materials) and a microorganism.

[0178] That is, the food product of this embodiment contains at least one of a cyclic compound and a derivative thereof derived from plant-derived sugars and a microorganism. In other words, the food product of this embodiment contains at least one of a cyclic compound and a derivative thereof produced by a reaction (bioprocess) between plant-derived sugars and a microorganism.

[0179] This makes it possible to provide foods that are free of petroleum-derived impurities, and such foods are safer than foods that contain petroleum-derived impurities.

[0180] At least one of the plant-derived sugars and the cyclic compounds derived from microorganisms and their derivatives can also be used as food additives.

[0181] This makes it possible to provide a food additive containing at least one of a cyclic compound and its derivative, which is free of petroleum-derived impurities, and which is therefore safer than food additives containing petroleum-derived impurities.

[0182] Examples of cyclic compounds contained in foods or food additives include compounds whose ring-constituting atoms are carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, etc., and whose ring members are about 3 to 12. The bond between the atoms constituting the ring may be a single bond or a double bond.

[0183] Such a cyclic compound is not limited, but is preferably a compound represented by the following general formula (1).

[0184] [ka]

[0185] [In the above general formula (1), ring A is a saturated ring, a partially saturated ring, or a five-membered aromatic ring, or a six-membered saturated ring, a partially saturated ring, or an aromatic ring; X is a single bond or a bond containing one or more carbon atoms; Y is a hydrogen atom or an alkyl group; and R 2 ~R 6 (When ring A is a five-membered ring, R 2 ~R 5 ) are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group.

[0186] Examples of the five-membered saturated ring, partially saturated ring, or aromatic ring include a furan structure, a thiophene structure, a pyrrole structure, a pyrrolidine structure, a tetrahydrofuran structure, a 2,3-dihydrofuran structure, a pyrazole structure, an imidazole structure, an oxazole structure, an isoxazole structure, a thiazole structure, and an isothiazole structure.

[0187] Examples of the six-membered saturated ring include hydrocarbon saturated rings such as a cyclohexane structure, nitrogen-containing saturated rings such as a piperidine structure, piperazine structure, triazinane structure, tetrazinane structure, pentazinane structure, and quinuclidine structure, oxygen-containing saturated rings such as a tetrahydropyran structure and a morpholine structure, and sulfur-containing saturated rings such as a tetrahydrothiopyran structure.

[0188] Examples of the six-membered partially saturated ring include hydrocarbon-based partially saturated rings such as a cyclohexene structure and a cyclohexadiene structure, nitrogen-containing partially saturated rings such as a piperidine structure, oxygen-containing partially saturated rings such as a pyran structure, and sulfur-containing partially saturated rings such as a thiazine structure.

[0189] Examples of the six-membered aromatic ring include hydrocarbon aromatic rings such as a benzene structure, and nitrogen-containing aromatic rings (nitrogen-containing unsaturated rings) such as a pyridine structure, pyridazine structure, pyrimidine structure, pyrazine structure, triazine structure, tetrazine structure, and pentazine structure.

[0190] X is a single bond or a bond containing one or more carbon atoms (having one or more carbon atoms). When X is a single bond, the oxygen atom is directly bonded to a ring-constituting atom of ring A.

[0191] On the other hand, examples of bonds containing one or more carbon atoms include hydrocarbon groups having 1 to 4 carbon atoms, ether bonds, ester bonds, amide bonds, carbonyl groups, vinylidene groups, etc., and may be one or a combination of two or more of these.

[0192] Among these, the hydrocarbon group having 1 to 4 carbon atoms may be either linear or branched, and may be either saturated or unsaturated. The hydrogen atoms of the hydrocarbon group may be substituted with a substituent such as an alkyl group having 1 to 2 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, or a halogen atom.

[0193] In addition to the above-mentioned bond, X may contain any atom or atomic group. For example, X may be an atomic group containing a carbonyl group and a bond containing one or more carbons.

[0194] Y is a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 4 carbon atoms.

[0195] When ring A is a 6-membered ring, R 2 ~R 6 are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group. When ring A is a five-membered ring, R 2 ~R 5 are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group.

[0196] When ring A is a 6-membered ring, R 2 ~R 6 or R when ring A is a 5-membered ring 2 ~R 5 When either of the above is a carbonyl group, the ring-constituting atom of ring A is a carbon atom, and the carbon atom and the oxygen atom form a double bond, which is referred to as a carbonyl group. When ring A is a 6-membered ring, the carbon atoms constituting ring A are independently bonded to one carbon atom by R 2 ~R 6 In addition, when ring A is a 5-membered ring, the carbon atoms constituting ring A may be independently bonded to one carbon atom constituting ring A by R 2 ~R 5 Any one of these may be bonded, or any two of these may be bonded.

[0197] Specific examples of cyclic compounds include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, mellophanic acid, prenitic acid, pyromellitic acid, phenylacetic acid, hydroxyphenylacetic acid, phenylbutyric acid (phenyl lactate), hydroxyphenylbutyric acid, phenylpyruvic acid, hydroxyphenylpyruvic acid, phenyllactic acid, hydroxyphenyllactic acid, anthranilic acid, hydratropic acid, atropic acid, and hydrobenzoic acid. Cinnamic acid (coumaric acid), cinnamic acid, salicylic acid (2-hydroxybenzoic acid), m-salicylic acid (3-hydroxybenzoic acid), p-salicylic acid (4-hydroxybenzoic acid), methoxybenzoic acid, aminobenzoic acid, hydroxybenzoic acid, pyrocatechuic acid (2,3-dihydroxybenzoic acid), β-resorcylic acid (2,4-dihydroxybenzoic acid), gentisic acid (2,5-dihydroxybenzoic acid), γ-resorcylic acid (2,6-dihydroxybenzoic acid), protocatechuic acid (3,4-dihydroxybenzoic acid), α-resorcylic acid (3,5-dihydroxybenzoic acid), trihydroxybenzoic acid, vanillic acid (4-hydroxy-3-methoxybenzoic acid), isovanillic acid (3-hydroxy-4-methoxybenzoic acid), veratric acid, gallic acid, syringic acid, asaronic acid, mandelic acid, vanillylmandelic acid, anisic acid, homoprotocatechuic acid, homovanillic acid, homoisovanillic acid, homoveratric acid, homophthalic acid, homoisophthalic acid, Examples of terephthalic acid, phthalonic acid, isophthalonic acid, terephthalonic acid, atrolactic acid, tropic acid, mellotic acid, phloretic acid, dihydrocaffeic acid, hydroferulic acid, hydroisoferulic acid, umbellic acid, caffeic acid (caffeic acid), ferulic acid, isoferulic acid, sinapic acid, syringic acid, dehydroquinic acid, dehydroshikimic acid, shikimic acid, chorismic acid, L-tryptophan, L-tyrosine, prephenic acid, arogenic acid, and L-phenylalanine.

[0198] Other specific examples of cyclic compounds include polyphenols such as flavonoids, lignans, chalcones, stilbenoids, alkaloids, curcuminoids, terpenoids, saponins, various glycosides, and various polyphenolic aromatic compounds, as well as amino acids and vitamins.

[0199] Among these, examples of flavonoids include anthocyanidins such as aurantidin, cyanidin, delphinidin, europinidin, luteolinidin, pelargonidin, malvidin, peonidin, petunidin, and rosinidin, anthocyanins such as procyanidins, flavanones such as naringenin, eriocitrin, pinocembrin, and eriodictyol, flavans such as catechin, flavones such as apigenin, luteolin, baicalein, and chrysin, flavonols such as quercetin and kaempferol, isoflavones, isoflavones, isoflavones, isoflavones, isoflavones, isoflavonediols, and isoflavonoids such as genistein, as well as neoflavonoids, biflavonoids, aurones, prenylated flavonoids, and O-methylated flavonoids.

[0200] Examples of lignans include pinoresinol, lariciresinol, secoisolariciresinol, matairesinol, hydroxymatairesinol, syringaresinol, sesamin, arctigenin, sesaminol, podophyllotoxin, and steganacin.

[0201] Further examples of stilbenoids include aglycones such as piceatannol, pinosylvin, pterostilbene, resveratrol, 4'-methoxyresveratrol, pinostilbene, and piceatannol, and oligomers such as α-viniferin, ampelopsin A, ampelopsin E, diptoindonesin C-kawane, diptoindonesin F-dammarbua, ε-viniferin, flexosol A, gnetin H, hemsleyanol D, hopeaphenol, diptoindonesin B, and vaticanol B.

[0202] Examples of curcuminoids include curcumin and shogaol.

[0203] Further, examples of terpenoids include carotenoids such as lutein, vitamin A, vitamin E, and β-carotene, as well as steroids such as sitosterol.

[0204] Examples of various glycosides include phenolic glycosides such as salicin, β-glucogallin, salicylic acid glucoside, salidroside, gastrodin, poplin, phloridzin, and arbutin, coumarin glycosides such as esculin, flavonoid glycosides such as hesperidin and rutin, and stilbenoid glycosides such as astringin, piceid, and diptoindonesin A.

[0205] Furthermore, examples of various polyphenolic aromatic compounds include tyrosol, hydroxytyrosol, esculetin, phloretin, rosmarinic acid, salvianic acid A, reticuline, paracoumaryl alcohol, coniferyl alcohol, and caffeyl alcohol.

[0206] The amino acids include, for example, phenylalanine and tyrosine. Furthermore, examples of vitamins include vitamin A, vitamin D, vitamin E, etc.

[0207] Further specific examples of the cyclic compound include aromatic compounds, alicyclic compounds, aliphatic compounds, heterocyclic compounds, and the like.

[0208] Among these, examples of aromatic compounds include vanillin, 2-phenylethanol, phenylacetic acid, cinnamic alcohol, isoeugenol, ferulic acid, 4-aminobenzoic acid, anethole, estragole, methyl anthranilate, methyl cinnamate, ethyl cinnamate, phenylacetaldehyde, cinnamic aldehyde, cinnamyl acetate, resorcinol, 4-vinylphenol, 4-vinyl-2-methoxyphenol, 3,4-dihydroxystyrene, dopamine, levodopa, hydroquinone, coumarin, 7-hydroxycoumarin, 4-hydroxycoumarin, and xiamenmycin A.

