A selenium-enriched biotin scalp care serum spray and a preparation method thereof

Abstract

A selenium-enriched biotin scalp care essence spray and its preparation method belong to the field of scalp care technology. The spray components are: selenium yeast extract, pearl active peptides, hair follicle repair core enzyme complex, biotin, plant extract micropowder, and the remainder being excipients and deionized water, with a pH of 5.0-5.5. The selenium yeast extract contains ≥60% selenocysteine; the pearl active peptides have a molecular weight <1kDa and an amino acid content ≥90mg / mL; the hair follicle repair core enzyme complex contains ≥2000U / mg superoxide dismutase and ≥50U / mg transglutaminase; and the plant extract micropowder is extracted using supercritical CO2. The use of ultrasonic high-pressure homogenization, iontophoresis encapsulation, and nitrogen-filled aluminum bottle packaging technology solves the problems of low transdermal penetration rate of active ingredients (traditional formulations <8%, this invention increases it to 28%) and poor stability.

Description

Technical Field

[0001] This invention belongs to the field of cosmetic technology, specifically relating to scalp care cosmetics, and more specifically, to a selenium-enriched biotin scalp care essence spray and its preparation method. Background Technology

[0002] The scalp has a unique physiological structure that distinguishes it from skin on other parts of the body: its stratum corneum is only one-third the thickness of facial skin, making its barrier fragile; its hair follicle density can reach 1000 per cm², and the number of sebaceous glands is twice that of the facial T-zone, with a sebum secretion rate ≥35μg / cm² / h, making it highly susceptible to abnormal sebum secretion and clogged hair follicles; at the same time, the scalp's epidermal renewal cycle is only 14 days, half that of body skin, making it less tolerant to external oxidative stimuli and microbial invasion. These physiological characteristics make the scalp susceptible to endogenous oxidative stress and exogenous environmental stimuli, leading to a series of problems such as scalp sebum imbalance, increased dandruff, hair follicle dysfunction, barrier damage, and sensitivity and itching, which are also the core research and development challenges in the current field of scalp care.

[0003] The current scalp care market faces significant technological bottlenecks: Product form limitations: Commercially available scalp care products are mainly rinse-off type (such as shampoo and conditioner), and the effective ingredients stay on the scalp for less than 5 minutes, making it difficult to achieve continuous care. Leave-in products often have problems such as poor ingredient compatibility and unstable system.

[0004] Insufficient ingredient delivery efficiency: Traditional dosage forms (aqueous solutions, ordinary emulsions) have difficulty penetrating the scalp stratum corneum barrier, with active ingredient transdermal penetration rate <8%, and selenium is easily oxidized and deactivated in an oily environment, with an activity retention rate of <40% after 3 months of storage at room temperature.

[0005] Microecological imbalance: Existing anti-dandruff and oil-controlling ingredients (such as zinc pyrithione and salicylic acid) can inhibit harmful bacteria, but they can also damage beneficial bacteria such as Staphylococcus epidermidis, leading to further damage to the scalp barrier and causing secondary problems such as dryness and sensitivity.

[0006] Lack of synergistic efficacy: Single ingredients are difficult to meet multiple needs such as anti-oxidation, hair follicle care, and oil regulation, and cannot achieve comprehensive scalp health maintenance. In addition, some products have insufficient safety data.

[0007] The applicant's patent application CN202610496024.3 discloses a selenium-enriched pearl general-purpose basic care formula that can be used in cosmetics. This formula improves the dissolution rate and delivery rate of pearl's active ingredients, as well as the stability of selenium. It also discloses its applicability to common cosmetics such as serums and masks. While theoretically this formula could be used in scalp sprays, the technical challenges remain to be overcome in introducing other active ingredients and adjusting the formulation to achieve synergistic effects among the components, ultimately resulting in a product that is highly permeable, multi-functional, microecologically friendly, and mildly safe. Summary of the Invention

[0008] This invention addresses the unique physiological characteristics of the scalp, such as thin stratum corneum, dense hair follicles, vigorous sebum secretion, and fragile barrier. It constructs a four-dimensional synergistic care system of "antioxidant-hair follicle repair-sebum regulation-microecological balance". Through targeted compounding of core functional components, combined with a functional excipient system adapted to the physiological environment of the scalp, it solves the core technical bottlenecks of existing technologies, such as low transdermal penetration rate of active ingredients, easy inactivation at room temperature, single efficacy, and damage to the scalp's microecology and barrier function.

[0009] To achieve the above objectives, this invention provides a selenium-enriched biotin scalp care essence spray and its preparation method. The selenium-enriched biotin scalp nourishing and repairing essence spray of this invention is scientifically compounded from core nourishing ingredients, hair follicle repair ingredients, oil regulation and transdermal system, moisturizing and repairing ingredients, and auxiliary ingredients. The total formula is made up to 100% by weight percentage with deionized water, and the pH of the system is precisely adjusted to 5.0-5.5, which is completely matched to the physiological acidic environment of the scalp.

[0010] The following is a detailed description of the technical solution of this invention.

[0011] 1. Four-element core efficacy system: Selenium yeast extract (0.05-0.1%, weight percentage): prepared by ultrasonic-high pressure homogenization composite process, selenocysteine ​​≥60%, total selenium content 2000±200μg / g.

[0012] Pearl active peptides (2-4%, weight percentage): prepared from pearl powder using reactive oxygen molecules for oxidation and depolymerization, 1kDa ultrafiltration purification and ultrasonic-high pressure homogenization composite process, with molecular weight <1kDa and amino acid content ≥90mg / mL.

[0013] Biotin (0.2-0.5%, weight percentage): also known as vitamin B7, with a purity ≥99.0%, conforming to the standards of the Pharmacopoeia of the People's Republic of China.

[0014] Hair follicle repair core enzyme complex (0.3-0.5%, weight percentage): prepared by ion gelation, containing superoxide dismutase (SOD) ≥2000U / mg, transglutaminase ≥50U / mL, and enzyme encapsulation rate ≥95%.

