A natural carbonated hot spring bath concentrate, its preparation method and application

Abstract

This invention discloses a natural carbonated hot spring bath concentrate, its preparation method, and its application. The concentrate comprises the following components: Component A: natural carbonated hot spring mineral concentrate; Component B: including calcium and magnesium salts; Component C: including 0.1-0.8 wt.% amphiphilic natural polysaccharides and 2.0-8.0 wt.% food-grade glycerol; Component D: including characteristic trace elements and 0.5%-2.0 wt.% pH buffer; the concentrate contains dispersed carbon dioxide nanobubbles with an average particle size ≤200 nm. The preparation method includes the following steps: employing an integrated process of "low-temperature membrane enrichment-ultra-high-pressure homogenization and nano-sizing". This invention is the first to achieve "physical transformation of active form" of free CO2 from natural hot springs, rather than "chemical substitution synthesis," truly starting from natural carbonated hot spring water to achieve efficient co-concentration and long-term stable storage of free CO2 and a complete mineral spectrum.

Description

Technical Field

[0001] This invention relates to the field of personal care products and the deep processing technology of natural products, and more specifically to a natural carbonated hot spring bath concentrate, its preparation method and application. Background Technology

[0002] Carbonated springs refer to hot spring water with a carbon dioxide content of ≥250 ppm per liter. Concentrations exceeding 1000 ppm have therapeutic effects. The carbon dioxide in carbonated springs can be absorbed through the skin, dilating blood vessels, lowering blood pressure, and improving cardiovascular function, offering auxiliary therapeutic effects for hypertension and arthritis. Their formation is related to surface water seeping deep into the earth's crust, being heated by geothermal energy, and then expanding and rising upwards carrying carbon dioxide gas. They are mostly distributed in valley and riverbed areas.

[0003] However, transforming this experience into a high-fidelity, commercialized home experience faces three long-standing technological challenges:

[0004] 1. The contradiction between activity retention and storage stability: CO2 gas is extremely unstable, and existing concentration processes (such as evaporation and membrane separation) inevitably lead to its complete dissipation. Commercially available products often compromise by using dry powder or tablets, which temporarily generate CO2 through acid-base chemical reactions (such as sodium bicarbonate reacting with organic acids) during use. This method cannot preserve the original, geologically formed equilibrium system of natural CO2 and minerals in hot spring water; it is essentially "artificial synthesis" rather than "natural extraction and restoration."

[0005] 2. The contradiction between immediate experience and lasting efficacy: Chemical gas generation methods often produce violent bursts that last for a very short time (usually <5 minutes). The bubbles are large and easily dissipate, which cannot simulate the delicate, gentle, and tingling sensation of natural hot springs that lasts for more than 20 minutes. In addition, a large amount of gas is wasted before it dissolves in water, resulting in low utilization.

[0006] 3. The contradiction between simple compounding and complete restoration: Existing technologies often focus on gas production or simply add a few macro minerals, ignoring the characteristic trace element spectrum of natural carbonated springs (such as metasilicic acid, strontium, lithium, etc.) and their possible biosynergistic effects with CO2, resulting in products with limited skin feel and efficacy.

[0007] Therefore, how to provide a bath concentrate containing the core active ingredients of natural carbonated hot springs and which can be stored stably for a long time is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0008] Therefore, the purpose of this invention is: 1. Provides a bath concentrate that is truly derived from natural carbonated hot spring water, and can simultaneously achieve efficient co-concentration of free CO2 and complete mineral spectrum and long-term stable storage.

[0009] 2. A method for preparing the above-mentioned concentrate is provided, which can create a novel formulation in which gas-liquid-solid (mineral) three phases coexist stably.

[0010] 3. Provides an application of this concentrate that allows for the reproduction of a lasting, delicate, and comprehensive therapeutic experience in the home bathtub, comparable to the microbubble sensation of natural spring water.

[0011] To achieve the above objectives, the present invention adopts the following technical solution: A natural carbonated hot spring bath concentrate, comprising the following components: Component A: Natural carbonated hot spring mineral concentrate, obtained from natural carbonated hot springs through membrane enrichment treatment, with total dissolved CO2 ≥ 1000 mg / L and metasilicic acid ≥ 50 mg / L; accounting for 35.0~65.0 wt.% of the concentrate. Component B: comprises calcium and magnesium salts, wherein the calcium salt is in the form of Ca²⁺. + It accounts for 0.8-3.5 wt.%, with magnesium salts as Mg² + It accounts for 0.5-2.0 wt.%; Component C: includes 0.1-0.8 wt.% amphiphilic natural polysaccharides and 2.0-8.0 wt.% food-grade glycerol; Component D: includes characteristic trace elements and 0.5%-2.0 wt.% pH buffer; The characteristic trace elements include sodium metasilicate, accounting for 0.2-1.5 wt.% as H₂SiO₃; lithium salt, accounting for Li + It accounts for 0.01-0.1 wt.%; and strontium salts, in Sr² + It accounts for 0.01-0.1 wt.%; Component F: Deionized water, to a final volume of 100 wt.%; The concentrate contains carbon dioxide nanobubbles with an average particle size of ≤200 nm.