[0209] Examples of alicyclic compounds include carveol, perilla alcohol, borneol, methyl jasmonate, 1,8-cineole, L-menthone, valencene, nootkatone, α-pinene, camphene, L-carvone, perilla aldehyde, myrtenal, L-menthyl acetate, and β-ionone.

[0210] Furthermore, examples of aliphatic compounds include cis-3-hexenol, cis-3-hexenyl acetate, acetoin, nerol, farnesol, arginine, muconic acid, and the like.

[0211] Examples of heterocyclic compounds include niacin, niacinamide, maltol, and indole.

[0212] On the other hand, derivatives of cyclic compounds include, for example, esters, acid anhydrides, amides, acid halides, salts, etc. of the above-mentioned compounds, or all compounds derived from cyclic compounds.

[0213] Among the above-mentioned cyclic compounds, the cyclic compound represented by the general formula (1) is preferably at least one selected from the group consisting of 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid. By using these, it is possible to realize foods or food additives with diverse efficacy and greater safety.

[0214] The molecular weight of the cyclic compound or its derivative is not limited, but is preferably 120-1000, and more preferably 130-800.

[0215] In addition, when ring A of the cyclic compound represented by the general formula (1) is a saturated or partially saturated five-membered ring in which all of the ring constituent atoms are carbon atoms, R 2 ~R 5and at least one of the carbon atoms of ring A to which X is bonded is preferably an asymmetric carbon atom. When ring A of the cyclic compound represented by the above general formula (1) is a saturated or partially saturated six-membered ring in which all of the ring constituent atoms are carbon atoms, R 2 ~R 6 and one or more of the carbon atoms of ring A to which X is attached are preferably asymmetric carbon atoms.

[0216] In such cases, the cyclic compound becomes a stereoisomer, which allows for the realization of a useful food or food additive. Furthermore, by producing such a cyclic compound from a plant-derived sugar, a food or food additive containing a specific stereoisomer at a high purity can be obtained. That is, a food or food additive containing a specific stereoisomer at a high purity and having a low content of other stereoisomers can be obtained. Such a food or food additive is useful from the viewpoint of realizing a food or food additive with excellent safety and efficacy. Furthermore, since a complicated manufacturing process associated with the removal of unwanted stereoisomers is not required, manufacturing costs can be reduced.

[0217] In addition, in the cyclic compound represented by the general formula (1), the carbon atom of ring A to which X is bonded is C 1 Let R 2 The carbon atom of ring A to which is attached is C 2 Let R 3 The carbon atom of ring A to which is attached is C 3 Let R 4 The carbon atom of ring A to which is attached is C 4 Let R 5 The carbon atom of ring A to which is attached is C 5 Let R 6 The carbon atom of ring A to which is attached is C 6 In this case, it is preferable that the combination of these asymmetric carbon atoms is one selected from the group consisting of the following (a) to (h): C 1 ~C 6 may be different carbon atoms, or C 1 ~C 6 Any two of the carbon atoms may be the same.

[0218] (a)C 1 (b)C 2 (c)C 3 (d)C 4 (e)C 1 and C 4 (f)C 3 and C 4 (g)C 1 , C 3 and C 4 (h)C 3 , C 4 and C 5

[0219] The following general formula (2) is a compound represented by the general formula (1) above, wherein the C 1 ~C 6 This is an equation with the display added.

[0220] [ka]

[0221] [In the above general formula (2), ring A is a saturated ring, a partially saturated ring, or a five-membered aromatic ring, or a six-membered saturated ring, a partially saturated ring, or an aromatic ring; X is a single bond or a bond containing one or more carbon atoms; Y is a hydrogen atom or an alkyl group; R 2 ~R 6 (When ring A is a five-membered ring, R 2 ~R 5 ) are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group. 1 ~C 6 are carbon atoms constituting ring A.

[0222] In such cases, the cyclic compound becomes a stereoisomer, which allows for the realization of a more effective food or food additive. Furthermore, by producing such a cyclic compound from a plant-derived sugar, a food or food additive containing a high purity of a specific stereoisomer selected from the group consisting of (a) to (h) above can be obtained. That is, a food or food additive containing a high purity of a specific stereoisomer and a low content of other stereoisomers can be obtained. Such a food or food additive is useful from the perspective of realizing a food or food additive with excellent safety and efficacy. Furthermore, the complex manufacturing process associated with the removal of unwanted stereoisomers can be reduced, thereby reducing manufacturing costs.

[0223] The cyclic compound and its derivative according to this embodiment are preferably compounds represented by the general formula (2) and further preferably 3-dehydroquinate, 3-dehydroshikimic acid, shikimic acid, chorismic acid, or prephenic acid. These compounds can be produced from plant-derived sugars and are useful as foods or food additives. Therefore, the use of these compounds produced from plant-derived sugars can result in foods or food additives that are safer and have better efficacy. The structures of these cyclic compounds are represented by the following formulas:

[0224] 3-Dehydroquinate

[0225] [ka]

[0226] 3-Dehydroshikimic acid

[0227] [ka]

[0228] Shikimic acid

[0229] [ka]

[0230] Chorismic acid

[0231] [ka]

[0232] Prephenic acid

[0233] [ka]

[0234] Foods containing at least one of the above-mentioned cyclic compounds and their derivatives are not limited to commonly eaten foods and beverages, and examples include oral compositions such as gum and candy, fish paste products such as kamaboko and chikuwa, livestock products such as sausage and ham, Western confectioneries, Japanese confectioneries, noodles such as Chinese noodles, udon and soba, seasonings such as sauces, soy sauces and tare sauces, side dishes, juices, soups, etc.

[0235] Additionally, when used as a supplement or health food, it may be provided in the form of capsules or tablets like pharmaceuticals, or it may be provided by adding it to various foods such as beverages, seasonings, confectioneries, etc. Functions of the supplement or health food include, for example, antioxidant effect, anti-arteriosclerosis, anti-hypertensive effect, radical scavenging activity, enzyme inhibitory effect, restoration of healthy cellular tissue inside the skin, regeneration of capillaries, strengthening of resistance to bacteria, regeneration of red blood cells, regulation of blood pressure, immune enhancement, anti-cancer effect, anti-viral effect, suppression of blood glucose level rise, improvement of liver function, improvement of intestinal flora, improvement of bowel movements, improvement of lipid metabolism, enhancement of antioxidant function, enhancement of physical strength, promotion of beautiful skin, hair growth, and the prevention or amelioration of at least one of vascular-related diseases (arteriosclerosis, hypertension, heart disease), neurodegenerative diseases, ischemic cerebrovascular disorders, ischemic heart disease, inflammatory bowel disease, and eye diseases.

[0236] Furthermore, food additives containing at least one of a cyclic compound and its derivatives include additives designated under the Food Sanitation Act. Examples include preservatives, sweeteners, coloring agents, and food flavors. Among these, protocatechuic acid, for example, is used as a sweetness enhancer. The use of such a sweetness enhancer can increase the sweetness intensity of foods, allowing for a relative reduction in the amount of added sugar. As a result, it is possible to realize foods that are both safe and have added value in terms of low sugar content. Furthermore, functions of food flavors include, for example, flavoring, aromatization, flavor correction, sweetness enhancement, sourness / bitterness reduction, and appetite stimulation.

[0237] The food additive may be in the form of, for example, a water-soluble liquid, an oil-soluble liquid, an emulsion, or a powder.

[0238] <Method for producing cyclic compound or derivative thereof> The above-mentioned cyclic compound or derivative thereof is produced by a bioprocess using a microorganism and plant-derived sugars as a raw material, i.e., the above-mentioned cyclic compound or derivative thereof is derived from plant-derived sugars and a microorganism.

[0239] Plant-derived sugars include, but are not limited to, monosaccharides, polysaccharides, and mixtures thereof.

[0240] The monosaccharides are not limited, and examples thereof include sugars that can be processed by the microbial transformant described below. From the viewpoint of improving the phenol productivity of the transformant, such sugars (monosaccharides) include, for example, tetrose (C4 sugar), pentose (C5 sugar), hexose (C6 sugar), and heptose (C7 sugar). Among these, the monosaccharide is preferably at least one selected from the group consisting of arabinose, xylose, glucose, mannitol, fructose, mannose, galactose, and sucrose. Furthermore, such sugars may be used alone or in combination to form a sugar mixture.

[0241] Polysaccharides are polymers of monosaccharides. The average degree of polymerization of polysaccharides is not limited, but is preferably 2 to 100, more preferably 2 to 50, from the viewpoint of improving productivity in bioprocesses using microorganisms. Polysaccharides may be used alone or in combination. Examples of polysaccharides include maltose, lactose, cellobiose, xylobiose, trehalose, acarbose, stachyose, fructooligosaccharides, galactooligosaccharides, and mannanoligosaccharides.

[0242] The plant-derived sugars are preferably produced from non-edible biomass resources, in other words, the raw material for the plant-derived sugars is preferably a non-edible biomass resource.

[0243] From the viewpoint of obtaining the sugars described above, various biomass resources can be used as long as they contain at least monosaccharides or polysaccharides. Examples of biomass resources include vegetation resources such as weeds growing in urban areas or cultivated land and thinned wood from forestry production areas, as well as waste cellulose, waste starch, and blackstrap molasses recovered as process residues or waste from the general food industry, sugarcane pomace in the sugar industry, and sake lees and shochu lees in the sake brewing industry. These can be used alone or in combination. Processed products can also be used as biomass resources.

[0244] The plant-derived sugars can be obtained by saccharifying such biomass resources. As such plant-derived sugars, cellulose-derived sugars obtained by saccharifying waste cellulose are preferred, and cellulose-derived mixed sugars are more preferred. Hereinafter, a process for producing a cyclic compound or a derivative thereof using a microorganism and plant-derived sugars as a raw material will be described in detail.

