Ultrafine bubble product and method for generating ultrafine bubbles

Abstract

The present invention provides an ultrafine bubble (UFB) generator and a UFB generation method. The present invention also provides a UFB-containing liquid and a method for producing the UFB-containing liquid.　The present invention prepares a UFB generator by combining the components (A), (B) and (C) described below. (A) a sophorolipid that contains an acid type sophorolipid and a lactone type sophorolipid at a ratio (mass ratio) of from 78:22 to 100:0 (B) a free fatty acid or a salt thereof (C) a gas generation component

Description

[Technical field]

[0001] The present invention relates to an ultra-fine bubble product and a method for generating ultra-fine bubbles. The present invention also relates to a liquid containing ultra-fine bubbles and a method for producing the same. [Background technology]

[0002] Fine bubbles, which are microscopic bubbles with a diameter of 100 μm or less, have cleaning, catalytic, sterilizing and disinfecting effects, deodorizing, microparticle adsorption, bioactivation, and friction reduction effects, and are used in many fields by utilizing these effects. Specifically, for example, in the environmental field, water purification and improvement of the living environment of living things by supplying oxygen gas to closed water bodies such as lakes and marshes, in the industrial field, wastewater and waste liquid treatment, cleaning, combustion improvement, and separation treatment, in the food field, sterilization, purification and cleaning of food, and freshness preservation, in the agricultural field, plant growth by application to agricultural water and hydroponic cultivation, in the fishery field, aquaculture and freshness preservation, in the medical field, disease diagnosis and application to medicine by introduction into contrast agents, and in the beauty field, relaxation by application to baths, and their usefulness has been pointed out in many situations (see Non-Patent Document 1, etc.).

[0003] Among fine bubbles, ultrafine bubbles with a diameter of less than 1 μm are called ultrafine bubbles according to the International Organization for Standardization (ISO) standard. Unlike microbubbles with a diameter of 1 μm or more, ultrafine bubbles are characterized by staying (stagnating) in water for a long period of time. In addition, since ultrafine bubbles have characteristics such as being electrically charged, they have a high cleaning power without using detergents or chemicals. For this reason, their application in the cleaning field, such as cleaning toilets at highway service areas, removing salt from bridges, and finishing cleaning of resin processed products, has already entered the practical stage. In addition, washing machines that utilize ultrafine bubbles are also on the market. Furthermore, due to the highly functional catalytic effect and sterilization and disinfection effects of ultrafine bubbles, they are expected to be applied in the medical and pharmaceutical fields, and the food and drinking water fields (Non-Patent Document 1, etc.).

[0004] Ultrafine bubbles are generally generated using a bubble generator, and there are several methods for generating fine bubbles by ejecting gas from small holes into a liquid containing a surfactant (surfactant-added micropore type), dissolving gas under pressure (pressure dissolution type), and swirling or shearing gas (swirling flow type / shear type). On the other hand, a method for generating bubbles without using a device is known in which bubbles are generated by combining carbonates and acids. Bath salts using this principle are also sold, but the bubbles generated from these preparations are called microbubbles or millibubbles (for example, Patent Document 1, etc.). In addition, a fine bubble generation promoter has been proposed to promote the generation of fine bubbles equivalent to ultrafine bubbles (Patent Documents 2 and 3), but both are supplied to a bubble generator and used, and do not propose a method for generating bubbles without using a device. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2015-071550 A [Patent Document 2] JP 2016-123925 A [Patent Document 3] WO2018 / 097019 [Non-patent literature]

[0006] [Non-Patent Document 1] Yoshihiro Arai, "Accelerating Industrialization of Fine Bubble Technology," ARC Report, November 2016, https: / / arc.asahi-kasei.co.jp / report / arc_report / pdf / rs-1007.pdf Summary of the Invention [Problem to be solved by the invention]

[0007] As described above, there has been no known method for generating fine bubbles equivalent to ultrafine bubbles without using a bubble generator. Therefore, an object of the present invention is to provide an ultrafine bubble product capable of generating fine bubbles equivalent to ultrafine bubbles. Another object of the present invention is to provide a method for generating ultra-fine bubbles. A further object of the present invention is to provide a liquid containing ultra-fine bubbles and a method for producing the same. [Means for solving the problem]

[0008] As a result of extensive research to solve the above-mentioned problems, the inventors have found that by using, in addition to a gas-generating component, (a) a sophorolipid containing an acid-type sophorolipid and a lactone-type sophorolipid in a mass ratio of 78:22 to 100:0, and (b) a fatty acid or a salt thereof, it is possible to generate fine bubbles equivalent to ultrafine bubbles in water. The present invention has been completed based on these findings and through further research, and has the following embodiments. Hereinafter, fine bubbles equivalent to ultrafine bubbles may be abbreviated as "UFB" and sophorolipids as "SL."

[0009] (I) UFB product (I-1) A UFB product comprising the following (A), (B) and (C) in combination: (A) an SL containing an acid-type SL and a lactone-type SL in a ratio of 78:22 to 100:0 (mass ratio); (B) Free fatty acid or its salt (C) Gas generating components. (I-2) The UFB product according to (I-1), wherein (C) is at least one selected from the group consisting of a carbon dioxide gas generating component, an oxygen gas generating component, a hydrogen gas generating component, and a chlorine gas generating component. (I-3) The UFB product according to (I-2), wherein the carbon dioxide gas generating component is a carbonate or bicarbonate salt, or a combination thereof with its counterpart; the oxygen gas generating component is hydrogen peroxide, or a combination thereof with its counterpart; the hydrogen gas generating component is a hydride salt, a borohydride salt, or hydrochloric acid, or a combination thereof with its counterpart; or the chlorine gas generating component is a hypochlorite salt, or a combination thereof with its counterpart. (I-4) The UFB product according to any one of (I-1) to (I-3), wherein the free fatty acid of (B) is a fatty acid having 12 to 20 carbon atoms. (I-5) A UFB product according to any one of (I-1) to (I-4), which is a blend of (A), (B) and (C), or a combination in which at least (C) is packaged separately from (A) and (B). (I-6) The UFB product according to any one of (I-1) to (I-5), which is used by adding to water having a hardness of 30 to 200 mg / L, preferably 50 to 200 mg / L. (I-7) The UFB product according to (I-6), in which (A) is used at a concentration of 0.005% by mass or more, preferably 0.005 to 0.4% by mass, and (B) is used at a concentration of 0.0001% by mass or more, preferably 0.0001 to 0.3% by mass, relative to the water. (I-8) The UFB product described in (I-7), in which (C) is used so that the concentration of the gas-generating main body relative to the water is 0.1% by mass or more, preferably 0.1 to 20% by mass. (I-9) The UFB product according to any one of (I-1) to (I-8), which generates fine bubbles having a scattering intensity of 10,000 cps or more, preferably 30,000 cps or more, and an average number particle size of less than 1,000 nm, preferably 500 nm or less, in water having a hardness of 30 to 200 mg / L. (I-10) A UFB product according to any one of (I-1) to (I-9), which is a cleaning agent, a bath additive, a cosmetic, a mouthwash, a gargle, a texture improver, a food or drink, a plant growth promoter, a fish and shellfish growth promoter, or a disinfectant.

[0010] (II) UFB generation method (II-1)(A) adding the following components (A), (B) and (C) to water having a hardness of 30 to 200 mg / L, preferably 50 to 200 mg / L, and allowing these three components to coexist in the water; (a) A process for generating microscopic bubbles in the water A method for generating UFB comprising: (A) an SL containing an acid-type SL and a lactone-type SL in a ratio of 78:22 to 100:0 (mass ratio); (B) Free fatty acid or its salt (C) Gas generating components. (II-2) The method for generating UFBs according to (II-1), wherein the fine bubbles generated in the step (i) have a scattering intensity of 10,000 cps or more, preferably 30,000 cps or more; and an average particle size by number of less than 1,000 nm, preferably 500 nm or less. (II-3) The method for producing UFB described in (II-1) or (II-2), wherein (C) is at least one selected from the group consisting of a carbon dioxide gas generating component, an oxygen gas generating component, a hydrogen gas generating component, and a chlorine gas generating component. (II-4) A method for generating UFB according to (II-3), in which the carbon dioxide gas generating component is a carbonate or bicarbonate, or a combination with its counterpart; the oxygen gas generating component is a combination with hydrogen peroxide, or a combination with its counterpart; the hydrogen gas generating component is a combination with a hydride, a borohydride, or hydrochloric acid, or a combination with its counterpart; or the chlorine gas generating component is a combination with a hypochlorite, or a combination with its counterpart. (II-5) A method for producing UFB according to any one of (II-1) to (II-4), characterized in that in the step (a), (A) and (B) are added to water so that the concentration of (A) in the water is 0.005% by mass or more, preferably 0.005 to 0.4% by mass, and the concentration of (B) in the water is 0.0001% by mass or more, preferably 0.0001 to 0.3% by mass. (II-6) A method for producing UFB as described in (II-4) or (II-5), characterized in that in the step (a), (C) is added to water so that the concentration of (C) in the water becomes 0.1 mass% or more, preferably 0.1 to 20 mass%, as the concentration of the gas generating body. (II-7) A method for generating UFBs according to any one of (II-1) to (II-6), wherein the step (i) is a step of generating fine bubbles in water without introducing gas from the outside.

[0011] (III) UFB-containing liquid (III-1) A UFB-containing liquid containing the following (A), (B), (c) and (d): (A) an SL containing an acid-type SL and a lactone-type SL in a ratio of 78:22 to 100:0 (mass ratio); (B) a free fatty acid or a salt thereof, (c) fine bubbles having an average number particle diameter of less than 1000 nm, formed from at least one gas selected from the group consisting of carbon dioxide gas, oxygen gas, hydrogen gas, and chlorine gas; and (d) Water. (III-2) The UFB-containing liquid according to (III-1), in which the average number particle size of the fine bubbles is 500 nm or less and the scattering intensity is 10,000 cps or more, preferably 30,000 cps or more. (III-3) The UFB-containing liquid according to (III-1) or (III-2), in which the concentration of (A) is 0.005% by mass or more, preferably 0.005 to 0.4% by mass, and the concentration of (B) is 0.0001% by mass or more, preferably 0.0001 to 0.3% by mass. (III-4) The UFB-containing liquid according to any one of (III-1) to (III-3), wherein (d) is water having a hardness of 30 to 200 mg / L, preferably 50 to 200 mg / L.