[0015] 2. Plant-based active ingredients: The plant-based active ingredient of this invention refers to plant extract micronized powder, prepared by supercritical carbon dioxide extraction technology, with a weight percentage of 3-6%. Specifically, it can be Platycladus orientalis leaf extract and / or Polygonum multiflorum extract, prepared from the corresponding dried medicinal materials using supercritical carbon dioxide extraction technology; when the two are used in combination, wherein: Platycladus orientalis leaf extract (2-4%, weight percentage): extracted using supercritical carbon dioxide low-temperature extraction process, with polyphenolic active ingredient content ≥5%; Polygonum multiflorum extract (1-2%, weight percentage): extracted using supercritical carbon dioxide low-temperature extraction process, with stilbene glycoside content ≥2%.

[0016] 3. Functional excipient system: Phytosterols (0.5-1.0%, weight percentage): of which β-sitosterol ≥95%, acid value ≤1.0 mgKOH / g; Zinc PCA (0.1-0.3%, weight percentage): Zinc pyrrolidone carboxylate complex, purity ≥98.0%, heavy metal content <10 ppm; Ethanol (15-20%, weight percentage): pharmaceutical grade, concentration 95±1%, impurity content conforms to GB / T 678-2002; Hyaluronic acid (0.5-1.0%, weight percentage): molecular weight 50kDa; purity ≥99.0%, conforming to USP standards; Panthenol (1-2%, weight percentage): purity ≥99.0%; Phenoxyethanol (0.5-1.0%, weight percentage): cosmetic grade, purity ≥99.5%; pH adjuster: Through citric acid / sodium citrate buffer pairing, the spray pH is precisely adjusted to 5.0-5.5 to match the physiologically acidic environment of the scalp.

[0017] Among the above components, the plant extracts (Platycladus orientalis leaf extract and Polygonum multiflorum extract) can be used alone or in combination; the hair follicle repair core enzyme complex is prepared into microcapsules by iontophoresis, with an enzyme encapsulation rate ≥95%; in the physiological environment of the scalp at pH 5.0-5.5, the cumulative release rate is ≥80% after 8 hours; after being sealed and stored at 4℃ for 6 months, the enzyme activity retention rate is >90%; the selenium yeast extract and pearl active peptides can form electrostatic adsorption composite particles in the formula, with a particle size <200nm and a dispersion zeta potential of +18 to +23mV; after being sealed and stored at 4℃ for 6 months, the selenocysteine ​​structure integrity rate is >95%.

[0018] This invention also provides a method for preparing the selenium-enriched biotin scalp care essence spray, the specific steps of which are as follows: 1. Preparation of Pearl Active Peptide Dispersion Pearl powder was mixed with deionized water and subjected to an oxidation reaction by passing active oxygen molecules through it. After centrifugation, the supernatant was collected and purified by ultrafiltration membrane with a molecular weight cutoff of 1 kDa. The mixture was then freeze-dried to obtain small molecule peptides. The small molecule peptides were reconstituted and then subjected to ultrasonic treatment and high-pressure homogenization to obtain a stable dispersion of pearl active peptides.

[0019] In one embodiment, pearl powder and deionized water are mixed at a weight ratio of 1:100 to 1:200, and 0.3 to 0.4 mg / L of active oxygen molecules are introduced for oxidation reaction for 30 to 40 min. The reaction solution is centrifuged at 10,000 rpm, and the supernatant is collected and purified by ultrafiltration membrane with a molecular weight cutoff of 1 kDa. The filtrate is collected and freeze-dried to obtain small molecule peptide powder. The obtained peptide powder is redissolved in deionized water and subjected to ultrasonic treatment and high-pressure homogenization in sequence to obtain a stable dispersion of pearl active peptides.

[0020] Preferably, the conditions for ultrasonic treatment are: power 300 W, frequency 20 kHz, and time 20 min; the conditions for high-pressure homogenization are: pressure 80-90 MPa and homogenization times 2.

[0021] More preferably, the obtained pearl active peptide dispersion has a particle size of <100 nm and an amino acid dissolution rate of ≥90%.

[0022] 2. Preparation of selenium yeast dispersion Lecithin and poloxamer 188 were mixed to prepare a compound emulsion; selenium yeast powder was mixed with the compound emulsion, ultrasonically treated under water bath conditions, and then homogenized under high pressure to obtain a stable dispersion of selenium yeast extract.

[0023] In one embodiment, lecithin with an HLB value of 7-9 is mixed with poloxamer 188 at a weight ratio of 1:1 to prepare a compound emulsion with a total concentration of 2 wt%; selenium yeast powder is mixed with the compound emulsion at a weight ratio of 1:10, and then subjected to ultrasonic treatment and high-pressure homogenization treatment in sequence under a water bath at 35°C to obtain a stable dispersion of selenium yeast extract.

[0024] Preferably, the conditions for ultrasonic treatment are: power 200 W, frequency 20 kHz, and time 30 min; the conditions for high-pressure homogenization are: pressure 90 MPa and homogenization times 2.

[0025] More preferably, the particle size of the prepared selenium yeast extract dispersion is 95–152 nm.

[0026] 3. Preparation of hair follicle repair core enzyme complex Superoxide dismutase and transglutaminase were dissolved in an acetate-sodium acetate buffer solution containing trehalose to prepare an enzyme solution; sodium alginate aqueous solution and chitosan hydrochloric acid solution were mixed and ultrasonically dispersed to prepare a carrier mixture; the enzyme solution was added dropwise to the carrier mixture, magnetically stirred to form an emulsion, calcium chloride solution was added dropwise for cross-linking, centrifuged and washed, and then freeze-dried and pulverized under vacuum to obtain the hair follicle repair core enzyme complex.

[0027] In one embodiment, superoxide dismutase (SOD, enzyme activity ≥2000 U / mg) and transglutaminase (enzyme activity ≥50 U / mg) were dissolved in a pH 5.5 acetate-sodium acetate buffer containing 1 wt% trehalose at a weight ratio of 1:1 to prepare an enzyme solution with a total enzyme concentration of 5 mg / mL. A 1 wt% sodium alginate aqueous solution and a 0.2 wt% chitosan hydrochloric acid solution were mixed at a volume ratio of 1:1 and ultrasonically dispersed for 10 min to prepare a carrier mixture. The enzyme solution was added dropwise to the carrier mixture at a rate of 1 mL / min, and magnetically stirred to form an emulsion. Then, 2 wt% calcium chloride solution was added dropwise, and the mixture was crosslinked for 30 min. The precipitate was collected by centrifugation, washed three times with deionized water, freeze-dried under vacuum, and pulverized to obtain the hair follicle repair core enzyme complex.

