Alcohol extract-based washing product and preparation method thereof

Abstract

The invention discloses a washing product based on a seaweed extract and a preparation method, and belongs to the technical field of daily cosmetics, the product takes two modified seaweed active ingredients as a core, and comprises a fucoic acid derivative modified by diallylation and quaternization, a sodium alginate copolymer modified by carboxymethylation and chitosan grafting, a sodium alginate copolymer modified by sodium alginate and chitosan grafting, and a sodium alginate copolymer modified by sodium alginate and chitosan grafting. A seaweed extract, a basic surfactant, an ampholytic surfactant, a humectant, a pH regulator and a preservative are used as auxiliary materials for compounding to form a washing product. Wherein the diallylation fucoic acid derivative is prepared through quaternization after reaction of fucoic acid and allyl bromide, and the chitosan grafted copolymer is prepared through cross-linking and grafting of sodium alginate and chitosan after carboxymethylation. Through the synergistic effect of the modified seaweed component and the natural extract, the cleaning, moisturizing and mild properties of the washing product are improved, and the natural and efficient requirements are met.

Description

Technical Field

[0001] The present invention relates to the technical field of daily cosmetics, and in particular to a cleaning product based on seaweed extract and a preparation method thereof. Background Art

[0002] As consumer demand for "natural, effective, and gentle" daily chemical products continues to escalate, seaweed extract, rich in natural active ingredients such as polysaccharides, fatty acids, amino acids, and minerals, has gradually become a highly sought-after functional ingredient in cleansing and chemical products. From basic facial cleansers and shower gels to high-end shampoos and body lotions, seaweed extract is widely used to enhance the user experience due to its excellent moisturizing, soothing, and low-irritation properties. Especially with the consumer trend of "natural ingredients first," renewable marine resources such as seaweed are increasingly considered an ideal alternative to traditional chemical synthetic raw materials, and their scope of application and market value are continuously expanding.

[0003] Traditional seaweed extracts face bottlenecks in their application in cleansing products: the natural active groups (such as carboxyl and hydroxyl groups) are susceptible to environmental influences such as pH, temperature, and light, leading to insufficient stability. Their single function is limited to basic moisturizing or soothing effects, making them incapable of meeting diverse requirements such as cleansing, antimicrobial properties, and film-forming properties. Existing technologies attempt to enhance performance through chemical modifications (such as carboxylation and sulfation), but these often focus on a single function (such as enhancing surface activity or antimicrobial properties) and can disrupt the natural structure, leading to reduced biocompatibility or the production of irritating byproducts, making it difficult to balance functionality and stability. Against this backdrop, some technologies are exploring biofermentation methods to develop seaweed active ingredients. For example, Chinese Invention Patent Publication No. CN106265360B discloses a facial cleanser containing a seaweed fermentation product and its preparation method. The product is prepared by pulverizing brown, red, or green algae, inoculating it with lactic acid bacteria and yeast, and then formulating it into a facial cleanser. This technology leverages microbial metabolism to enhance activity, but it still fails to address core issues: fermentation products are primarily natural ingredients, and their functionality is limited to enhancing basic activity, failing to overcome a single limitation; fermentation does not modify the structure to address stability deficiencies, leaving active groups susceptible to environmental influences and degradation during storage or use; and fermentation products are used only as an auxiliary component (0.05%-10%) in the formula, lacking synergistic effects with other ingredients, making it difficult to meet complex requirements for cleansing power and antimicrobial properties. Therefore, existing technologies still have significant shortcomings in functionality, stability, and multi-effect synergy.

[0004] Furthermore, the limitations of existing modification technologies have become a key obstacle to the upgrading of seaweed-based cleaning products. On the one hand, modification of a single functional group makes it difficult to impart sufficient functional diversity to seaweed ingredients. For example, while carboxymethylated sodium alginate can enhance hydrophilicity, its high charge density makes it susceptible to interactions with other ingredients, affecting the stability of product formulations. Furthermore, the preparation processes of traditional modified products often require harsh conditions (such as high temperatures and strong acid and alkaline environments), which not only increases production energy consumption but also may lead to degradation of active ingredients, reducing the efficacy of the final product. Furthermore, as personal care products that come into direct contact with the skin, cleaning products require extremely high mildness and low irritation properties. However, existing modified seaweed ingredients often increase the risk of allergies due to excessive structural modifications. Against this backdrop, the development of novel modified seaweed compounds that retain the natural activity of seaweed while enhancing functionality through multi-dimensional structural modifications, while also exhibiting excellent stability, and their synergistic application with seaweed extracts in cleaning products, has become an urgent technical challenge for the industry. Summary of the Invention

[0005] The purpose of the present invention is to provide a cleaning product based on seaweed extract and a preparation method, which solves the technical problems of existing seaweed extracts in cleaning products, such as single function, poor stability and limited modification methods.