[0245] The process using microorganisms that use plant-derived sugars as a raw material includes the steps of obtaining a culture solution containing at least one of the cyclic compound and its derivatives produced by microorganisms using the plant-derived sugars as a raw material (i.e., produced by the conversion of plant-derived sugars by microorganisms), concentrating the culture solution to obtain a concentrate, and recovering at least one of the cyclic compound and its derivatives from the concentrate by crystallization, precipitation, extraction, sublimation purification, or distillation. Through this process, at least one of the cyclic compound and its derivatives can be efficiently obtained. Furthermore, in this process using microorganisms, the cyclic compound or its derivative is produced as a result of the reaction between the raw material and the microorganism. Therefore, by limiting the types of raw material and microorganisms (e.g., by limiting the raw material to plant-derived sugars and the type of microorganism to bacteria), the cyclic compound or its derivative can be efficiently obtained. This effect can be more pronounced by further limiting the types of raw material and microorganisms (e.g., by limiting the raw material to a cellulose-derived sugar mixture and the type of bacteria). In this respect, it differs from processes that do not use microorganisms (for example, processes that use extracts from plants). From this perspective, plant-derived sugars and cyclic compounds and derivatives thereof derived from microorganisms can be referred to as cyclic compounds and derivatives thereof (excluding those derived from plant extracts).

[0246] In the bioprocess, the recovery rate of the cyclic compound and its derivatives can be improved by appropriately selecting the microorganism, medium, culture equipment, and culture conditions.

[0247] <Step of preparing culture medium> First, a culture solution is prepared containing raw materials, microorganisms, a medium, etc. In this culture solution, the microorganisms are cultured, and the raw materials, etc. are reacted with the microorganisms (by a bioprocess) to produce at least one of a cyclic compound and a derivative thereof.

[0248] The microorganism may be of any type as long as it can produce the cyclic compound and its derivatives with high efficiency. Generally, examples of the microorganism include bacteria such as Escherichia coli, Bacillus subtilis, Staphylococcus aureus, and Corynebacterium glutamicum, actinomycetes such as Streptomyces griseus, cyanobacteria such as Microcystis aeruginosa, archaea such as Methanogens (Methanobacterium thermoautotrophicum), halophiles (Halobacterium salinarum), thermoacidophiles (Sulfolobus acidocaldarius), thermotolerant acidophiles (Alicyclobacillus acidoterrestris), and acid-fast bacteria, molds such as Aspergillus oryzae, and yeasts such as Saccharomyces cerevisiae. A yeast such as Saccharomyces cerevisiae is selected according to the purpose, and a transformant obtained by a known method is used as needed.

[0249] The medium may be a medium commonly used for culturing microorganisms. The medium contains medium components to create the environment necessary for the growth of the microorganisms. The medium components preferably contain carbon sources, nitrogen sources, inorganic salts, or other nutrients in appropriate amounts depending on the type of microorganism used. Therefore, the culture solution before bioprocessing preferably contains raw materials, microorganisms, and medium components.

[0250] Examples of carbon sources include carbohydrates or sugar alcohols such as glucose, fructose, sucrose, mannose, maltose, mannitol, xylose, arabinose, galactose, starch, molasses, sorbitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; and alcohols such as ethanol and propanol. As the carbon source, one of these may be used alone, or two or more may be used in combination.

[0251] Examples of nitrogen sources include inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate. Nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. As the nitrogen source, one of these may be used alone, or two or more may be used in combination.

[0252] Examples of inorganic salts include monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, etc. As the inorganic salts, one of these may be used alone, or two or more may be used in combination.

[0253] Examples of nutrients include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, hydrolyzed skim soybeans with hydrochloric acid, and extracts of animals, plants, or microbial cells, or their decomposition products. Furthermore, vitamins can be added to the medium as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid.

[0254] The fermentation equipment can be batch, fed-batch, or continuous, although batch fermentation is preferred when multi-product production is envisioned. A seed culture method is generally employed, in which a culture is expanded stepwise starting from a flask-scale culture, and a group of culture vessels of several different sizes is used as a set depending on the production scale. The preferred culture conditions are a medium temperature of approximately 15 to 45°C, and a medium pH of approximately 6 to 8. Other parameters, such as the aeration method and aeration rate for the fermentation tank, the agitation method and rotation speed, the shape of the agitator blades, and the culture time, are appropriately set according to the size and specifications of the fermentation equipment and the type and concentration of the microorganisms used, and the fermentation process is appropriately adjusted through real-time monitoring.

[0255] <Concentration process and isolation and purification process> The culture medium obtained by the bioprocess can be prepared in a state containing the cyclic compound or its derivative at a suitable concentration if the microbial growth environment is appropriately selected. For the purpose of selectively and efficiently recovering the cyclic compound or its derivative from the culture medium prepared in this manner, a recovery process including a culture medium concentration step and an isolation and purification step is applied. According to this method, the cyclic compound or its derivative can be efficiently produced.

[0256] The concentration step is carried out for the purpose of increasing the concentration of at least one of the cyclic compound and its derivative in the culture solution obtained after the bioprocess, and recovering the target compound in high yield and high purity in the subsequent isolation and purification step. The concentration step will be described below.

[0257] The culture solution after bioprocessing contains at least one of the cyclic compounds and their derivatives produced by the bioprocessing, as well as medium components such as a carbon source, a nitrogen source, inorganic salts, and nutrients, as well as organic acids, amino acids, and their salts that are by-produced during the bioprocessing. Water typically accounts for 70 to 99% of the total weight of the culture solution after bioprocessing. Therefore, a concentration process that can efficiently remove water without altering or depleting the cyclic compounds or their derivatives and without increasing the amount of by-products associated with concentration is desirable. To achieve this goal, chemical engineering techniques such as thermal concentration, vacuum distillation, solvent extraction, solid extraction, and membrane separation can be applied. However, vacuum concentration is more preferred to avoid alteration and depletion of the cyclic compounds or their derivatives due to heat or oxidation during the concentration process and to reduce the thermal energy input required for water removal.

[0258] The isolation and purification step is carried out for the purpose of selectively recovering at least one of the cyclic compound and its derivative from the concentrate obtained in the concentration step.

[0259] In the isolation and purification process, various chemical engineering techniques can be applied, such as steam distillation, precision fractional distillation, temperature crystallization, acid crystallization, salting out, reprecipitation, sublimation, column purification, extraction, and membrane separation. An appropriate technique is selected taking into consideration the properties of the target compound and the properties of the impurities and by-products to be removed. The properties of cyclic compounds vary depending on the type and number of substituents. However, when a cyclic compound or its derivative is solid at room temperature and the impurities and by-products have relatively high water solubility, a crystallization method (temperature crystallization or acid crystallization) is preferably used.

[0260] <Processing into food or food additives> The cyclic compound or its derivative produced as described above can be processed as needed to obtain a food or food additive. One example of such processing is the addition of an optional ingredient. The food or food additive of this embodiment may contain any other ingredient within a range that does not impair the effects of this embodiment.

[0261] Other ingredients include, for example, sugar, condensed milk, wheat flour, shortening, salt, glucose, eggs, butter, margarine, starch syrup, calcium, iron, seasonings, spices, and oils (animal and vegetable oils, mineral oil, ester oil, wax oil, silicone oil, higher alcohols, phospholipids, fatty acids, etc.), surfactants (anionic, cationic, amphoteric, or nonionic surfactants), vitamins (vitamin A group, vitamin B group, folic acid, nicotinic acid, pantothenic acid, biotin, vitamin C group, vitamin D group, vitamin E group, ferulic acid, γ-oryzanol, etc.), UV absorbers (p-aminobenzoic acid, anthranilic acid, salicylic acid, coumarin, benzotriazole, tetrazole, imidazoline, pyrimidine, dioxane, furan, pyrone, camphor, nucleic acid, allantoin or derivatives thereof, amino acid compounds, shikonin, baicalin, baicalein, berberine, etc.). , antioxidants (stearic acid esters, nordihydroguaiaretic acid, dibutylhydroxytoluene, butylhydroxyanisole, parahydroxyanisole, propyl gallate, sesamol, sesamolin, gossypol, etc.), thickeners (hydroxyethyl cellulose, ethyl cellulose, carboxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, polyvinyl methacrylate, polyacrylates, carboxyvinyl polymers, gum arabic, gum tragacanth, agar, casein, dextrin, gelatin, pectin, starch, alginic acid or its salts, etc.), humectants (propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerin, 1,Examples of such additives include 2-pentanediol, hexylene glycol, octylene glycol, chondroitin sulfate or its salts, hyaluronic acid or its salts, sodium lactate, etc.), lower alcohols, polyhydric alcohols, water-soluble polymers, pH adjusters, antiseptics and antifungals, colorants, fragrances, refreshing agents, stabilizers, animal and plant extracts, animal and plant proteins or their decomposition products, animal and plant polysaccharides or their decomposition products, animal and plant glycoproteins or their decomposition products, microbial culture metabolic components, blood flow promoters, anti-inflammatory agents, anti-allergic agents, cell activators, amino acids or their salts, keratolytic agents, astringents, wound healing agents, foaming agents, oral care agents, deodorizing agents, and emulsifiers. These may be used alone or in combination.

[0262] The form of the food product of this embodiment is arbitrary and not limited. The food or food additive of this embodiment has been described above, but specific examples of the food or food additive are not limited to those described above and may be any.

[0263] (Fifth embodiment) The present embodiment relates to a method for producing a fragrance, and a cyclic compound or a derivative thereof.

[0264] It is known that cyclic compounds having specific structures are used as fragrances. For example, Patent Document 9 (JP-A-8-92589) discloses a fragrance composition containing alcohols and aromatic aldehydes.

[0265] However, cyclic compounds such as the aromatic aldehydes are usually obtained from petroleum. In such cases, the petroleum-derived cyclic compounds (chemicals) that can be recovered by fractional distillation and refining of petroleum are so-called backbone compounds with simple chemical structures. On the other hand, high-value-added compounds with more complex chemical structures must be derived from these backbone compounds through a synthetic process. In this case, unless petroleum is fractionally refined to a high degree, regardless of production costs, various isomers derived from the raw materials and synthetic process, as well as trace components, ionic components, mineral components, etc. derived from catalysts, may remain in the petroleum-derived chemicals. These impurities contained in petroleum-derived chemicals are not desirable from the perspective of safety for the human body.

[0266] An object of the present embodiment is to provide a safer fragrance that does not contain petroleum-derived impurities, and to provide a method for producing a cyclic compound or a derivative thereof that can be used as a fragrance.

[0267] Such an object can be achieved by the present embodiment described in (V-1) to (V-9) below. (V-1) A fragrance containing at least one of plant-derived sugars and cyclic compounds derived from microorganisms and their derivatives.