[0028] Preferably, the particle size of the hair follicle repair core enzyme complex is 1-3 μm, and the encapsulation rate is ≥95%.

[0029] More preferably, the obtained hair follicle repair core enzyme complex has a cumulative release rate of ≥80% in an environment of pH 5.0-5.5 after 8 hours; and an enzyme activity retention rate of >90% after 6 months of sealed storage at 4°C.

[0030] 4. Preparation of plant extract micro powder Dry branches and leaves of Platycladus orientalis and dried tuberous roots of Polygonum multiflorum were taken separately, crushed and sieved, and loaded into a supercritical carbon dioxide extraction vessel. After static extraction, dynamic extraction, vacuum separation and vacuum freeze drying, Platycladus orientalis leaf extract powder and Polygonum multiflorum extract powder were obtained respectively. They were then mixed evenly according to the weight ratio requirements of the target formula to obtain plant extract powder.

[0031] In one embodiment, dried branches and leaves of Platycladus orientalis conforming to the standards of the Pharmacopoeia of the People's Republic of China are taken, pulverized, and passed through a 40-mesh sieve. They are then placed in a supercritical CO2 extraction vessel. Static extraction is performed for 1 h at a pressure of 30±1 MPa and a temperature of 40±2℃, followed by dynamic extraction for 1 h. The extract is then separated and collected in a vacuum separation vessel at a pressure of 5±0.5 MPa and a temperature of 35±2℃. The extract is then freeze-dried under vacuum for 24 h to obtain Platycladus orientalis leaf extract powder.

[0032] In one embodiment, dried Polygonum multiflorum tuberous roots conforming to the standards of the Pharmacopoeia of the People's Republic of China were pulverized and passed through a 40-mesh sieve, and then loaded into a supercritical CO2 extraction vessel. Static extraction was performed for 1 hour under a pressure of 30±1 MPa and a temperature of 40±2℃, followed by dynamic extraction for 1 hour. The extract was then separated and collected in a vacuum separation vessel under a pressure of 5±0.5 MPa and a temperature of 35±2℃, and then freeze-dried under vacuum for 24 hours to obtain Polygonum multiflorum extract powder.

[0033] The above-mentioned Platycladus orientalis leaf extract powder and Polygonum multiflorum extract powder were mixed evenly according to the weight ratio of the target formula to obtain a mixture of plant extract powders.

[0034] More preferably, the polyphenol content in the Platycladus orientalis leaf extract powder is ≥5%, and the polyphenol retention rate is ≥92%; the stilbene glycoside content in the Polygonum multiflorum extract powder is ≥2%.

[0035] 5. Multiphase system compounding Ethanol, phytosterol, and zinc PCA were mixed and dissolved according to the formula to obtain the oleo-ethanol phase; the remaining deionized water was taken, and biotin, hyaluronic acid, panthenol, and phenoxyethanol were added. The mixture was stirred and swollen, and the pH was adjusted to 5.0-5.5 with a citrate-sodium citrate buffer to obtain the aqueous phase; the oleo-ethanol phase and the aqueous phase were mixed, and the products from steps 1-4 were added to obtain a homogeneous and stable O / W type emulsion.

[0036] In one embodiment, ethanol, phytosterol, and zinc pyrrolidone carboxylate (zinc PCA) were taken according to the formula and stirred in a water bath at 35±2℃ for 30 min until completely dissolved to obtain an oil-ethanol phase; the remaining deionized water was taken, and biotin, hyaluronic acid, panthenol, and phenoxyethanol were added, and the mixture was stirred at 500 rpm for 1 h to swell. The pH was adjusted to 5.0-5.5 with a citrate-sodium citrate buffer to obtain an aqueous phase; the oil-ethanol phase and the aqueous phase were mixed at a volume ratio of 1:3 while stirring, and then the pearl active peptide dispersion prepared in step 1 and the selenium yeast extract dispersion prepared in step 2 were added dropwise, along with the hair follicle repair core enzyme complex prepared in step 3 and the plant extract micro powder mixture prepared in step 4. The mixture was homogenized to obtain a uniform and stable O / W type emulsion.

[0037] Preferably, the homogenization conditions are: rotation speed 2500±100 rpm, time 20 min, and temperature ≤35℃.

[0038] More preferably, the prepared emulsion dispersion has a particle size of <180 nm and does not separate into layers after centrifugation at 3000 rpm for 30 min.

[0039] 6. Aseptic and Dispensing The emulsion obtained in step 5 was sterilized by pressure filtration through a 0.22 μm filter membrane, and the total number of microorganisms was controlled to be <10 CFU / mL. The filtrate was injected into an aluminum light-proof bottle through a sterile peristaltic pump. The bottle was filled with nitrogen gas with a purity of ≥99.99% to replace the air inside. An air pressure pump nozzle was installed, and the bottle was sealed and stored at 4°C in the dark.

[0040] Preferably, the oxygen permeability of the aluminum light-proof bottle is <5 cm³ / m²·24h.

[0041] More preferably, the assembled spray nozzle has a spray droplet diameter D50 of 35-38 μm; and the core active ingredient loss rate is <5% when the finished product is stored at 4°C in the dark for 6 months.

[0042] Compared with the prior art, the present invention has the following beneficial effects: 1. Comprehensive efficacy, multi-target synergistic care A four-dimensional system of "antioxidant, hair follicle nourishment, sebum regulation, and microecological balance" was constructed. In vitro experiments showed that the superoxide anion clearance rate was ≥93% (93.2% in Example 1), the hair follicle stem cell proliferation rate increased by more than 38%, and the Malassezia antibacterial rate was ≥90%. After 12 weeks of human trials: scalp sebum secretion rate decreased by 37%, hair follicle density increased by 17%, transepidermal water loss (TEWL) decreased by 25%, and the incidence of scalp itching decreased from 33.3% to 3.3%.

[0043] 2. High transdermal penetration rate, ensuring full utilization of ingredients. Employing an ultrasonic-high pressure homogenization process, the emulsion particle size is <180 nm, increasing the transdermal penetration rate of active ingredients from <8% in traditional formulations to 28% (Franz diffusion cell method). The core enzyme complex for hair follicle repair has a cumulative release rate of ≥80% in the scalp's pH environment over 8 hours, achieving continuous maintenance.