[0006] The present invention achieves the above-mentioned purpose through the following technical solutions: A cleaning product based on seaweed extract, comprising the following raw materials in parts by weight: Diallyl fucose quaternary ammonium salt: 10-50 parts by weight; Carboxymethyl-sodium alginate-chitosan graft copolymer: 20-60 parts by weight; Seaweed extract: 50-100 parts by weight; Sodium lauryl sulfate: 80-120 parts by weight; Glycerol: 30-50 parts by weight; Lauramidopropyl betaine: 20-40 parts by weight; Citric acid: 1-3 parts by weight; Phenoxyethanol: 2-5 parts by weight; Deionized water: 600-750 parts by weight; The preparation method of the bisallyl fucoate quaternary ammonium salt includes the following steps: A1, dissolving fucoate in deionized water, adding 4-dimethylaminopyridine, and stirring under nitrogen protection until completely dissolved; heating the solution to 50-52°C, adding allyl bromide dropwise, keeping the temperature for reaction after the addition is complete, centrifuging to obtain the supernatant, precipitating with anhydrous ethanol, filtering, and vacuum drying to obtain a bisallyl fucoate intermediate; A2, dissolving the intermediate in dimethyl sulfoxide, adding N,N-dimethyl-1,3-propylenediamine, reacting at 60-64°C, pouring acetone into the precipitate after the reaction is completed, filtering, washing, and vacuum drying.

[0007] According to a preferred embodiment of the present invention, the fucosilicate was purchased from Qingdao Mingyue Seaweed Group Co., Ltd. (Model: MY-FA-01).

[0008] According to a preferred embodiment of the present invention, the deionized water was purchased from Hangzhou Wahaha Group Co., Ltd. (model: WFD-100).

[0009] According to a preferred embodiment of the present invention, the 4-dimethylaminopyridine was purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd. (model: DMAP-99).

[0010] According to a preferred embodiment of the present invention, the nitrogen is purchased from Hangzhou Oxygen Group Co., Ltd. (model: N2-99.999%).

[0011] According to a preferred embodiment of the present invention, the allyl bromide is purchased from Jiangsu Feixiang Chemical Co., Ltd. (model: ALLYL-BROMIDE-AR).

[0012] According to a preferred embodiment of the present invention, the ethanol was purchased from Sichuan Shuke Pharmaceutical Co., Ltd. (model: ETHANOL-95).

[0013] According to a preferred embodiment of the present invention, the dimethyl sulfoxide was purchased from Shanghai Yuanye Biotechnology Co., Ltd. (model: DMSO-AR).

[0014] According to a preferred embodiment of the present invention, the N,N-dimethyl-1,3-propylenediamine was purchased from Jiangsu Feixiang Chemical Co., Ltd. (model: DMPA-99).

[0015] According to a preferred embodiment of the present invention, the acetone was purchased from Jiangsu Qiangsheng Functional Chemical Co., Ltd. (model: ACETONE-AR).

[0016] According to a preferred embodiment of the present invention, the seaweed extract was purchased from Qingdao Haizhiyuan Biotechnology Co., Ltd. (model: SEAWeed-EX-02).

[0017] According to a preferred embodiment of the present invention, the sodium lauryl sulfate is purchased from Hunan Lichen Industrial Co., Ltd. (model: AES-70%).

[0018] According to a preferred embodiment of the present invention, the glycerol is purchased from Hunan Erkang Pharmaceutical Co., Ltd. (model: GLYCERIN-99.5%).

[0019] According to a preferred embodiment of the present invention, the lauramidopropyl betaine was purchased from Jiangsu Man's Biotechnology Co., Ltd. (model: CAPB-30%).

[0020] According to a preferred embodiment of the present invention, the citric acid is purchased from Shandong Baolingbao Biological Co., Ltd. (model: CITRIC-ACID-99.5%).

[0021] According to a preferred embodiment of the present invention, the phenoxyethanol is purchased from Jiangsu Yida Chemical Co., Ltd. (model: PHENOXYETHANOL-99%).

[0022] According to a preferred embodiment of the present invention, in step A1, the insulation reaction time is 4-6 hours; the centrifugation speed is 4000-5000 rpm, and the time is 10-20 minutes; and the volume ratio of the supernatant to ethanol is 1:3.

[0023] According to a preferred embodiment of the present invention, in step A2, the reaction time at 60-64° C. is 8-10 h.

[0024] According to a preferred embodiment of the present invention, the preparation method of the carboxymethyl-sodium alginate-chitosan graft copolymer includes: B1, taking sodium alginate, dispersing it in an isopropanol-water mixed solvent, and stirring until there is no agglomeration; adding chloroacetic acid, reacting at 60-64°C, adjusting the pH to 7-8 with NaOH to terminate the reaction, centrifuging to obtain a precipitate, re-dissolving it with deionized water, dialyzing, and freeze-drying to obtain sodium carboxymethyl alginate; B2, dissolving sodium carboxymethyl alginate in deionized water, adding chitosan, and stirring until the chitosan is dissolved; adding glutaraldehyde, reacting at 24-26°C, adjusting the pH to 10 with NaOH to terminate the reaction, centrifuging to obtain a supernatant, dialyzing, and freeze-drying.

[0025] According to a preferred embodiment of the present invention, the sodium alginate is purchased from Qingdao Mingyue Seaweed Group Co., Ltd. (model: MY-SC-01).