[0268] (V-2) The fragrance according to (V-1) above, wherein the cyclic compound is a compound represented by the following general formula (1): [ka] [In the above general formula (1), ring A is a saturated ring, a partially saturated ring, or a five-membered aromatic ring, or a six-membered saturated ring, a partially saturated ring, or an aromatic ring; X is a single bond or a bond containing one or more carbon atoms; Y is a hydrogen atom or an alkyl group; and R 2 ~R 6 (When ring A is a five-membered ring, R 2 ~R 5 ) are independently a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, a carboxyl group, or a carbonyl group.

[0269] (V-3) The fragrance according to (V-2) above, wherein the cyclic compound is at least one selected from the group consisting of 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid.

[0270] (V-4) When ring A of the cyclic compound is a saturated or partially saturated five-membered ring in which all of the ring constituent atoms are carbon atoms, R 2 ~R 5 and when one or more of the carbon atoms of ring A to which X is bonded is an asymmetric carbon atom, and ring A of the cyclic compound is a saturated or partially saturated six-membered ring in which all of the ring constituent atoms are carbon atoms, R 2 ~R 6 and the fragrance according to (V-2) above, wherein one or more of the carbon atoms of ring A to which X is bonded are asymmetric carbon atoms.

[0271] (V-5) In the cyclic compound, the carbon atom of ring A to which X is bonded is C 1 Let R 2 The carbon atom of ring A to which is attached is C 2 Let R 3 The carbon atom of ring A to which is attached is C 3 Let R 4 The carbon atom of ring A to which is attached is C 4 Let R 5 The carbon atom of ring A to which is attached is C 5 Let R 6 The carbon atom of ring A to which is attached is C 6 The fragrance according to (V-4) above, wherein the combination of asymmetric carbon atoms is one selected from the group consisting of the following (a) to (h): (a)C 1 (b)C 2 (c)C 3 (d)C 4 (e)C 1 and C 4 (f)C 3 and C 4 (g)C 1 , C 3 and C 4 (h)C 3 , C 4 and C 5

[0272] (V-6) The fragrance according to (V-1) above, wherein the cyclic compound or a derivative thereof is 3-dehydroquinate, 3-dehydroshikimic acid, shikimic acid, chorismic acid, or prephenic acid.

[0273] (V-7) A fragrance according to any one of (V-1) to (V-6) above, wherein the microorganism is Escherichia coli, Bacillus subtilis, Staphylococcus aureus, Corynebacterium, Actinomycete, Cyanobacteria, methanogens, halophiles, thermotolerant acidophiles, acid-fast bacteria, mold, yeast, or a transformant thereof.

[0274] (V-8) The flavoring according to any one of (V-1) to (V-7) above, wherein the raw material of the plant-derived sugar is a non-edible biomass resource.

[0275] (V-9) A method for producing a cyclic compound or a derivative thereof used as a fragrance, comprising: preparing a culture solution containing plant-derived sugars and a microorganism so as to produce at least one of the cyclic compound and its derivatives; Concentrating the culture solution to obtain a concentrate; recovering at least one of the cyclic compound and its derivative from the concentrated solution by crystallization, precipitation, extraction, sublimation purification, or distillation; A method for producing a cyclic compound or a derivative thereof, comprising:

[0276] According to this embodiment, a safer fragrance that does not contain petroleum-derived impurities can be provided.

[0277] Furthermore, according to the present embodiment, safer flavorings that do not contain petroleum-derived impurities can be efficiently produced.

[0278] Hereinafter, the method for producing the fragrance of this embodiment and the cyclic compound or its derivative will be described in detail based on preferred embodiments.

[0279] ≪Fragrance≫ As a result of intensive research, the present inventors have found that a fragrance free from petroleum-derived impurities can be provided by including at least one of a plant-derived sugar and a cyclic compound or a derivative thereof derived from a microorganism. In this regard, they have found that it is preferable to produce the cyclic compound or a derivative thereof by a bioprocess using a plant-derived sugar (raw material) and a microorganism.

[0280] That is, the fragrance of the present embodiment contains at least one of a cyclic compound and a derivative thereof derived from plant-derived sugars and a microorganism. In other words, the fragrance of the present embodiment contains at least one of a cyclic compound and a derivative thereof produced by a reaction between plant-derived sugars and a microorganism (bioprocess).

[0281] This makes it possible to provide a fragrance that is free of petroleum-derived impurities, and such a fragrance is safer than a fragrance that contains petroleum-derived impurities.

[0282] Examples of cyclic compounds contained in fragrances include compounds whose ring-constituting atoms are carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, etc., and whose ring members are about 3 to 12. The bond between the atoms constituting the ring may be a single bond or a double bond.

[0283] Such a cyclic compound is not limited, but is preferably a compound represented by the general formula (1) described above in the fourth embodiment. The specific structure of the compound represented by the general formula (1) can be the structure described above in the fourth embodiment.

[0284] Specific examples of cyclic compounds include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, mellophanic acid, prenitic acid, pyromellitic acid, phenylacetic acid, hydroxyphenylacetic acid, phenylbutyric acid (phenyl lactate), hydroxyphenylbutyric acid, phenylpyruvic acid, hydroxyphenylpyruvic acid, phenyllactic acid, hydroxyphenyllactic acid, anthranilic acid, hydratropic acid, atropic acid, and hydrobenzoic acid. Cinnamic acid (coumaric acid), cinnamic acid, salicylic acid (2-hydroxybenzoic acid), m-salicylic acid (3-hydroxybenzoic acid), p-salicylic acid (4-hydroxybenzoic acid), methoxybenzoic acid, aminobenzoic acid, hydroxybenzoic acid, pyrocatechuic acid (2,3-dihydroxybenzoic acid), β-resorcylic acid (2,4-dihydroxybenzoic acid), gentisic acid (2,5-dihydroxybenzoic acid), γ-resorcylic acid (2,6-dihydroxybenzoic acid), protocatechuic acid (3,4-dihydroxybenzoic acid), α-resorcylic acid (3,5-dihydroxybenzoic acid), trihydroxybenzoic acid, vanillic acid (4-hydroxy-3-methoxybenzoic acid), isovanillic acid (3-hydroxy-4-methoxybenzoic acid), veratric acid, gallic acid, syringic acid, asaronic acid, mandelic acid, vanillylmandelic acid, anisic acid, homoprotocatechuic acid, homovanillic acid, homoisovanillic acid, homoveratric acid, homophthalic acid, homoisophthalic acid, Examples of terephthalic acid, phthalonic acid, isophthalonic acid, terephthalonic acid, atrolactic acid, tropic acid, mellotic acid, phloretic acid, dihydrocaffeic acid, hydroferulic acid, hydroisoferulic acid, umbellic acid, caffeic acid (caffeic acid), ferulic acid, isoferulic acid, sinapic acid, syringic acid, dehydroquinic acid, dehydroshikimic acid, shikimic acid, chorismic acid, L-tryptophan, L-tyrosine, prephenic acid, arogenic acid, and L-phenylalanine.

[0285] Other specific examples of cyclic compounds include polyphenols such as flavonoids, lignans, chalcones, stilbenoids, alkaloids, curcuminoids, terpenoids, saponins, various glycosides, and various polyphenolic aromatic compounds, as well as amino acids and vitamins.

[0286] Among these, examples of flavonoids include anthocyanidins such as aurantidin, cyanidin, delphinidin, europinidin, luteolinidin, pelargonidin, malvidin, peonidin, petunidin, and rosinidin, anthocyanins such as procyanidins, flavanones such as naringenin, eriocitrin, pinocembrin, and eriodictyol, flavans such as catechin, flavones such as apigenin, luteolin, baicalein, and chrysin, flavonols such as quercetin and kaempferol, isoflavones, isoflavones, isoflavones, isoflavones, isoflavones, isoflavonediols, and isoflavonoids such as genistein, as well as neoflavonoids, biflavonoids, aurones, prenylated flavonoids, and O-methylated flavonoids.

[0287] Examples of lignans include pinoresinol, lariciresinol, secoisolariciresinol, matairesinol, hydroxymatairesinol, syringaresinol, sesamin, arctigenin, sesaminol, podophyllotoxin, and steganacin.

[0288] Further examples of stilbenoids include aglycones such as piceatannol, pinosylvin, pterostilbene, resveratrol, 4'-methoxyresveratrol, pinostilbene, and piceatannol, and oligomers such as α-viniferin, ampelopsin A, ampelopsin E, diptoindonesin C-kawane, diptoindonesin F-dammarbua, ε-viniferin, flexosol A, gnetin H, hemsleyanol D, hopeaphenol, diptoindonesin B, and vaticanol B.

[0289] Examples of curcuminoids include curcumin and shogaol.

[0290] Further, examples of terpenoids include carotenoids such as lutein, vitamin A, vitamin E, and β-carotene, as well as steroids such as sitosterol.

[0291] Examples of various glycosides include phenolic glycosides such as salicin, β-glucogallin, salicylic acid glucoside, salidroside, gastrodin, poplin, phloridzin, and arbutin, coumarin glycosides such as esculin, flavonoid glycosides such as hesperidin and rutin, and stilbenoid glycosides such as astringin, piceid, and diptoindonesin A.

[0292] Furthermore, examples of various polyphenolic aromatic compounds include tyrosol, hydroxytyrosol, esculetin, phloretin, rosmarinic acid, salvianic acid A, reticuline, paracoumaryl alcohol, coniferyl alcohol, and caffeyl alcohol.

[0293] The amino acids include, for example, phenylalanine and tyrosine. Furthermore, examples of vitamins include vitamin A, vitamin D, vitamin E, etc.

[0294] Further specific examples of the cyclic compound include aromatic compounds, alicyclic compounds, aliphatic compounds, heterocyclic compounds, and the like.

[0295] Among these, examples of aromatic compounds include vanillin, 2-phenylethanol, phenylacetic acid, cinnamic alcohol, isoeugenol, ferulic acid, 4-aminobenzoic acid, anethole, estragole, methyl anthranilate, methyl cinnamate, ethyl cinnamate, phenylacetaldehyde, cinnamic aldehyde, cinnamyl acetate, resorcinol, 4-vinylphenol, 4-vinyl-2-methoxyphenol, 3,4-dihydroxystyrene, dopamine, levodopa, hydroquinone, coumarin, 7-hydroxycoumarin, 4-hydroxycoumarin, and xiamenmycin A.