[0012] The beneficial effects of the above technical solution are as follows: Component A provides the source of CO2 nanobubbles and characteristic mineral framework; Component B replicates the "hardness" system of natural carbonated springs, stabilizes the interfacial charge of nanobubbles, and improves skin feel; Component C forms a gas-liquid interface protective film, inhibits nanobubble aggregation, and provides a dispersion medium and moisturizing synergistic effect; Component D constitutes geological fingerprint characteristics, synergistically enhances pH, and prevents mineral precipitation. This invention achieves the replication of natural hot spring effects through the combination of "natural hot spring mineral concentrate + complete trace element spectrum + specific ratio of calcium and magnesium + nanobubble stabilization system," with each component working synergistically and inseparable.

[0013] Preferably, the calcium salt is calcium chloride or calcium lactate; the magnesium salt is magnesium chloride or magnesium sulfate; the amphiphilic natural polysaccharide is selected from inulin, guar gum hydroxypropyltrimethylammonium chloride or gellan gum; the lithium salt is lithium chloride or lithium carbonate; the strontium salt is strontium chloride; the pH buffer is a citrate-sodium citrate buffer pair; and the pH buffer adjusts the pH to 6.0-7.2.

[0014] Preferably, the mass ratio of calcium ions to magnesium ions in component B is Ca². + :Mg² + The ratio is 1.2:1 to 2.0:1.

[0015] The beneficial effects of the above technical solution: Ca² in component B + :Mg² + The mass ratio is controlled between 1.2:1 and 2.0:1, which can simulate the characteristic ratio of world-renowned carbonated hot springs such as Tengchong and Hakone. Deviating from this range will lead to a decrease in the zeta potential of nanobubbles and a deterioration in skin feel.

[0016] Preferably, the number concentration of carbon dioxide nanobubbles in the concentrate is ≥5×10⁻⁶. 8 The concentration of particles per mL is ≤0.25, and the polydispersity index (PDI) is ≤0.25.

[0017] The beneficial effects of the above technical solution are as follows: the amount of amphiphilic polysaccharide added in component C is coupled with the specific surface area of ​​nanobubbles in component A. At the above-mentioned number concentration of carbon dioxide nanobubbles, if the amount of amphiphilic polysaccharide added is less than 0.1%, the bubble stability is insufficient; if it is greater than 0.8%, bubble release is hindered, and the user experience is reduced.

[0018] Preferably, the A component natural carbonated hot spring mineral concentrate is prepared by the following steps: natural carbonated hot spring water is circulated and concentrated through a nanofiltration membrane with a molecular weight cutoff of ≤300 Da at 2-10℃, 0.3-0.6 MPa back pressure, and 0.8-1.5 MPa transmembrane pressure, with a concentration ratio of 2.5-4.0 times. Concentration is stopped when the total dissolved CO2 concentration in the concentrate is ≥1000 mg / L and the metasilicic acid concentration is ≥50 mg / L. After concentration, the concentrate is subjected to ultra-high pressure microjets for homogenization at 200-350 MPa, circulated 2-5 times, and the temperature is controlled at ≤15℃ to form a nanobubble dispersion.

[0019] The beneficial effects of the above technical solution are: the concentration temperature must be ≤10℃, otherwise the CO2 escape rate will be >60%; the membrane molecular weight cutoff must be ≤300 Da, otherwise HCO2 will be insufficient. - And the rejection rate of divalent ions is <50%.

[0020] Preferably, it also includes component E, which contains 0.3-1.0 wt.% natural preservatives and / or 0.02-0.1 wt.% natural plant essential oils. Component E can extend shelf life and provide a fresh olfactory experience.

[0021] Preferably, the natural preservative is selected from citrus or peppermint; the natural plant essential oil is selected from capryloyl hydroxamic acid or 1,2-pentanediol.