[0012] (IV) Method for producing UFB-containing liquid (IV-1)(A) adding the following components (A), (B) and (C) to water having a hardness of 30 to 200 mg / L, preferably 50 to 200 mg / L, and allowing these three components to coexist in the water; (a) A process for generating microscopic bubbles in the water A method for producing a UFB-containing liquid comprising: (A) an SL containing an acid-type SL and a lactone-type SL in a ratio of 78:22 to 100:0 (mass ratio); (B) Free fatty acid or its salt (C) Gas generating components. (IV-2) The production method according to (IV-1), wherein the fine bubbles generated in the step (i) have a scattering intensity of 10,000 cps or more, preferably 30,000 cps or more, and an average number particle size of less than 1,000 nm, preferably 500 nm or less. (IV-3) The production method according to (IV-1) or (IV-2), wherein (C) is at least one selected from the group consisting of a carbon dioxide gas generating component, an oxygen gas generating component, a hydrogen gas generating component, and a chlorine gas generating component. (IV-4) The method according to (IV-3), wherein the carbon dioxide gas generating component is a carbonate or bicarbonate, or a combination with its counterpart; the oxygen gas generating component is hydrogen peroxide, or a combination with its counterpart; the hydrogen gas generating component is a hydride, a borohydride, or hydrochloric acid, or a combination with its counterpart; or the chlorine gas generating component is a hypochlorite, or a combination with its counterpart. (IV-5) The method according to any one of (IV-1) to (IV-4), characterized in that in the step (a), (A) and (B) are added to water so that the concentration of (A) in the water is 0.005% by mass or more, preferably 0.005 to 0.4% by mass, and the concentration of (B) in the water is 0.0001% by mass or more, preferably 0.0001 to 0.3% by mass. (IV-6) The production method described in (IV-4) or (IV-5), characterized in that in the step (a), (C) is added to water so that the concentration of (C) in the water becomes 0.1 mass% or more, preferably 0.1 to 20 mass%, as the concentration of the gas-generating main body. (IV-7) The production method according to any one of (IV-1) to (IV-6), wherein the step (i) is a step of generating microbubbles in water without introducing a gas from the outside. Effect of the Invention

[0013] According to the UFB product and UFB production method of the present invention, UFB can be produced in water without using a bubble generator. Also, according to the UFB production method and UFB-containing liquid production method of the present invention, UFB-containing liquid can be produced and obtained without using a bubble generator. The UFB-containing liquid thus obtained contains fine bubbles having an average particle size of less than 1000 nm in a relatively stable manner, and therefore can exert the effects attributable to the ultra-fine bubbles for a relatively long period of time. [Brief description of the drawings]

[0014] [Figure 1] The results of Experimental Example 13, which was performed with a surfactant concentration of 0.01% by mass, are shown below. The relationship between each line in Figure 1 and the surfactant used is as follows (same as in Figure 2): -■-: SL-containing composition 1, -△-: alkyl polyoxyethylene sodium sulfate, -◇-: dimethyl didecyl ammonium chloride, -◆-: benzalkonium chloride, -×-: lauryl dimethyl amino acetate betaine, -+-: lauryl dimethyl amine oxide, -●-: POE lauryl ether, -○-: POE stearyl ether (6EO). [Diagram 2] The results of Experimental Example 13, which was carried out with a surfactant concentration of 0.05% by mass, are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Definition of UFB and how to measure it Ultra-fine bubbles are defined as bubbles with a diameter of less than 1 μm (ISO 20480-1:2017 Fine bubble technology).

[0016] The UFBs targeted by the present invention are microbubbles having the above-mentioned bubble diameter. The bubble diameter of the microbubbles can be measured using a measuring device (dynamic light scattering photometer) based on the principle of dynamic light scattering. Specifically, when the particle diameter of bubbles contained in a test sample (liquid) is measured, if the average number particle diameter is less than 1000 nm, the test sample can be determined to contain UFBs. The average number particle diameter of UFBs may be less than 1000 nm, and the lower limit is not particularly limited. UFBs can be classified into microbubbles having an average number particle diameter of less than 50 to 200 nm, microbubbles having an average number particle diameter of less than 200 to 500 nm, and microbubbles having an average number particle diameter of less than 500 to 1000 nm. Microbubbles having an average number particle diameter of 500 nm or less are preferable. These samples (liquids) can be used in various fields (environmental, industrial, agricultural, fisheries, medical and pharmaceutical, cosmetics, food and beverage, etc.) according to the functions that they have depending on the bubble size. In the following description, the term "particle size" or "bubble size" means the average number particle size.

[0017] In order for a liquid having such fine bubbles (UFB) with a bubble diameter of less than 1000 nm to effectively exert its function, it is desirable to contain the UFB in a predetermined concentration in the liquid. The UFB in the liquid undergoes Brownian motion dependent on the particle diameter. For this reason, when a liquid containing UFB is irradiated with laser light (He-Ne specification) and the scattered light that emerges is detected by a dynamic light scattering photometer, the scattering intensity dependent on the Brownian motion of the UFB particles can be measured. For this reason, the ratio (concentration) of UFB contained in a liquid can be evaluated by measuring the scattering intensity (cps) of the UFB in the liquid containing UFB. The specific measurement method and measurement conditions are as described in Experimental Example 1. As described later, the scattering intensity of the UFB in the liquid containing UFB can be evaluated by subtracting the scattering intensity caused by particles other than UFB from the scattering intensity of the liquid containing UFB. The scattering intensity of the UFB is not limited, but is preferably 5000 cps or more, more preferably 10000 cps or more, and particularly preferably 30000 cps or more. The upper limit of the scattering intensity of UFB is not particularly limited, but is limited to 100,000,000 cps.

[0018] In addition, the autocorrelation function is obtained from the scattered light obtained by the above method by the photon correlation method, and the diffusion coefficient indicating the Brownian motion speed, as well as the particle size and particle size distribution, can be obtained by using the cumulant method and histogram method analysis. In the present invention, the particle size of UFB can be measured and evaluated according to the method and conditions described in Experimental Example 1 described later.

[0019] It is known that UFBs once generated in a liquid do not rise to the surface and burst quickly, and that UFBs remain in the liquid for a long time while diffusing and floating in the liquid due to Brownian motion, unlike millibubbles that rise to the surface and burst quickly, and microbubbles that float and disappear slowly. In the present invention, it is also desired that the scattering intensity continues for a long time. The period is not limited, and examples include a case where the scattering intensity continues for a day such as one day to several days, a month such as one month to several months, or a year such as one year to several years. Although not limited, the target period is 6 months or more, preferably 1 year or more, more preferably 2 years or more, and particularly preferably 3 years or more.

[0020] In the following embodiments of the present invention, the particle size and scattering intensity of UFB were measured using a dynamic light scattering photometer (DLS 6500-HL: manufactured by Otsuka Electronics Co., Ltd.) under the following conditions at atmospheric pressure and room temperature (25°C). Laser specifications: He-Ne laser Number of times: 400 Sampling time: 10μsec Measurement channels: 1024ch Measurement angle: 30° Pinhole 1:0.5, Pinhole 2:0.2.

[0021] (I) UFB product The UFB product of the present invention is one that, when added to a target liquid, produces the above-mentioned UFB in the liquid. The target liquid is not limited as long as it is a liquid in which UFB is generated when the UFB product of the present invention is blended, but is preferably an aqueous solvent, more preferably an aqueous solvent having a hardness in the range of 30 to 200 mg / L, particularly preferably 50 to 200 mg / L, and water within this hardness range can be suitably used. Here, hardness (mg / L) means American hardness (or Japanese hardness), and specifically, it can be calculated by converting the amounts of calcium and magnesium into the amount of calcium carbonate (CaCO3) according to the following formula 1. [Formula 1] Hardness [mg / l] = (Calcium content [mg / l] x 2.5) + (Magnesium content [mg / l] x 4.1)

[0022] Such a UFB product is characterized by comprising a combination of the following (A), (B) and (C): (A) a sophorolipid containing an acid-type sophorolipid and a lactone-type sophorolipid in a ratio of 78:22 to 100:0 (mass ratio); (B) Free fatty acid or its salt (C) Gas generating components.

[0023] (A) Sophorolipid (SL) Sophorolipid (SL) is a glycolipid composed of sophorose or sophorose with a hydroxy group partially acetylated or esterified, and hydroxy fatty acid. Sophorose is a sugar composed of two glucose molecules with a β1→2 bond. Hydroxy fatty acid is a fatty acid having a hydroxy group. SL is broadly classified into an acid type in which the carboxy group of the hydroxy fatty acid is free, and a lactone type in which sophorose is bonded within the molecule. An example of an acid type SL is SL represented by the following general formula (1), and an example of a lactone type SL is SL represented by the following general formula (2). SL obtained by fermentation of SL-producing yeast is usually a mixture of acid-type SL and lactone-type SL, and is obtained as a collection of more than 30 structural homologues, such as SLs with different fatty acid chain lengths (R2), SLs in which the 6' (R3) and 6" positions (R4) of sophorose are acetylated or protonated, and SLs in which one of the 3', 4', 2", 3", and 4" positions (R5) of sophorose is esterified.

[0024] [ka]

[0025] [In formula (1), R1 represents a hydrogen atom or a methyl group; R3 and R4 are the same or different and each represent a hydrogen atom or an acetyl group; All R5's are hydrogen atoms, or of the five R5's, one is a saturated fatty acid residue which may have a hydroxyl group or an unsaturated fatty acid residue which may have a hydroxyl group, and the rest are hydrogen atoms; R2 is a saturated aliphatic hydrocarbon chain or an unsaturated aliphatic hydrocarbon chain having at least one double bond, which may have one or more substituents; R6 represents a hydroxy group.

[0026] [ka]

[0027] (In formula (2), R1 to R4 are defined as in formula (1).)

[0028] Furthermore, the SLs covered by the present invention may include a dimer (dimeric SL) formed by combining R6 at the C-1 position of an acid-type SL represented by the above formula (1) in which one R5 is a saturated fatty acid residue which may have a hydroxyl group or an unsaturated fatty acid residue which may have a hydroxyl group, and the remaining four R5 are hydrogen atoms, with any one of the R7s of an acid-type SL represented by the following formula (3) to form a single bond.

[0029] [ka]

[0030] [In formula (3), R 1’ indicates a hydrogen atom or a methyl group; R 3’ and R 4’ are the same or different and represent a hydrogen atom or an acetyl group; R 2’ is a saturated aliphatic hydrocarbon chain or an unsaturated aliphatic hydrocarbon chain having at least one double bond, which may have one or more substituents; One of R7 is combined with R6 of the acid type SL represented by formula (1) to form a single bond, and the rest are all hydrogen atoms.

[0031] In the general formulas (1) to (3), R2 or R 2’ The number of carbon atoms in the saturated or unsaturated aliphatic hydrocarbon chain represented by is not limited, but can be exemplified as usually 9 to 20, preferably 9 to 18, more preferably 11 to 16, and particularly preferably 14 to 16. The saturated aliphatic hydrocarbon chain can be exemplified as a linear or branched alkylene group. A linear alkylene group is preferred. The unsaturated aliphatic hydrocarbon chain can be exemplified as an alkenylene group having 1 to 3 double bonds. An alkenylene group having 1 to 2 double bonds is preferred, and an alkenylene group having 1 double bond is more preferred. R2 or R 2’ The substituent of the saturated or unsaturated aliphatic hydrocarbon chain represented by is not particularly limited, but may be, for example, a halogen atom, a hydroxyl group, a lower (C 1~6 ) alkyl group, halo lower (C 1~6 ) alkyl group, hydroxy lower (C 1~6 ) alkyl group, halo lower (C 1~6 ) an alkoxy group, etc. Here, examples of the halogen atom or the halogen atom bonded to an alkyl group or an alkoxy group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0032] In the general formula (1), examples of the saturated fatty acid residue represented by R5 include linear fatty acid residues having 12 to 20 carbon atoms (lauric acid residue, myristic acid residue, pentadecylic acid residue, palmitic acid residue, margaric acid residue, stearic acid residue, and arachidonic acid residue). The linear fatty acid residues having 14 to 20 carbon atoms, more preferably 16 to 20 carbon atoms, and even more preferably 16 to 18 carbon atoms, are particularly preferably palmitic acid residues having 16 carbon atoms and stearic acid residues having 18 carbon atoms. The unsaturated fatty acid residues include linear fatty acid residues having 12 to 20 carbon atoms and 1 to 3 double bonds. The number of double bonds is preferably 1 to 2, and more preferably 1. The number of carbon atoms is preferably 16 to 20, more preferably 16 to 18, and especially preferably 18. Suitable unsaturated fatty acid residues include palmitoleic acid residues having one double bond and a carbon number of 16; oleic acid residues or vaccenic acid residues having one double bond and a carbon number of 18 (preferably oleic acid residues); linoleic acid residues having two double bonds and a carbon number of 18; (9,12,15) linolenic acid residues, (6,9,12) linolenic acid residues, and eleostearic acid residues having three double bonds and a carbon number of 18; (9,12,15) linolenic acid residues, (6,9,12) linolenic acid residues, and eleostearic acid residues having two double bonds and a carbon number of 20. More preferred are palmitoleic acid residues having one double bond and a carbon number of 16; and oleic acid residues having one double bond and a carbon number of 18, with oleic acid residues having one double bond and a carbon number of 18 being particularly preferred.