[0296] Examples of alicyclic compounds include carveol, perilla alcohol, borneol, methyl jasmonate, 1,8-cineole, L-menthone, valencene, nootkatone, α-pinene, camphene, L-carvone, perilla aldehyde, myrtenal, L-menthyl acetate, and β-ionone.

[0297] Furthermore, examples of aliphatic compounds include cis-3-hexenol, cis-3-hexenyl acetate, acetoin, nerol, farnesol, arginine, muconic acid, and the like.

[0298] Examples of heterocyclic compounds include niacin, niacinamide, maltol, and indole.

[0299] On the other hand, derivatives of cyclic compounds include, for example, esters, acid anhydrides, amides, acid halides, salts, etc. of the above-mentioned compounds, or all compounds derived from cyclic compounds.

[0300] Among the above-mentioned cyclic compounds, the cyclic compound represented by the general formula (1) is preferably at least one selected from the group consisting of 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid. By using these, it is possible to realize a fragrance that has diverse efficacy and is safer.

[0301] The molecular weight of the cyclic compound or its derivative is not limited, but is preferably 120-1000, and more preferably 130-800.

[0302] In addition, when ring A of the cyclic compound represented by the general formula (1) is a saturated or partially saturated five-membered ring in which all of the ring constituent atoms are carbon atoms, R 2 ~R 5and at least one of the carbon atoms of ring A to which X is bonded is preferably an asymmetric carbon atom. When ring A of the cyclic compound represented by the above general formula (1) is a saturated or partially saturated six-membered ring in which all of the ring constituent atoms are carbon atoms, R 2 ~R 6 and one or more of the carbon atoms of ring A to which X is attached are preferably asymmetric carbon atoms.

[0303] In such cases, the cyclic compound becomes a stereoisomer, which allows for the realization of a meaningful fragrance. Furthermore, by producing such a cyclic compound from a plant-derived sugar, a fragrance containing a specific stereoisomer at a high purity can be obtained. That is, a fragrance containing a specific stereoisomer at a high purity and with a low content of other stereoisomers can be obtained. Such a fragrance is useful from the viewpoint of realizing a fragrance with excellent safety and efficacy. Furthermore, since a complicated production process associated with the removal of unwanted stereoisomers is not required, production costs can be reduced.

[0304] In addition, in the cyclic compound represented by the general formula (1), the carbon atom of ring A to which X is bonded is C 1 Let R 2 The carbon atom of ring A to which is attached is C 2 Let R 3 The carbon atom of ring A to which is attached is C 3 Let R 4 The carbon atom of ring A to which is attached is C 4 Let R 5 The carbon atom of ring A to which is attached is C 5 Let R 6 The carbon atom of ring A to which is attached is C 6 In this case, it is preferable that the combination of these asymmetric carbon atoms is one selected from the group consisting of the following (a) to (h):

[0305] (a)C 1 (b)C 2 (c)C 3 (d)C 4 (e)C 1 and C 4 (f)C 3 and C 4 (g)C 1 , C 3 and C 4 (h)C 3 , C 4 and C 5

[0306] The general formula (2) described in the fourth embodiment is a compound represented by the general formula (1) above, wherein the C 1 ~C 6 This is an equation with the display added.

[0307] In such cases, the cyclic compound becomes a stereoisomer, which allows for the realization of a more effective fragrance. Furthermore, by producing such a cyclic compound from a plant-derived sugar, a fragrance containing a specific stereoisomer selected from the group consisting of (a) to (h) above at a high purity can be obtained. That is, a fragrance containing a specific stereoisomer at a high purity and having a low content of other stereoisomers can be obtained. Such a fragrance is useful from the viewpoint of realizing a fragrance with excellent safety and efficacy. Furthermore, the complicated manufacturing process associated with the removal of unwanted stereoisomers can be reduced, thereby reducing manufacturing costs.

[0308] The cyclic compound and its derivative according to this embodiment are preferably compounds represented by the general formula (2) and further preferably 3-dehydroquinate, 3-dehydroshikimic acid, shikimic acid, chorismic acid, or prephenic acid. These compounds can be produced from plant-derived sugars and are useful as fragrances. Therefore, by using these compounds produced from plant-derived sugars, it is possible to realize fragrances that are safer and have better efficacy. The structures of these cyclic compounds are represented by the following formulas:

[0309] 3-Dehydroquinate

[0310] [ka]

[0311] 3-Dehydroshikimic acid

[0312] [ka]

[0313] Shikimic acid

[0314] [ka]

[0315] Chorismic acid

[0316] [ka]

[0317] Prephenic acid

[0318] [ka]

[0319] Flavors containing at least one of the above-described cyclic compounds and their derivatives include food flavors, cosmetic flavors, etc. Functions of food flavors include flavoring, aromatizing, flavor correction, sweetness enhancement, sourness / bitterness reduction, appetite stimulation, etc. Applications of cosmetic flavors include perfumes, colognes, toiletries, household products, air fresheners, etc.

[0320] The form of the fragrance may be, for example, a water-soluble liquid, an oil-soluble liquid, an emulsion, or a powder.

[0321] <Method for producing cyclic compound or derivative thereof> The above-mentioned cyclic compound or derivative thereof is produced by a bioprocess using a microorganism and plant-derived sugars as a raw material, i.e., the above-mentioned cyclic compound or derivative thereof is derived from plant-derived sugars and a microorganism. Specific examples of the materials, raw materials, materials used, etc. from which the cyclic compound or its derivatives are derived and the production method can be, for example, the method described in the fourth embodiment. More specifically, the step of preparing a culture solution, as well as the concentration step and isolation and purification step, can be carried out in accordance with the fourth embodiment.

[0322] <Processing into fragrances> The cyclic compound or its derivative produced as described above can be processed as needed to obtain a fragrance. One example of such processing is the addition of an optional component. The fragrance of this embodiment may contain any other component within a range that does not impair the effects of this embodiment.

[0323] Other ingredients include, for example, sugar, condensed milk, wheat flour, shortening, salt, glucose, eggs, butter, margarine, starch syrup, calcium, iron, seasonings, spices, and oils (animal and vegetable oils, mineral oil, ester oil, wax oil, silicone oil, higher alcohols, phospholipids, fatty acids, etc.), surfactants (anionic, cationic, amphoteric, or nonionic surfactants), vitamins (vitamin A group, vitamin B group, folic acid, nicotinic acid, pantothenic acid, biotin, vitamin C group, vitamin D group, vitamin E group, ferulic acid, γ-oryzanol, etc.), ultraviolet absorbers (p-aminobenzoic acid, anthranilic acid, salicylic acid, salicylic acid glucoside, benzotriazole, tetrazole, imidazoline, pyrimidine, dioxane, furan, pyrone, camphor, nucleic acid, allantoin or derivatives thereof, amino acid compounds, shikonin, baicalin, baicalein, berberis Antioxidants (stearic acid esters, nordihydroguaiaretic acid, dibutylhydroxytoluene, butylhydroxyanisole, parahydroxyanisole, propyl gallate, sesamol, sesamolin, gossypol, etc.), thickeners (hydroxyethyl cellulose, ethyl cellulose, carboxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, polyvinyl methacrylate, polyacrylates, carboxyvinyl polymers, gum arabic, gum tragacanth, agar, casein, dextrin, gelatin, pectin, starch, alginic acid or its salts, etc.), humectants (propylene glycol, 1,3-butylene glycol, polyethylene glycol, glycerin, 1,Examples of such additives include 2-pentanediol, hexylene glycol, octylene glycol, chondroitin sulfate or its salts, hyaluronic acid or its salts, sodium lactate, etc.), lower alcohols, polyhydric alcohols, water-soluble polymers, pH adjusters, antiseptics and antifungals, colorants, fragrances, refreshing agents, stabilizers, animal and plant extracts, animal and plant proteins or their decomposition products, animal and plant polysaccharides or their decomposition products, animal and plant glycoproteins or their decomposition products, microbial culture metabolic components, blood flow promoters, anti-inflammatory agents, anti-allergic agents, cell activators, amino acids or their salts, keratolytic agents, astringents, wound healing agents, foaming agents, oral care agents, deodorizing agents, and emulsifiers. These may be used alone or in combination.

[0324] The fragrance of this embodiment has been described above, but specific examples of the fragrance are not limited to those described above and may be any fragrance.

[0325] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. [Example]

[0326] Example I (Examples I-1 to I-4, Comparative Examples I-1 to I-4) In this example, the antimicrobial properties of the composition were evaluated. The components were blended according to the formulations shown in Tables 1 to 4 to obtain the water-soluble additive compositions of each example, specifically the antibacterial compositions. That is, in each example, 98% by mass of protocatechuic acid (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2% by mass of gallic acid were mixed to obtain the antibacterial compositions. On the other hand, in each comparative example, the protocatechuic acid was used as is.

[0327] For each example, the obtained composition was used to prepare aqueous solutions (antibacterial composition blended solutions) with antibacterial composition concentrations of 0.1 mass %, 0.2 mass %, 0.3 mass % and 0.5 mass %. The antibacterial properties of the resulting compositions were evaluated by the following method.

[0328] (Evaluation method) For each example, the test solution adjusted to the respective concentrations described above and the test bacteria were mixed into a bacterial medium containing 1% polyoxyethylene polyoxypropylene alkyl ether. After stirring, the absorbance at 650 nm was measured and used as the initial value. After 24 hours of incubation under aerobic conditions at 37°C, the absorbance at 650 nm was measured again, and the initial value was subtracted from this to determine the turbidity derived from the bacteria. The test results were expressed as a percentage (%), with the absorbance of 0% test sample taken as 100. The test bacteria used were Staphylococcus aureus (Example I-1 and Comparative Example I-1), Escherichia coli (Example I-2 and Comparative Example I-2), Pseudomonas aeruginosa (Example I-3 and Comparative Example I-3), and Candida albicans (yeast, Example I-4 and Comparative Example I-4). The evaluation results are shown in Tables 1 to 4 and in Figures 1 to 4. Figures 1 to 4 are diagrams showing the evaluation results of the antibacterial compositions.