[0044] 3. Excellent stability and long shelf life. Supercritical CO2 extraction resulted in a polyphenol retention rate of ≥92%; microencapsulation resulted in an enzyme activity retention rate of >90% after 6 months, which is 60% higher than the unencapsulated group; selenocysteine ​​maintained a structural integrity rate of >95% after 6 months; and nitrogen-filled aluminum bottle packaging resulted in a core component loss of <5% after 6 months.

[0045] 4. High safety and strong physiological adaptability The spray has a pH of 5.0–5.5, matching the physiological environment of the scalp; a skin irritation score of 0 (Draize test); heavy metal content complies with the "Cosmetic Safety Technical Specifications"; and a sensitization rate of 0% in patch tests for the formula suitable for sensitive skin.

[0046] 5. Highly feasible for industrialization and suitable for large-scale production: The equipment used in the preparation process is all general-purpose equipment in the cosmetics industry, and no special customization is required; the key process parameters are clearly quantified and highly repeatable; and it meets the requirements of industrial production. Detailed Implementation

[0047] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following embodiments. All other implementations obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0048] Example 1: Standard Formula Selenium-Enriched Biotin Scalp Care Essence Spray I. Composition (by weight percentage per 1000g) Selenium yeast extract (0.08%): 62% selenocysteine, 2050 μg / g total selenium content, 96% cell wall breakage rate, 102 nm particle size, and +21 mV zeta potential.

[0049] Pearl hydrolyzed active peptides (3.00%): molecular weight <1kDa, amino acid content 105mg / mL, glycine 38% + alanine 14%, HPLC analysis showed uniform molecular weight distribution; Biotin (0.30%): Purity 99.2%, conforming to the standards of the 2020 edition of the Pharmacopoeia of the People's Republic of China. Hair follicle repair enzyme complex (0.40%): SOD 2050U / mg, transglutaminase 52U / mL, particle size 2.2μm;

[0050] Platycladus orientalis leaf extract (3.5%): supercritical CO2 extraction, polyphenol content 5.3%, moisture <5%, particle size <50μm; Polygonum multiflorum extract (1.2%): supercritical CO2 extraction, stilbene glycoside content 2.1%, moisture <5%, particle size <50μm; Phytosterols (0.8%): β-sitosterol 96%, acid value 0.8 mg KOH / g; Zinc PCA (0.2%): purity 98.5%, heavy metal content <5ppm; Ethanol (18%): Pharmaceutical grade, concentration 95.2%, conforming to GB / T678-2002; Hyaluronic acid (0.8%): molecular weight 52kDa, purity 98.3%, detected by gel filtration chromatography; Panthenol (1.5%): 99.1% purity, conforming to USP45 standards; Phenoxyethanol (0.7%): 99.6% purity, cosmetic grade; Citric acid-sodium citrate buffer pair (appropriate amount): Adjust pH to 5.2 ± 0.1; Deionized water (to bring up to 100%): conductivity <10μS / cm³.

[0051] II. Preparation Steps Step 1: Preparation of Pearl Active Peptide Solution Pearl powder was mixed with deionized water at a weight ratio of 1:150, and 0.35 mg / L of active oxygen molecules were introduced for oxidation reaction for 35 min. The reaction solution was centrifuged at 10,000 rpm, and the supernatant was purified by ultrafiltration membrane with a molecular weight cutoff of 1 kDa. The filtrate was collected and freeze-dried to obtain small molecule peptide powder. The peptide powder was reconstituted in deionized water, ultrasonicated at 300 W and 20 kHz for 20 min, and then homogenized twice under high pressure at 85 MPa to obtain pearl active peptide dispersion. The particle size was detected to be 85 nm, which was then used for later use. Step 2: Preparation of selenium yeast extract dispersion: Lecithin with an HLB value of 7-9 was mixed with poloxamer 188 at a weight ratio of 1:1 to prepare a compound emulsion with a total concentration of 2 wt%. Selenium yeast powder was mixed with the compound emulsion at a weight ratio of 1:10 and subjected to ultrasonic treatment at 200 W and 20 kHz for 30 min in a 35℃ water bath. Then, it was homogenized twice under high pressure at 90 MPa to obtain a dispersion of selenium yeast extract. The particle size was measured to be 102 nm and the zeta potential was +21 mV. This mixture was then set aside for later use. Step 3: Preparation of the hair follicle repair core enzyme complex Superoxide dismutase (SOD, 2050 U / mg) and transglutaminase (52 U / mg) were dissolved in a 1:1 weight ratio in a pH 5.5 acetate-sodium acetate buffer solution containing 1 wt% trehalose to prepare an enzyme solution with a total enzyme concentration of 5 mg / mL. A 1 wt% sodium alginate aqueous solution and a 0.2 wt% chitosan hydrochloric acid solution were mixed in a 1:1 volume ratio and ultrasonically dispersed for 10 min to prepare a carrier mixture. The enzyme solution was added dropwise to the carrier mixture at a rate of 1 mL / min, and the mixture was magnetically stirred to form an emulsion. A 2 wt% calcium chloride solution was added dropwise, and the mixture was cross-linked for 30 min. The precipitate was collected by centrifugation, washed three times with deionized water, freeze-dried under vacuum, and pulverized to obtain the hair follicle repair core enzyme complex. The particle size was 2.2 μm, and the encapsulation efficiency was 96%. This was then prepared for use. Step 4: Preparation of plant extract micronized powder Dried branches and leaves of Platycladus orientalis conforming to the standards of the Pharmacopoeia of the People's Republic of China were pulverized and passed through a 40-mesh sieve. The pulverized material was then placed in a supercritical CO2 extraction vessel. Static extraction was performed for 1 h at 30 MPa and 40℃, followed by dynamic extraction for 1 h. The extract was then separated and collected in a vacuum separation vessel (5 MPa, 35℃) and freeze-dried under vacuum for 24 h to obtain Platycladus orientalis leaf extract powder. Polygonum multiflorum extract powder was obtained using the same method. The two powders were mixed evenly at a weight ratio of 3.5:1.2 and set aside for later use. Step 5: Multiphase system compounding Weigh out ethanol (180 g), phytosterols (8 g), and zinc PCA (2 g) according to the formula, add them to a stirred tank, and stir in a 35℃ water bath for 30 min until completely dissolved to obtain the oleo-ethanol phase; take deionized water (about 697.2 g), add biotin (3 g), hyaluronic acid (8 g), panthenol (15 g), and phenoxyethanol (7 g), stir at 500 rpm for 1 h to swell, and adjust the pH to 5.2±0.1 with a citrate-sodium citrate buffer to obtain the aqueous phase; mix the oleo-ethanol phase and the aqueous phase at a volume ratio of 1:3 (in actual operation, the oleo-ethanol phase can be slowly added to the aqueous phase), stirring while adding, and then add the pearl active peptide dispersion prepared in step 1, the selenium yeast extract dispersion prepared in step 2, the hair follicle repair core enzyme complex prepared in step 3 (4 g), and the plant extract micro powder mixture prepared in step 4 (35 g of arborvitae leaf extract + 12 g of Polygonum multiflorum extract). An O / W emulsion was prepared by homogenization at 2500 rpm for 20 min at ≤35℃. The particle size of the dispersed phase in the emulsion was found to be 165 nm, and no stratification was observed after centrifugation at 3000 rpm for 30 min. Step 6: Sterilization and Packaging The emulsion obtained in step 5 was sterilized by pressure filtration through a 0.22 μm filter membrane, and the total microbial count was found to be 6 CFU / mL. The filtrate was injected into an aluminum light-proof bottle using a sterile peristaltic pump, and the air inside the bottle was replaced with nitrogen gas of ≥99.99% purity. An air pressure pump nozzle was then attached, and the bottle was sealed and stored at 4°C in the dark. The droplet size D50 of the spray was determined to be 36 μm.