[0033] These fatty acid residues may or may not have a hydroxy group. When a hydroxy group is present, the number of hydroxy groups may be 1 to 2, preferably 1. The position of the hydroxy group on the fatty acid residue may be the ω position or the ω-1 position. In the acid type SL(1), when R5 is a saturated fatty acid residue which may have a hydroxy group or an unsaturated fatty acid residue which may have a hydroxy group, the position of -OR5 may be any of the 3', 4', 2", 3", and 4" positions of the sophorose ring. In other words, the acid type SL(1) includes an SL compound in which an -OR5 group having R5, which is the fatty acid residue, is bound to any one of these positions. More preferred is a compound (1) in which -OR5, in which R5 is a saturated fatty acid residue which may have a hydroxy group or an unsaturated fatty acid residue which may have a hydroxy group, is bound to the 4" position of the sophorose ring.

[0034] As described above, in the culture medium obtained by fermentation of SL-producing yeast, SL is usually present as a mixture of the acid-type SL (monomeric SL represented by general formula (1)) and the lactone-type SL (monomeric SL represented by general formula (2)). Of these, lactone-type SL is itself a nonionic oily substance and is extremely insoluble in water, so if there is a large amount of lactone-type SL, the entire sophorolipid mixture becomes poorly water-soluble, which is not preferable. On the other hand, acid-type SL is chemically more stable than lactone-type SL, so a higher proportion of acid-type SL is preferable.

[0035] A suitable example of the SL-producing yeast is Candida bombicola. The genus Candida has now been renamed to the genus Starmerella. The yeast is a known SL-producing yeast that is known to produce significant amounts of SL (acid type, lactone type) [Canadian Journal of Chemistry, 39,846 (1961) (Note: the genus Torulopsis described in this document corresponds to the genus Candida, but as mentioned above, it is currently classified as the genus Starmerella.), Applied and Environmental Microbiology, 47,173 (1984), etc.]. Candida bombicola is registered with the American Type Culture Collection (ATCC), a biological resource bank, and can be obtained from there (Candida bombicola ATCC22214, etc.). Other SL-producing yeasts belonging to the genus Candida (Stamerella), which are known to produce SL (acid type, lactone type), can also be used. Examples of such SL-producing yeasts include Candida magnoliae, Candida gropengisseri, Candida apicola, Candida petrophilum, Candida bogoriensis, and Candida batistae.

[0036] For the cultivation of these SL-producing yeasts, a medium containing sugars such as glucose as a carbon source (hydrophilic substrate), and fatty acids, fatty acid esters such as fatty acid triglycerides, or fats and oils such as vegetable oils containing fatty acids as constituents (hydrophobic substrate) is used. There are no particular limitations on the other components of the medium, and they can be appropriately selected from medium components generally used for yeasts.

[0037] The SL used in the present invention means that, of the total amount of 100% by mass of the acid-type SL represented by general formula (1) and the lactone-type SL represented by general formula (2), 78% by mass or more is the acid-type SL, and the remaining 22% by mass or less is the lactone-type SL represented by general formula (2). A composition in which the proportion of the acid-type SL is 85% by mass or more and the proportion of the lactone-type SL is 15% by mass or less is preferable; a composition in which the proportion of the acid-type SL is 90% by mass or more and the proportion of the lactone-type SL is 10% by mass or less is more preferable; and a composition in which the proportion of the acid-type SL is 95% by mass or more and the proportion of the lactone-type SL is 5% by mass or less is even more preferable. An SL in which the proportion of the acid-type SL is 100% by mass and does not contain a lactone-type SL may be used.

[0038] The ratio of acid-type SL to lactone-type SL contained in an SL-containing composition, such as a culture solution of an SL-producing yeast or a processed product thereof, can be determined, for example, by the measurement method described in International Publication WO2015 / 020114. The contents of this publication can be incorporated herein by reference. Specifically, a mixture of acid-type SL and lactone-type SL (SL-containing composition) is mixed with an equal amount of 50% by volume ethanol aqueous solution, and the content of SL contained in each eluted fraction is subjected to reverse phase column chromatography as described below, and the method includes quantitative analysis using high performance liquid chromatography (HPLC) as described below.

[0039] [Fractionation by reversed-phase column chromatography] (1) 600 g of the SL-containing composition is mixed with an equal amount of 50% by volume aqueous ethanol solution and the solution is subjected to the following reverse phase column chromatography. Stationary phase: C18 column (Cosmosil 40C18-PREP, manufactured by Nacalai Tesque, Inc., 7.5 kg) Mobile phase: ethanol aqueous solution with ethanol concentration of 50 to 95% by volume (2) Specifically, 10 L of a 50% by volume aqueous ethanol solution, 10 L of an 80% by volume aqueous ethanol solution, 15 L of a 90% by volume aqueous ethanol solution, and 15 L of a 95% by volume aqueous ethanol solution are sequentially applied to the stationary phase, and a fraction eluted with the 80% by volume aqueous ethanol solution, a fraction eluted with the 90% by volume aqueous ethanol solution, and a fraction eluted with the 95% by volume aqueous ethanol solution are recovered. (3) Each eluted fraction is evaporated to dryness, dissolved in ethanol, and subjected to HPLC under the following conditions as test samples.

[0040] [Quantitative analysis by HPLC] <Condition> Equipment: Shimadzu LC-10AD-VP Column: Inertsil ODS-3 (4.6 mm x 250 mm) Column temperature: 40℃ Mobile phase: [A] distilled water, [B] methanol containing 0.1% by volume formic acid Gradient: 0 min → 60 min: [B] 70 → 100% by volume 60 minutes → 70 minutes: [B] 100 → 70 capacity% Flow rate: 1.0mL / min Sample injection volume: 10 μL Detector: Evaporative light scattering detector (ELSD-LTII: Shimadzu Corporation) Detector temperature: 40℃ Gain: 5 Gas pressure: 350kpa (N2 gas)

[0041] The fraction eluted with 80% by volume aqueous ethanol contains an acid-form SL represented by the following formula (1a) among the acid-form SLs represented by formula (1). The acid-form SL is an acid-form SL (1) in which all R5s are hydrogen atoms. The acid-form SL (1a) is eluted in the retention time region of 10 to 25 minutes in HPLC under the above conditions.

[0042] [ka]

[0043] (In formula (2), R1 to R4 are defined as in formula (1).)

[0044] The fraction eluted with 80% by volume ethanol aqueous solution contains the lactone type SL represented by the above formula (2) in addition to the acid type SL (1a). The lactone type SL (2) is eluted in the retention time region of 25 to 40 minutes in HPLC under the above conditions.

[0045] The fraction eluted with 90% by volume aqueous ethanol contains acid-form SL (1b) represented by formula (1), in which one of R5 is a saturated fatty acid residue which may have a hydroxyl group or an unsaturated fatty acid residue which may have a hydroxyl group, and the remaining are hydrogen atoms. The acid-form SL (1b) is eluted in the retention time region of 45 to 60 minutes in HPLC under the above conditions.

[0046] Incidentally, the fraction eluted with 95% by volume aqueous ethanol solution contains a dimeric SL represented by formula (3). The dimeric SL (3) is eluted in the retention time region of 60 to 70 minutes in HPLC under the above conditions.

[0047] In this way, the ratio of acid-type SL and lactone-type SL contained in the SL-containing composition, specifically the ratio of each SL per 100% by mass of the total amount of acid-type SL and lactone-type SL, can be determined from the area ratio of the peaks detected in each retention time region in HPLC under the above conditions.

[0048] In the present invention, the form of SL is not particularly limited, and it may be liquid, emulsion, or solid. Examples of such solid forms include dry solid forms such as freeze-dried products, spray-dried products, and evaporated to dryness products; tablets; pills; powders; granules; and capsules. The ratio of acid-type SL and lactone-type SL in the UFB product of the present invention can be appropriately selected from the range of 1 to 80% by mass per 100% by mass of the total amount of components (A), (B), and (C) as long as the effects of the present invention are achieved.

[0049] (B) Free fatty acid or its salt The free fatty acid targeted by the present invention may be either saturated or unsaturated, as long as the effect of the present invention is achieved. Examples of saturated fatty acids include fatty acids having 12 to 20 carbon atoms (lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, and arachidic acid). Fatty acids having 14 to 20 carbon atoms, more preferably 16 to 20 carbon atoms, and even more preferably 16 to 18 carbon atoms, and palmitic acid having 16 carbon atoms is particularly preferred. Examples of unsaturated fatty acids include fatty acids having 12 to 20 carbon atoms and 1 to 3 double bonds. The number of double bonds is preferably 1 to 2, and more preferably 1. The number of carbon atoms is preferably 16 to 20, more preferably 16 to 18, and especially preferably 18. Suitable unsaturated fatty acids include palmitoleic acid having one double bond and a carbon number of 16; oleic acid or vaccenic acid (preferably oleic acid) having one double bond and a carbon number of 18; linoleic acid having two double bonds and a carbon number of 18; (9,12,15) linolenic acid, (6,9,12) linolenic acid, and eleostearic acid having three double bonds and a carbon number of 18; (9,12,15) linolenic acid, (6,9,12) linolenic acid, and eleostearic acid having two double bonds and a carbon number of 20. More preferred are palmitoleic acid having one double bond and a carbon number of 16, and oleic acid having a carbon number of 18, and particularly preferred is oleic acid.

[0050] The salts of these fatty acids are not particularly limited as long as they do not interfere with the effects of the present invention. In addition, it is preferable that they do not interfere with the solubility of free fatty acids in water. Specifically, there can be mentioned alkali metal salts such as sodium and potassium, and alkaline earth metal salts such as calcium and magnesium. Alkali metal salts are preferable.

[0051] In the present invention, the form of the free fatty acid or its salt is not particularly limited, and it may be liquid, emulsion, or solid. Examples of such solid forms include dry solids, tablets, pills, powders, granules, and capsules. The proportion of component (B) in the UFB product of the present invention can be appropriately selected from the range of 0.0001 to 10% by mass per 100% by mass of the total amount of components (A), (B), and (C) as long as the effects of the present invention are achieved.

[0052] (C) Gas-generating components The gas generating component targeted by the present invention is a component that reacts in the presence of water to generate gas (vapor). To that extent, it may be composed of a single component or a combination of two or more components. The gas generating component may be composed of a combination of a gas generating main body and a counterpart, as described below. Target gases (gases) include, but are not limited to, carbon dioxide gas, oxygen gas, hydrogen gas, and chlorine gas, with carbon dioxide gas, oxygen gas, and hydrogen gas being preferred.