[0022] A natural carbonated hot spring bath concentrate, comprising the following steps: (1) Natural carbonated hot spring water is concentrated by circulating it through a nanofiltration membrane with a molecular weight cutoff of ≤300 Da under the conditions of 2-10℃, 0.3-0.6 MPa back pressure and 0.8-1.5 MPa transmembrane pressure; after concentration, it is subjected to ultra-high pressure micro-jet homogenization treatment at 200-350 MPa pressure, circulated 2-5 times, and the temperature is controlled at ≤15℃ to form a nanobubble dispersion, thus obtaining component A; (2) Under nitrogen protection at ≤15℃, add other components according to the mass percentage and mix evenly; (3) Aseptic filling: After being sterilized by 0.22μm filtration, it is filled into a high-barrier packaging container under the protection of inert gas. The high-barrier packaging container is selected from aluminum-plastic composite tubes or opaque PET bottles.

[0023] Preferably, step (2) specifically includes: (2.1) Add component B slowly after partially dissolving component F, and stir until homogeneous; (2.2) Disperse the amphiphilic natural polysaccharide in part of the preheated F component to 40°C, cool it, and add it to the mixture. Stir well. (2.3) Dissolve the food-grade glycerin and characteristic trace elements separately and add them in sequence; (2.4) Slowly add component A to the above mixture while stirring; (2.5) Add component F to the total volume and continue stirring until homogeneous; (2.6) Adjust the pH of the system to 6.0-7.2 using a pH buffer.

[0024] The above-mentioned natural carbonated hot spring bath concentrate is used in the preparation of home bath products for promoting skin microcirculation, relieving physical fatigue, and simulating the experience of natural carbonated hot spring bathing.

[0025] The concentrate of this invention can be used directly. It is recommended to add 30-50 mL to a standard bathtub (150-200L, water temperature 38-42℃), stir manually for a few seconds, and then soak for 15-25 minutes. The nanobubbles can be continuously released in the water for more than 20 minutes, providing a lasting, mild tingling sensation.

[0026] As can be seen from the above technical solution, compared with the prior art, the beneficial effects of the present invention are as follows: (1) It has a core active system: the natural carbonated hot spring mineral concentrate is a nano-bubble natural CO2 and mineral ion complex, which is the fundamental difference from all "chemical gas generation methods". It does not generate CO2 through chemical reaction, but rather modifies and enriches the existing free CO2 in the natural hot spring water through physical transformation.

[0027] Technical approach: An integrated process of "low-temperature membrane enrichment - ultra-high pressure homogenization and nanofiltration" is employed. First, under low-temperature (<10℃) and pressure-maintaining conditions, the raw spring water undergoes selective nanofiltration to enrich HCO3. - Ca 2+ Mg 2+ The CO2 in the water is then "cut" into nanobubbles with an average hydrodynamic diameter of ≤200 nm (preferably 50-150 nm) using an ultra-high pressure homogenizer in a closed-loop system. Due to Brownian motion and surface charge effects, these nanobubbles can remain stably suspended in the liquid for extended periods.

[0028] Final form: A mineral concentrate rich in nanobubble CO2 was obtained. The total dissolved CO2 concentration (including nanobubble and HCO3-) is... - (Bound state) ≥1000 mg / L, and fully retains the characteristic mineral proportions derived from the original spring water.

[0029] (2) It has a ternary steady-state and efficiency-enhancing system To ensure the superior performance of the above active units during shelf life and use, the following collaborative system must be built: 1. Ion buffering and colloidal stabilization systems Function: To maintain the stability of the system's ionic strength and pH (6.0-7.5), and to prevent mineral precipitation and nanobubble aggregation.

[0030] Key components: a specific ratio of calcium and magnesium ions, and trace amounts of metasilicic acid. Metasilicic acid forms a protective layer at the nanobubble interface, giving the finished "hot spring water" its unique smooth, skin-feeling quality.

[0031] 2. Interface design and long-lasting sustained-release system Function: To further stabilize nanobubbles and control their release rate during bathing, thus extending the experience time.

[0032] Key technology: Adding trace amounts of amphiphilic natural polysaccharides. These molecules can anchor at the gas-liquid interface of nanobubbles, enhancing steric stability and forming a weak gel network in hot water, allowing for slow and continuous release of the nanobubbles, achieving a sustained tingling sensation lasting >20 minutes.

[0033] 3. Characteristic fingerprints and synergistic trace element systems Function: It creates a "chemical fingerprint" that is difficult for products to imitate and enhances efficacy.