[0052] III. Effect Verification 1. In vitro efficacy testing 2. Human trial results (30 volunteers, once in the morning and once in the evening, spray evenly on the scalp and massage until absorbed, for 12 weeks) Testing items Baseline value After 12 weeks of use Detection methods Scalp sebum secretion rate (μg / cm² / h) 35.2±6.1 22.2±4.3 Sebumeter SM815 sebum analyzer Hair follicle density (numbers / cm²) 985±118 1152±136 Dermoscopy (DermLite DL4) Transepidermal water loss (TEWL) 22.5±3.4 16.9±2.1 VapoMeter (transdermal moisture loss meter) Incidence of scalp itching 33.3% 3.3% Subjective ratings from participants (0-4 points) 3. Safety testing Skin irritation: Draize test score 0, no erythema or edema; Heavy metal content: Lead < 1 ppm, Mercury < 0.1 ppm, Mercury not detected, in compliance with the "Cosmetic Safety Technical Specifications". Total microbial count: 6 CFU / mL, which complies with the "Cosmetic Safety Technical Specifications".

[0053] Example 2: Formula for Sensitive Skin (Low Irritation Optimized) I. Raw material composition (by weight percentage per 1000 g) Selenium yeast extract (0.08%): 62% selenocysteine, total selenium content 2050 μg / g;

[0054] Pearl hydrolyzed active peptides (3.00%): molecular weight < 1 kDa, amino acid content 105 mg / mL; Biotin (0.30%): 99.2% purity; Hair follicle repair core enzyme complex (0.30%): contains only superoxide dismutase (SOD), enzyme activity ≥2000U / mg; Platycladus orientalis leaf extract (2%): supercritical CO2 extraction, polyphenol content 5.1%; Polygonum multiflorum extract (1%): supercritical CO2 extraction, stilbene glycoside content 2.0%; Phytosterols (0.8%): β-sitosterol 95%, acid value 0.7 mg KOH / g; Zinc PCA (0.2%): purity 98.5%, heavy metal content <5ppm; Ethanol (15%): Pharmaceutical grade, concentration 95.2%, conforming to GB / T678-2002; Hyaluronic acid (0.8%): molecular weight 52kDa, purity 98.3%, detected by gel filtration chromatography; 1,2-Hexanediol (0.50%): Cosmetic grade, 99.5% purity, auxiliary preservative / moisturizer; Panthenol (1.5%): 99.1% purity, conforming to USP45 standards; Phenoxyethanol (0.7%): 99.6% purity, cosmetic grade; Citric acid-sodium citrate buffer pair (appropriate amount): Adjust pH to 5.2 ± 0.1; Deionized water (to bring up to 100%): conductivity <10μS / cm³.

[0055] II. Preparation Steps Step 1: Preparation of Pearl Active Peptide Dispersion Same as step 1 in Example 1. A pearl active peptide dispersion was prepared, with a particle size of 85 nm, for later use. Step 2: Preparation of selenium yeast dispersion Same as step 2 in Example 1. A dispersion of selenium yeast extract was prepared, with a particle size of 102 nm, and set aside for later use. Step 3: Preparation of the hair follicle repair core enzyme complex The procedure is essentially the same as step 3 in Example 1, but only superoxide dismutase (SOD, 2000 U / mg) is used, without the addition of transglutaminase (this example uses a low-stimulation adaptation, reducing the number of enzyme types). Specific steps: SOD is dissolved in a pH 5.5 acetate-sodium acetate buffer containing 1 wt% trehalose to prepare an enzyme solution with a concentration of 5 mg / mL; subsequent encapsulation steps are the same as in Example 1. The hair follicle repair core enzyme complex is obtained, with a particle size of 2.0 μm and an encapsulation rate ≥95%, for later use. Step 4: Preparation of plant extract micronized powder Same as step 4 in Example 1. Prepare micronized powders of Platycladus orientalis leaf extract (polyphenol content 5.1%) and Polygonum multiflorum extract (stilbene glycoside content 2.0%). Mix the two powders evenly at a weight ratio of 2:1 and set aside. Step 5: Multiphase system compounding Weigh out ethanol (150g), phytosterols (8g), zinc PCA (2g), and 1,2-hexanediol (5g) according to the formula, add them to a stirred tank, and stir in a 35℃ water bath for 30 min until completely dissolved to obtain the oil-alcohol phase; take deionized water (about 730.2g), add biotin (3g), hyaluronic acid (8g), panthenol (15g), and phenoxyethanol (7g), and stir at 500 rpm until swollen. h, the pH was adjusted to 5.0±0.1 using a citrate-sodium citrate buffer to obtain an aqueous phase; the oleic-ethanol phase was slowly added to the aqueous phase while stirring, and the pearl active peptide dispersion prepared in step 1 and the selenium yeast extract dispersion prepared in step 2 were added dropwise, followed by the hair follicle repair core enzyme complex (3g) prepared in step 3 and the plant extract micro powder mixture (20g of Platycladus orientalis leaf extract + 10g of Polygonum multiflorum extract) prepared in step 4. The mixture was homogenized at 2500rpm for 20min at ≤35℃ to obtain an O / W type emulsion. The particle size of the emulsion dispersion was 170nm, and it did not separate into layers after centrifugation at 3000rpm for 30min. Step 6: Sterilization and Packaging Same as step 6 in Example 1. The total number of microorganisms was detected as 5 CFU / mL, and the droplet size D50 of the spray was 35 μm.