[0053] The carbon dioxide gas generating component may be any component that reacts in the presence of water to generate carbon dioxide gas (carbon dioxide gas), and examples thereof include carbonates and hydrogen carbonates. Carbon dioxide gas is generated when carbonates or hydrogen carbonates are placed in an aqueous solution containing the above-mentioned component (A). It is also known that hydrogen carbonates generate carbon dioxide gas when heated in water. Suitable examples of carbonates include alkali metal salts such as sodium carbonate and potassium carbonate. Suitable examples of hydrogen carbonates include alkali metal salts such as sodium hydrogen carbonate and potassium hydrogen carbonate. Carbonates or hydrogen carbonates can also be used in combination with a component that decomposes them in the presence of water to generate carbon dioxide gas. In the present invention, a component that contributes to gas generation by decomposing a gas-generating main body such as a carbonate or promoting the decomposition is referred to as a "counterpart" as a component used in combination with the gas-generating main body. Here, examples of counterparts used in combination with a carbonate or hydrogen carbonate (gas-generating main body) include acids and acid salts. The acid is not particularly limited as long as it reacts with a carbonate or hydrogencarbonate in the presence of water to generate carbon dioxide gas and does not impair the effects of the present invention, and examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as succinic acid, fumaric acid, adipic acid, tartaric acid, benzoic acid, citric acid, pyrrolidone carboxylic acid, salicylic acid, maleic acid, phthalic acid, glutaric acid, and oxalic acid. These may be used alone or in any combination of two or more. Suitable examples of the acid salt include salts with alkali metal salts such as sodium and potassium.

[0054] The oxygen gas generating component may be any component that reacts in the presence of water to generate oxygen gas, and for example, hydrogen peroxide can be used as an oxygen gas generating main body. Hydrogen peroxide can also be used in combination with a component (counterpart) that decomposes hydrogen peroxide in the presence of water to generate oxygen gas. Counterparts used in combination with hydrogen peroxide include hydrogen peroxide decomposing enzymes such as catalase and catalysts such as manganese dioxide.

[0055] The hydrogen gas generating component may be any component that reacts in the presence of water to generate hydrogen gas, and examples of the hydrogen gas generating main body include hydride salts, borohydride salts, and hydrochloric acid. Here, the salt in the hydride salt or borohydride salt may be any salt that exerts the above-mentioned action, and examples of the salt include alkali metal salts such as sodium and potassium, and alkaline earth metal salts such as calcium and magnesium. Specifically, the hydride salts include sodium hydride, potassium hydride, calcium hydride, and magnesium hydride. Furthermore, the borohydride salts include sodium borohydride. Hydrochloric acid can also be used in combination with a component (counterpart) that decomposes in the presence of water to produce hydrogen gas. Counterparts that can be used in combination with hydrochloric acid include metals such as iron, zinc, and magnesium.

[0056] The chlorine gas generating component may be any component that reacts in the presence of water to generate chlorine gas, and for example, hypochlorites such as sodium hypochlorite can be used as the chlorine gas generating main body. Hypochlorites can also be used in combination with a component (counterpart) that decomposes in the presence of water to generate chlorine gas. An example of the counterpart used in combination with hypochlorites is an acid. The acid is not particularly limited, and examples include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as succinic acid, fumaric acid, adipic acid, tartaric acid, benzoic acid, citric acid, pyrrolidone carboxylic acid, salicylic acid, maleic acid, phthalic acid, glutaric acid, and oxalic acid. These can be used in combination of one or more of them.

[0057] In the UFB product of the present invention, the gas generating component is not particularly limited as long as it is configured to generate gas only when it comes into contact with water, and is preferably in a solid form. Examples of such solid forms include dry solid form, tablet form, pill form, powder form, granule form, and capsule form. As described above, the gas generating component can be used in a state of being combined with the gas generating main body and its counterpart, but in this case, it is preferable to combine the gas generating main body and its counterpart in a separate state so that they come into contact and react only when they come into contact with water. The proportion of the (C) component in the UFB product of the present invention can be appropriately selected from the range of 0.1 to 98.9999 mass% per 100 mass% of the total amount of the (A), (B), and (C) components, as long as the effects of the present invention are achieved.

[0058] (D) Other ingredients The UFB product of the present invention may contain components other than the above-mentioned (A), (B), and (C) to the extent that the effects of the present invention are not impaired. Such other components may be appropriately selected depending on the use and field of application of the UFB product. Note that the following are merely examples and are not limited to these.

[0059] [Oral cleansers (mouthwash, gargle, etc.)] For example, humectants (e.g., glycerin, propylene glycol, ethanol, isopropanol, etc.), sweeteners (e.g., steviaside, sorbitol, erythritol, sodium saccharin, etc.), bactericides (e.g., dipotassium glycyrrhizinate, cetylpyridinium chloride, tranexamic acid, isopropyl methylphenol, povidone iodine, benzalkonium chloride, chlorhexidine gluconate ethanol, etc.), sodium fluoride, etc.

[0060] [Cosmetics] For example, ethanol, glycerin, butylene glycol, dipropylene glycol, propylene glycol, petrolatum, mineral oil, squalane, higher fatty acids, higher alcohols (e.g., stearyl alcohol, behenyl alcohol, cetanol, etc.), oils and fats (e.g., olive oil, coconut oil, shea butter, jojoba seed oil, horse oil, etc.), waxes (e.g., beeswax, lanolin, etc.), plant extracts, cetyl ethylhexanoate, triethylhexanone, isopropyl myristate, dimethicone, cyclopentane siloxane, etc.

[0061] [Bath additives] For example, inorganic salts (e.g. potassium carbonate, calcium carbonate, sodium sesquicarbonate, sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate, sodium metasilicate), herbal medicines and plant extracts (e.g. fennel, scutellaria, phellodendron bark, chamomile, magnolia bark, jossica, calamus, seikyo, tangerine peel, angelica tree, spruce, chili pepper, carrot, yuzu, mugwort, scutellaria, peppermint, ginger, licorice, cinnamon), enzymes (e.g. papain, pancreatin, proteolytic enzymes), acids (e.g. fumaric acid, succinic acid, malic acid, citric acid) , maleic acid, tartaric acid, lactic acid), moisturizers, vegetable oils (e.g. jojoba oil, olive oil, soybean oil, rice oil), isoflavones, lanolin, glycerin, casein, stearyl alcohol, liquid paraffin, white petrolatum, propylene glycol, skim milk powder, squalane, honey, polyethylene glycol, colorants (e.g. riboflavin, carotene, chlorophyll, Yellow No. 202, Yellow No. 4, Blue No. 1, Green No. 201, Green No. 204), silicic anhydride, camphor, methyl salicylate, terpine oil, menthol, dextrin, titanium oxide, fragrances, etc.

[0062] [Food and drink] For example, amino acids (e.g. arginine, lysine, glutamine, etc.), minerals (e.g. iron, potassium, calcium, etc.), essential fatty acids (e.g. linoleic acid, DHA, EPA, etc.), vitamins, collagen, peptides, sesamin, chondroitin, dietary fiber, etc.

[0063] [Plant growth promoter] For example, nitrates (e.g. ammonium nitrate, magnesium nitrate, potassium nitrate, etc.), sulfates (e.g. ammonium sulfate, magnesium sulfate, potassium sulfate, etc.), phosphates or hydrogen phosphates (e.g. ammonium phosphate, magnesium phosphate, potassium phosphate, dipotassium hydrogen phosphate, etc.), chlorides (e.g. ammonium chloride, magnesium chloride, potassium chloride, etc.), urea, magnesium, calcium, manganese, citric acid, tartaric acid, oxalic acid, acetic acid, edetic acid, etc.

[0064] [Fish and shellfish growth promoter] For example, soybean meal, fish meal, meat, bone meal, amino acids, proteins and carbohydrates such as corn and wheat flour, vitamins such as ascorbic acid, minerals and trace elements.

[0065] [Cleaning and disinfecting agents] For example, anionic surfactants (e.g., alkyl polyoxyethylene sulfates, linear alkyl benzene sulfonates, alpha olefin sulfonates, etc.), cationic surfactants (e.g., dialkyl dimethyl ammonium chloride, alkyl benzalkonium chloride, etc.), amphoteric surfactants (e.g., alkyl betaines, alkyl diethylene triamino acetates, alkyl amine oxides, etc.), nonionic surfactants (e.g., polyoxyethylene alkyl ethers, glycerin fatty acid esters, polyoxyethylene polyoxypropylene glycol, etc.), alkaline compounds (e.g., organic alkaline compounds such as alkanolamines and alkyl amines, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium phosphate, potassium phosphate, etc.), solvents (e.g., ethanol, propylene glycol, etc.), glycol, glycerin, etc.), hydrotropes (e.g., paratoluenesulfonic acid, xylenesulfonic acid or its salts, etc.), chelating agents (e.g., EDTA, NTA, MDA, etc.), enzymes (e.g., protease, amylase, lipase, cellulase, etc.), bactericides (e.g., polyhexamethylene biguanidine hydrochloride, chlorhexidine and its salts, isopropylmethylphenol, alkyldiaminoethylglycine hydrochloride, bensalkonium chloride , isopropanol, ethanol, povidone-iodine, sodium hypochlorite, phthalal, glutaral, peracetic acid, etc.), dispersants (e.g. sodium polyacrylate, polyvinylpyrrolidone, etc.), antioxidants (e.g. butylhydroxytoluene, sodium sulfite, sodium hydrogen sulfite, etc.), pH adjusters (e.g. citric acid, gluconic acid, malic acid, succinic acid, acetic acid, etc.), thickeners, viscosity adjusters, fragrances, colorants, preservatives, bleaching agents, bleach activators, etc.

[0066] (F) Form, composition, dosage, etc. The form of the UFB product of the present invention includes a blend (single agent) containing the above-mentioned (A), (B) and (C) components, and a combination (kit or set) in which at least the (C) component is packaged separately from the (A) and (B) components, and is used in combination when used. Furthermore, the (C) component may be a combination (kit or set) in which a gas generating main body and its counterpart are packaged separately, and is used in combination when used. In the case of a blend (single agent), the form is not particularly limited as long as it is configured to generate gas only when added to water, and is preferably a solid form. Such solid forms include a dry solid form; a tablet form; a pill form; a powder form; a granule form; and a capsule form.

[0067] In the UFB product of the present invention, the blending ratios of the above-mentioned (A), (B) and (C) components are not particularly limited as long as they do not impair the effects of the present invention. It is preferable that the UFB product is prepared and used so that the concentration of the (A) component is 0.005 mass% or more and the concentration of the (B) component is 0.0001 mass% or more when added to water. The blending ratio of the UFB product to water when added to water can also be determined taking the above concentrations into consideration. The concentration of component (A) in the water is preferably 0.01% by mass or more, more preferably 0.01 to 0.4% by mass, and the concentration of component (B) is preferably 0.0005% by mass or more, more preferably 0.0005 to 0.3% by mass. The water referred to here broadly includes aqueous solvents and aqueous solutions. When added to water, the concentration of the gas generating substance in component (C) can be 0.1% by mass or more. In particular, when component (C) is a carbon dioxide gas generating component, it is preferable that the concentration of the carbon dioxide gas generating substance (carbonate, hydrogen carbonate) in water is adjusted and used to be 0.1% by mass or more. The concentration of the gas generating substance in water is preferably 0.1% by mass or more, more preferably 0.1 to 20% by mass, and particularly preferably 0.5 to 1% by mass.

[0068] (II) Method for generating UFB The UFB production method of the present invention can be carried out by adding the above-mentioned components (A), (B) and (C) to water having a hardness of 30 to 200 mg / L, preferably 50 to 200 mg / L, and allowing these three components to coexist in the water. The UFB production method of the present invention is characterized in that it is a method capable of generating UFB in water without introducing gas from the outside.