[0329] [Table 1]

[0330] [Table 2]

[0331] [Table 3]

[0332] [Table 4]

[0333] As can be seen from Tables 1 to 4 and Figs. 1 to 4, the compositions obtained in the examples tended to have lower absorbance than those in the comparative examples, and were excellent in antibacterial properties.

[0334] (Examples I-5 to I-7, Comparative Examples I-5 to I-7) The components were blended according to the formulations shown in Tables 5 to 7, and water-soluble additive compositions containing cyclic carboxylic acids were obtained in accordance with Example I-1 or Comparative Example I-1. Here, in Example I-5 and Comparative Example I-5, shikimic acid (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used. In Example I-6 and Comparative Example I-6, 4-hydroxybenzoic acid (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used. In Example I-7 and Comparative Example I-7, 4-aminobenzoic acid (reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used.

[0335] For each example, the obtained composition was used to prepare aqueous solutions (antibacterial composition blended solutions) with antibacterial composition concentrations of 0.1 mass %, 0.2 mass %, 0.3 mass % and 0.5 mass %. The antibacterial properties of the obtained compositions were evaluated in accordance with Example I-1 or Comparative Example I-1 using Staphylococcus aureus as the test bacterial organism. The evaluation results are shown in Tables 5 to 7.

[0336] [Table 5]

[0337] [Table 6]

[0338] [Table 7]

[0339] Example II (Examples II-1 to II-4, Comparative Examples II-1 and II-2) In this example, a water-soluble additive composition was prepared and its solubility characteristics were evaluated, as well as the purity of the cyclic carboxylic acid in the composition.

[0340] (Example II-1) <Production of protocatechuic acid using bioprocesses> Protocatechuic acid was produced by bioprocessing in a 10 L jar fermenter. The medium used was LB medium, to which 10% refined sugar from sugarcane pomace was dissolved.

[0341] <Recovery of protocatechuic acid composition from culture medium through a concentration and purification process> The culture solution obtained by the bioprocess was concentrated by vacuum concentration to a total solids concentration of 15 to 30% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100 to 5000 Pa and a liquid temperature of 30 to 80°C. The concentration level depended on the treatment time, but a concentrated solution with a total solids concentration of 15 to 30% by mass was recovered after 6 to 8 hours of concentration treatment. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and the solution was further cooled to 0°C to room temperature. The crystallized product was recovered by filtration, washed three times with pure water in an amount 20 times the mass of the precipitate, and then dried under reduced pressure to recover a powdery water-soluble additive composition containing protocatechuic acid.

[0342] (Example II-2) After concentrating the culture solution, a composition containing protocatechuic acid was recovered in the same manner as in Example II-1, except that the filtered precipitate was washed four times with pure water in an amount 20 times by mass.

[0343] (Example II-3) After concentrating the culture solution, a composition containing protocatechuic acid was recovered in the same manner as in Example II-1, except that the filtered precipitate was washed twice with pure water in an amount 20 times by mass.

[0344] (Example II-4) After concentrating the culture solution, a composition containing protocatechuic acid was recovered in the same manner as in Example II-1, except that the filtered precipitate was washed once with pure water in an amount 20 times by mass.

[0345] (Comparative Example II-1) A commercially available protocatechuic acid reagent (Tokyo Chemical Industry Co., Ltd.) was prepared.

[0346] (Comparative Example II-2) After concentrating the culture broth, a composition containing protocatechuic acid was recovered in the same manner as in Example II-1, except that the filtered precipitate was not washed.

[0347] (Evaluation method) (cyclic carboxylic acid concentration) The concentration of the cyclic carboxylic acid in each composition was measured by high performance liquid chromatography (HPLC) under the following conditions: Column: COSMOSIL 5C18-AR-II (φ4.6 mm × 250 mm) manufactured by Nacalai Tesque Mobile phase: Water / methanol / perchloric acid = 4 / 1 / 0.0075 (vol / vol / vol) isocratic elution Flow rate: 1mL / mmin Column temperature: 40℃ Detection method: Photodiode array (PDA) detector (210 nm)

[0348] (ion concentration) The compositions obtained in each example were analyzed by ion chromatography to determine Na + , NH4 + , K. + , SO4 2- , PO4 3- , NO2 - , NO3 - and Cl - The concentration of each ion and the total inorganic ion concentration (ppm, excluding hydrogen ions and hydroxyl ions) were measured under the following conditions. Column: (cation) Shim-pack IC-C4 (Shimadzu Corporation), (anion) Shim-pack IC-SA2 (Shimadzu Corporation) Mobile phase: (cation) water / oxalic acid dihydrate = 1000 / 0.315 (mass / mass), (anion) water / sodium bicarbonate / sodium carbonate = 1000 / 1.008 / 0.0636 (mass / mass / mass), isocratic elution for both anions and cations Flow rate: (both cation and anion) 1 mL / mm Column temperature: (cation) 40°C, (anion) 30°C Detection method: Electrical conductivity detector The concentration of each ion was calculated as the ratio (ppm) of the concentration (ppm) of each ion to the concentration (ppm) of the cyclic carboxylic acid in the composition measured by HPLC. The measurement results are shown in Table 8.

[0349] (purity) The purity of the cyclic carboxylic acid in the composition was judged based on the total inorganic ion concentration (excluding hydrogen ions and hydroxyl ions) from the ion concentration measurement results described above, according to the following criteria, and those with the following "◎" and "○" were deemed to have passed. The results are shown in Table 8. ◎: Total inorganic ion amount is 0 to less than 1000 ○: Total inorganic ion amount is 1000 to less than 5000 ×: Total inorganic ion amount is 5000 ppm or more

[0350] (Solubility) For each composition obtained in each example, 50 g of the composition was added to 1 L of pure water adjusted to a liquid temperature of 25°C, and the mixture was stirred with a stirrer for one day. The cyclic carboxylic acid concentration in the supernatant was then measured by HPLC to calculate the solubility. A solubility of 12 g / L or more was deemed acceptable. The measurement results are shown in Table 8.

[0351] [Table 8]

[0352] As can be seen from Table 8, the compositions obtained in each Example had high purity of protocatechuic acid and excellent water solubility of protocatechuic acid.

[0353] (Examples II-5 to II-8, Comparative Examples II-3 and II-4) A water-soluble additive composition containing shikimic acid instead of protocatechuic acid was prepared, and its solubility characteristics were evaluated, as well as the purity of the cyclic carboxylic acid in the composition.

[0354] (Example II-5) <Production of shikimic acid using bioprocesses> Shikimic acid was produced by bioprocessing in a 10 L jar fermenter. The medium used was LB medium, to which 10% refined sugar from sugarcane pomace was dissolved.

[0355] <Recovery of shikimic acid composition from culture medium through a concentration and purification process> The culture solution obtained by the bioprocess was concentrated by vacuum concentration to a total solids concentration of 15 to 30% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100 to 5000 Pa and a liquid temperature of 30 to 80°C. The concentration level depended on the treatment time, but a concentrated solution with a total solids concentration of 15 to 30% by mass was recovered after 6 to 8 hours of concentration treatment. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and the solution was then cooled to 0°C to room temperature. The crystallized product was recovered by filtration, washed three times with pure water in an amount 20 times the mass of the precipitate, and then dried under reduced pressure to recover a powdery water-soluble additive composition containing shikimic acid.

[0356] (Example II-6) After concentrating the culture solution, a composition containing shikimic acid was recovered in the same manner as in Example II-5, except that the filtered precipitate was washed four times with pure water in an amount 20 times by mass.

[0357] (Example II-7) After concentrating the culture solution, a composition containing shikimic acid was recovered in the same manner as in Example II-5, except that the filtered precipitate was washed twice with 20 times the mass of pure water.

[0358] (Example II-8) After concentrating the culture solution, a composition containing shikimic acid was recovered in the same manner as in Example II-5, except that the filtered precipitate was washed once with pure water in an amount 20 times by mass.

[0359] (Comparative Example II-3) A commercially available shikimic acid reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared.

[0360] (Comparative Example II-4) After concentrating the culture broth, a composition containing shikimic acid was recovered in the same manner as in Example II-5, except that the filtered precipitate was not washed.

[0361] (Evaluation method) The compositions obtained in each example were evaluated for cyclic carboxylic acid concentration, ion concentration, purity, and solubility in accordance with the procedures described in Examples II-1 to II-4 and Comparative Examples II-1 and II-2. The results are shown in Table 9.

[0362] [Table 9]

[0363] (Examples II-9 to II-12, Comparative Examples II-5 and II-6) A water-soluble additive composition containing 4-hydroxybenzoic acid instead of protocatechuic acid was prepared, and its solubility characteristics and the purity of the cyclic carboxylic acid in the composition were evaluated.

[0364] (Example II-9) <Production of 4-hydroxybenzoic acid using bioprocesses> 4-Hydroxybenzoic acid was produced by bioprocessing in a 10 L jar fermenter. The medium used was LB medium, to which 10% refined sugar from sugarcane pomace was dissolved.

[0365] <Recovery of 4-hydroxybenzoic acid composition from culture medium through concentration and purification process> The culture solution obtained by the bioprocess was concentrated by vacuum concentration to a total solids concentration of 15 to 30% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100 to 5000 Pa and a liquid temperature of 30 to 80°C. The concentration level depended on the treatment time, but a concentrated solution with a total solids concentration of 15 to 30% by mass was recovered after 6 to 8 hours of concentration treatment. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and the solution was then cooled to 0°C to room temperature. The crystallized product was recovered by filtration, washed three times with pure water in an amount 20 times the mass of the precipitate, and then dried under reduced pressure to recover a powdery water-soluble additive composition containing 4-hydroxybenzoic acid.

[0366] (Example II-10) After concentrating the culture solution, a composition containing 4-hydroxybenzoic acid was recovered in the same manner as in Example II-9, except that the filtered precipitate was washed four times with pure water in an amount 20 times by mass.

[0367] (Example II-11) After concentrating the culture solution, a composition containing 4-hydroxybenzoic acid was recovered in the same manner as in Example II-9, except that the filtered precipitate was washed twice with pure water in an amount 20 times by mass.