[0026] According to a preferred embodiment of the present invention, the isopropyl alcohol was purchased from Jiangsu Yida Chemical Co., Ltd. (model: IPA-99.7%).

[0027] According to a preferred embodiment of the present invention, the chloroacetic acid is purchased from Hebei Jinniu Chemical Co., Ltd. (model: CHLOROACETIC-AR).

[0028] According to a preferred embodiment of the present invention, the NaOH was purchased from Tangshan Sanyou Chemical Co., Ltd. (model: NaOH-99%).

[0029] According to a preferred embodiment of the present invention, the chitosan was purchased from Shandong Weixiang Biotechnology Co., Ltd. (model: CHITOSAN-85%).

[0030] According to a preferred embodiment of the present invention, the glutaraldehyde is purchased from Jiangsu Feixiang Chemical Co., Ltd. (model: GLUTARALDEHYDE-50%).

[0031] According to a preferred embodiment of the present invention, in step B1, the reaction time at 60-64° C. is 3-4 h; the centrifugal speed is 5000-6000 rpm, the time is 15-20 min; and the dialysis time is 48-50 h.

[0032] According to a preferred embodiment of the present invention, in step B2, the reaction time is 2-4 hours at 24-26°C; the centrifugal speed is 6000-8000 rpm, and the time is 20-40 minutes; the dialysis molecular weight cutoff is 5000 Da, and the dialysis time is 72-80 hours.

[0033] The present invention also provides a method for preparing the cleaning product based on seaweed extract, comprising the following steps: S1. Weigh deionized water, heat to 60-64°C, add sodium lauryl sulfate and lauroyl amide propyl betaine, and stir until completely dissolved; S2. Cool down to 40-42°C, add bisallyl fucose quaternary ammonium salt, carboxymethyl-sodium alginate-chitosan graft copolymer, seaweed extract, and glycerin in sequence, and stir until uniform; add citric acid to adjust the pH to 5.5-6.5 and continue stirring; S3. Finally, add phenoxyethanol, stir, and cool to 24-26°C.

[0034] According to a preferred embodiment of the present invention, in step S1, the stirring speed is 200-300 rpm, and the stirring time is 10-20 min.

[0035] According to a preferred embodiment of the present invention, in step S2, the stirring speed is 300-400 rpm, the stirring time is 20-40 min, and the continued stirring time is 10-20 min.

[0036] According to a preferred embodiment of the present invention, in step S3, the stirring time is 5-10 minutes.

[0037] The beneficial effects of the present invention are: Through the design and application of two novel modified seaweed active compounds, this invention effectively addresses the single-function and instability issues of traditional seaweed extracts, significantly improving the overall performance of cleaning products. First, structural innovations impart multiple functional advantages: Diallyl fucose quaternary ammonium salt is quaternized by introducing a hydrophobic chain through diallylation, forming an amphiphilic structure that combines high-efficiency cleaning power with low interfacial tension and strong antimicrobial properties by damaging microbial membranes through positive charges. Furthermore, the carboxymethyl-sodium alginate-chitosan graft copolymer is carboxymethylated (retaining the hydrophilic backbone and adding polar groups) and grafted onto chitosan (forming a three-dimensional network), enhancing its water solubility, film-forming properties, and moisturizing properties by forming a breathable protective film on the skin surface. These two compounds transcend the traditional seaweed's reliance on natural ingredients alone, achieving multi-dimensional performance enhancements such as antimicrobial and film-forming properties.

[0038] Secondly, the synergistic effect and production feasibility highlight the application value: the modified compounds and seaweed extracts (including alginate, fucoidan, etc.) form a stable system through hydrogen bonds and electrostatic effects, which not only retains the soothing and barrier functions of natural ingredients, but also optimizes the stability of the formula. The electrostatic attraction between quaternary ammonium salts and negatively charged polysaccharides reduces irritation, and the film-forming properties of chitosan and moisturizing ingredients synergistically build a "protection-moisturizing" double barrier to enhance the user experience (stronger cleaning power and longer-lasting moisturizing). At the same time, the modified compounds use common chemical raw materials and deep-processed seaweed products as raw materials, the reaction conditions are mild, the detergent product formula is simple, the process is conventional (heating and stirring are sufficient), and performance and cost are taken into account. The proportion of natural ingredients is high, and the use of chemical synthetic ingredients is reduced, providing a feasible path for the upgrading of seaweed detergent products. DETAILED DESCRIPTION

[0039] The following specific implementation methods are only used to further illustrate the present application and should not be understood as limiting the scope of protection of the present application. Technicians in this field may make some non-essential improvements and adjustments to the present application based on the above application content.