[0069] The temperature of the water is not particularly limited as long as it is a temperature at which UFB production is not hindered, but is preferably 50° C. or lower. The components (A), (B) and (C) can be used in a premixed state (in the form of a one-agent combination). Also, at least the component (C) can be packaged separately from the components (A) and (B) (set or kit), which can be mixed before or at the time of use before being added to water, or the three components can be added to water simultaneously. In other words, the desired UFB can be produced simply by using the UFB product (combination) of the present invention described above.

[0070] Water with a hardness of 30 to 200 mg / L includes tap water as well as aqueous solutions containing various components depending on the purpose and field of application (e.g., the environmental field, the industrial field, the agricultural field, the fisheries field, the medical and pharmaceutical fields, the cosmetics field, the food and beverage field, etc.) Examples of such components include, but are not limited to, the above-mentioned component (D).

[0071] For example, by blending the components (A), (B) and (C) or the UFB product of the present invention described above with a lotion having a hardness of 30 to 200 mg / L, the desired UFB can be generated in the lotion, and a lotion containing UFB can be prepared. The lotion containing UFB may be prepared each time it is used, but since UFB remains stable in water, it can also be prepared at the time of first use and used continuously. As another example, by blending the components (A), (B) and (C) or the UFB product of the present invention described above into an aqueous solution containing a bactericidal component with a hardness of 30 to 200 mg / L (for example, a disinfectant, a pesticide, etc.), the desired UFB can be generated in the aqueous solution, and a disinfectant or a pesticide containing UFB can be prepared and obtained. By blending the components (A), (B) and (C) or the UFB product of the present invention described above into an aqueous solution containing a component such as a fertilizer or growth agent with a hardness of 30 to 200 mg / L, the desired UFB can be generated in the aqueous solution, and a fertilizer or growth agent containing UFB can be prepared and obtained. These UFB-containing solutions may be prepared each time they are used, but they can also be prepared at the time of first use and used continuously.

[0072] The components (A), (B), and (C) used in the UFB production method of the present invention are as described in (I), and the descriptions in (I) can be used to refer to the amounts used when mixed with water (concentration in water), the hardness of the water used, the scattering intensity and particle size of the UFB produced, and the like.

[0073] (III) UFB-containing liquid and its manufacturing method The UFB-containing liquid of the present invention is characterized in that it contains the following (A), (B), (c) and (d): (A) an SL containing an acid-type SL and a lactone-type SL in a ratio of 78:22 to 100:0 (mass ratio); (B) a free fatty acid or a salt thereof, (c) fine bubbles having an average number particle diameter of less than 1000 nm, formed from at least one gas selected from the group consisting of carbon dioxide gas, oxygen gas, hydrogen gas, and chlorine gas; and (d) Water.

[0074] The types and amounts (concentrations) of the (A), (B) and (c) components are as described in (I), and the descriptions therein are incorporated herein by reference. The (d) component is water having a hardness of 30 to 200 mg / L, preferably 50 to 200 mg / L. The water may be used in a state in which the (D) component described above is dissolved, provided that the hardness does not deviate from the range of 30 to 200 mg / L. The (D) component may be appropriately selected and used depending on the application or field of application (e.g., the environmental field, the industrial field, the agricultural field, the fishery field, the medical and pharmaceutical fields, the cosmetics field, the food and beverage field, etc.), and the UFB-containing liquid of the present invention may be used in the various fields described above depending on the (D) component.

[0075] The particle size of the UFB contained in the UFB-containing liquid of the present invention may be less than 1000 nm. The UFB include fine bubbles with a particle size of less than 50 to 200 nm, fine bubbles with a particle size of less than 200 to 500 nm, and fine bubbles with a particle size of less than 500 to 1000 nm. Fine bubbles with a particle size of 500 nm or less are preferable. These UFB-containing liquids can be used in various fields (environmental field, industrial field, agricultural field, fishery field, medical / pharmaceutical field, cosmetics field, food and beverage field, etc.) according to the functions that correspond to the particle size of the UFB.

[0076] The UFB-containing liquid of the present invention has a scattering intensity measured by the above-mentioned method, which is not limited, but is preferably 5,000 cps or more, more preferably 10,000 cps or more, and particularly preferably 30,000 cps or more.

[0077] The UFB-containing liquid of the present invention can be produced by the following method. (A) adding the following components (A), (B) and (C) to water having a hardness of 30 to 200 mg / L, preferably 50 to 200 mg / L, and allowing these three components to coexist in the water; (a) A process for generating air bubbles in the water A method for producing a UFB-containing liquid comprising: (A) an SL containing an acid-type SL and a lactone-type SL in a ratio of 78:22 to 100:0 (mass ratio); (B) Free fatty acid or its salt (C) Gas generating components. According to this method, UFBs can be generated in water without introducing any particular gas from the outside, and the above-mentioned UFB-containing liquid of the present invention can be prepared and obtained. As described above, in this specification, the terms "comprise" and "contain" include the meanings of "consisting of" and "consisting essentially of". EXAMPLES

[0078] In the following, the present invention will be described using experimental examples to aid in understanding the configuration and effects of the present invention. However, the present invention is not limited by these experimental examples. The following experiments were carried out at room temperature (25±5°C) and atmospheric pressure conditions unless otherwise specified. In the following, "%" means "% by mass" and "parts" means "parts by mass" unless otherwise specified.

[0079] Reference Manufacturing Example 1: Preparation of SL-containing composition 2 (1) As the culture medium, a liquid medium containing 10 g of hydrated glucose (manufactured by Nippon Shokuhin Kako Co., Ltd., product name: Nisshoku hydrated crystalline glucose), 10 g of peptone (manufactured by Oriental Yeast Co., Ltd., product name: Peptone CB90M), and 5 g of yeast extract (manufactured by Asahi Food and Healthcare Co., Ltd., product name: Meast Powder N) per liter was used. Candida bombicola ATCC22214 was cultured with shaking at 30°C for 2 days, and this was used as a preculture solution.

[0080] (2) This preculture solution was inoculated into the main culture medium (3 L) in a 5 L fermenter at a ratio of 4% of the amount of the culture medium, and cultured and fermented under conditions of 0.6 vvm aeration at 30 ° C. for 6 days. The main culture medium used was a medium (pH 4.5 to 4.8 before sterilization) containing 100 g of hydrated glucose, 50 g of palm olein (NOF Corp., product name: Palmary 2000), 50 g of oleic acid (ACID CHEM Corp., product name: Palmac 760), 1 g of sodium chloride, 10 g of potassium phosphate monobasic, 10 g of magnesium sulfate heptahydrate, 2.5 g of yeast extract (Asahi Food & Healthcare Corp., product name: Meast Powder N), and 1 g of urea per 1 L.

[0081] Fermentation was stopped on the sixth day after the start of cultivation, and the culture solution removed from the fermentation tank was heated and then returned to room temperature, and left to stand for 2 to 3 days, and separated into three layers, from the bottom: a liquid brown precipitate layer, a milky white solid layer that is thought to be mainly bacterial cells, and a supernatant. After removing the supernatant, industrial water or groundwater was added in the same amount as the removed supernatant. While stirring, 48% by mass sodium hydroxide solution was gradually added to adjust the pH to 6.5 to 6.9, and the SL contained in the culture solution was solubilized. This was centrifuged with a tabletop centrifuge (Westfalia: manufactured by Westfalia Separator AG) to precipitate the milky white solid, and the supernatant was collected. While stirring the collected supernatant, 62.5% by mass sulfuric acid was gradually added to adjust the pH to 2.5 to 3.0, and the SL was re-insolubilized. After leaving this to stand for 2 days, the supernatant was removed as much as possible by decantation, and the residue was obtained as "SL-containing composition 2" (about 50% water content).

[0082] Reference Manufacturing Example 2: Preparation of SL-containing composition 1 The SL-containing composition 2 separated in Reference Production Example 1 was adjusted to pH 14 by adding an aqueous sodium hydroxide solution, and hydrolyzed (alkaline hydrolysis) by treating at 80° C. for 2 hours. Then, after returning to room temperature, the pH was adjusted to 10 using sulfuric acid (9.8 M aqueous solution), and the resulting insoluble matter was removed by filtration, to obtain the filtrate as "SL-containing composition 1" (about 30% water content).

[0083] Reference Manufacturing Example 3: Preparation of SL-containing composition 3 The SL-containing composition 1 prepared in Reference Production Example 2 was purified based on Example 1 of WO2015 / 034007, and the resulting powder was obtained as "SL-containing composition 3".

[0084] Experimental Example 1 Carbon dioxide gas (CO 2 Generation of microscopic bubbles consisting of gas (part 1) The raw materials used in Experimental Example 1 are as follows. SL-containing composition 1: A SL-containing composition containing 34% SL (acid-type SL:lactone-type SL=100:0 [mass ratio]) and 2.5% oleic acid (see Reference Production Example 2) SL-containing composition 2: A SL-containing composition containing 58% SL (acid-type SL:lactone-type SL=78:22 [mass ratio]) and 4.3% oleic acid (see Reference Manufacturing Example 1) Sodium alkyl polyoxyethylene sulfate: Teikapol NE1230 (containing 27% sodium alkyl polyoxyethylene sulfate) (manufactured by Teika Co., Ltd.) Alkyl polyglycoside: TRITON(R) CG-50 (containing 50% alkyl polyglycoside) (manufactured by Dow Chemical) Lauryl dimethylaminoacetate betaine: Rikabion A-100 (containing 30% lauryl dimethylaminoacetate betaine) (manufactured by New Japan Chemical Co., Ltd.)

[0085] The components were mixed so that the final concentrations in water were as shown in Tables 1 to 3 (final concentration: mass %), and then added to 1 L of tap water (hardness 100 mg / L) (room temperature) in a glass beaker, and stirred with a stirrer and stirrer to dissolve (pH 8.3), allowing each component to react (generation of carbon dioxide gas). This was left at room temperature for 12 hours, after which the scattering intensity and the average number particle size (hereinafter sometimes simply referred to as "particle size") were measured. A dynamic light scattering photometer (DLS 6500-HL: manufactured by Otsuka Electronics Co., Ltd.) was used to measure the scattering intensity and particle size. Specifically, the aqueous solution prepared above was filtered with a 0.45 μm filter using a 10 mL syringe to remove solid impurities, and the filtrate was collected in a cylindrical measurement cell with a diameter of 21 mm, which was used as a measurement sample in the dynamic light scattering photometer under the following conditions.

[0086] [Dynamic light scattering photometer measurement conditions] Measurement temperature: 25℃, Accumulation times: 400 times, Sampling time: 10μsec, Measurement channels: 1024ch, Measurement angle: 30°, Pinhole 1:0.5, Pinhole 2:0.2.

[0087] The results are shown in Tables 1 to 3. The scattering intensity was calculated by subtracting the scattering intensity of the aqueous solution (control sample 1) in which the A&B components (SL-containing composition 1 or 2) or surfactant was dissolved, and the scattering intensity of the aqueous solution (control sample 2) in which the C component (C1: gas generating main body, and C2: counterpart) was dissolved, from the scattering intensity of the aqueous solution (test sample) in which all the components were dissolved, as shown in the following formula 2. Tap water (hardness 100 mg / L) with a scattering intensity of 585 cps was used to dissolve each component. [Formula 2] Scattering intensity = [Scattering intensity of test sample] - [Scattering intensity of control sample 1] - [Scattering intensity of control sample 2]

[0088] The evaluations shown in Tables 1 to 3 are based on the following criteria. [Scattering intensity] ◎:30000cps or more ○: 10,000 cps or more and less than 30,000 cps △: 5000cps or more and less than 10000cps ×: Less than 5000cps [Average number particle size] ◎: 50nm or more and less than 200nm ○: 200nm or more and less than 500nm △: 500nm or more and less than 1000nm ×: 1000nm or more When the scattering intensity is below 8000 cps, the particle size cannot be measured, and therefore the evaluation column is marked with "-".