[0034] Key components: Based on the water quality report of the natural carbonated spring, characteristic trace elements such as lithium, strontium, and sodium metasilicate are added in quantitative amounts. These components are markers of the geological background, not simply mineral salts, but are organically integrated with the core active system. Detailed Implementation

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Example 1: Baseline Formulation A natural carbonated hot spring bath concentrate, comprising the following components: Component A: Natural carbonated hot spring mineral concentrate (CO2 1150 mg / L, metasilicic acid 62 mg / L), accounting for 45.0 wt.% of the concentrate; Component B: B1 Calcium chloride (in Ca²⁺) + (Calculated) 2.2 wt.% of the concentrate, B2 magnesium chloride (as Mg²) + (by weight) accounted for 1.3 wt.% of the concentrate; Component C: C1 inulin (food grade, degree of polymerization ≥23) accounts for 0.5 wt.% of the concentrate, and C2 glycerol (99.5%) accounts for 5.0 wt.% of the concentrate; Component D: D1 Sodium metasilicate (calculated as H2SiO3) accounts for 0.8 wt.% of the concentrate, D2 Lithium chloride (calculated as Li + (Calculated as Sr²) 0.03 wt.% of the concentrate, D3 Sr² chloride (as Sr²) + (Total) 0.02 wt.% of the concentrate, D4 ​​citrate-sodium citrate buffer (pH 6.5) 1.2 wt.% of the concentrate; Component E: E1 Capryloyl hydroxamic acid: 1,2-pentanediol = 1:4, accounting for 0.6 wt.% of the concentrate; E2 Sweet orange essential oil, accounting for 0.05 wt.% of the concentrate; Component F: Deionized water to bring the total to 100.0 wt.%.

[0037] The preparation method is as follows: A natural carbonated hot spring bath concentrate, comprising the following steps: (1) Natural carbonated hot spring water was concentrated through a nanofiltration membrane with a molecular weight cutoff of 200 Da at 6℃, 0.4 MPa nitrogen back pressure and 1.2 MPa transmembrane pressure; the concentration factor was 3.2 times. After concentration, it was subjected to ultra-high pressure micro-jet homogenization treatment at 280 MPa pressure, 3 times, and the temperature was controlled ≤12℃ to form a nanobubble dispersion with an average nanobubble particle size of 136 nm (PDI 0.19), thus obtaining component A. (2) Under nitrogen protection at ≤15℃, add other components according to the following mass percentage: (2.1) Add component B slowly after partially dissolving component F. After pre-dissolving, the concentration of calcium chloride is 26% and the concentration of magnesium chloride is 12%. Stir until homogeneous. (2.2) Disperse the amphiphilic natural polysaccharide in part of the preheated F component to 40°C, cool it, and add it to the mixture. Stir well. (2.3) Dissolve the food-grade glycerol and the characteristic trace elements separately and add them in sequence. After dissolution, the concentrations of sodium metasilicate are 28%, lithium chloride is 16%, and strontium chloride is 34%. (2.4) Slowly add component A to the above mixture while stirring; (2.5) Add component F to the total volume and continue stirring until homogeneous; (2.6) Adjust the pH of the system to 6.5 using a pH buffer.

[0038] (3) Aseptic filling: After being sterilized by 0.22μm filtration, the product is filled into high-barrier, opaque PET bottles under inert gas protection. The number concentration of carbon dioxide nanobubbles in the concentrate is 5.2×10⁻⁶. 8 per mL.

[0039] The product showed no packaging swelling during its shelf life. After 90 days of accelerated storage at 40℃, the CO2 concentration retention rate was >85%, with no stratification or sedimentation. When 30mL of this product was placed in 150L of 40℃ bath water, it immediately generated a large number of fine, silent microbubbles. Skin contact produced a continuous, gentle tingling sensation lasting over 25 minutes (traditional effervescent bath salts ≤5 minutes), promoting microcirculation: using infrared thermal imaging, volunteers' average hand temperature increased by 2.8℃ after soaking, and remained at a relatively high temperature even after 1 hour. Subjective experience evaluation showed it to be significantly superior to commercially available chemically produced bubble bath tablets.

[0040] Example 2: High Stability Enhanced Formula Component A 50 wt.%, Component C1 0.8 wt.%, Component C2 8 wt.%, Component B1 calcium chloride (as Ca²⁺) + 1.8 wt.% (calculated as Mg²⁺), B₂ magnesium chloride (as Mg²⁺) + (Total) 1.0 wt.%, the rest is the same as in Example 1.

[0041] Features: Stronger gel network, accelerated stability at 40℃, 90-day CO2 retention rate of 93%, no stratification or sedimentation. When 30mL of this product is placed in 150L of 40℃ bathwater, the initial release of bubbles is relatively slow, lasting for more than 25 minutes. This product not only provides gas stimulation but also replicates the complete mineral spectrum of Tengchong carbonated springs through a precise calcium-magnesium ion ratio and optional characteristic trace elements, making the skin feel (smoothness, hard water feel) and physiological effects closer to nature.