[0040] Example 1

[0041] Preparation of bisallyl fucose quaternary ammonium salt: 100 g of fucose was added to 2000 g of deionized water, and 2 g of 4-dimethylaminopyridine was added as a catalyst with stirring. Stirring was continued under nitrogen protection until the fucose was completely dissolved. The solution was heated to 50°C, and 7.26 g of allyl bromide was slowly added dropwise through a constant pressure dropping funnel. The addition process was controlled to be completed within 10 min. After the addition was completed, the temperature was maintained at 50°C and the reaction was continued for 5 h. After the reaction was completed, the mixture was centrifuged at 4500 rpm for 15 min. The supernatant was collected and mixed with 6000 g of anhydrous ethanol (volume ratio of supernatant to ethanol = 1:3). The mixture was allowed to settle for 2 h and then filtered. The precipitate was washed three times with acetone (500 g acetone each time) and finally dried in vacuo (40°C for 8 h) to obtain the bisallyl fucose quaternary ammonium salt. 50 g of the above intermediate was dissolved in 1000 g of dimethyl sulfoxide (DMSO), 2.43 g of N,N-dimethyl-1,3-propylenediamine was added with stirring, and the temperature was raised to 62°C and kept constant for 9 hours. After the reaction was completed, the solution was poured into 5000 g of acetone to precipitate, which was collected by filtration and washed twice with acetone (1000 g of acetone each time), and finally vacuum dried (40°C, 6 hours) to obtain bisallyl fucol ester quaternary ammonium salt.

[0042] Preparation of carboxymethyl-sodium alginate-chitosan graft copolymer: 100 g of sodium alginate was dispersed in 400 g of isopropanol-water mixed solvent (300 g of isopropanol and 100 g of deionized water) and magnetically stirred for 30 min until no lumps were formed; 18.90 g of chloroacetic acid was added, the temperature was raised to 62°C and the reaction was carried out at a constant temperature for 3.5 h. After the reaction, the pH was adjusted to 8 with 5 g of NaOH solid to terminate the reaction, and the precipitate was collected by centrifugation at 5500 rpm for 18 min; the precipitate was re-dissolved in deionized water (concentration 10% w / v), placed in a dialysis bag (molecular weight cutoff 1000 Da) and dialyzed in deionized water for 50 h (the solution was changed once every 12 h), and the dialyzate was freeze-dried (-50°C, 24 h) to obtain the sodium carboxymethyl alginate intermediate. 50 g of carboxymethyl sodium alginate intermediate was dissolved in 500 g of deionized water, and 5 g of chitosan was added with stirring. The pH was adjusted to 5.5 with 1 M HCl to promote the dissolution of chitosan. 5 g of glutaraldehyde (final concentration 0.5% v / v) was added, and the reaction was maintained at 25°C for 3 h. After the reaction was completed, the pH was adjusted to 10 with 10 g of NaOH solid to terminate the reaction. The supernatant was collected by centrifugation at 7000 rpm for 30 min. The supernatant was placed in a dialysis bag (molecular weight cutoff 5000 Da) and dialyzed in deionized water for 80 h (the liquid was changed once every 12 h). The dialyzate was freeze-dried (-50°C, 24 h) to obtain a carboxymethyl-sodium alginate-chitosan graft copolymer.

[0043] Preparation of a cleaning product based on seaweed extract: weigh 600g of deionized water and add it to a constant temperature water bath, heat it to 60°C, add 80g of sodium lauryl sulfate and 20g of lauramidopropyl betaine in sequence while stirring at 250rpm, and continue stirring for 15min until completely dissolved (the system is clear and free of particles); stop heating, cool naturally to 40°C, and add 10g of compound A, 20g of compound B, 50g of seaweed extract, and 30g of glycerin in sequence while stirring at 350rpm, and continue stirring for 30min until the system is uniform (no obvious stratification); add 1g of citric acid solid (previously dissolved in 10g of deionized water), adjust the pH to 6.5 (detected with precision pH test paper), and keep stirring for 15min; finally, add 2g of phenoxyethanol, stir slowly and evenly within 7min (to avoid violent bubbling), cool to 24°C, discharge, and divide into 500mL plastic bottles to obtain a facial cleanser product.

