A herbally sourced food grade dishwasher detergent composition and method of making the same

Abstract

The present application belongs to the field of detergent, disclose a kind of herb source food-grade dishwasher detergent composition and preparation method thereof, and the detergent composition includes the following raw materials: soapberry extract, tea branch pomelo extract, green grape seed extract, modified cellulose microcrystalline, sodium bicarbonate, chelating agent, thickening agent, stabilizer, multiple plant enzyme, modified nano titanium dioxide, preservative, citric acid and deionized water;Modified cellulose microcrystalline is cellulose nanocrystal surface bromination after grafting lipophilic long-chain hydrophobic alkyl chain and hydrophilic carboxymethyl chain, and modified nano titanium dioxide is nano titanium dioxide modified by green tea polyphenol;The present application is combined with multiple plant enzymes by green grape seed, tea branch pomelo and soapberry three kinds of herb source surfactants, to build food-grade dishwasher detergent composition, further improve washing effect and antibacterial effect by adding modified cellulose microcrystalline and modified nano titanium dioxide.

Description

Technical Field

[0001] This invention belongs to the field of detergent technology, specifically relating to a herbal-derived food-grade dishwasher detergent composition and its preparation method. Background Technology

[0002] With rising living standards and increased health awareness, consumers' demands for dishwashing products have moved beyond basic stain removal capabilities. They now seek comprehensive performance features such as food safety, environmental friendliness, and multifunctionality (e.g., antibacterial and protective properties). As a common appliance in modern kitchens, dishwashers are experiencing a continuous increase in market demand for specialized detergents. An ideal dishwasher detergent should effectively remove various stubborn stains (such as protein, starch, and heavy grease), leave low residue, be gentle and non-irritating, and inhibit bacterial growth during the washing process.

[0003] Currently, mainstream dishwasher detergents on the market are mainly divided into two categories: one is traditional synthetic detergents with petroleum-based surfactants, phosphate or EDTA chelating agents, and chlorine bleach as core ingredients. While these products have strong cleaning power, they suffer from poor biodegradability, potential risks of eutrophication, skin irritation from residues, and high energy consumption during production. The other category is the "natural" or "plant-based" detergents that have emerged in recent years, mostly based on natural surfactants such as tea saponin and soapberry saponin, supplemented with additives such as citric acid. However, these products often face several technical bottlenecks in practical applications: First, natural surfactants generally have lower solubility and cleaning power than synthetic surfactants under low-temperature, hard water conditions, and easily combine with calcium and magnesium ions in the water to form soap scum, leaving grayish-white residues on dishes, affecting the washing effect and the shine of the dishes. Second, for heavy oil stains and dried protein and starch stains, the emulsifying effect of natural surfactants alone is insufficient for thorough removal, resulting in unsatisfactory washing results. Furthermore, most existing natural detergents lack a long-lasting antibacterial mechanism, failing to meet consumers' high demands for tableware hygiene. Summary of the Invention

[0004] To address the shortcomings mentioned in the background art, the present invention aims to provide a herbal-derived food-grade dishwasher detergent composition and its preparation method. The food-grade dishwasher detergent composition is constructed by combining three herbal surfactants—green grape seed, tea branch orange, and soapberry—with multiple plant enzymes. Modified cellulose microcrystals and modified nano titanium dioxide are added to further improve the washing and antibacterial effects.

[0005] The objective of this invention can be achieved through the following technical solutions: A herbal-derived food-grade dishwasher detergent composition comprises the following raw materials in parts by weight: 150-200 parts of Sapindus mukorossi extract, 20-50 parts of Citrus aurantium extract, 5-20 parts of green grape seed extract, 30-60 parts of modified cellulose microcrystals, 40-80 parts of sodium bicarbonate, 30-60 parts of chelating agent, 20-50 parts of thickener, 1-5 parts of stabilizer, 30-70 parts of multiple plant enzymes, 15-40 parts of modified nano titanium dioxide, 1-3 parts of preservative, 10-15 parts of citric acid, and 500-550 parts of deionized water; The modified cellulose microcrystals are obtained by brominating the surface of cellulose nanocrystals and then grafting lipophilic long-chain hydrophobic alkyl chains and hydrophilic carboxymethyl chains onto the Pickering emulsion interface via atomic transfer radical polymerization. The modified nano-titanium dioxide is obtained by synthesizing nano-titanium dioxide with green tea polyphenol surface modification via sol-gel method.