[0042] Example 3: Refreshing Skin-Feel Formula Component A 38 wt.%, B1 calcium chloride (as Ca²) + 1.2 wt.% (calculated as Mg²⁺), B₂ magnesium chloride (as Mg²⁺) + (Total) 1.0 wt.%, C1 component 0.2 wt.%, C2 component 3 wt.%, the rest are the same as in Example 1.

[0043] Features: More active bubble release, noticeable tingling sensation upon initial bathing, suitable for consumers who prefer a strong bubble sensation.

[0044] The product was stored at 40℃ for 90 days under accelerated testing, and the CO2 concentration retention rate was >80%, with no stratification or sedimentation.

[0045] Example 4: Natural-feeling formula A natural carbonated hot spring bath concentrate, comprising the following components: Component A: Natural carbonated hot spring mineral concentrate (CO2 1050 mg / L, metasilicic acid 52 mg / L), accounting for 65.0 wt.% of the concentrate; Component B: B1 Calcium chloride (in Ca²⁺) + (Calculated as Mg²⁺) accounts for 0.6 wt.% of the concentrate, B₂ magnesium chloride (as Mg²⁺) + (by weight) 0.5 wt.% of the concentrate; Component C: C1 gellan gum (food grade, Hunan Guangyi Biotechnology Co., Ltd.) accounts for 0.1 wt.% of the concentrate, and C2 glycerol (99.5%) accounts for 2.0 wt.% of the concentrate; Component D: D1 Sodium metasilicate (calculated as H2SiO3) accounts for 0.2 wt.% of the concentrate, D2 Lithium carbonate (calculated as Li + (Based on) 0.01 wt.% of the concentrate, D3 strontium chloride (as Sr²) + The concentrate contained 0.01 wt.% D4 citrate-sodium citrate buffer (pH 6.0) and 0.5 wt.% D4 citrate-sodium citrate buffer (pH 6.0). Component E: E1 Capryloyl hydroxamic acid, 0.3 wt.% of concentrate; E2 Peppermint oil, 0.02 wt.% of concentrate; Component F: Deionized water to bring the total to 100.0 wt.%.

[0046] The preparation method is as follows: A natural carbonated hot spring bath concentrate, comprising the following steps: (1) Natural carbonated hot spring water was concentrated at 6℃, 0.6 MPa nitrogen back pressure, and 1.5 MPa transmembrane pressure through a nanofiltration membrane with a molecular weight cutoff of 150 Da; the concentration factor was 2.5 times. After concentration, it was subjected to ultra-high pressure micro-jet homogenization treatment at 350 MPa pressure, circulated twice, and the temperature was controlled to ≤15℃ to form a nanobubble dispersion with an average nanobubble particle size of 185 nm (PDI 0.22), thus obtaining component A. (2) Under nitrogen protection at ≤15℃, add other components according to the following mass percentage: (2.1) Add component B slowly after partially dissolving component F. After pre-dissolving, the concentration of calcium chloride is 35% and the concentration of magnesium chloride is 15%. Stir until homogeneous. (2.2) Disperse the amphiphilic natural polysaccharide in part of the preheated F component to 40°C, cool it, and add it to the mixture. Stir well. (2.3) Dissolve the food-grade glycerol and the characteristic trace elements separately and add them in sequence. After dissolution, the concentrations of sodium metasilicate are 40%, lithium chloride is 25%, and strontium chloride is 30%. (2.4) Slowly add component A to the above mixture while stirring; (2.5) Add component F to the total volume and continue stirring until homogeneous; (2.6) Adjust the pH of the system to 6.0 using a pH buffer.

[0047] (3) Aseptic filling: After 0.22μm sterilization filtration, the product is filled into a high-barrier aluminum-plastic composite tube under inert gas protection. The number concentration of carbon dioxide nanobubbles in the concentrate is 5.1×10⁻⁶. 8 per mL.

[0048] Features: High content of natural carbonated hot spring mineral concentrate, more closely resembling the complete experience of natural carbonated water.

[0049] The product was stored at 40℃ for 90 days under accelerated testing, and the CO2 concentration retention rate was >85%, with no stratification or sedimentation.

