Production method and production apparatus for nano-bubble-containing composition

Abstract

To provide a production method and a production apparatus for a nano-bubble-containing composition (hydrogen gas and / or carbon dioxide gas composition) having high productivity, high dispersibility and a high safety property, in particular, suitable for cosmetics and quasi-drugs, and capable of dispersing and holding hygienically safe nano-sized hydrogen gas and / or carbon dioxide gas for a long time.SOLUTION: A production method for a nano-bubble-containing composition includes: a dispersion step of dispersing, through a membrane filter, hydrogen gas and / or carbon dioxide gas into a fluid base material which is a physiologically acceptable medium; and a micronizing step of micronizing, by ultrasonic waves, the hydrogen gas and / or carbon dioxide gas dispersed in the base material.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method and an apparatus for preparing a nanobubble-containing composition (hydrogen gas and / or carbon dioxide gas composition) that contains nano-sized hydrogen gas and / or carbon dioxide gas and can be suitably used in massage oils and body care cosmetics. [Background technology]

[0002] It has long been known that applying skin oil to the body can provide the skin with moisturizing, lubricating and moisturizing effects. Roughly speaking, this mechanism is due to the oil film or the like suppressing the evaporation of water from the skin. In particular, in the case of massage oils used in beauty salons, the lubricating properties of the oil film make it possible to massage without damaging the skin, and skin oils and massage oils can also be used for body care by adding aromatic oils with sedative effects or nutrients that are absorbed through the skin.

[0003] In particular, with regard to the additives to be added to the above-mentioned skin oil, if the additives are not lipophilic, they will separate from the skin oil, and therefore need to be emulsified with a surfactant, as described in, for example, Patent Document 1 (JP Patent Publication No. 2012-518601). However, the method of Patent Document 1 has a problem that the dispersibility is insufficient, although the production process is somewhat complicated, and further, since a surfactant is contained, there is a concern that it may affect the skin, etc., due to allergies, etc. In other words, there is room for improvement in terms of productivity, dispersibility, and safety.

[0004] Conventional cosmetics and quasi-drugs that contain hydrogen gas include (1) those in which hydrogen is dissolved in water or oil, and (2) those that generate hydrogen just before use using hydrogen-generating metal salts such as sodium hydride or magnesium hydride. Conventional cosmetics and quasi-drugs that contain carbon dioxide include (3) those in which carbon dioxide is compressed and melted and mixed in like a carbonated drink, (4) those in which carbon dioxide is generated by reacting sodium bicarbonate with an acid such as citric acid or succinic acid, and (5) those in which carbon dioxide is used as the propellant in an aerosol and is sprayed together with the propellant liquid.

[0005] However, the above (1) cannot be stored in liquid for long periods of time due to the small size of the hydrogen molecules and high diffusion coefficient. Even if hydrogen is stored in a leak-proof container such as aluminum, hydrogen gas will escape from the liquid and be released to the outside when the container is opened. The above (2) requires the user to mix it immediately after purchase and cannot be used immediately after taking it out of the container. In addition, water is required for the reaction that releases hydrogen, making it unsuitable for cosmetic oils or massage oils that do not contain moisture. Furthermore, with the above (3), the amount of carbon dioxide gas decreases if the container is opened repeatedly or if it is left open for a long time, and people with sensitive skin often find it irritating and cannot use it. In addition, the above (4) requires the user to mix it immediately after purchase and cannot be used immediately after taking it out of the container. The above (5) has the disadvantage that it can only be manufactured as an aerosol product.

[0006] On the other hand, for example, Patent Document 2 (WO 2020 / 136716) and Patent Document 3 (JP 2019-181336 A) disclose techniques for producing nanobubble-containing compositions. However, in the technology of Patent Document 2, if the gas release member with many open gas release holes is not always in the liquid, the holes will become clogged, and if the nanobubble-containing composition is oil or fat, wax ester, coconut oil, horse oil, etc., may solidify in some cases. If a cleaning solution or solvent is used for cleaning, the cleaning agent will remain, and even a small amount of contamination will affect the skin, making it unsuitable for cosmetics and quasi-drugs. In addition, when dispersing nanobubbles in oil or fat, the surface tension is too low, making it difficult to create a stable number of nanobubbles. In addition, the technology of Patent Document 3 places a load on the ultrasonic vibrator and cannot be used for long periods of time, and if ultrasonic waves are continuously irradiated onto the liquid containing nanobubbles, the nanobubbles themselves are deaerated by the ultrasonic waves, causing a cavitation phenomenon. Furthermore, as in the case of Patent Document 2, the holes become clogged, and in the case of oils and fats, the nanobubble-containing composition may solidify in some cases, such as wax esters, coconut oil, and horse oil. If a cleaning solution or solvent is used for cleaning, the cleaning agent remains, and even a small amount of contamination can affect the skin, making it unsuitable for cosmetics and quasi-drugs. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 2012-518601 [Patent Document 2] International Publication No. 2020 / 136716 [Patent Document 3] JP 2019-181336 A Summary of the Invention [Problem to be solved by the invention]