[0368] (Example II-12) After concentrating the culture solution, a composition containing 4-hydroxybenzoic acid was recovered in the same manner as in Example II-9, except that the filtered precipitate was washed once with pure water in an amount 20 times by mass.

[0369] (Comparative Example II-5) A commercially available 4-hydroxybenzoic acid reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared.

[0370] (Comparative Example II-6) After concentrating the culture broth, a composition containing 4-hydroxybenzoic acid was recovered in the same manner as in Example II-9, except that the filtered precipitate was not washed.

[0371] (Evaluation method) The compositions obtained in each example were evaluated for cyclic carboxylic acid concentration, ion concentration, purity, and solubility in accordance with the procedures described in Examples II-1 to II-4 and Comparative Examples II-1 and II-2. The results are shown in Table 10.

[0372] [Table 10]

[0373] (Examples II-13 to II-16, Comparative Examples II-7 and II-8) A water-soluble additive composition containing 4-aminobenzoic acid instead of protocatechuic acid was prepared, and its solubility characteristics were evaluated, as well as the purity of the cyclic carboxylic acid in the composition.

[0374] (Example II-13) <Production of 4-aminobenzoic acid using bioprocesses> 4-Aminobenzoic acid was produced by bioprocessing in a 10 L jar fermenter. The culture medium used was LB medium, to which 10% refined sugar from sugarcane pomace was dissolved.

[0375] <Recovery of 4-aminobenzoic acid composition from culture medium through a concentration and purification process> The culture solution obtained by the bioprocess was concentrated by vacuum concentration to a total solids concentration of 15 to 30% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100 to 5000 Pa and a liquid temperature of 30 to 80°C. The concentration level depended on the treatment time, but a concentrated solution with a total solids concentration of 15 to 30% by mass was recovered after 6 to 8 hours of concentration treatment. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and the solution was then cooled to 0°C or room temperature. The crystallized product was recovered by filtration, washed three times with pure water in an amount 20 times the mass of the precipitate, and then dried under reduced pressure to recover a powdery water-soluble additive composition containing 4-aminobenzoic acid.

[0376] (Example II-14) After concentrating the culture solution, a composition containing 4-aminobenzoic acid was recovered in the same manner as in Example II-13, except that the filtered precipitate was washed four times with pure water in an amount 20 times by mass.

[0377] (Example II-15) After concentrating the culture solution, a composition containing 4-aminobenzoic acid was recovered in the same manner as in Example II-13, except that the filtered precipitate was washed twice with pure water in an amount 20 times by mass.

[0378] (Example II-16) After concentrating the culture solution, a composition containing 4-aminobenzoic acid was recovered in the same manner as in Example II-13, except that the filtered precipitate was washed once with pure water in an amount 20 times by mass.

[0379] (Comparative Example II-7) A commercially available 4-aminobenzoic acid reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared.

[0380] (Comparative Example II-8) After concentrating the culture broth, a composition containing 4-aminobenzoic acid was recovered in the same manner as in Example II-13, except that the filtered precipitate was not washed.

[0381] (Evaluation method) The compositions obtained in each example were evaluated for cyclic carboxylic acid concentration, ion concentration, purity, and solubility in accordance with the procedures described in Examples II-1 to II-4 and Comparative Examples II-1 and II-2. The results are shown in Table 11.

[0382] [Table 11]

[0383] Example III (Examples III-1 to III-4, Comparative Example III-1) In the present examples, compositions were prepared and evaluated for their moisturizing and antibacterial properties. The methods for producing and evaluating the compositions of each example are as follows.

[0384] (Example III-1) Washing 1 <Production of protocatechuic acid using bioprocesses> Protocatechuic acid was produced by bioprocessing in a 10 L jar fermenter. The medium used was LB medium, to which 10% refined sugar from sugarcane pomace was dissolved.

[0385] <Recovery of protocatechuic acid composition from culture medium through a concentration and purification process> The culture solution obtained by the bioprocess was concentrated by vacuum concentration to a total solids concentration of 30 to 50% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100 to 5000 Pa and a liquid temperature of 30 to 80°C. Although the degree of concentration depends on the treatment time, a concentrated solution with a total solids concentration of 30 to 50% by mass was recovered after 6 to 8 hours of concentration treatment. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and the solution was further cooled to 0°C to room temperature. The crystallized product was recovered by filtration, washed once with pure water in an amount 20 times the mass of the precipitate, and then dried under reduced pressure to recover a powdery water-soluble additive composition containing protocatechuic acid.

[0386] (Example III-2) Washing 2 After concentrating the culture solution, a composition containing protocatechuic acid was recovered in the same manner as in Example III-1, except that the filtered precipitate was washed twice with pure water in an amount 20 times by mass.

[0387] (Example III-3) Washing 3 After concentrating the culture solution, a composition containing protocatechuic acid was recovered in the same manner as in Example III-1, except that the filtered precipitate was washed three times with pure water in an amount 20 times by mass of the precipitate.

[0388] (Example III-4) Washing 4 After concentrating the culture solution, a composition containing protocatechuic acid was recovered in the same manner as in Example III-1, except that the filtered precipitate was washed four times with pure water in an amount 20 times by mass.

[0389] (Comparative Example III-1) Reagent A commercially available protocatechuic acid reagent (Tokyo Chemical Industry Co., Ltd.) was prepared.

[0390] (amino acid concentration) The concentration of each amino acid in the composition obtained in each example was measured by high performance liquid chromatography (HPLC, post-column fluorescence detection using ortho-phthalaldehyde as a reaction reagent, column: Shim-pack Amino-Na, manufactured by Shimadzu Corporation). The results are shown in Table 12.

[0391] (PCA purity) The purity of the cyclic carboxylic acid in the composition obtained in each example was measured. First, the concentration of cyclic carboxylic acid in the composition obtained in each example was measured by high performance liquid chromatography (HPLC) under the following measurement conditions. Column: COSMOSIL 5C18-AR-II (φ4.6 mm × 250 mm) manufactured by Nacalai Tesque Mobile phase: Water / methanol / perchloric acid = 4 / 1 / 0.0075 (vol / vol / vol) isocratic elution Flow rate: 1mL / mmin Column temperature: 40℃ Detection method: Photodiode array (PDA) detector (210 nm) The total inorganic ion concentration (ppm) was measured by ion chromatography, where the concentration of each ion was calculated as the ratio (ppm) of the concentration (ppm) of each ion to the concentration (ppm) of cyclic carboxylic acid in the composition measured by HPLC. The purity of the cyclic carboxylic acid in the composition was determined based on the measured total inorganic ion concentration according to the following criteria. The results are shown in Table 12. ◎: Total inorganic ion amount is 0 to less than 1000 ○: Total inorganic ion amount is 1000 to less than 5000 ×: Total inorganic ion amount is 5000 ppm or more

[0392] (moisturizing properties) A 2.0% by mass aqueous solution of the water-soluble additive composition obtained in each example was prepared and used as a test solution. The moisture content of the stratum corneum was measured immediately after application of the test solution to the skin and 15 minutes later. The test results were expressed as a percentage, with the moisture content of the stratum corneum immediately after application being taken as 100. The evaluation criteria are as follows. Products with evaluation results of "◎" and "○" were considered to have passed. ◎: The reduction in stratum corneum moisture content is less than 10% 〇: The reduction in stratum corneum moisture is 10% or more but less than 50% ×: The reduction in stratum corneum moisture is 50% or more. The evaluation results are also shown in Table 12.

[0393] (Antibacterial) A 2.0% by mass aqueous solution of the water-soluble additive composition obtained in each example was prepared as a test solution. The test solution and test bacteria were mixed in a bacterial culture medium containing 1% polyoxyethylene polyoxypropylene alkyl ether. After stirring, the absorbance at 650 nm was measured and used as the initial value. After 24 hours of cultivation under aerobic conditions at 37°C, the absorbance at 650 nm was measured again, and the initial value was subtracted from this to determine the turbidity derived from the bacteria. The test results were expressed as a percentage, with the absorbance of 0% test sample taken as 100. Four types of test bacteria were used: Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans. The evaluation criteria are as follows: Evaluation results of "A" and "B" were considered to be acceptable. ◎: Absorbance is less than 10% ○: Absorbance is 10% or more but less than 50% ×: absorbance is 50% or more The evaluation results are also shown in Table 12.

[0394] [Table 12]

[0395] As can be seen from Table 12, the compositions obtained in each example were excellent in moisturizing properties and antibacterial properties.

[0396] (Examples III-5 to III-8, Comparative Example III-2) In this example, compositions containing shikimic acid instead of protocatechuic acid were prepared and evaluated for their moisturizing and antibacterial properties. The methods for producing and evaluating the compositions of each example are as follows.

[0397] (Example III-5) Washing 1 <Production of shikimic acid using bioprocesses> Shikimic acid was produced by bioprocessing in a 10 L jar fermenter. The medium used was LB medium, to which 10% refined sugar from sugarcane pomace was dissolved.

[0398] <Recovery of shikimic acid composition from culture medium through a concentration and purification process> The culture solution obtained by the bioprocess was concentrated by vacuum concentration to a total solids concentration of 30 to 50% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100 to 5000 Pa and a liquid temperature of 30 to 80°C. Although the concentration level depends on the treatment time, a concentrated solution with a total solids concentration of 30 to 50% by mass was recovered after 6 to 8 hours of concentration treatment. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and the solution was further cooled to 0°C to room temperature. The crystallized product was recovered by filtration, washed once with pure water in an amount 20 times the mass of the precipitate, and then dried under reduced pressure to recover a powdery water-soluble additive composition containing shikimic acid.

[0399] (Example III-6) Washing 2 After concentrating the culture solution, a composition containing shikimic acid was recovered in the same manner as in Example III-5, except that the filtered precipitate was washed twice with 20 times the mass of pure water.

[0400] (Example III-7) Washing 3 After concentrating the culture solution, a composition containing shikimic acid was recovered in the same manner as in Example III-5, except that the filtered precipitate was washed three times with pure water in an amount 20 times by mass of the precipitate.

[0401] (Example III-8) Washing 4 After concentrating the culture solution, a composition containing shikimic acid was recovered in the same manner as in Example III-5, except that the filtered precipitate was washed four times with pure water in an amount 20 times by mass.