[0056] III. Effect Verification 1. In vitro efficacy testing 2. Human trial results (30 volunteers with sensitive scalps, sprayed evenly onto the scalp and massaged until absorbed twice daily, morning and evening, for 12 weeks). Testing items Baseline value After 12 weeks of use Detection methods Scalp sebum secretion rate (μg / cm² / h) 32.5±5.8 21.1±3.9 Sebumeter SM815 sebum analyzer Hair follicle density (numbers / cm²) 985±115 1125±128 Dermoscopy (DermLite DL4) Transepidermal water loss (TEWL) 23.2±3.6 17.2±2.3 VapoMeter (transdermal moisture loss meter) Incidence of scalp tingling 26.7% 0% Subjective ratings from participants (0-4 points) 3. Safety testing Skin irritation: Draize test score 0, no erythema or edema; Heavy metal content: Lead < 1 ppm, Mercury < 0.1 ppm, Mercury not detected, in compliance with the "Cosmetic Safety Technical Specifications". Total microbial count: 5 CFU / mL, which complies with the "Cosmetic Safety Technical Specifications".

[0057] Patch test: No sensitization reaction was observed in any of the 30 volunteers (sensitization rate 0%). Example 3: Oil-controlling and strengthening formula (for oily scalp) I. Raw material composition (percentage by weight per 1000g) Selenium yeast extract (0.08%): 62% selenocysteine, total selenium content 2050 μg / g; Pearl active peptides (4.0%): molecular weight < 1 kDa, amino acid content 105 mg / mL; Biotin (0.3%): 99.2% purity; Hair follicle repair core enzyme complex (0.4%): SOD enzyme activity 2050U / mg, glutamine transaminase enzyme activity 52U / mL, particle size 2.2μm; Platycladus orientalis leaf extract (3.8%): supercritical CO2 extraction, polyphenol content 5.4%; Polygonum multiflorum extract (1.8%): supercritical CO2 extraction, stilbene glycoside content 2.2%; Linolenic acid (0.8%): 98% purity, acid value ≤1.0mgKOH / g, a substitute for plant extracts; Zinc PCA (0.3%): purity 98.5%, heavy metal content <5ppm; Ethanol (20%): Pharmaceutical grade, concentration 95.2%; Hyaluronic acid (0.8%): molecular weight 52kDa, purity 98.3%; Panthenol (1.5%): 99.1% purity; Phenoxyethanol (0.7%): 99.6% purity, cosmetic grade; Citric acid-sodium citrate buffer pair: appropriate amount, adjust pH to 5.0±0.1; Deionized water (balance, approximately 65.32%): conductivity ≤10μS / cm³.

[0058] II. Preparation Steps Step 1: Preparation of Pearl Active Peptide Dispersion Same as step 1 in Example 1. A pearl active peptide dispersion was prepared, with a particle size of 82 nm, and set aside for later use.

[0059] Step 2: Preparation of Selenium Yeast Extract Dispersion Same as step 2 in Example 1. A dispersion of selenium yeast extract was prepared, and the particle size was measured to be 102 nm. It was then set aside for later use.

[0060] Step 3: Preparation of the hair follicle repair core enzyme complex Superoxide dismutase (SOD, 2000 U / mg) was dissolved in a pH 5.5 acetate-sodium acetate buffer solution containing 1 wt% trehalose to prepare an enzyme solution with an enzyme concentration of 5 mg / mL. Other steps were the same as in step 3 of Example 1. The particle size was measured to be 2.2 μm, and the encapsulation efficiency was ≥95%. The solution was then prepared for use.

[0061] Step 4: Preparation of plant extract micronized powder Same as step 4 in Example 1. Prepare micronized powders of Platycladus orientalis leaf extract (polyphenol content 5.4%) and Polygonum multiflorum extract (stilbene glycoside content 2.2%). Mix the two powders evenly at a weight ratio of 3.8:1.8 and set aside.

[0062] Step 5: Multiphase system compounding Weigh out ethanol (200g), linolenic acid (8g), and zinc PCA (3g) according to the formula, add them to a mixing tank, and stir in a 35℃ water bath for 30 min until completely dissolved to obtain the oil-ethanol phase; take deionized water (about 653.2g), add biotin (3g), hyaluronic acid (8g), panthenol (15g), and phenoxyethanol (7g), stir at 500 rpm to swell for 1h, adjust the pH to 5.0±0.1 with a citrate-sodium citrate buffer to obtain the aqueous phase; slowly add the oil-ethanol phase to the aqueous phase while stirring, and add the pearl active peptide dispersion prepared in step 1, the selenium yeast extract dispersion prepared in step 2, the hair follicle repair core enzyme complex prepared in step 3 (4g), and the plant extract micro powder mixture prepared in step 4 (38g of arborvitae leaf extract + 18g of Polygonum multiflorum extract) dropwise at 2500 rpm for 20 min under ≤35℃ conditions to obtain the O / W type emulsion. The particle size of the emulsion dispersion was found to be 160 nm, and it did not separate into layers after centrifugation at 3000 rpm for 30 min.

[0063] Step 6: Sterilization and Packaging Same as step 6 in Example 1. The total microbial count was 7 CFU / mL, and the spray droplet size D50 = 37 μm.