[0008] In view of the above-mentioned problems in the conventional art, an object of the present invention is to provide a method and an apparatus for producing a nanobubble-containing composition (hydrogen gas and / or carbon dioxide gas composition) that has high productivity, dispersibility and safety, and is capable of dispersing and maintaining hygienically safe nano-sized hydrogen gas and / or carbon dioxide gas for a long period of time, which is particularly suitable for cosmetics and quasi-drugs. DISCLOSURE OF THEINVENTION [Means for solving the problem]

[0009] In order to solve the above problems, the present inventors conducted extensive experiments and studies, and as a result, made repeated improvements to the nanobubble production technology, and realized a production method and production apparatus for a nanobubble-containing composition (hydrogen gas and / or carbon dioxide gas composition) that has high productivity, dispersibility and safety, and is capable of dispersing and maintaining hygienically safe nano-sized hydrogen gas and / or carbon dioxide gas for a long period of time, which is particularly suitable for cosmetics and quasi-drugs.

[0010] That is, the present invention provides: A dispersion step of dispersing hydrogen gas and / or carbon dioxide gas through a membrane filter into a fluid base material that is a physiologically acceptable medium; a micronization step of micronizing the hydrogen gas and / or carbon dioxide gas dispersed in the base material by ultrasonic waves; containing, The present invention provides a method for producing a nanobubble-containing composition, comprising the steps of:

[0011] In the method for producing the nanobubble-containing composition of the present invention, In the dispersion step, while irradiating the base material with ultrasonic waves by a vibrator, hydrogen gas and / or carbon dioxide gas is dispersed into the base material through the membrane filter; is preferred.

[0012] In the method for producing the nanobubble-containing composition of the present invention, The wavelength of the oscillator is 0.5 MHz to 3 MHz; is preferred.

[0013] Furthermore, in the method for producing the nanobubble-containing composition of the present invention, carrying out the dispersion step and the micronization step simultaneously; is preferred.

[0014] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: a first pump for supplying a fluid substrate, the fluid substrate being a physiologically acceptable medium; A second pump for dispersing hydrogen gas and / or carbon dioxide gas into the substrate; a membrane filter through which the hydrogen gas and / or carbon dioxide gas passes before being dispersed in the base material; A vibrator for irradiating the substrate with ultrasonic waves to disperse the hydrogen gas and / or carbon dioxide gas; The provision of: The present invention also provides an apparatus for producing a nanobubble-containing composition, comprising: Effect of the Invention

[0015] According to the present invention having the above configuration, it is possible to realize a method and apparatus for producing a nanobubble-containing composition (hydrogen gas and / or carbon dioxide gas composition) that has high productivity, dispersibility and safety, and is capable of maintaining hygienically safe nano-sized hydrogen gas and / or carbon dioxide gas in a dispersed state for a long period of time, which is particularly suitable for cosmetics and quasi-drugs.

[0016] According to the above-mentioned method and apparatus for producing a nanobubble-containing composition of the present invention, it is possible to obtain a composition in which hydrogen and / or carbon dioxide gas in the form of nanobubbles is dispersed in a base liquid of cosmetics or quasi-drugs. The obtained composition makes it possible to produce cosmetics or quasi-drugs that are excellent in retarding the oxidation and deterioration of ingredients (only hydrogen) and improving the permeability of ingredients into the skin, thereby improving skin quality and blood flow. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a conceptual diagram for explaining the flow of a method for producing a nanobubble-containing composition according to an embodiment of the present invention. [Diagram 2] FIG. 1 is a schematic diagram illustrating a production apparatus for a nanobubble-containing composition according to an embodiment of the present invention. [Diagram 3] FIG. 3 is a schematic enlarged view of the dashed line portion in FIG. 2. [Figure 4] FIG. 4 is a schematic enlarged view of the dashed line portion in FIG. [Diagram 5] 1 is a photograph showing a microscope image of the cuticle of a nail in an example of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Representative embodiments of the method and apparatus for producing a nanobubble-containing composition according to the present invention will be described in detail below with reference to the drawings. However, the present invention is not limited to those shown in the drawings. Since the drawings are intended to conceptually explain the present invention, dimensions, ratios, or numbers may be exaggerated or simplified as necessary for ease of understanding. In the following description, the same or equivalent parts are denoted by the same reference numerals, and duplicated descriptions may be omitted.

[0019] As shown in FIG. 1, in the method for producing a nanobubble-containing composition (also referred to as a nanobubble composition) according to this embodiment, hydrogen gas and / or carbon dioxide gas G1 are added to and mixed with a fluid base material L1, which is a physiologically acceptable medium, to obtain a nanobubble-containing composition L2 containing nano-sized hydrogen gas and / or carbon dioxide gas.