[0089] [Table 1] [Table 2] [Table 3]

[0090] From the results in Tables 1 and 3, it was confirmed that by combining the SL-containing composition containing free fatty acid (SL-containing composition 1 or 2) with a gas-generating component (carbonate or bicarbonate) and adding both to water, CO2 bubbles were generated, and the bubbles remained stable in the water even after being left for at least 12 hours. In addition, from the particle size and scattering intensity, it was confirmed that the bubbles were fine bubbles equivalent to ultrafine bubbles. In addition, the SL concentration in the aqueous solution that generated the fine bubbles (UFB) was 0.005% or more, preferably 0.01% or more, the free fatty acid concentration was 0.0004% or more, and the concentration of the gas generating main body was 0.1% or more. From the results shown in Table 3, stable fine bubbles (UFB) were obtained even at a high concentration of the gas generating main body, such as 20% by mass, so it is considered that the upper limit of the concentration of the gas generating main body is not particularly limited, except for the limit of dissolution in water. From this, it was confirmed that ultrafine bubbles (UFB) can be generated by creating a coexistence state, at least in water, of SL at a concentration of 0.005% or more, free fatty acids at a concentration of 0.0004% or more, and a gas generator at a concentration of 0.1% or more. On the other hand, when the composition contained only the gas-generating body and did not contain SL or free fatty acid, or when the gas-generating body was combined with a surfactant instead of the SL-containing composition, it was confirmed that CO2 bubbles were produced but no UFB were produced (Table 2).

[0091] Experimental Example 2 CO 2 Generation of fine gas bubbles (part 2) The effect of free fatty acids in the reaction system was evaluated. The raw materials used in Experimental Example 2 are as follows. SL-containing composition 1: A SL-containing composition containing 34% SL (acid-type SL:lactone-type SL=100:0 [mass ratio]) and 2.5% oleic acid (see Reference Production Example 2) SL-containing composition 3: A SL-containing composition containing 99.8% SL (acid-type SL:lactone-type SL=100:0 [mass ratio]) and 0.2% oleic acid (see Reference Production Example 3)

[0092] The components were mixed so that the final concentration in water would be the ratio (mass%) shown in Table 4, and then added to 1 L of tap water (hardness 100 mg / L) (room temperature) in a glass beaker, and stirred using a stirrer and agitator to dissolve (pH 8.3), allowing each component to react (CO2 gas generation). This was left to stand at room temperature for 12 hours, after which the scattering intensity and particle size were measured in the same manner as in Experimental Example 1. The scattering intensity was calculated by subtracting the scattering intensity value of the aqueous solution in which SL-containing composition 1 or 3 was dissolved (control sample 1) and the scattering intensity value of the aqueous solution in which components B and C were dissolved (control sample 2) from the scattering intensity value of the aqueous solution in which all components were dissolved (test sample), as shown in the above formula 2.

[0093] The results are shown in Table 4.

[0094] [Table 4]

[0095] From the results in Table 4, it was confirmed that in order to generate fine bubbles equivalent to ultrafine bubbles and keep them stable in water even after being left for at least 12 hours, the presence of a certain amount of free fatty acid is necessary in addition to the SL and gas generator. The concentration of free fatty acid required to generate and maintain fine bubbles (UFB) in an aqueous solution is thought to be at least 0.0001%.

[0096] Experimental Example 3 CO 2 Generation of fine gas bubbles (part 3) As the surfactant, SL or a nonionic surfactant having an HLB of 6 to 12 described in Patent Document 1 (JP Patent Publication 2013-207122 A) was used, and CO2 gas was generated in water in the same manner as in Experimental Example 1, and the generated bubbles were evaluated.

[0097] The raw materials used in Experimental Example 3 are as follows. SL-containing composition 1: Same as Experimental Example 1 POE tetraoleate sorbitol (40EO): Rheodol 440V (Kao Corporation) Polyoxyethylene hydrogenated castor oil (25EO): Emanon CH-25 (Kao Corporation) POE lauryl ether: Emulgen 103 (Kao Corporation) Sorbitan monooleate (6EO): Rheodor TW-O106V (Kao Corporation) POE stearyl ether (6EO): Emulgen 306P (Kao Corporation)

[0098] The components were mixed so that the final concentration in water would be the ratio (mass%) shown in Table 5, and then added to 1 L of tap water (hardness 100 mg / L) (room temperature) in a glass beaker, and stirred with a stirrer and stirrer to dissolve (pH 8.3), allowing the components to react (generation of carbon dioxide gas). This was left to stand at room temperature for 12 hours, after which the scattering intensity and particle size were measured in the same manner as in Experimental Example 1. The scattering intensity was calculated by subtracting the scattering intensity value of the aqueous solution in which the SL-containing composition 1 or the surfactant was dissolved (control sample 1) and the scattering intensity value of the aqueous solution in which the C component was dissolved (control sample 2) from the scattering intensity value of the aqueous solution in which all the components were dissolved (test sample), as shown in the above formula 2.

[0099] The results are shown in Table 5.

[0100] [Table 5]

[0101] As shown in Table 5, when a surfactant (nonionic surfactant) was used instead of the SL-containing composition 1 (SL and free fatty acid), the generation of fine bubbles equivalent to ultrafine bubbles was not confirmed. This confirmed that the presence of SL and free fatty acid in addition to the gas generating body is necessary for the generation of fine bubbles (UFB).

[0102] Experimental Example 4: Generation of fine bubbles consisting of oxygen gas, hydrogen gas, or chlorine gas Instead of CO2 gas, O2 gas, H2 gas, or Cl2 gas was generated in water and the generated bubbles were evaluated.

[0103] The raw materials used in Experimental Example 4 are as follows. SL-containing composition 1: Same as Experimental Example 1 Catalase: Ask Super 25 (MGC Advanced Chemical Co., Ltd.)

[0104] The components were mixed so that the final concentration in water would be the ratio (mass%) shown in Table 6, and then added to 1 L of tap water (hardness 100 mg / l) (room temperature) in a glass beaker, and stirred with a stirrer and stirrer to dissolve (pH 8.0), allowing the components to react (gas generation). This was left at room temperature for 12 hours, after which the scattering intensity and particle size were measured in the same manner as in Experimental Example 1. The scattering intensity was calculated by subtracting the scattering intensity value of the aqueous solution in which the SL-containing composition 1 was dissolved (control sample 1) and the scattering intensity value of the aqueous solution in which the C components (C1: gas-generating main body, C2: counterpart) were dissolved (control sample 2) from the scattering intensity value of the aqueous solution in which all the components were dissolved (test sample), as shown in the above formula 2.

[0105] The results are shown in Table 6.

[0106] [Table 6]

[0107] As shown in Table 6, it was confirmed that by allowing SL, free fatty acids, and various gas generating components (C1: gas generating main body, C2: counterpart) to coexist in water, bubbles of various gases (oxygen gas, hydrogen gas, chlorine gas) were generated and stably remained in the water. In addition, based on the particle size and scattering intensity, it was confirmed that all of the bubbles were fine bubbles equivalent to ultrafine bubbles.

[0108] Experimental Example 5 Preparation and evaluation of mouthwash According to the formulation listed in Table 7, each component was mixed and dissolved in purified water (hardness: 80 mg / L) to prepare mouthwashes (mouthwashes of the present invention 1-2, comparative mouthwashes 1-3) (pH 6.5). Specifically, components 1-3 listed in Table 7 were mixed as necessary, and then this was added to and dissolved in a solution (components 4-6 and 8) that had been mixed in advance, and the pH was adjusted to 6.5 with a pH adjuster (component 7) to prepare the mouthwash. The prepared mouthwashes were evaluated for the presence or absence of ultra-fine bubbles and their cleansing properties using the methods described below.

[0109] (1) Evaluation of the presence or absence of ultrafine bubble generation After leaving it at room temperature for 12 hours, the scattering intensity and particle size were measured in the same manner as in Experimental Example 1, and evaluated according to the same criteria as in Experimental Example 1.

[0110] (2) Evaluation of cleaning ability A 2% mucin aqueous solution was dropped onto a HAP disk (apatite pellet APP-100, 10 mm x 10 mm x 2 mm) and dried to prepare a test piece simulating intraoral stains. This was immersed in each mouthwash (mouthwashes 1-2 of the present invention, and comparative mouthwashes 1-3) (37°C) for 3 minutes. After immersion, the piece was rinsed with running water for 30 seconds, dried, and visually observed. Pieces on which no stains could be visually confirmed were stained using "Power Quick Residual Protein Detection Solution" (manufactured by Saraya Co., Ltd.). The degree of staining was visually observed again, and the cleansing ability was evaluated according to the following criteria.

[0111] [Cleaning evaluation] ⊚: No residual stains (undyed) were observed, and almost no stains (stains) were observed even after the dyeing treatment. ◯: Almost no residual stains (undyed) are observed, but some residual stains (dirt) are observed after dyeing treatment. △: Slight residual dirt (uncolored) is observed. ×: A large amount of residual stains (undyed) was observed.

[0112] The results are also shown in Table 7. [Table 7]

[0113] As shown in Table 7, it was confirmed that the mouthwash of the present invention generates fine bubbles (UFB) when components 1 and 2 are added to and dissolved in an aqueous solution, and that the bubbles remain stable in the water. It was also confirmed that the mouthwash of the present invention has superior cleaning properties compared to the comparative mouthwash in which no fine bubbles (UFB) were observed to be generated.

[0114] Experimental Example 6 Preparation and evaluation of mouthwash Gargles (gargles 1-2 of the present invention, and comparative gargles 1-3) (pH 6.5) were prepared by mixing and dissolving each component in purified water (hardness: 80 mg / L) according to the formulations shown in Table 8. Specifically, components 1-3 shown in Table 8 were mixed as necessary, and then added to and dissolved in aqueous solutions (components 4-5 and 7) that had been mixed in advance. The pH was adjusted to 6.5 with a pH adjuster (component 6) to prepare gargles. The prepared gargle solutions were evaluated for the generation of ultra-fine bubbles and their bactericidal properties using the methods described below.

[0115] (1) Evaluation of the presence or absence of ultrafine bubble generation After leaving it at room temperature for 12 hours, the scattering intensity and particle size were measured in the same manner as in Experimental Example 1, and evaluated according to the same criteria as in Experimental Example 1.

[0116] (2) Evaluation of bactericidal activity The gargle solutions (gargle solutions 1-2 of the present invention, and comparative gargle solutions 1-3) adjusted to 30°C and the bacterial solution (Streptococcus mutans: ATCC25175) (10 7 CFU / mL) was mixed at a mass ratio of 9:1, and the reaction was stopped after 1 minute with an inactivating agent (containing 4% polysorbate 80, 0.3% lecithin Tween 80 (NOF Corp.), and soybean-derived lecithin (Fujifilm Wako Pure Chemical Industries, Ltd.). The resulting reaction solution was serially diluted and mixed with a medium (tryptone soy agar medium), and the number of colonies after 24 hours of incubation at 37°C was counted. The number of colonies counted was used as the initial bacterial count (10 7 The logarithmic reduction was calculated by comparing the CFU / mL. The bactericidal activity of each gargle solution was evaluated based on the calculated logarithmic reduction according to the following criteria.