[0044] Example 2

[0045] The specific implementation method is the same as that of Example 1, except that: bisallyl fucose quaternary ammonium salt is prepared as follows: 100 g of fucose is dissolved in 2000 g of deionized water, 2 g of 4-dimethylaminopyridine is added, and the mixture is stirred under nitrogen until completely dissolved; the temperature is raised to 51° C., 7.26 g of allyl bromide is added dropwise, the mixture is kept warm for 5.5 h, the mixture is centrifuged at 4800 rpm for 18 min, the supernatant is taken, precipitated with 6000 g of anhydrous ethanol, filtered, and vacuum-dried to obtain an intermediate; 50 g of the intermediate is dissolved in 1000 g of dimethyl sulfoxide, 2.43 g of N,N-dimethyl-1,3-propylenediamine is added, the mixture is reacted at 63° C. for 9.5 h, 5000 g of acetone is poured into the precipitate, the precipitate is filtered, washed, and vacuum-dried to obtain bisallyl fucose quaternary ammonium salt. Preparation of carboxymethyl-sodium alginate-chitosan graft copolymer: 100 g of sodium alginate was dispersed in 400 g of an isopropanol-water mixed solvent (300 g of isopropanol and 100 g of water) and stirred until no lumps were formed; 18.90 g of chloroacetic acid was added, the mixture was reacted at 63°C for 3.8 h, the pH was adjusted to 7 with 5 g of NaOH to terminate the reaction, the precipitate was collected by centrifugation at 5800 rpm for 19 min, the precipitate was redissolved with deionized water (concentration 10% w / v), dialyzed for 50 h, and freeze-dried to obtain sodium carboxymethyl alginate; 50 g of sodium carboxymethyl alginate was dissolved in 500 g of deionized water, 5 g of chitosan was added, and stirred until dissolved, 5 g of glutaraldehyde was added, the mixture was reacted at 25°C for 3.5 h, the pH was adjusted to 10 with 10 g of NaOH to terminate the reaction, the supernatant was collected by centrifugation at 7000 rpm for 35 min, the supernatant was dialyzed for 80 h with a 5000 Da molecular weight cutoff, and the graft copolymer was obtained by freeze-drying. Preparation of detergent product: weigh 650g deionized water, heat to 62°C, add 100g sodium lauryl sulfate and 30g lauramide propyl betaine, stir at 280rpm for 18min until completely dissolved; cool to 41°C, add 30g bisallyl fucose quaternary ammonium salt, 40g carboxymethyl-sodium alginate-chitosan graft copolymer, 70g seaweed extract, 40g glycerol in sequence, stir at 380rpm for 35min until uniform; add 2g citric acid to adjust the pH to 5.5, continue stirring for 18min; finally, add 3g phenoxyethanol, stir for 8min, cool to 25°C, and discharge and package.

[0046] Example 3

[0047] The specific implementation method is the same as that of Example 1, except that: the preparation of bisallyl fucose quaternary ammonium salt is as follows: 100 g of fucose is dissolved in 2000 g of deionized water, 2 g of 4-dimethylaminopyridine is added, and the mixture is stirred under nitrogen until completely dissolved; the temperature is raised to 52° C., 7.26 g of allyl bromide is added dropwise, and the mixture is kept warm for 6 h after the addition is completed. The supernatant is centrifuged at 5000 rpm for 20 min, the supernatant is taken, precipitated with 6000 g of anhydrous ethanol, filtered, and vacuum-dried to obtain an intermediate; 50 g of the intermediate is dissolved in 1000 g of dimethyl sulfoxide, 2.43 g of N,N-dimethyl-1,3-propylenediamine is added, the mixture is reacted at 64° C. for 10 h, 5000 g of acetone is poured into the precipitate, and the precipitate is filtered, washed, and vacuum-dried to obtain bisallyl fucose quaternary ammonium salt. Preparation of carboxymethyl-sodium alginate-chitosan graft copolymer: 100 g of sodium alginate was dispersed in 400 g of isopropanol-water mixed solvent (300 g of isopropanol and 100 g of water) and stirred until no lumps were formed; 18.90 g of chloroacetic acid was added and the mixture was reacted at 64°C for 4 h. The pH was adjusted to 7.5 with 5 g of NaOH to terminate the reaction. The precipitate was collected by centrifugation at 6000 rpm for 20 min, and the precipitate was redissolved with deionized water (concentration 10% w / v). After 50 h of dialyzing, the precipitate was freeze-dried to obtain sodium carboxymethyl alginate; 50 g of sodium carboxymethyl alginate was dissolved in 500 g of deionized water, 5 g of chitosan was added and stirred until dissolved, 5 g of glutaraldehyde was added, the mixture was reacted at 25°C for 4 h, the pH was adjusted to 10 with 10 g of NaOH to terminate the reaction, the supernatant was collected by centrifugation at 8000 rpm for 40 min, and the supernatant was dialyzed for 80 h with a 5000 Da molecular weight cutoff to obtain the graft copolymer. Preparation of detergent product: weigh 700g deionized water, heat to 64°C, add 120g sodium lauryl sulfate and 40g lauramide propyl betaine, stir at 300rpm for 20min until completely dissolved; cool to 42°C, add 50g bisallyl fucose quaternary ammonium salt, 60g carboxymethyl-sodium alginate-chitosan graft copolymer, 100g seaweed extract, 50g glycerol in sequence, stir at 400rpm for 40min until uniform; add 3g citric acid to adjust the pH to 6.0, continue stirring for 20min; finally, add 5g phenoxyethanol, stir for 10min, cool to 26°C, and discharge and package.

[0048] Comparative Example 1 The specific implementation method is the same as that of Example 1, except that the formula of the cleaning product is: 20 g of carboxymethyl-sodium alginate-chitosan graft copolymer, 50 g of seaweed extract, 80 g of sodium lauryl sulfate, 30 g of glycerin, 20 g of lauramidopropyl betaine, 1 g of citric acid, 2 g of phenoxyethanol, and 600 g of deionized water; the preparation steps are the same as those of Example 1 (diallyl fucol ester quaternary ammonium salt is not added in S2).