[0020] According to the present invention, by converting hydrogen gas and / or carbon dioxide gas into nanobubbles, Brownian motion can be caused in the liquid, allowing the bubbles to exist for a long period of time. In addition, it is difficult to mix carbonated water and hydrogen water because both release gas within a short time. In fact, when carbonated water and hydrogen water are mixed, when 10g of hydrogen water is added to 100g of carbonated purified water with a pH of 5.8, the pH becomes close to 7 within one minute. This is thought to be because the equilibrium reaction in which carbon dioxide gas reacts with water to produce carbonate ions and hydrogen ions is disrupted by the addition of hydrogen ions to the right side, causing the reaction to proceed to the left. CO2+H2O ⇔ CO3 2- + 2H + In contrast, when nanobubbled carbon dioxide gas and hydrogen gas are dispersed in water according to the present invention, it is possible for hydrogen gas and carbon dioxide gas to exist simultaneously.

[0021] In the present invention, hydrogen gas and / or carbon dioxide gas are used because hydrogen has high reducing properties and binds with active oxygen, making it possible to prevent oxidative deterioration of the target cosmetics and quasi-drugs. This is particularly effective for cosmetic oils, massage oils, and products that contain oils with activators. The purpose of adding carbon dioxide gas to cosmetics is to promote blood flow, known as the Bohr effect, which can deliver sufficient nutrients to skin cells and regulate turnover. In addition, hydrogen and carbon dioxide gas (and other gases) nanobubbles have the property of easily adsorbing proteins such as makeup, sebum, and old keratin, and are effective in keeping the skin healthy when washing the face.

[0022] Regarding carbon dioxide, the aroma of emulsions of oils and fats and herbal water changes after about two months at room temperature (for example, in the case of water and olive oil, the oxidized smell of the oil was noticeable after two months, and in the case of rose water, the aroma became weaker compared to the blank after about two weeks). This is thought to be due to the carbon dioxide causing the pH to shift to the acidic side, and this can be easily and safely prevented by adjusting the pH to near neutral (pH = 6-7) using an alkali.

[0023] One embodiment of an apparatus for producing a nanobubble-containing composition that can be suitably used in the method for producing a nanobubble-containing composition of the present invention is shown in Fig. 2. As shown in Fig. 2, the apparatus for producing a nanobubble-containing composition 1 of this embodiment includes a first pump for supplying a fluid base material that is a physiologically acceptable medium, a second pump 4 for dispersing hydrogen gas and / or carbon dioxide gas in the base material, a membrane filter 6 through which the hydrogen gas and / or carbon dioxide gas passes before being dispersed in the base material, and a vibrator 8 for irradiating ultrasonic waves to the base material in which the hydrogen gas and / or carbon dioxide gas is dispersed.

[0024] [Dispersion process] The manufacturing method of this embodiment first includes a dispersion step of supplying hydrogen gas and / or carbon dioxide gas through a membrane filter into a fluid base material, which is a physiologically acceptable medium, and mixing and dispersing the gas in the fluid. That is, as shown in Fig. 3, which is a schematic enlarged view of the dashed line portion in Fig. 2, hydrogen gas and / or carbon dioxide gas are mixed and dispersed in the base material supplied to the pipe 10a through the pipe 10a and the membrane filter 6.

[0025] As the fluid substrate, which is the physiologically acceptable medium, various liquids, solutions, fluids, dispersions, etc. (including water such as distilled water and oils and fats) can be used, but it is preferable that the medium is physiologically acceptable. Examples of such substrates (mediums) include the following. In addition, various additives may be included as long as they do not impair the effects of the present invention.

[0026] Jojoba oil Sweet almond oil Grapeseed oil Apricot kernel oil Macadamia nut oil Olive oil Olive squalane Sunflower oil Camellia oil Sesame oil Argan oil Raspberry seed oil Coconut oil Walnut oil Kukui nut oil Calophyllum oil (Tamanu oil) Passion flower oil Peach kernel oil Hazelnut oil Hemp seed oil Avocado oil Aloe vera oil Evening primrose oil Wheatgerm oil Castor oil Orange seed oil · Sea buckthorn oil (Sea buckthorn oil) Flaxseed oil Borage oil Rosehip oil Prune seed oil Marula oil Squalane oil Perilla seed oil Andiroba Oil Inca Inchi Oil Cashew nut oil Camelina oil Kiwi seed oil Cucumber seed oil Guava seed oil Cranberry seed oil Grapefruit seed oil ·Rice oil Rice bran oil Rice bran oil <Leached oil> Echinacea oil St. John's Ward Oil Calendula oil Arnica oil Carrot oil Gotu kola oil, hydrocotyle oil Comfrey oil