[0117] [Bactericidal evaluation] ◎: Logarithmic reduction value of 2.0 or more ○: log reduction value less than 1.5 △: log reduction value less than 1.0 ×: logarithmic reduction value less than 0.5

[0118] The results are also shown in Table 8. [Table 8]

[0119] As shown in Table 8, it was confirmed that the gargle solution of the present invention generates fine bubbles (UFB) by adding and dissolving components 1 and 2 in an aqueous solution, and the bubbles remain stable in the water. It was also confirmed that the gargle solution of the present invention has superior bactericidal power compared to the comparative gargle solution in which the generation of fine bubbles (UFB) was not confirmed.

[0120] Experimental Example 7 Preparation and evaluation of lotion According to the formulations shown in Table 9, each component was mixed and dissolved in purified water (hardness: 80 mg / L) to prepare lotions (lotions of the present invention 1-2, comparative lotions 1-3) (pH 5.0). Specifically, components 1-3 shown in Table 9 were mixed as necessary, and then added to and dissolved in a solution (components 4-5 and 7) that had been mixed in advance. The pH was adjusted to 5.0 with a pH adjuster (component 6) to prepare the lotions. The prepared lotions were evaluated for their moisturizing and irritating properties by measuring the presence or absence of ultra-fine bubbles and the sensation of use (moisturizing sensation, irritating sensation) when applied to the skin using the methods described below.

[0121] (1) Evaluation of the presence or absence of ultrafine bubble generation After leaving it at room temperature for 12 hours, the scattering intensity and particle size were measured in the same manner as in Experimental Example 1, and evaluated according to the same criteria as in Experimental Example 1.

[0122] (2) Skin sensation measurement Five expert panelists applied each lotion (lotions of the present invention 1-2, comparative lotions 1-3) to their faces after washing (amount applied to face: 5 mL), and evaluated the moist feeling and irritation sensation according to the following criteria. [Moisturizing feeling (moisturizing)] After application and leaving the product on for one hour, the moist feeling when touched was evaluated by comparing the applied skin (face) with the unapplied skin (control skin). ◎: Moist (compared to control skin) ○: (〃) Slightly moist. △: (〃) Not very moist. ×: (〃) Not moist. [Irritating sensation (irritation)] Skin irritation upon application was evaluated. ○: No irritation at all. △: Slight irritation. ×: Very irritating.

[0123] The results are also shown in Table 9. [Table 9]

[0124] As shown in Table 9, it was confirmed that the lotion of the present invention generates fine bubbles (UFB) when ingredients 1 and 2 are added to an aqueous solution and dissolved, and that the bubbles remain stable in the water. Furthermore, it was confirmed that the lotion of the present invention is less irritating and has excellent moisturizing properties compared to the comparative lotion in which the generation of fine bubbles (UFB) was not confirmed.

[0125] Experimental Example 8 Preparation and evaluation of bath additives According to the formulation shown in Table 10, each component was mixed in powder form and molded into powder or tablet form according to a conventional method to prepare solid bath additives (Bath additives of the present invention 1-2, Comparative bath additives 1-2).

[0126] (1) Evaluation of the presence or absence of ultrafine bubble generation 50 g of the prepared bath additive was added to 10 L of 38°C hot water (hardness 100 mg / L) (pH 8.2), and the presence or absence of ultra-fine bubble generation was evaluated. Specifically, the hot water was left as it was for 12 hours, after which the scattering intensity and particle size were measured in the same manner as in Experimental Example 1, and evaluation was performed according to the same criteria as in Experimental Example 1.

[0127] (2) Evaluation of bathing effects In addition, 50 g of the prepared bath additive was added to 38°C warm water (hardness 100 mg / L) (pH 8.2), and the bathing effects (body warmth and duration of warmth) were evaluated by three panelists. (a) Warmth 50 g of the bath agent of the present invention or the comparative bath agent was added to 38°C bath water (150 L), and the panelists were then asked to immediately immerse themselves in the bath up to their shoulders for 10 minutes, and the sense of warmth felt immediately after leaving the bath was evaluated. The sense of warmth felt was compared to the sense of warmth felt when bathing for 10 minutes in plain water at 38°C without the bath agent, and was evaluated according to the following criteria: [Warmth evaluation] ◎: Warmed me up much better than plain water. ○: Warmed me up better than plain water. △: Slightly warmer than plain water. ×: Warmed to the same extent as plain water.

[0128] (b) Durability of warmth In a room at 24°C, 5g of the bath agent of the present invention or the comparative bath agent was put into 38°C warm water (10L) in a thermostatic device, and then both feet were immersed in this water for 15 minutes. After 15 minutes, both feet were taken out of the water, water droplets were thoroughly wiped off, and the feet were left barefoot at room temperature for 20 minutes, after which the surface of the feet was photographed with a thermograph (Thermo Shot F30S: manufactured by Nippon Avionics). The persistence of warmth on the skin surface was evaluated based on the color of the photographed screen according to the following criteria. [Evaluation of sustained warmth] ◎: The entire image is red (warmth is extremely well-maintained) ○: The shooting screen is red and yellow (evaluated as having good warmth retention). △: The entire photographed image is yellow (there is some persistence of warmth). ×: The image is mostly blue (the warmth lasts the same as with regular hot water)

[0129] The results are also shown in Table 10. [Table 10]

[0130] As shown in Table 10, it was confirmed that the bath agent of the present invention generates fine bubbles (UFB) when added to warm water and dissolved, and the bubbles remain stable in the water. In addition, it was confirmed that the bath agent of the present invention is superior in warmth and long-lasting warmth compared to the comparative bath agent which did not generate fine bubbles (UFB) even when added to warm water.

[0131] Experimental Example 9 Preparation and evaluation of cleaning agents for medical instruments According to the formulation shown in Table 11, each component was mixed in powder form and molded into powder or tablet form according to a conventional method to prepare solid medical instrument cleaners (medical instrument cleaners of the present invention 1 to 3 and comparative medical instrument cleaners 1 to 3). 0.5 g of the prepared bath additive was added to 100 mL of 20°C water (hardness 100 mg / L) placed in a beaker (pH 9.0), and the presence or absence of ultra-fine bubbles was evaluated, as well as the cleaning ability against blood stains.

[0132] (1) Evaluation of the presence or absence of ultrafine bubble generation The sample was placed in water and allowed to stand for 12 hours, after which the scattering intensity and average number particle size were measured in the same manner as in Experimental Example 1, and evaluated according to the same criteria as in Experimental Example 1.

[0133] (2) Cleaning evaluation of blood stains Cleaning evaluation was performed using a cleaning evaluation indicator TOSI (manufactured by Pereg) contaminated with blood. This was immersed in medical instrument cleaners (medical instrument cleaners 1-3 of the present invention, and comparative medical instrument cleaners 1-3) (20°C) for 120 minutes. After immersion, it was rinsed with running water for 30 seconds, dried, and visually observed. Those in which no dirt was found were stained with "Power Quick Residual Protein Detection Solution" (manufactured by Saraya Co., Ltd.). The degree of staining was visually observed again, and the cleaning ability was evaluated according to the following criteria. [Cleaning evaluation] ⊚: No residual stains (undyed) were observed, and almost no stains (stains) were observed even after the dyeing treatment. ◯: Almost no residual stains (undyed) are observed, but some residual stains (dirt) are observed after dyeing treatment. △: Slight residual dirt (uncolored) is observed. ×: A large amount of residual stains (undyed) was observed.

[0134] The results are also shown in Table 11. [Table 11]

[0135] As shown in Table 11, it was confirmed that the medical instrument cleaner of the present invention generates fine bubbles (UFB) when added to water and dissolved, and that the bubbles remain stably in the water. Furthermore, it was confirmed that the medical instrument cleaner of the present invention has superior cleaning ability against blood stains compared to the comparative medical instrument cleaner, which was not confirmed to generate fine bubbles (UFB) when added to water.

[0136] Experimental Example 10: Preparation and evaluation of dishwashing detergents According to the formulation shown in Table 12, each component was mixed in powder form and molded into powder or tablet form according to a conventional method to prepare solid dishwashing detergents (dishwashing detergents 1 to 3 of the present invention and comparative dishwashing detergents 1 to 3). 50 g of the prepared dishwashing detergent was added to 10 L of water (hardness 100 mg / L) at 40°C (pH 8.2) placed in an immersion tank, and the presence or absence of ultra-fine bubbles was evaluated, as well as the cleaning ability against starch.

[0137] (1) Evaluation of the presence or absence of ultrafine bubble generation The particles were placed in water at 40° C. and left for 12 hours, after which the scattering intensity and particle size were measured in the same manner as in Experimental Example 1, and evaluated according to the same criteria as in Experimental Example 1.

[0138] (2) Cleaning evaluation of starch stains Packed rice (S&B Foods) was heated in a microwave oven and approximately 100 g was spread over the entire center of a porcelain dish with a diameter of 19 cm. After leaving it for 10 minutes, the rice was removed from the dish and dried at room temperature for 1 hour. The rice was then immersed in water (40°C) for 5 minutes in an immersion tank containing dishwashing detergents (dishwashing detergents 1 to 3 of the present invention and comparative dishwashing detergents 1 to 3). The dish was immediately removed from the immersion tank and washed in hot water at 60°C for 1 minute using a commercial dishwasher (ZANUSSI520), and then dried. After drying, the entire inside of the dish was dyed with an iodine solution. After dyeing, the degree of dyeing was visually observed to evaluate the cleaning properties.

[0139] [Cleaning evaluation] ○: Almost no staining (residual dirt) is observed. △: Slight staining (residual dirt) is observed. ×: Much staining (residual dirt) is observed.

[0140] The results are also shown in Table 12. [Table 12]

[0141] As shown in Table 12, it was confirmed that the dishwashing detergent of the present invention generates fine bubbles (UFB) when added to water and dissolved, and the bubbles remain stable in the water. Furthermore, it was confirmed that the dishwashing detergent of the present invention has excellent cleaning properties, particularly cleaning properties for starch stains, compared with the comparative dishwashing detergent that was not confirmed to generate fine bubbles (UFB) when added to water.

[0142] Experimental Example 11 Preparation and Evaluation of Laundry Detergent According to the formulation shown in Table 13, each component was mixed in powder form and molded into powder or tablet form according to a conventional method to prepare solid laundry detergents (Laundry detergents 1 to 3 of the present invention and Comparative laundry detergents 1 to 3). 1 g of the prepared laundry detergent was added to 1 L of warm water (hardness 100 mg / L) at 30°C in a beaker (pH 8.2 or 11.1), and the presence or absence of ultra-fine bubbles was evaluated, as well as the cleaning ability for artificially soiled cloth. The results are shown in Table 13.

[0143] (1) Evaluation of the presence or absence of ultrafine bubble generation The sample was placed in 30° C. warm water and left there for 12 hours, after which the scattering intensity and particle size were measured in the same manner as in Experimental Example 1, and evaluated according to the same criteria as in Experimental Example 1.

[0144] (2) Washing evaluation of artificially soiled fabrics The evaluation was carried out using a wet artificially soiled cloth modeled on collar dirt and a tergotometer. 1 L of tap water was placed in the test cup of a tergotometer (TM-8, manufactured by Daiei Kagaku Seiki Seisakusho), and 5 g of laundry detergent (laundry detergents 1-3 of the present invention, and comparative laundry detergents 1-3) and the artificially soiled cloth were placed in the test cup. The cloth was washed at 120 rpm at 30°C for 10 minutes. The cloth was then rinsed with 1 L of 30°C tap water for 3 minutes and drained twice. The cloth was lightly squeezed by hand and finished by ironing and dried. The whiteness of the soiled cloth before and after washing was measured using a reflectometer (CM-600D, Minolta), and the cleaning rate was calculated using the following formula 3. [Formula 3] Cleaning rate (%) = (Whiteness of soiled cloth after washing - Whiteness of soiled cloth before washing) / (Whiteness of standard white cloth - Whiteness of soiled cloth before washing) x 100

[0145] [Cleaning evaluation] 〇: Cleaning rate is 60% or more △: Cleaning rate is 50% or more ×: cleaning rate is 40% or less.