[0050] Example 5: Durable Stability Formulation A natural carbonated hot spring bath concentrate, comprising the following components: Component A: Natural carbonated hot spring mineral concentrate (CO2 1200 mg / L, metasilicic acid 60 mg / L), accounting for 35.0 wt.% of the concentrate; Component B: B1 Calcium chloride (in Ca²⁺)+ (Calculated) accounts for 3.5 wt.% of the concentrate, B2 magnesium chloride (as Mg²) + (Total) 2.0 wt.% of the concentrate; Component C: C1 guar hydroxypropyltrimethylammonium chloride (Maclean) accounted for 0.8 wt.% of the concentrate, and C2 glycerol (99.5%) accounted for 4.0 wt.% of the concentrate; Component D: D1 Sodium metasilicate (calculated as H2SiO3) accounts for 1.5 wt.% of the concentrate, D2 Lithium chloride (calculated as Li + (Based on) 0.1 wt.% of the concentrate, D3 strontium chloride (as Sr²) + The concentrate contained 0.1 wt.% D4 citrate-sodium citrate buffer (pH 7.0) and 2.0 wt.% D4 citrate-sodium citrate buffer (pH 7.0). Component E: 1,2-Pentanediol, 1.0 wt.% of concentrate; E2: Sweet orange essential oil, 0.1 wt.% of concentrate. Component F: Deionized water to bring the total to 100.0 wt.%.

[0051] The preparation method is as follows: A natural carbonated hot spring bath concentrate, comprising the following steps: (1) Natural carbonated hot spring water was concentrated by passing it through a nanofiltration membrane with a molecular weight cutoff of 150 Da at 2℃, 0.3 MPa nitrogen back pressure and 0.8 MPa transmembrane pressure. The concentration factor was 4.0 times. After concentration, it was subjected to ultra-high pressure micro-jet homogenization treatment at 200 MPa pressure and circulated 5 times. The temperature was controlled at ≤12℃ to form a nanobubble dispersion with an average nanobubble particle size of 155 nm (PDI 0.21). Component A was obtained. (2) Under nitrogen protection at ≤15℃, add other components according to the following mass percentage: (2.1) Add component B slowly after partially dissolving component F. After pre-dissolving, the concentration of calcium chloride is 25% and the concentration of magnesium chloride is 16%. Stir until homogeneous. (2.2) Disperse the amphiphilic natural polysaccharide in part of the preheated F component to 40°C, cool it, and add it to the mixture. Stir well. (2.3) Dissolve the food-grade glycerol and the characteristic trace elements separately and add them in sequence. After dissolution, the concentrations of sodium metasilicate, lithium chloride, and strontium chloride are 25%, 15%, and 25%, respectively. (2.4) Slowly add component A to the above mixture while stirring; (2.5) Add component F to the total volume and continue stirring until homogeneous; (2.6) Adjust the pH of the system to 7.0 using a pH buffer.

[0052] (3) Aseptic filling: After being sterilized by 0.22μm filtration, the product is filled into high-barrier, opaque PET bottles under inert gas protection. The number concentration of carbon dioxide nanobubbles in the concentrate is 5.3×10⁻⁶. 8 per mL.

[0053] Features: Excellent product stability; the high zeta potential of nanobubbles and the spatial barrier effect of the gel network ensure that the physicochemical properties of the product are highly stable throughout its shelf life.

[0054] The product was stored at 40℃ for 90 days under accelerated testing, and the CO2 concentration retention rate was >95%, with no stratification or bulging. Bubble persistence: In still water at 40℃, visible fine bubbles continued to be generated for ≥40 minutes.

[0055] Comparative Example 1: Without Component A (Chemical Synthesis Method) Sodium bicarbonate was added to replace the natural hot spring mineral concentrate, and the rest was the same as in Example 1; Results: No nanobubble characteristics, bubble duration <5 minutes, no slippery skin feel, no characteristic trace element fingerprints.

[0056] Comparative Example 2: CO2 in component A has dissipated. Component A was not concentrated under low temperature and pressure; natural hot spring water was added directly, with a CO2 concentration of 450 mg / L and a metasilicic acid content of 45 mg / L. Result: After homogenization, a stable nanobubble system could not be formed, and the product did not have a lasting bubble experience.

[0057] Comparative Example 3: Calcium-to-magnesium ratio exceeds the range B1 calcium chloride (in Ca²⁺) + (Calculated) 3.0 wt.% of the concentrate, B2 magnesium chloride (as Mg²) + (Calculated) accounted for 1.0 wt.% of the concentrate; the rest was the same as in Example 1.

[0058] Result: Slight precipitation occurred in the system, and the stability decreased significantly.

[0059] Comparative Example 4 Ultra-high pressure nanobubble homogenization was not performed; otherwise, it was the same as in Example 1.

[0060] Result: Nanobubbles could not be formed, and the product did not provide a lasting bubble experience.

[0061] Comparative Example 5 The C1 amphiphilic natural polysaccharide was not added; otherwise, it was the same as in Example 1.

[0062] Result: Stable nanobubbles could not be formed.

[0063] Comparative Example 6 The amount of amphiphilic polysaccharide added was 1.0 wt.%, and the rest was the same as in Example 1.

[0064] Result: Bubble release was hindered, the amount of bubbles released in the early stage decreased significantly, and the user experience declined.