[0027] Here, when the nanobubble-containing composition obtained by the present invention is used as a cosmetic, examples of the base material include emollient cream, moisture milk, moisturizing lotion, treatment rinse, skin lotion for sensitive skin, skin lotion for wiping off, skin lotion for keeping makeup, hair straightening water, lotion for men, milky lotion for children, baby lotion, summer lotion, daytime milky lotion, etc. Examples of the applicable cosmetic products include the following. ·Skin cosmetics Skin lotions, lotions, softening lotions, astringent lotions, astringents and other lotions, moisturizing liquids, beauty serums, essences and other cosmetic liquids, creams such as oily creams, medium oily creams, weak oily creams, milk lotions, skin milks, milk and other emulsions Suntan, Sunprotect and other sunscreen cosmetics Facial cleansers, cleansers, make-up removers, face washes, facial soaps, scrub cosmetics, body shampoos, body soaps, body washes, hand soaps and other cleansing products Pre-shaving, after-shaving, and other shaving and hair removal cosmetics Other facial rinses and mask pack liquids Hair cosmetics Hair oil, camellia oil, styling (fee), set (fee), blow dry (fee) Hair styling products such as brushing products, hair sticks, pomades, hair creams, hair milks, hair solids, hair wax, hair balms, hair sprays, hair mist, hair lacquers, hair liquids, hair water, hair foams, and hair gels Tonics, hair lotions, hair essences, hair treatments, hair conditioners, hair packs, and other hair care products Other scalp treatments, shampoos, hair treatments, hair rinses Nail cosmetics Nail enamel, manicure, nail color, nail polish, pedicure, nail lacquer, enamel thinner, nail cream, nail oil, nail polish remover, enamel remover, nail color remover, nail essence, gel nails Perfume, cologne, etc.

[0028] The nanobubble-containing composition obtained by the present invention contains nano-sized hydrogen gas and / or carbon dioxide gas bubbles, and the size of these nanobubbles is preferably 200 μm or less in diameter, and more preferably 10 μm or more and 200 μm or less. If the size is within this range, when the nanobubble-containing composition of the present invention is applied to the body, air and additives that are smaller than the pores in cells can easily penetrate into the body, thereby exerting their effects and efficacy. In particular, gases such as hydrogen are stably taken into the body due to the effect of nanobubbles, and are expected to have effects such as increasing metabolism.

[0029] Furthermore, in the nanobubble-containing composition of the present invention, it is preferable that the number of nanobubbles of nanohydrogen gas and / or nanocarbon dioxide gas having the above-mentioned size is as large as possible in the substrate, for example, more than 600 million, more preferably 1 billion or more. There is no upper limit, but it is particularly preferable that, for example, 100 billion are present.

[0030] In addition, it is preferable that the number of nanobubbles of hydrogen gas and / or carbon dioxide gas does not decrease as much as possible over time, and specifically, it is preferable that the decrease rate after 5 hours is 99% or more. In the case of conventional hydrogen water with dissolved hydrogen molecules, the decrease rate after 5 hours is close to 100%.

[0031] In the above dispersion step, the flow rates of the base material, hydrogen gas, and carbon dioxide gas may be appropriately adjusted within a range that does not impair the effects of the present invention. However, the inventors have confirmed through experiments that the effects of the present invention can be obtained more reliably if the flow rates are within the following ranges. Hydrogen gas 0.1~5.0mL / min Preferably 0.5 to 2.0 mL / min More preferably, 1.0 mL / min Carbon dioxide gas 0.1~30.0mL / min Preferably 1.0 to 10.0 mL / min Gas pressure (equipment inlet) 0.01~0.05MPa Preferably 0.02 to 0.04 MPa More preferably, 0.03 MPa -Base material flow rate: 0.5~2.0L / min Preferably 1.0 to 2.0 L / min More preferably 1.5 L / min

[0032] [Refining process] Next, the manufacturing method of this embodiment includes a micronization step in which the hydrogen gas and / or carbon dioxide gas mixed and dispersed in the base material is micronized by ultrasonic waves. In particular, as shown in Fig. 3, when hydrogen gas and / or carbon dioxide gas are mixed and dispersed in the base material supplied to the pipe 10a through the pipe 10a and the membrane filter 6, the base material membrane filter 6 is irradiated with ultrasonic waves. This causes the hydrogen gas and / or carbon dioxide gas to be micronized in the base material to become nanobubbles. In other words, the dispersion step and the micronization step are carried out simultaneously.

[0033] Here, various types of membrane filters can be used as the membrane filter 6, including porous membranes with uniform pore sizes made of, for example, fluororesin or cellulose acetate, and commercially available products with various pore sizes can be used. For example, a filter with a hole diameter of 100 μm or less, a diameter of 10 mm or more, and a thickness of 150 μm or more can be used. In particular, the pore diameter may be 0.2 to 8.0 μm, preferably 0.2 to 5.0 μm, and more preferably 0.2 to 1.0 μm.

[0034] Furthermore, the membrane filter 6 is lightweight and its thin film easily resonates with ultrasonic vibrations, so that vibrations in the liquid are sufficient to generate nanobubbles without directly connecting a vibrating plate to the filter. This also extends the life of the ultrasonic transmitter. Furthermore, the membrane filter 6 is only about 10 μm to 20 μm thick, so it is easy to clean and replace, making it suitable for the manufacture of cosmetics and quasi-drugs that must be protected from contamination by bacteria, etc.