[0064] III. Effect Verification 1. In vitro efficacy testing 2. Human trial results (30 volunteers with oily scalps, sprayed evenly on the scalp and massaged until absorbed twice a day, morning and evening, for 12 weeks) Testing items Baseline value After 12 weeks of use Detection methods Scalp sebum secretion rate (μg / cm² / h) 38.5±6.3 24.3±4.1 Sebumeter SM815 sebum analyzer Hair follicle density (numbers / cm²) 965±120 1148±132 Dermoscopy (DermLite DL4) Transepidermal water loss (TEWL) 21.8±3.2 17.2±2.4 VapoMeter (transdermal moisture loss meter) Improvement rate of hair follicle sebum blockage 35.2%±4.8% 88.6%±3.5% Dermoscopy (DermLite DL4) Dandruff reduction rate - 82.5% Skin imaging device + subject subjective rating (0-4 points) Incidence of scalp odor 40.0% 6.7% Subjective ratings from participants (0-4 points) 3. Safety testing Skin irritation: Draize test score 0, no erythema or edema; Heavy metal content: Lead < 1 ppm, Mercury < 0.1 ppm, Mercury not detected, in compliance with the "Cosmetic Safety Technical Specifications". Total microbial count: 7 CFU / mL, which complies with the "Cosmetic Safety Technical Specifications".

[0065] Long-term safety: No scalp barrier damage was observed after 12 weeks of continuous use, and TEWL remained within a healthy range. Comparative Example 1: Commercially available chemical oil-controlling scalp spray (containing salicylic acid + ketoconazole) I. Raw material composition (percentage by weight per 1000g) Salicylic acid (BHA) (1.5%): Cosmetic grade, purity ≥99.0%; Ketoconazole (0.5%): Pharmaceutical grade, purity ≥99.0%; Ethanol (20%): Pharmaceutical grade, 95% concentration; Sodium carbomer (0.4%): Cosmetic grade, thickener; Triethanolamine (0.3%): pH adjuster, purity ≥99.0%; Menthol (0.2%): Cosmetic grade, purity ≥99.0%; Sodium benzoate (0.8%): Cosmetic-grade preservative, purity ≥99.0%; Deionized water (balance, approximately 76.3%): conductivity ≤10μS / cm.

[0066] II. Preparation Process (1) Dissolve salicylic acid and ketoconazole in ethanol, add menthol, and stir until completely dissolved to obtain an oil phase solution.

[0067] (2) Slowly sprinkle sodium carbomer into deionized water, stir at 500 rpm for 2 h to swell, add triethanolamine dropwise, adjust pH to 6.0±0.1, and form a gel-like aqueous phase.

[0068] (3) Mix the oil phase solution with the water phase solution and stir evenly to obtain a transparent gel-like spray stock solution.

[0069] (4) Sterilization was achieved by filtration using a 0.45μm filter membrane, with a total microbial count of <100 CFU / mL; the product was filled into ordinary plastic spray bottles without any light protection or nitrogen filling treatment. The spray droplet size D50 = 55μm.

[0070] III. Effect Comparison Thirty volunteers with oily scalps, using the same inclusion criteria as in Example 3, applied the product from Comparative Example 1 twice daily, morning and evening, spraying it evenly onto the scalp and massaging until absorbed, for 12 consecutive weeks. The results compared to Example 3 are as follows: As can be seen from in vitro experiments, the present invention achieves a superoxide anion scavenging rate of ≥93% and increases hair follicle stem cell proliferation rate by ≥38%. After 12 weeks of human trials, scalp sebum secretion decreased by 37%, transdermal water loss decreased by 25%, and skin irritation score was 0, meeting the requirements of the "Cosmetic Safety Technical Specifications." This invention possesses advantages such as multi-target synergistic care, high transdermal penetration, good stability, and high safety, making it suitable for large-scale production.

[0071] In summary, this invention, through the aforementioned core technologies and scientific compounding system, effectively solves the technical bottlenecks of insufficient ingredient penetration, poor stability, and inappropriate microecological intervention in existing scalp care products. Example data shows that this product can significantly regulate scalp sebum secretion, maintain hair follicle health, and improve scalp barrier function, while being gentle and safe, suitable for different scalp types. Its preparation process parameters are clearly quantifiable and highly repeatable, possessing feasibility for industrial production, and providing a scientifically feasible technical solution for the research and development of scalp nourishing and repairing products.

[0072] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them; those skilled in the art can make appropriate adjustments to the process parameters and raw material ratios without departing from the technical principles of the present invention, and all such adjustments should be covered within the protection scope of the present invention.

Claims

1. A selenium-enriched biotin scalp care essence spray, characterized in that, The components, by weight percentage, are: 0.05-0.1% selenium yeast extract, 2-4% pearl active peptide, 0.3-0.5% hair follicle repair core enzyme complex, 0.2-0.5% biotin, 3-6% plant extract micro powder, excipients, and the balance being deionized water; the pH of the spray system is 5.0-5.

5. The selenium yeast extract was prepared by an ultrasonic-high pressure homogenization composite process, wherein selenocysteine ​​≥60% and total selenium content 2000±200μg / g; The pearl active peptides are prepared by a composite process of pearl powder using active oxygen molecule oxidation and depolymerization, 1kDa ultrafiltration purification and ultrasonic-high pressure homogenization, with a molecular weight of <1kDa and an amino acid content of ≥90mg / mL. The hair follicle repair core enzyme complex is prepared by ion gelation and contains superoxide dismutase ≥2000U / mg and transglutaminase ≥50U / mg. The biotin has a purity of ≥99.0%; The plant extract powder is prepared by supercritical carbon dioxide extraction.

2. The selenium-enriched biotin scalp care essence spray according to claim 1, characterized in that, The plant extract powder is arborvitae leaf extract and / or Polygonum multiflorum extract; when the two are used in combination, the content of arborvitae leaf extract in the spray is 2-4% by weight and the content of Polygonum multiflorum extract is 1-2%; the arborvitae leaf extract and Polygonum multiflorum extract are prepared by supercritical carbon dioxide extraction technology using the corresponding dried medicinal materials as raw materials.

3. The selenium-enriched biotin scalp care essence spray according to claim 1, characterized in that, The components of the excipient, based on a weight percentage of the spray, are as follows: Phytosterols 0.5-1.0%, Zinc PCA 0.1-0.3%, Ethanol 15-20%, Hyaluronic Acid 0.5-1.0%, Panthenol 1-2%, Phenoxyethanol 0.5-1.0%, and pH adjuster.

4. The selenium-enriched biotin scalp care essence spray according to claim 3, characterized in that, Of the phytosterols, β-sitosterol ≥ 95% and acid value ≤ 1.0 mg KOH / g; the zinc PCA has a purity ≥ 98.0% and heavy metal content < 10 ppm; the ethanol is pharmaceutical grade with a concentration of 95 ± 1% and impurity content conforming to GB / T 678-2002; the hyaluronic acid has a molecular weight of 50 kDa; its purity ≥ 99.0% and conforms to USP standards; the phenoxyethanol is cosmetic grade with a purity ≥ 99.5%; and the pH adjuster is citric acid-sodium citrate.