[0065] Comparative Example 7 Add commercially available effervescent bath salts to prepared warm water according to the instructions, dissolve them first, and then enter the bath. Commercially available Bathclin effervescent bath salts produce CO2 gas through the reaction of citric acid and sodium bicarbonate, which escapes in the form of bubbles, creating a hissing bubbling phenomenon.

[0066] Comparative Example 8 Ordinary pressurized carbonated water, without nano-processing, is used for carbonated hot spring baths.

[0067] Comparative Example 9 Component B is not added; otherwise, it is the same as in Example 1.

[0068] Comparative Example 10 The characteristic trace elements in component D are not added; otherwise, it is the same as in Example 1.

[0069] Performance test Experiment 1 The products of Example 1, Comparative Example 5, and Comparative Examples 7-8 were tested using a laser nanoparticle size analyzer (DLS), a nanoparticle tracking analyzer (NTA), electrophoretic light scattering, and NTA tracking. The test results are shown in Table 1. This experiment demonstrates that the present invention achieves commercial-grade storage stability.

[0070] Table 1

[0071] Experiment 2 The products of Example 1, Comparative Example 3, Comparative Example 5, and Comparative Examples 9-10 were tested, and the test results are shown in Table 2.

[0072] Table 2

[0073] As can be seen from Table 2, the initial nanobubble concentrations of each group are not significantly different. Components B, C1, and D all affect long-term stability. Imbalance in the calcium-magnesium ratio has the greatest impact on charge destruction, while C1 contributes the most to sustained release. Imbalance in the calcium-magnesium ratio severely degrades the skin feel.

[0074] This experiment demonstrates that the "amphiphilic polysaccharide interface modification + calcium and magnesium ion balance" system of this invention (for carbonated springs) has a synergistic effect, and neither can be omitted.

[0075] Experiment 3 Thirty healthy volunteers were recruited and randomly divided into three groups of 10 each. The three groups used the product from Example 1 (30 mL), the commercially available product from Comparative Example 7 (one tablet), and ordinary warm water (blank control), respectively. A double-blind, controlled trial was conducted, with uniform bathing conditions: 40℃ water temperature, 150L water, and 20 minutes of immersion. Laser Doppler flowmeter and thermometer were used to measure skin surface blood perfusion and skin surface temperature rise. Other parameters were scored by the volunteers, and the average values ​​were calculated. The experimental results are shown in Table 3.

[0076] Table 3

[0077] As can be seen from Table 3, the product of this invention is significantly superior to the prior art in three core indicators: promoting microcirculation, maintaining body temperature, and prolonging the bubble experience; the difference from the prior art is statistically significant, satisfying the requirement of "unexpected technical effects".

[0078] Experiment 4 Influence of process parameters on bubble formation The values ​​of a certain parameter in the preparation process of Example 1 were modified, and experimental designs were carried out for each group. The modified parameters for each group are shown in Table 4.

[0079] Table 4

[0080] As can be seen from Table 4: 1. The concentration temperature must be ≤10℃, which is crucial for retaining CO2; 2. The membrane molecular weight cutoff must be ≤300 Da to retain HCO3-. - And the key to divalent ions; 3. The homogenization pressure must be ≥200MPa, which is a necessary condition for the generation of nanoscale bubbles; 4. The process parameter range of the present invention has been systematically optimized and has reasonable technical boundaries.

[0081] The above embodiments demonstrate that the present invention has the following advantages: 1. Technological Originality: For the first time, the "physical transformation of active form" of free CO2 from natural hot springs has been achieved instead of "chemical substitution synthesis". This is a technological innovation in the field. It truly starts from natural carbonated hot spring water and can simultaneously achieve efficient co-concentration and long-term stable storage of free CO2 and complete mineral spectrum.

[0082] 2. Revolutionary Experience: The persistent and delicate bubble sensation it provides solves the core pain point of home product experience, creating a generational gap with existing products.

[0083] 3. Unique dosage form: The final product is a unique liquid concentrate, which is clearly distinguished from the mainstream powders and tablets on the market.