[0035] Here, as the transducer 8 used for irradiating the membrane filter 6 and the base material with ultrasonic waves, a conventionally known transducer may be used, and the operating conditions of the above-mentioned production apparatus 1 are generally as follows. Resonant frequency fr: 1.66MHz±50KHz Resonant impedance Zm: <2Ω Electrical coupling coefficient Kt:>40% Capacitance Cs: 2050pF±20% ·Environmental temperature and humidity: 23±3℃ and 40~70%RH ·Average atomization: 400cc / hr Transducer life: 10,000 hours (min) at water temperature of 5 to 40°C 3000hr(min) at water temperature 55~60℃ Dimensions: Silicone rubber diameter 30mm Cable UL1007 24AWG 80mm Ultrasonic transducer wavelength 0.5~3.0MHz Preferably 1.0 to 3.0 MHz More preferably, 1.5 to 2.4 MHz

[0036] Under the above conditions, for example, 1.54 × 10 9 It is possible to obtain a nanobubble-containing composition having a nanobubble content of nanobubbles / mL (min). Although one embodiment of the present invention has been described, the present invention is not limited to these embodiments, and there are other improvements and modifications within the scope of the spirit and teachings of the claims, all of which are included in the technical scope of the present invention.

[0037] The present inventors have found through experiments that the difference in the number of nanobubbles (hydrogen) generated in 1 mL (pieces / mL) at each wavelength is as follows. [Table 1]

[0038] From these results, it is believed that bubbles break down due to cavitation when the wavelength is 0.2 MHz or less, and that at wavelengths of 5.0 MHz or more, microbubbles and millibubbles are often formed, which tend to aggregate and grow larger, causing the nanobubbles to disappear. EXAMPLES

[0039] Nanobubble compositions were prepared using a production apparatus 1 having the structure shown in Figs. 1 to 4, and the following experiments were carried out to evaluate their effects (oxidative deterioration of jojoba oil, etc.).

[0040] A major issue with regard to the quality of cosmetics and quasi-drugs is the susceptibility of base liquids (solvents) and additives such as essential oils to oxidative degradation. As oxidative degradation progresses, odor, color, and the ingredients deteriorate and their effectiveness decrease. In particular, when oils and fats are used, oxidation and deterioration of the liquid are noticeable, so how to prevent this is an important factor in determining the product's expiration date and the amount of anti-deterioration agent to be added. Not only cosmetics and quasi-drugs, but also food products are treated to prevent oxidation and deterioration over time. In particular, massage oils, hair oils, nail oils, cosmetic oils, etc. are often made up of 100% oils and fats, and contain many double bonds such as omega-3, making them susceptible to oxidation and deterioration. In addition, when aromatic substances such as essential oils and fragrance waters are added, the quality of the scent changes in a short period of time.

[0041] The cause of oxidative deterioration is that heat and light cause the double bonds in lipids to be oxidized by active oxygen and singlet oxygen, which are present at approximately 2% in oxygen, and then an autoxidation reaction occurs, which leads to decomposition. At present, the general method of preventing oxidative deterioration in cosmetics and quasi-drugs is to store them in a sealed, cool, dark place if they do not contain antioxidants. However, since it will freeze in a cool, dark place and will deteriorate as it freezes and thaws repeatedly, it is difficult to prevent oxidation and deterioration by relying solely on storage methods.

[0042] Therefore, antioxidants, such as vitamin E for oil-based products and vitamin C for water-based products, have traditionally been added to prevent oxidation. Examples of antioxidants include vitamin C, tocopherol, tocotrienol, and other vitamins, as well as carotenes such as β-carotene and vitamin A, xanthophylls such as lutein, and melanoidins, which are antioxidants that utilize the Maillard reaction. These ingredients combine with oxygen to produce peroxides, which prevent the product's physical properties from changing over time. However, when antioxidants are oxidized, the resulting substances can cause skin irritation and allergic reactions in the human body, making them unsuitable for long-term storage and limiting the amount used.

[0043] Therefore, in this experiment, it was demonstrated that oxidation can be delayed by dispersing hydrogen in nanobubbles in the liquid base. Hydrogen has the characteristic that it selectively reacts with this active oxygen, especially hydroxyl radicals, to become water due to its reducing properties. However, even if hydrogen is dissolved in water or oil, it has the characteristic that it escapes from the liquid within an hour, which is not realistic. This is because hydrogen molecules are small and have a high diffusion coefficient. According to the present invention, by forming hydrogen into nanobubbles, Brownian motion occurs in the liquid, making it possible for hydrogen to exist for a long period of time.