[0049] Comparative Example 2 The specific implementation method is the same as that of Example 1, except that the formula of the cleaning product is: 10 g of diallyl fucose quaternary ammonium salt, 50 g of seaweed extract, 80 g of sodium lauryl sulfate, 30 g of glycerin, 20 g of lauramidopropyl betaine, 1 g of citric acid, 2 g of phenoxyethanol, and 600 g of deionized water; the preparation steps are the same as those of Example 1 (no carboxymethyl-sodium alginate-chitosan graft copolymer is added in S2).

[0050] Comparative Example 3 The specific implementation method is the same as that of Example 1, except that the formula of the cleaning product is: 50 g of seaweed extract, 80 g of sodium lauryl sulfate, 30 g of glycerin, 20 g of lauramidopropyl betaine, 1 g of citric acid, 2 g of phenoxyethanol, and 600 g of deionized water; the preparation steps are the same as those of Example 1 (diallyl fucol ester quaternary ammonium salt and carboxymethyl-sodium alginate-chitosan graft copolymer are not added in S2).

[0051] Performance Testing The facial cleansing milk products prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests according to the following methods. The performance testing methods include a cleaning power test (determination of oil removal rate), a mildness test (skin irritation evaluation), a moisturizing test (determination of skin moisture content), an antibacterial test (determination of antibacterial rate), and a stability test, as follows: 1. The cleaning power test adopts the standard artificial sebum film oil removal rate determination, using an electronic balance, a standard artificial sebum film preparation device and deionized water, and the steps are as follows: 1) Prepare the standard artificial sebum film: take stearic acid (2g), palmitic acid (1g), and squalane (1g) and heat them to 70°C to melt, evenly apply them on a round glass slide with a diameter of 2cm, and cool to room temperature to form a sebum film with a thickness of about 0.5mm, which is weighed and recorded as m0; 2) Cleaning test: take 1g of the example / comparative example sample, add 50mL deionized water (25°C) and stir until uniform, immerse the sebum film glass slide in the sample solution and oscillate at a constant temperature of 37°C (100rpm) for 10min, take it out and rinse it with deionized water twice (10mL each time), drain the surface moisture and weigh it and record it as m1; 3) Calculate the oil removal rate: Oil removal rate (%) = [(m0-m1) / m0]×100.

[0052] 2. The mildness test was conducted using a human occluded patch test (in accordance with the 2015 edition of the "Safety Technical Specifications for Cosmetics"). The steps were as follows: 1) 30 healthy women aged 20-30 years (with no history of skin diseases) were selected as subjects; 2) Sample preparation: The sample was diluted 10-fold with normal saline (simulating the actual usage concentration); 3) Patch test: Four 2cm×2cm areas were marked on the inner forearm, and the sample, blank control (normal saline), and positive control (2% sodium lauryl sulfate) were applied respectively. Each area was fixed with non-irritating adhesive tape at 2cm intervals and covered with occlusive dressings; 4) Observation and evaluation: After 48 hours of application, the dressing was removed and the skin reaction (erythema, edema, itching, etc.) was observed and scored on a scale of 0-4 (0: no reaction; 1: mild erythema; 2: moderate erythema; 3: severe erythema with edema; 4: necrosis or ulceration). The average irritation index (IS) was calculated as: total score / number of subjects.

[0053] 3. Moisturizing properties were tested using a Corneometer CM 825 skin moisture meter. The following steps were used: ① Subject preparation: Avoid using skincare products 24 hours before testing. On the day of testing, cleanse and dry your face; ② Baseline measurement: Measure the same area of ​​the subject's face (cheek) three times in a row, and take the average value as the initial moisture content (C0); ③ Sample application: Apply 0.5g of sample evenly to the test area and pat until absorbed; ④ Subsequent measurements: Measure skin moisture content 1 hour, 2 hours, and 4 hours after application, and take the average values ​​as C1, C2, and C4; ⑤ Calculate moisturizing efficiency: Moisturizing efficiency (%) = [(C4 - C0) / C0] × 100 (based on the 4-hour data).

[0054] 4. Antibacterial activity was tested using the agar diffusion method (according to GB / T 26513-2011). The test strains were Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 8739). The steps were as follows: 1) Bacterial liquid preparation: The strain was inoculated into nutrient broth medium and cultured at 37°C for 18 hours. The cells were collected by centrifugation (5000 rpm, 10 minutes) and diluted to 1×10 6 CFU / mL; 2) Plate preparation: Pour nutrient agar medium (15 mL) into a culture dish and evenly spread 100 μL of bacterial solution (approximately 1×10 5 CFU); 3) Sample addition: Take 0.1 g of sample (sample group) and 0.1 mL of normal saline (negative control) and drop them in the center of the plate, and spread them evenly with a sterile spreading stick; 4) Incubation: Incubate the plate upside down at 37°C for 24 h, measure the diameter of the inhibition zone (d), and calculate the inhibition rate: Inhibition rate (%) = [(d sample - d negative) / d negative] × 100 (the negative control is considered 0 if there is no inhibition zone).