[0084] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A natural carbonated hot spring bath concentrate, characterized in that, Includes the following components: Component A: Natural carbonated hot spring mineral concentrate, obtained from natural carbonated hot springs through membrane enrichment treatment, with total dissolved CO2 ≥ 1000 mg / L and metasilicic acid ≥ 50 mg / L; accounting for 35.0~65.0 wt.% of the concentrate. Component B: comprises calcium and magnesium salts, wherein the calcium salt is in the form of Ca²⁺. + It accounts for 0.8-3.5 wt.%, with magnesium salts as Mg² + It accounts for 0.5-2.0 wt.%; Component C: includes 0.1-0.8 wt.% amphiphilic natural polysaccharides and 2.0-8.0 wt.% food-grade glycerol; Component D: Includes characteristic trace elements and 0.5%-2.0 wt.% pH buffer; The characteristic trace elements include sodium metasilicate, accounting for 0.2-1.5 wt.% as H₂SiO₃; lithium salt, accounting for Li + It accounts for 0.01-0.1 wt.%; and strontium salts, in Sr² + It accounts for 0.01-0.1 wt.%; Component F: Deionized water, to a final volume of 100 wt.%; The concentrate contains carbon dioxide nanobubbles with an average particle size of ≤200 nm.

2. The natural carbonated hot spring bath concentrate according to claim 1, characterized in that, The calcium salt is calcium chloride or calcium lactate; the magnesium salt is magnesium chloride or magnesium sulfate; the amphiphilic natural polysaccharide is selected from inulin, guar gum hydroxypropyltrimethylammonium chloride or gellan gum; the lithium salt is lithium chloride or lithium carbonate; the strontium salt is strontium chloride; the pH buffer is a citrate-sodium citrate buffer pair; the pH buffer adjusts the pH to 6.0-7.

2.

3. The natural carbonated hot spring bath concentrate according to claim 1, characterized in that, The mass ratio of calcium ions to magnesium ions in component B is Ca² + :Mg² + The ratio is 1.2:1 to 2.0:

1.

4. The natural carbonated hot spring bath concentrate according to claim 1, characterized in that, The number concentration of carbon dioxide nanobubbles in the concentrate is ≥5×10⁻⁶. 8 The concentration of particles per mL is ≤0.25, and the polydispersity index (PDI) is ≤0.

25.

5. The natural carbonated hot spring bath concentrate according to claim 1, characterized in that, The A component of the natural carbonated hot spring mineral concentrate is prepared by the following steps: natural carbonated hot spring water is circulated and concentrated through a nanofiltration membrane with a molecular weight cutoff of ≤300 Da at 2-10℃, 0.3-0.6 MPa back pressure, and 0.8-1.5 MPa transmembrane pressure, with a concentration ratio of 2.5-4.0 times; after concentration, it is subjected to ultra-high pressure micro-jet homogenization treatment at 200-350 MPa pressure, circulated 2-5 times, and the temperature is controlled at ≤15℃ to form a nanobubble dispersion.

6. The natural carbonated hot spring bath concentrate according to claim 1, characterized in that, It also includes component E, which comprises 0.3-1.0 wt.% natural preservatives and / or 0.02-0.1 wt.% natural plant essential oils.

7. A natural carbonated hot spring bath concentrate according to claim 6, characterized in that, The natural preservative is selected from citrus or peppermint; the natural plant essential oil is selected from capryloyl hydroxamic acid or 1,2-pentanediol.

8. A method for preparing a natural carbonated hot spring bath concentrate according to any one of claims 1 to 7, characterized in that, Includes the following steps: (1) Natural carbonated hot spring water is concentrated by circulating it through a nanofiltration membrane with a molecular weight cutoff of ≤300 Da under the conditions of 2-10℃, 0.3-0.6 MPa back pressure and 0.8-1.5 MPa transmembrane pressure; after concentration, it is subjected to ultra-high pressure micro-jet homogenization treatment at 200-350 MPa pressure, circulated 2-5 times, and the temperature is controlled at ≤15℃ to form a nanobubble dispersion, thus obtaining component A; (2) Under nitrogen protection at ≤15℃, add other components in sequence according to the formula and mix evenly; (3) Aseptic filling: After being sterilized by 0.22μm filtration, it is filled into a high-barrier packaging container under the protection of inert gas. The high-barrier packaging container is selected from aluminum-plastic composite tubes or opaque PET bottles.

9. The method for preparing a natural carbonated hot spring bath concentrate according to claim 8, characterized in that, Step (2) is as follows: (2.1) Add component B slowly after partially dissolving component F, and stir until homogeneous; (2.2) Disperse the amphiphilic natural polysaccharide in part of the preheated F component to 40°C, cool it, and add it to the mixture. Stir well. (2.3) Dissolve the food-grade glycerin and characteristic trace elements separately and add them in sequence; (2.4) Slowly add component A to the above mixture while stirring; (2.5) Add component F to the total volume and continue stirring until homogeneous; (2.6) Adjust the pH of the system to 6.0-7.2 using a pH buffer.

10. The use of the natural carbonated hot spring bath concentrate according to any one of claims 1 to 7 in the preparation of home bath products for promoting skin microcirculation, relieving physical fatigue, and simulating the experience of natural carbonated hot spring bathing.

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