[0044] (1) Experiment 1 In order to measure the reducing power of each gas, various gases were dispersed in distilled water as a base material in the form of nanobubbles, left open at room temperature, and the change in the redox potential was measured. The redox potential is reducing if it is negative, and oxidizing if it is positive. The blank distilled water was +23. Hydrogen nanobubbles are added to distilled water at 4.3 x 10 8 When dispersed at 10 nanobubbles / mL, the redox potential was -457. It was left for 30 minutes, but remained at -457, and remained at -457 even after 60 minutes. It dropped to -258 after 24 hours, and was 0 after one week. The amount of nanobubbles in the water was 4.3 x 10 8The cells / mL were maintained. In addition, hydrogen nanobubbles are 8.5 x 10 3 When nanobubbles were dispersed at 10 nanobubbles / mL, the redox potential was -442. If left as is, it remained at -442 even after 30 minutes, was -420 after 60 minutes, and was -227 after 24 hours. If left for a further period, it became +10 after one week, but when the amount of nanobubbles in the water was examined, it was 8.5 x 10 3 The cells / mL were maintained. When the type of gas was changed and oxygen gas was dispersed in distilled water to examine the redox potential, it was already +356, indicating oxidation. When carbon dioxide gas was dispersed in the water to examine the redox potential, it was +123, but the pH had dropped from 7 to 4.3. From the above, it is clear that hydrogen gas nanobubbles have an anti-oxidation effect.

[0045] (2) Experiment 2 Next, the antioxidant effect was examined for fats and oils. The degree of oxidation was examined for grape seed oil, olive oil, and rice bran oil. For each oil, untreated oil and oil with dispersed hydrogen nanobubbles were prepared, and left for one month under fluorescent light at room temperature, after which the change in acid value was confirmed. Since no electricity is passed through fats and oils, the oxidation-reduction potential cannot be measured, so after fats and oils are oxidized, they are decomposed by radicals, and the acid value rises, so the degree of deterioration was confirmed by measuring the change in acid value. As a result, as shown in the table below, it was found that oil with dispersed hydrogen nanobubbles (6.2 x 10^6 bubbles / mL containing H2) had a lesser increase in acid value than untreated oil. [Table 2]

[0046] (3) Experiment 3 In addition, changes in acid value (mgKOH / ml) were confirmed for unrefined jojoba oil. Jojoba oil is a wax ester, so it is difficult to oxidize and its acid value is not thought to increase much, but it can be decomposed by exposure to ultraviolet light or heating to 180°C or higher, causing an increase in its acid value. Therefore, the difference between oils that contain hydrogen nanobubbles and those that do not was confirmed. In the case of UV irradiation, it was found that hydrogen nanobubbles dispersed in the oil were more effective in suppressing the increase in acid value. 9 ) it was found that the oxidation rate was slower than that of the old device (Institute of Nanoscience). [Table 3]

[0047] In the case of heating, refined jojoba oil containing hydrogen nanobubbles and standard jojoba oil were heated to 180°C and stirred, and the change in acid value (mgKOH / ml) over time was confirmed. As a result, it was found that dispersing hydrogen nanobubbles delayed the change in acid value. It was also found that the oxidation rate was delayed in the hydrogen nanobubble jojoba oil prepared by the manufacturing device of the present invention. [Table 4]

[0048] (4) Experiment 4 Next, among the things that are said to be "oxidation of oil," the bad smell that comes from oil is also generally referred to as "oxidation." However, this bad smell is caused by the oil being oxidized by heat or ultraviolet rays, etc., and the oil being decomposed by the radicals, resulting in the generation of hydrocarbons and higher alcohols. Therefore, jojoba oil with hydrogen nanobubbles dispersed and jojoba oil without any treatment were left under the same conditions for one year, and when the blank jojoba oil started to have a foul odor, it was analyzed by GC-MS / MS (gas chromatography mass spectrometry). The jojoba oil with hydrogen nanobubbles dispersed also had a slight foul odor, but it was not as bad as the blank.

[0049] GC-MS / MS analysis data (Jojoba oil with H2 nanobubbles, blank jojoba oil) Shimadzu HS-20 Oven temperature 140℃ Sample line temperature 150℃ Trap cooling temperature -10℃ Trap heating temperature 280℃ Trap standby temperature 25℃ Vial warming time: 20 minutes Vial pressurization time: 1 minute Load equilibration time 0.1 min Dry purge time: 1 minute Injection time: 3 minutes Needle flush time: 5 minutes GC cycle time: 45 min GC Shimadzu GC-2030 Column oven temperature: 60℃ Pressure 55.8kPa Total flow rate 23.6mL / min Column flow rate: 0.98mL / min Linear speed 36.1cm / sec Purge flow rate: 3mL / min Split ratio 20 Temperature rise: 60℃ (0mL) → 60℃ (1.5min) → 240℃ (19.5min) → 240℃ (33min) MS Shimadzu GCMS-TQ8050NX Ion source temperature: 200℃ Interface temperature: 250℃ Measurement mode Q3 scan m / z 40-600

[0050] The results are shown in the table below. At each retention time, peaks of decomposition substances that may be the cause of the odor were observed, but a comparison of the peak heights (intensity) revealed that more of each decomposition substance was detected in the untreated jojoba oil than in the jojoba oil in which hydrogen nanobubbles were dispersed. In particular, when the number of hydrogen nanobubbles was 10 8 Compared to those at the cell / mL level, 9 It was found that the generation of propanal, hexanal, and octanal, which are the source of odorous substances with small molecular weights, was particularly low at the particles / mL concentration. [Table 5]