[0402] (Comparative Example III-2) Reagent A commercially available shikimic acid reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared.

[0403] (Evaluation method) The compositions obtained in each example were evaluated for amino acid concentration, purity, moisturizing property, and antibacterial property in accordance with the above-mentioned Examples III-1 to III-4 and Comparative Example III-1. The results are shown in Table 13.

[0404] [Table 13]

[0405] (Examples III-9 to III-12, Comparative Example III-3) In this example, compositions containing 4-hydroxybenzoic acid instead of protocatechuic acid were prepared and evaluated for their moisturizing and antibacterial properties. The methods for producing and evaluating the compositions of each example are as follows.

[0406] (Example III-9) Washing 1 <Production of 4-hydroxybenzoic acid using bioprocesses> 4-Hydroxybenzoic acid was produced by bioprocessing in a 10 L jar fermenter. The medium used was LB medium, to which 10% refined sugar from sugarcane pomace was dissolved.

[0407] <Recovery of 4-hydroxybenzoic acid composition from culture medium through concentration and purification process> The culture solution obtained by the bioprocess was concentrated by vacuum concentration to a total solids concentration of 30 to 50% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100 to 5000 Pa and a liquid temperature of 30 to 80°C. The concentration level depended on the treatment time, but a concentrated solution with a total solids concentration of 30 to 50% by mass was recovered after 6 to 8 hours of concentration treatment. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and the solution was then cooled to 0°C or room temperature. The crystallized product was recovered by filtration, washed once with pure water in an amount 20 times the mass of the precipitate, and then dried under reduced pressure to recover a powdery water-soluble additive composition containing 4-hydroxybenzoic acid.

[0408] (Example III-10) Washing 2 After concentrating the culture solution, a composition containing 4-hydroxybenzoic acid was recovered in the same manner as in Example III-9, except that the filtered precipitate was washed twice with pure water in an amount 20 times by mass.

[0409] (Example III-11) Washing 3 After concentrating the culture solution, a composition containing 4-hydroxybenzoic acid was recovered in the same manner as in Example III-9, except that the filtered precipitate was washed three times with pure water in an amount 20 times by mass.

[0410] (Example III-12) Washing 4 After concentrating the culture solution, a composition containing 4-hydroxybenzoic acid was recovered in the same manner as in Example III-9, except that the filtered precipitate was washed four times with pure water in an amount 20 times by mass.

[0411] (Comparative Example III-3) Reagent A commercially available 4-hydroxybenzoic acid reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared.

[0412] (Evaluation method) The compositions obtained in each example were evaluated for amino acid concentration, purity, moisturizing property, and antibacterial property in accordance with the above-mentioned Examples III-1 to III-4 and Comparative Example III-1. The results are shown in Table 14.

[0413] [Table 14]

[0414] (Examples III-13 to III-16, Comparative Example III-4) In this example, compositions containing 4-aminobenzoic acid instead of protocatechuic acid were prepared and evaluated for their moisturizing and antibacterial properties. The methods for producing and evaluating the compositions of each example are as follows.

[0415] (Example III-13) Washing 1 <Production of 4-aminobenzoic acid using bioprocesses> 4-Aminobenzoic acid was produced by bioprocessing in a 10 L jar fermenter. The culture medium used was LB medium, to which 10% refined sugar from sugarcane pomace was dissolved.

[0416] <Recovery of 4-aminobenzoic acid composition from culture medium through a concentration and purification process> The culture solution obtained by the bioprocess was concentrated by vacuum concentration to a total solids concentration of 30 to 50% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100 to 5000 Pa and a liquid temperature of 30 to 80°C. The concentration level depended on the treatment time, but a concentrated solution with a total solids concentration of 30 to 50% by mass was recovered after 6 to 8 hours of concentration treatment. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and the solution was then cooled to 0°C or room temperature. The crystallized product was recovered by filtration, washed once with pure water in an amount 20 times the mass of the precipitate, and then dried under reduced pressure to recover a powdery water-soluble additive composition containing 4-aminobenzoic acid.

[0417] (Example III-14) Washing 2 After concentrating the culture solution, a composition containing 4-aminobenzoic acid was recovered in the same manner as in Example III-13, except that the filtered precipitate was washed twice with 20 times the mass of pure water.

[0418] (Example III-15) Washing 3 After concentrating the culture solution, a composition containing 4-aminobenzoic acid was recovered in the same manner as in Example III-13, except that the filtered precipitate was washed three times with pure water in an amount 20 times by mass.

[0419] (Example III-16) Washing 4 After concentrating the culture solution, a composition containing 4-aminobenzoic acid was recovered in the same manner as in Example III-13, except that the filtered precipitate was washed four times with pure water in an amount 20 times by mass.

[0420] (Comparative Example III-4) Reagent A commercially available 4-aminobenzoic acid reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared.

[0421] (Evaluation method) The compositions obtained in each example were evaluated for amino acid concentration, purity, moisturizing property, and antibacterial property in accordance with the above-mentioned Examples III-1 to III-4 and Comparative Example III-1. The results are shown in Table 15.

[0422] [Table 15]

[0423] Example VI (Example VI-1) <Production of 3,4-dihydroxybenzoic acid using bioprocesses> The culture solution obtained through a bioprocess using plant-derived sugars and microorganisms was concentrated under reduced pressure to a total solids concentration of 15-30% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100-5000 Pa and a liquid temperature of 30-80°C. The degree of concentration depended on the processing time, but after 6-8 hours of concentration, a concentrated solution with a total solids concentration of 15-30% by mass was recovered. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and it was then cooled to 0°C or room temperature. The crystallized product was collected by filtration, washed appropriately, and then dried under reduced pressure to recover high-purity 3,4-dihydroxybenzoic acid with a purity of 99% or more.

[0424] The recovered high-purity 3,4-dihydroxybenzoic acid, i.e., cyclic compound, was free of petroleum-derived impurities.

[0425] (Example VI-2) <Production of shikimic acid using bioprocesses> Activated carbon was added to a culture solution obtained through a bioprocess using plant-derived sugars and microorganisms, and the solution was treated with activated carbon. Next, a column packed with ion exchange resin was prepared and treated with 2 mol / L aqueous sodium hydroxide solution. The ion exchange resin used was a strongly basic anion exchange resin. Pure water was passed through the column until the effluent became neutral. Then, the activated carbon-treated raw liquid was passed through the column, followed by pure water. A 2 mol / L aqueous acetic acid solution was then passed through as the eluent, and the acidic fraction was recovered. The shikimic acid concentration was measured for each recovered fraction, and the eluent was passed through until the elution of shikimic acid was complete. Solids were precipitated from the eluent by concentration crystallization, yielding solid shikimic acid. Concentration crystallization refers to a process in which a concentration treatment and a cooling crystallization treatment are sequentially performed to precipitate solid shikimic acid.

[0426] The recovered high-purity shikimic acid, i.e., cyclic compound, was free of petroleum-derived impurities.

[0427] Example V (Example V-1) <Production of 3,4-dihydroxybenzoic acid using bioprocesses> The culture solution obtained through a bioprocess using plant-derived sugars and microorganisms was concentrated under reduced pressure to a total solids concentration of 15-30% by mass. The concentration was performed using vacuum distillation equipment at a reduced pressure of 100-5000 Pa and a liquid temperature of 30-80°C. The degree of concentration depended on the processing time, but after 6-8 hours of concentration, a concentrated solution with a total solids concentration of 15-30% by mass was recovered. Hydrochloric acid was added to this concentrated solution to adjust the pH to 4 or less, and it was then cooled to 0°C or room temperature. The crystallized product was collected by filtration, washed appropriately, and then dried under reduced pressure to recover high-purity 3,4-dihydroxybenzoic acid with a purity of 99% or more.

[0428] The recovered high-purity 3,4-dihydroxybenzoic acid, i.e., cyclic compound, was free of petroleum-derived impurities.

[0429] (Example V-2) <Production of shikimic acid using bioprocesses> Activated carbon was added to a culture solution obtained through a bioprocess using plant-derived sugars and microorganisms, and the solution was treated with activated carbon. Next, a column packed with ion exchange resin was prepared and treated with 2 mol / L aqueous sodium hydroxide solution. The ion exchange resin used was a strongly basic anion exchange resin. Pure water was passed through the column until the effluent became neutral. Then, the activated carbon-treated raw liquid was passed through the column, followed by pure water. A 2 mol / L aqueous acetic acid solution was then passed through as the eluent, and the acidic fraction was recovered. The shikimic acid concentration was measured for each recovered fraction, and the eluent was passed through until the elution of shikimic acid was complete. Solids were precipitated from the eluent by concentration crystallization, yielding solid shikimic acid. Concentration crystallization refers to a process in which a concentration treatment and a cooling crystallization treatment are sequentially performed to precipitate solid shikimic acid.

[0430] The recovered high-purity shikimic acid, i.e., cyclic compound, was free of petroleum-derived impurities.

Claims

1. a cyclic carboxylic acid; A water-soluble additive composition comprising inorganic ions (excluding hydrogen ions and hydroxyl ions), the cyclic carboxylic acid is at least one selected from the group consisting of protocatechuic acid, shikimic acid, 4-hydroxybenzoic acid, and 4-aminobenzoic acid; the inorganic ions are Na + , NH 4 + , K + , SO 4 2− , PO 4 3− , NO 2 − , NO 3 − and Cl − ; The water-soluble additive composition contains the cyclic carboxylic acid in an amount of 95% by mass or more and 99.97% by mass or less based on the entire water-soluble additive composition, A water-soluble additive composition having a total inorganic ion content of 300 ppm or more and 5059 ppm or less based on the cyclic carboxylic acid.

2. A water-soluble additive composition as described in claim 1, wherein the total inorganic ion content is 300 ppm or more and 5000 ppm or less relative to the cyclic carboxylic acid.

3. 3. The water-soluble additive composition according to claim 2, wherein the cyclic carboxylic acid is one or more selected from the group consisting of protocatechuic acid, shikimic acid, and 4-aminobenzoic acid.

4. The water-soluble additive composition according to any one of claims 1 to 3, wherein the content of the cyclic carboxylic acid in the water-soluble additive composition is 95% by mass or more and 99.9% by mass or less based on the total mass of the water-soluble additive composition.

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