[0055] 5. Stability test includes heat stability, cold stability and pH stability. The steps are as follows: 1) Heat stability: Place the sample in a 45℃ constant temperature box for 30 days to observe whether there is stratification, discoloration or odor; 2) Cold stability: Place the sample in a -10℃ refrigerator for 7 days, then return to room temperature and observe whether it solidifies or stratifies; 3) pH stability: Take the sample and dilute it 10 times with deionized water. Use a precision pH meter to measure the pH value at 25℃, 37℃ and 45℃ to calculate the pH change range (ΔpH).

[0056] 6. Performance test results: Test items Test methods / indicators Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Cleaning power (oil removal rate) Oil removal rate of standard artificial sebum film (%) 87.2 89.5 91.3 72.1 75.4 68.3 Mildness Average irritation index (IS) of human patch test 0.2 0.3 0.3 0.8 1.1 1.5 Moisturizing (4h) Skin moisture increase efficiency (%) 35.6 38.2 41.5 22.1 25.3 18.7 Antibacterial properties (Staphylococcus aureus) Antibacterial rate (%) 99.1 99.4 99.6 82.3 85.7 71.2 Antibacterial properties (E. coli) Antibacterial rate (%) 98.7 99.0 99.2 79.8 83.1 68.5 Stability (45℃ / 30 days) Delamination / discoloration / odor No delamination, no discoloration, no odor No delamination, no discoloration, no odor No delamination, no discoloration, no odor Slightly delaminated, no odor Slight discoloration (yellowing), no odor Severe stratification, flocculent precipitation Stability (-10℃ / 7 days) Solidification / stratification No solidification, no stratification No solidification, no stratification No solidification, no stratification No solidification, slight stratification Solidification (resolvable), stratification Solidified and cannot be redissolved, severe stratification pH stability (ΔpH) 25℃-45℃ pH range 5.6-5.8 (ΔpH=0.2) 5.5-5.7 (ΔpH=0.2) 5.4-5.6 (ΔpH=0.2) 5.8-6.2 (ΔpH=0.4) 5.9-6.3 (ΔpH=0.4) 6.1-6.5 (ΔpH=0.4) As can be seen from Table 1, the comparative analysis of the performance test results of Examples 1-3 and Comparative Examples 1-3 shows that the present invention, by synthesizing two modified seaweed compounds, bisallyl fucoalginate quaternary ammonium salt and carboxymethyl-sodium alginate-chitosan graft copolymer, and synergistically applying them with seaweed extracts in detergent products, effectively solves the problems of single function, poor stability and limited modification methods of traditional seaweed extracts in detergent products.

[0057] In terms of functional singularity, traditional seaweed extracts primarily rely on natural ingredients (such as polysaccharides and fatty acids) to provide basic moisturizing or soothing functions, resulting in relatively single functions. In the examples, by adding diallyl fucose quaternary ammonium salt (containing hydrophobic chains and quaternary ammonium salt groups) and carboxymethyl-sodium alginate-chitosan graft copolymer (containing carboxymethyl and chitosan groups), the product not only retains the natural moisturizing properties of seaweed extract (4-hour moisturizing enhancement efficiency of 35.6%-41.5%), but also enhances antibacterial properties (99.1%-99.6% inhibition rate against Staphylococcus aureus) through the positively charged groups of the quaternary ammonium salt. Furthermore, the film-forming properties of the hydrophobic chains and chitosan improve cleaning efficiency (87.2%-91.3% oil removal rate), achieving synergistic enhancement of multiple functions such as cleaning, antibacterial, and moisturizing, significantly breaking through the limitations of traditional seaweed extracts with single functions.

[0058] In terms of stability, traditional seaweed extracts are susceptible to delamination and denaturation due to their active groups (such as carboxyl and hydroxyl groups) being susceptible to environmental factors (temperature and pH). In the examples, two modified compounds enhance the stability of the active groups through chemical modification (such as quaternization and etherification) and form intermolecular interactions (such as hydrogen bonding and electrostatic attraction) with the polysaccharide components of the seaweed extract, improving the compatibility of the overall formulation. Test results showed that Examples 1-3 showed no delamination, discoloration, or significant pH fluctuations after 30 days of constant temperature at 45°C, 7 days of refrigeration at -10°C, and a pH fluctuation of 25-45°C (ΔpH 0.2). However, Comparative Examples 1-3, lacking the modified compounds, showed significant decreases in heat resistance (severe delamination in Comparative Example 3), cold resistance (solidification in Comparative Example 2), and pH stability (ΔpH 0.4 in Comparative Example 2). This demonstrates that the modified seaweed components effectively address the poor stability issues of traditional seaweed extracts.

[0059] In terms of the limitations of modification methods, traditional seaweed modification often uses a single functional group modification (such as carboxymethylation), which can only improve a specific property (such as hydrophilicity) and may destroy the natural structure, leading to a decrease in biocompatibility. In the examples, a dual modification strategy of "bisallylation-quaternization" and "carboxymethylation-chitosan grafting" is adopted: bisallylation introduces a hydrophobic chain into the alginate molecule, which, combined with quaternization, forms an amphiphilic structure, simultaneously enhancing surface activity and antimicrobial properties; carboxymethylation adds polar groups while retaining the hydrophilic backbone of sodium alginate, while chitosan grafting forms a three-dimensional network through intermolecular forces, enhancing film-forming and moisturizing properties. These two modification methods respectively enhance different functional dimensions (surface activity / antimicrobial properties, film-forming properties / moisturizing properties), and through synergistic effects, they avoid the functional limitations of single modifications while retaining the natural active ingredients of the seaweed extract (such as alginate), improving the biocompatibility and safety of the product.