[0051] (5) Experiment 5 In addition, measurements were performed on jojoba oil, which is said to be resistant to oxidation, using Anton Paar's oxidation stability tester "RapidOxy 100." Specifically, a cell containing a reagent was heated in a high-pressure oxygen environment, and the rate of oxidation was measured by measuring the drop in oxygen pressure. Hydrogen nanobubbles are 5.0 x 10 8 / mL or 1.58 x 10 9 When the test was performed with jojoba oil containing 5.0 × 10 nanobubbles / mL and blank jojoba oil, it was found that the oxidation rates were different. 8 It was found that the onset of oxidation was delayed by about 500-600 seconds when the nanobubbles of jojoba (1.58 × 10 9 It was found that oxidation of the 1,2-dichlorophenyl phosphate (pH 7.0 / mL) began approximately 800 seconds later. The jojoba oil used here was refined jojoba oil (an oil that is generally resistant to deterioration and from which only the wax esters have been refined).

[0052] (6) Experiment 6 By dispersing hydrogen nanobubbles or carbonate nanobubbles in oils that have high skin penetration, such as jojoba oil and squalane, highly penetrating cosmetic oils, massage oils, etc., can be made. By increasing the penetration, the moisture inside the human sebum is prevented from escaping and the moisture is retained within the stratum corneum, resulting in cosmetic oils and massage oils with an emollient effect, i.e., high moisturizing properties. In addition to oil-based cosmetics, water-based cosmetics such as lotions and serums also benefit from the high penetration power, which improves the emollient effect and astringent effect of the skin, leading to moisturizing and fine skin texture. In cosmetics and quasi-drugs, the efficacy and beneficial ingredients of the cosmetics are absorbed together, so cosmetics with high penetration power are more likely to be effective. In particular, in quasi-drugs, it is necessary for the active ingredients to penetrate through the stratum corneum to the granular layer, spinous layer, and basal layer. In cosmetics, the creation of an epidermal film by penetration into the epidermis plays an important role as a moisturizer that prevents the evaporation of moisture from inside the skin. The permeability of cosmetics and quasi-drugs is an important factor. This is because high permeability enhances the effectiveness and efficacy of the product in order to allow important active ingredients to penetrate into the skin. Traditionally, cosmetics have often been mixed with penetrating agents to allow the active ingredients to penetrate. Quasi-drugs in particular often contain percutaneous absorption enhancers (ethanol, isopropanol, BG, PG, surfactants, lactic acid, salicylic acid, dimethyl sulfoxide, etc.). In addition, for oil-based cosmetics such as massage oil, cosmetic oil, hair oil, and nail oil, methods are used in which highly penetrating oils are used or the penetration is increased with surfactants, etc. As for the active ingredients of cosmetics to be penetrated, for example, emollients, fat-adding agents, blood circulation promoters, moisturizers, vitamins, and other raw oils and fats and extracts, it is important that the effective materials contained in the oils and fats are easily penetrated into the skin. Other water-based cosmetics such as lotions, beauty essences, scalp care products, and hair growth products use penetrating agents to moisturize, emollient, and astringent skin. Penetrating agents are important for anti-aging effects by removing active oxygen using fragrance water, nano-bubbled hydrogen gas, and carbon dioxide gas, as well as for improving the complexion and preventing dullness through the Bohr effect of carbon dioxide. In terms of the physical properties and chemical structure of the substances used as penetrating agents, those with low molecular weights and lipid solubility are generally considered to have high penetration. When active ingredients in cosmetics penetrate the epidermis and dermis of the skin, this is called "high penetration," and highly penetrating ingredients have three characteristics: "small molecular weight," "lipid solubility," and "low viscosity."

[0053] Regarding the molecular weight of an ingredient, the smaller the molecular weight, the easier it is to penetrate the skin. In the case of polymers used in cosmetics, the molecular weight is expressed in units called Daltons, specifically 1000 Daltons or less, and ingredients that are said to have high permeability are 500 Daltons or less. For example, recently developed low molecular weight collagen is said to have permeability of 500 to 1000 Daltons. Hyaluronic acid is said to have a molecular weight of 1 to 2 million Daltons, and collagen and hyaluronic acid with large molecular weights blend well with the skin and have the effect of moisturizing the surface of the skin, but they do not have high permeability. In comparison, triglycerides, which are typified by animal and vegetable oils, have a molecular weight of 500 to 1000 and are fat-soluble, so they are easily absorbed into the skin and have a delayed but penetrating effect. However, although the molecular weight of triglycerides is smaller than that of collagen or hyaluronic acid, it takes time for them to penetrate the skin, and for them to be used as cosmetics, it is necessary to use highly penetrating chemicals such as surfactants to penetrate the skin. In contrast, oils that are low molecular weight, fat-soluble, and have a low viscosity are used, such as jojoba oil, Euglena, wax esters, and deep-sea fish oils and fats such as squalane. These have a molecular weight of 400 to 500 daltons and are highly penetrating.