[0146] The results are also shown in Table 13. [Table 13]

[0147] As shown in Table 13, it was confirmed that the laundry detergent of the present invention generates fine bubbles (UFB) when added to warm water and dissolved, and the bubbles remain stable in the water. In addition, it was confirmed that the laundry detergent of the present invention has excellent cleaning properties against dirt and grime, compared with the comparative laundry detergent, which was not confirmed to generate fine bubbles (UFB) even when added to warm water.

[0148] Experimental Example 12 CO 2 Stability of microscopic gas bubbles The stability test was carried out using test sample 1-2 shown in Experimental Example 1 (see Table 1). Specifically, each component was mixed so that the final concentration in water would be the ratio (final concentration: mass %) shown in Table 1 (Test Sample 1-2), and then added to 1 L of tap water (hardness 100 mg / L) (room temperature) in a glass beaker, and stirred using a stirrer and a stirrer to dissolve (pH 8.2), allowing each component to react (generation of CO2 gas). This was placed in a 50 mL glass bottle and stored in a dark place at room temperature for 1 month, 6 months, and 12 months.

[0149] The results are shown in Table 14. The results shown in Table 14 were evaluated based on the same criteria as in Experimental Example 1. [Table 14]

[0150] As shown in Table 14, both the scattering intensity and the average number particle size were stable for as long as one year. This confirmed that the fine bubbles (UFB) generated in water by the method of the present invention remained stably in water for a long period of time.

[0151] Experimental Example 13: Measurement of dynamic surface tension Using SL or various surfactants shown in Tables 15 and 16 as the surfactant, CO2 gas was generated in water and the generated bubbles were evaluated in the same manner as in Experimental Example 1. In addition, the dynamic surface tension of the prepared aqueous solution was measured over time to investigate the relationship between the state of the generated bubbles and the dynamic surface tension.

[0152] The surfactant raw materials used in Experimental Example 13 are as follows. Note that the parentheses indicate the symbols of the lines shown in Figures 1 and 2. [Test Samples 13-A1, B1] SL-containing composition 1: Same as Experimental Example 1 (-■-) [Test Sample 13-A2, B2] Sodium alkyl polyoxyethylene sulfate: Teikapol NE1230 (manufactured by Teika Co., Ltd.) (-△-) [Test Sample 13-A3, B3] Dimethyldidecylammonium chloride: Cationic DDC-80T (manufactured by Sanyo Chemical Industries, Ltd.) (―◇―) [Test sample 13-A4, B4] Benzalkonium chloride: Albumin 1214 (manufactured by Taikai Chemical) (―◆―) [Test Sample 13-A5, B5] Lauryl dimethylaminoacetate betaine: Rikabion A-100 (manufactured by Shin Nippon Rika Co., Ltd.) (-x-) [Test sample 13-A6, B6] Lauryl dimethylamine oxide: Amphitol 20N (Kao Corporation) (-+-) [Test Sample 13-A7, B7] POE lauryl ether: Emulgen 103 (Kao Corporation) (-●-) [Test Sample 13-A8, B8] POE stearyl ether (6EO): Emulgen 306 (Kao Corporation) (-○-)

[0153] (1) Preparation of test samples Each component was added so that the final concentration in water would be the ratio (mass%) shown in Tables 15 and 16, and then added to 1 L of tap water (hardness 100 mg / L) (room temperature) in a glass beaker, and dissolved (pH 8.2) by stirring using a stirrer and a stirrer, and each component was allowed to react (CO2 gas generation).

[0154] (2) Measurement of scattering intensity and particle size of bubbles Each test sample prepared above was left to stand at room temperature for 12 hours, after which the scattering intensity and particle size were measured in the same manner as in Experimental Example 1. The scattering intensity was calculated by subtracting the scattering intensity value of the SL-containing composition 1 or the aqueous solution in which various surfactants were dissolved (control sample 1) and the scattering intensity value of the aqueous solution in which component C was dissolved (control sample 2) from the scattering intensity value of the aqueous solution in which all components were dissolved (test sample), as shown in the above formula 2.

[0155] (3) Measurement of dynamic surface tension The dynamic surface tension of each surfactant used in the preparation of each test sample was measured. A bubble pressure dynamic surface tensiometer (BP-100: manufactured by KURSS) was used to measure the dynamic surface tension. Specifically, aqueous solutions of each surfactant (0.01% and 0.05%) were placed in special petri dishes and subjected to dynamic surface tension measurements under the following conditions. Surface age refers to the time from when the interface begins to form until the pressure reaches its maximum. Measurement temperature: 25℃, Surface life: 10msec~10000msec.

[0156] The results for a surfactant concentration of 0.01% are shown in Table 15 and Figure 1, and the results for a surfactant concentration of 0.05% are shown in Table 16 and Figure 2, respectively. [Table 15] [Table 16]

[0157] As shown in Tables 15 and 16 and Figures 1 and 2, it was confirmed that CO2 gas was generated by coexisting bicarbonate with a surfactant in water, but after 12 hours, the generation of fine particles (UFB) was confirmed based on the scattering intensity and particle size only in test samples 13-A1 and 13-B1 (in each figure, --■-) using SL-containing compositions. The surface tension of these samples decreased more slowly than that of test samples 13-A2 to 7 and test samples 13-B2 to 7 using other surfactants except POE stearyl ether, and it was confirmed that they were easily compatible with water. Specifically, the surface tension of test sample 13-A1 (SL concentration: 0.01%) remained at 70 mN / m or more even after 1 second, but all of test samples 13-A2 to 7 had decreased to less than 70 mN / m. Furthermore, the surface tension of test sample 13-B1 (SL concentration: 0.05%) remained at 60 mN / m or more even after 10 seconds, but test samples 13-B2 to 13-B7 all significantly decreased to less than 60 mN / m.

[0158] On the other hand, in the test samples 13-A8 and B8 (-○- in each figure), which used POE stearyl ether (6EO) as a surfactant, fine particles (UFB) were not generated, even though the speed at which the dynamic surface tension decreased was slow. The reason for this is that POE stearyl ether (6EO) is a non-ionic surfactant.

[0159] The fine bubbles generated from the gas generating component targeted by the present invention have a negative charge. Therefore, positively charged substances gather around them, forming a positive / negative electric double layer. Since SL has a negative charge on its hydrophilic group, it is considered to be attracted to the positive charge of the electric double layer of the fine bubbles, adsorbed to the fine bubbles, and stabilized. On the other hand, since POE stearyl ether (6EO) does not have a charge on its hydrophilic group, it is considered to be not attracted to the electric double layer of the fine bubbles and not adsorbed to the fine bubbles. From these facts, it is considered that the generation and stability (retention) of fine bubbles in water are influenced by the surface tension characteristics (anionicity, slow dynamic surface tension) of the SL-containing composition, although this is not limited thereto.

Claims

1. An ultra-fine bubble generator for generating ultra-fine bubbles in an aqueous solvent without using a bubble generator, comprising: The ultra-fine bubble product is obtained by combining the following (A), (B) and (C): (A) a sophorolipid containing an acid-type sophorolipid and a lactone-type sophorolipid in a ratio of 78:22 to 100:0 (mass ratio); (B) Free fatty acid or its salt (C) A gas generating component.

2. The ultra-fine bubble product according to claim 1, wherein (C) is at least one selected from the group consisting of a carbon dioxide gas generating component, an oxygen gas generating component, a hydrogen gas generating component, and a chlorine gas generating component.

3. The ultra-fine bubble product according to claim 2, wherein the carbon dioxide gas generating component is a carbonate or bicarbonate salt, or a combination with its counterpart; the oxygen gas generating component is hydrogen peroxide, or a combination with its counterpart; the hydrogen gas generating component is a hydride salt, a borohydride salt, or hydrochloric acid, or a combination with its counterpart; or the chlorine gas generating component is a hypochlorite, or a combination with its counterpart.

4. The ultra-fine bubble product according to any one of claims 1 to 3, which is a blend of (A), (B) and (C), or a combination in which at least (C) is packaged separately from (A) and (B).

5. The ultra-fine bubble product according to any one of claims 1 to 4, which is a cleaning agent, a bath additive, a cosmetic, a mouthwash, a gargle, a texture improver, a food or drink, a plant growth promoter, a fish and shellfish growth promoter, or a bactericide.

6. (A) adding the following (A), (B), and (C) to water having a hardness of 30 to 200 mg / L and allowing these three components to coexist in the water; and (a) generating bubbles in the water without introducing gas from the outside; A method for generating ultra-fine bubbles comprising: (A) a sophorolipid containing an acid-type sophorolipid and a lactone-type sophorolipid in a ratio of 78:22 to 100:0 (mass ratio); (B) Free fatty acid or its salt (C) A gas generating component.

7. 7. The method for generating ultra-fine bubbles according to claim 6, wherein in the step (a), (A) and (B) are added to water so that the concentration of (A) in the water is 0.005% by mass or more and the concentration of (B) in the water is 0.0001% by mass or more.

8. 8. The method for generating ultra-fine bubbles according to claim 6 or 7, characterized in that in the step (a), (C) is added to water so that the concentration of (C) in the water is 0.1 mass% or more as a concentration of the gas generating body.

9. An ultra-fine bubble-containing liquid containing the following (A), (B), (c) and (d): (A) a sophorolipid containing an acid-type sophorolipid and a lactone-type sophorolipid in a ratio of 78:22 to 100:0 (mass ratio); (B) a free fatty acid or a salt thereof, (c) fine bubbles having an average particle size of less than 1000 nm, formed from at least one gas selected from the group consisting of carbon dioxide gas, oxygen gas, hydrogen gas, and chlorine gas; and (d) water; However, this does not include liquids containing ultra-fine bubbles that are generated using a bubble generating device by introducing gas from the outside.

10. 10. The ultra-fine bubble-containing liquid according to claim 9, wherein the concentration of (A) is 0.005% by mass or more and the concentration of (B) is 0.0001% by mass or more.

11. The ultra-fine bubble-containing liquid according to claim 9 or 10, wherein (d) is water having a hardness of 30 to 200 mg / L.

12. (A) adding the following (A), (B), and (C) to water having a hardness of 30 to 200 mg / L and allowing these three components to coexist in the water; and (a) generating bubbles in the water without introducing gas from the outside; A method for producing an ultra-fine bubble-containing liquid comprising the steps of: (A) a sophorolipid containing an acid-type sophorolipid and a lactone-type sophorolipid in a ratio of 78:22 to 100:0 (mass ratio); (B) Free fatty acid or its salt (C) A gas generating component.

13. 13. The method according to claim 12, wherein the (C) is at least one selected from the group consisting of a carbon dioxide gas generating component, an oxygen gas generating component, a hydrogen gas generating component, and a chlorine gas generating component.

14. 14. The method according to claim 12 or 13, wherein in the step (a), (A) and (B) are added to water so that the concentration of (A) in the water is 0.005% by mass or more and the concentration of (B) in the water is 0.0001% by mass or more.

15. The manufacturing method according to any one of claims 12 to 14, characterized in that in the step (a), (C) is added to water so that the concentration of (C) in the water is 0.1 mass% or more as a concentration of the gas generating main body.

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