[0060] In summary, Examples 1-3, through the design and application of two new modified seaweed compounds, effectively address the core defects of traditional seaweed extracts in detergent products from three aspects: functional diversity, stability, and comprehensiveness of modification methods, and provide a feasible solution for the development of high-performance seaweed-based detergent products.

[0061] The above-described embodiments merely illustrate several implementations of the present invention. While the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, and all such variations and improvements fall within the scope of protection of the present invention.

Claims

1. A cleaning product based on seaweed extract, characterized in that: The invention comprises the following raw materials in parts by weight: Diallyl fucose quaternary ammonium salt: 10-50 parts by weight; Carboxymethyl-sodium alginate-chitosan graft copolymer: 20-60 parts by weight; Seaweed extract: 50-100 parts by weight; Sodium lauryl sulfate: 80-120 parts by weight; Glycerol: 30-50 parts by weight; Lauramidopropyl betaine: 20-40 parts by weight; Citric acid: 1-3 parts by weight; Phenoxyethanol: 2-5 parts by weight; Deionized water: 600-750 parts by weight; The preparation method of the bisallyl fucoate quaternary ammonium salt includes the following steps: A1, dissolving fucoate in deionized water, adding 4-dimethylaminopyridine, and stirring under nitrogen protection until completely dissolved; heating the solution to 50-52°C, adding allyl bromide dropwise, keeping the temperature for reaction after the addition is complete, centrifuging to obtain the supernatant, precipitating with anhydrous ethanol, filtering, and vacuum drying to obtain a bisallyl fucoate intermediate; A2, dissolving the intermediate in dimethyl sulfoxide, adding N,N-dimethyl-1,3-propylenediamine, reacting at 60-64°C, pouring acetone into the precipitate after the reaction is completed, filtering, washing, and vacuum drying.

2. The cleaning product based on seaweed extract according to claim 1, characterized in that: In step A1, the insulation reaction time is 4-6 hours; the centrifugation speed is 4000-5000 rpm, and the time is 10-20 minutes; the volume ratio of the supernatant to ethanol is 1:

3.

3. The cleaning product based on seaweed extract according to claim 1, characterized in that: In step A2, the reaction time is 8-10 h at 60-64°C.

4. The cleaning product based on seaweed extract according to claim 1, characterized in that The preparation method of the carboxymethyl-sodium alginate-chitosan graft copolymer comprises the following steps: B1, dispersing sodium alginate in an isopropyl alcohol-water mixed solvent and stirring until no lumps are formed; adding chloroacetic acid, reacting at 60-64° C., adjusting the pH to 7-8 with NaOH to terminate the reaction, centrifuging to obtain a precipitate, redissolving it with deionized water, dialyzing it, and freeze-drying it to obtain sodium carboxymethyl alginate; B2, dissolving the sodium carboxymethyl alginate in deionized water, adding chitosan, and stirring it until the chitosan is dissolved; adding glutaraldehyde, reacting at 24-26° C., adjusting the pH to 10 with NaOH to terminate the reaction, centrifuging to obtain a supernatant, dialyzing it, and freeze-drying it.

5. The cleaning product based on seaweed extract according to claim 4, characterized in that: In step B1, the reaction time is 3-4 hours at 60-64° C.; the centrifugation speed is 5000-6000 rpm, the time is 15-20 minutes; and the dialysis time is 48-50 hours.

6. The cleaning product based on seaweed extract according to claim 4, characterized in that: In step B2, the reaction time is 2-4 hours at 24-26° C.; the centrifugation speed is 6000-8000 rpm, and the time is 20-40 minutes; the dialysis molecular weight cutoff is 5000 Da, and the dialysis time is 72-80 hours.

7. A method for preparing a cleaning product based on seaweed extract according to any one of claims 1 to 6, characterized in that the steps include: S1. Weigh deionized water, heat to 60-64°C, add sodium lauryl sulfate and lauroyl amide propyl betaine, and stir until completely dissolved; S2. Cool down to 40-42°C, add bisallyl fucose quaternary ammonium salt, carboxymethyl-sodium alginate-chitosan graft copolymer, seaweed extract, and glycerin in sequence, and stir until uniform; add citric acid to adjust the pH to 5.5-6.5 and continue stirring; S3. Finally, add phenoxyethanol, stir, and cool to 24-26°C.

8. The preparation method according to claim 7, characterized in that In step S1, the stirring speed is 200-300 rpm, and the stirring time is 10-20 min.

9. The preparation method according to claim 7, characterized in that In step S2, the stirring speed is 300-400 rpm, the stirring time is 20-40 min, and the stirring time is continued for 10-20 min.

10. The preparation method according to claim 7, characterized in that In step S3, the stirring time is 5-10 minutes.