5. The selenium-enriched biotin scalp care essence spray according to claim 1, characterized in that, The selenium yeast extract and pearl active peptides form composite particles through electrostatic adsorption. The particle size of the composite particles is <200nm, and the zeta potential of the dispersion is +18 to +23mV. After being sealed and stored at 4℃ for 6 months, the structural integrity of selenocysteine ​​is >95%.

6. The selenium-enriched biotin scalp care essence spray according to claim 1, characterized in that, The encapsulation rate of the hair follicle repair core enzyme complex is ≥95%; the cumulative release rate is ≥80% after 8 hours in a scalp physiological environment of pH 5.0-5.5; and the enzyme activity retention rate is >90% after 6 months of sealed storage at 4℃.

7. The selenium-enriched biotin scalp care essence spray according to claim 1, characterized in that, The spray is filled in an aluminum light-proof bottle and equipped with an air pressure pump nozzle. The spray droplet diameter D50 is 35-38μm. Within 6 months of storage at 4℃ in the dark, the loss of the core active ingredients is <5%.

8. A method for preparing the selenium-enriched biotin scalp care essence spray according to claim 1, characterized in that, Includes the following steps: Step 1: Mix pearl powder with deionized water, pass active oxygen molecules through for oxidation reaction, centrifuge the reaction solution and take the supernatant, purify it through an ultrafiltration membrane with a molecular weight cutoff of 1 kDa, freeze dry to obtain small molecule peptides; after reconstitute the small molecule peptides, treat them with ultrasound and homogenize them under high pressure to obtain a stable dispersion of pearl active peptides. Step 2: Mix lecithin with HLB value 7-9 with poloxamer 188 to prepare a compound emulsion; mix selenium yeast powder with the compound emulsion, sonicate under water bath conditions, and then homogenize under high pressure to obtain a stable dispersion of selenium yeast extract. Step 3: Dissolve superoxide dismutase and transglutaminase in trehalose-acetic acid-sodium acetate buffer solution to prepare enzyme solution; mix sodium alginate aqueous solution and chitosan hydrochloric acid solution, and disperse by ultrasonication to prepare carrier mixture; add enzyme solution dropwise to carrier mixture, stir magnetically to form emulsion, add calcium chloride solution dropwise for crosslinking, centrifuge and wash, freeze dry and pulverize under vacuum to obtain hair follicle repair core enzyme complex; Step 4: Take the dried branches and leaves of Platycladus orientalis and the dried tuberous roots of Polygonum multiflorum, crush and sieve them, and put them into a supercritical carbon dioxide extraction vessel; after static extraction, dynamic extraction, vacuum separation and vacuum freeze drying, Platycladus orientalis leaf extract powder and Polygonum multiflorum extract powder are obtained respectively; and mix them evenly according to the weight ratio requirements of the target formula to obtain plant extract powder. Step 5: Mix ethanol, phytosterol, and zinc PCA according to the formula, dissolve them, and obtain the oleo-ethanol phase; take the remaining deionized water according to the formula, add biotin, hyaluronic acid, panthenol, and phenoxyethanol, stir to swell, adjust the pH to 5.0-5.5 with a citrate-sodium citrate buffer pair, and obtain the aqueous phase; mix the oleo-ethanol phase and the aqueous phase, and then add the products from steps 1-4 to obtain a homogeneous and stable O / W type emulsion, sterilize and package it.

9. The preparation method according to claim 8, characterized in that: In step 1, the weight ratio of pearl powder to deionized water is 1:100-1:200, the amount of active oxygen molecules introduced is 0.3-0.4 mg / L, the oxidation reaction time is 30-40 min, the ultrasonic treatment parameters are 300 W, 20 kHz, 20 min, and the high-pressure homogenization parameters are 80-90 MPa, twice; the particle size of the pearl active peptides in the resulting dispersion is <100 nm. In step 2, the weight ratio of lecithin to poloxamer 188 is 1:1, the concentration of the compound emulsion is 2wt%, the weight ratio of selenium yeast powder to the compound emulsion is 1:10, the water bath temperature is 35℃, the ultrasonic treatment parameters are 200W, 20kHz, 30min, and the high-pressure homogenization parameters are 90MPa, twice. In step 3, the weight ratio of superoxide dismutase to transglutaminase is 1:1, the pH of the acetate-sodium acetate buffer is 5.5, the concentration of trehalose is 1 wt%, and the concentration of the resulting enzyme solution is 5 mg / mL; the concentration of sodium alginate aqueous solution is 1 wt%, the concentration of chitosan hydrochloric acid solution is 0.2 wt%, and they are mixed at a volume ratio of 1:1 and ultrasonically dispersed for 10 min to obtain the carrier mixture; the enzyme solution is added dropwise to the carrier mixture at a rate of 1 mL / min, and the concentration of calcium chloride solution is 2 wt%, added dropwise and cross-linked for 30 min; In step 5, the volume ratio of the oil-ethanol phase to the water phase is 1:

3. After adding the products from steps 1-4, homogenize at 2500±100 rpm for 20 min. The sterilization and dispensing process involves filtration of the emulsion under pressure through a 0.22μm filter membrane, followed by sterilization with 254nm ultraviolet light to control the total microbial count to <10CFU / mL; the emulsion is then injected into an aluminum light-proof bottle using a sterile peristaltic pump, the bottle is filled with nitrogen gas of ≥99.99% purity to replace the air inside, an air pressure pump nozzle is installed, and the bottle is sealed and stored at 4°C in the dark.

10. The preparation method according to claim 8, characterized in that, The core process parameters for each step must meet the following requirements: the amino acid dissolution rate of the dispersion obtained in step 1 is ≥90%; the particle size of the selenium yeast dispersion obtained in step 2 is 95-152nm; the particle size of the enzyme complex obtained in step 3 is 1-3μm, and the encapsulation rate is ≥95%; the particle size of the emulsion dispersion obtained in step 5 is <180nm, and it does not separate into layers after centrifugation at 3000rpm for 30min; the loss of core active ingredients in the finished product is <5% within 6 months of storage at 4℃ in the dark.

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