[0054] In addition, generally speaking, the viscosity that allows penetration is said to be 47mPa or less, like olive oil, which has immediate penetration power, but for instant penetration, 25mPa of jojoba oil and 20mPa of refined jojoba oil are desirable. In contrast, effective oils such as tamanu oil have a viscosity of over 250mPa, so they take time to penetrate. In this way, high viscosity oils and fats can be mixed with low viscosity oils and fats such as jojoba oil to make cosmetic oil, which allows the active ingredients to penetrate the skin. However, it has been found that the penetration of the active ingredients can also be increased by dispersing hydrogen or carbon dioxide nanobubbles.

[0055] The permeability was confirmed using thin layer chromatography. First, to check the permeability of the oil itself, a silica gel plate (TLC plate) was soaked in hydrogen nanobubble oil (hydrogen NB) and oil without hydrogen, and the difference in permeability was measured by measuring the rate at which the oil rose up. The permeability was confirmed by the height of the solvent front. The higher the value, the higher the permeability. As shown in the table below, it was found that the product containing hydrogen nanobubbles had higher permeability. Similarly, when the same test was performed with carbon dioxide gas, it was found that the product containing carbon dioxide nanobubbles had higher permeability.

[0056] We also confirmed the permeability of Tamanu extract and Calendula extract. Tamanu extract or Calendula extract was adsorbed as a spot on a TLC plate, and then the plate was soaked in hydrogen nanobubble oil (hydrogen NB) and oil without hydrogen, and the difference in permeability was measured by measuring the speed at which the spot moved. The speed of movement was measured as the Rf value, calculated as the distance the spot moved divided by the distance the solvent front moved, and the higher the value, the higher the permeability. [Table 6] [Table 7]

[0057] (7) Experiment 7 The greater the number of nanobubbles, the faster the blood flow will be. 9 The blood flow increased significantly at concentrations of 10 9 At concentrations of 10 or more per mL, a large change in the blood flow rate was observed. 8 The data was based on nanobubbles per mL, and the increase in blood flow velocity was an average of 6.6% for hydrogen nanobubbles. There were some cases where blood flow did not increase at all. For carbon dioxide, the increase was 11.4%. In contrast, the 10 9 At nanobubbles / mL, the increase in blood flow velocity was 19.9% ​​on average for hydrogen nanobubbles and 43.5% for carbon dioxide gas. 8 There were cases where the number of cells / mL did not increase, but 9 At levels above 50 / mL, the lowest value showed an increase of 10.2%.

[0058] Capillaries near the cuticle of the nail were observed under a microscope. As shown in Figure 5, blood vessels that were easy to see from point A to point B were selected and videotaped. First, unadjusted refined jojoba oil was applied and blood flow was confirmed. At this time, blood flow could be confirmed as visible objects such as white blood cells passed through. After that, refined jojoba oil with dispersed nanobubbles was applied to the back of the hand and blood flow was confirmed after about 20 seconds. The speed of blood flow was measured using the time code of the video and the difference in blood flow before and after application was calculated. The number of data points was confirmed by 40 subjects, using capillaries in the cuticle of the ring finger of the dominant and non-dominant hands. The sample was also applied to the back of the non-dominant hand to confirm the changes. Note that once a test is performed, it takes time for the increased blood flow to return to normal, and there are individual differences, so each test was performed on a different subject. [Table 8] [Table 9] [Industrial Applicability]

[0059] The method and apparatus for producing a nanobubble-containing composition according to the present invention can be applied not only to cosmetics and quasi-drugs, but also to other materials (e.g., edible oils, combustion improvers, fuels, fuel additives, etc.).

Claims

1. A dispersion step of dispersing hydrogen gas and / or carbon dioxide gas through a membrane filter into a fluid base material that is a physiologically acceptable medium; a micronization step of micronizing the hydrogen gas and / or carbon dioxide gas dispersed in the base material by ultrasonic waves; containing, A method for producing a nanobubble-containing composition, comprising the steps of:

2. In the dispersion step, while irradiating the substrate with ultrasonic waves by a vibrator, hydrogen gas and / or carbon dioxide gas are dispersed into the substrate through the membrane filter; The method for producing the nanobubble-containing composition according to claim 1,

3. The wavelength of the oscillator is 0.5 MHz to 3 MHz; The method for producing a nanobubble-containing composition according to claim 2,

4. carrying out the dispersion step and the micronization step simultaneously; The method for producing the nanobubble-containing composition according to claim 1,

5. a first pump for supplying a fluid substrate, the fluid substrate being a physiologically acceptable medium; A second pump for dispersing hydrogen gas and / or carbon dioxide gas into the substrate; a membrane filter through which the hydrogen gas and / or carbon dioxide gas passes before being dispersed in the substrate; A vibrator for irradiating the substrate with ultrasonic waves in which the hydrogen gas and / or carbon dioxide gas is dispersed; The provision of: An apparatus for producing a nanobubble-containing composition, comprising:

Images