[0006] Preferably, the multiple plant enzymes include 10-25 parts of protease, 10-20 parts of amylase, 5-15 parts of lipase and 5-10 parts of cellulase.

[0007] Preferably, the chelating agent is sodium citrate, the thickener is vegetable glycerin, the stabilizer is xanthan gum, and the preservative is potassium sorbate.

[0008] Preferably, the method for preparing modified cellulose microcrystals includes the following steps: (1) Cellulose nanocrystals were ultrasonically dispersed in N,N-dimethylformamide to obtain a uniform suspension. 4-Dimethylaminopyridine and triethylamine were added and stirred for 20-40 min under ice bath conditions. 2-Bromoisobutyryl bromide in N,N-dimethylformamide solution was slowly added dropwise. After the addition was completed, the reaction was carried out at room temperature under nitrogen protection for 18-30 h. After the reaction was completed, the nanocrystals were washed 3-5 times by centrifugation with ethanol and deionized water, and then freeze-dried to obtain brominated cellulose nanocrystals. (2) Disperse cellulose bromide nanocrystals in deionized water by ultrasonication, add N-isopropylacrylamide, stir evenly to obtain an aqueous phase, mix liquid paraffin with styrene, degas by ultrasonication to obtain an oil phase, slowly add the oil phase to the aqueous phase, and emulsify for 4-6 minutes using a high-shear emulsifier to form a stable oil-in-water Pickering emulsion. (3) Transfer the emulsion to a three-necked flask, purge with nitrogen for 20-40 min to remove oxygen, add cuprous bromide and pentamethyldiethylenetriamine under nitrogen protection, stir in a water bath at 30°C for 8-16 h, add a large amount of methanol to break the emulsion after the reaction, collect the solid product by centrifugation, wash with tetrahydrofuran, ethanol and deionized water 2-4 times in sequence, and freeze dry to obtain modified cellulose microcrystals.

[0009] Preferably, the mass ratio of cellulose nanocrystals, 2-bromoisobutyryl bromide, and 4-dimethylaminopyridine is 1:2.2:0.3, and the grafting rate of the brominated cellulose nanocrystals is 0.5~2.0 mmol / g.

[0010] Preferably, the mass ratio of cellulose bromide nanocrystals, N-isopropylacrylamide, styrene, cuprous bromide, and pentamethyldiethylenetriamine is 4:10:10:1:2.

[0011] Preferably, the preparation method of modified nano-titanium dioxide includes the following steps: A. Dissolve the tea polyphenol extract in a mixture of deionized water and anhydrous ethanol, filter with a 0.4~0.5 μm filter membrane to remove insoluble matter, and obtain a clear tea polyphenol solution. Adjust the pH to 5.0~6.0. B. Slowly add tetrabutyl titanate to anhydrous ethanol and stir magnetically for 20-40 minutes to obtain solution A. Add glacial acetic acid to the above tea polyphenol solution and stir until homogeneous to obtain solution B. Under vigorous stirring, slowly add solution A to solution B at a rate of 1-2 drops / second. After the addition is complete, continue stirring for 1.5-2.5 hours to form a homogeneous sol system. C. Transfer the sol to a hydrothermal reactor and treat it at 120℃ for 8-16 hours. After the hydrothermal reaction is completed, cool it naturally to room temperature, collect the precipitate by centrifugation, and wash it 2-4 times alternately with deionized water and anhydrous ethanol to remove the physically adsorbed free polyphenols. After vacuum drying, grind the product to obtain modified nano titanium dioxide.

[0012] Preferably, the content of epigallocatechin gallate (EGCG) in the tea polyphenol extract is ≥50%.

[0013] Preferably, the mass ratio of tea polyphenol extract to tetrabutyl titanate is 1:5~10.

[0014] A method for preparing a herbal-derived food-grade dishwasher detergent composition includes the following steps: S1. Add deionized water to the reactor, and slowly add chelating agent and sodium bicarbonate while stirring. Stir until completely dissolved, then add thickener and stabilizer, and stir at high speed until completely dispersed and uniform to form a transparent viscous base. S2. After pre-dispersing the modified cellulose microcrystals with a small amount of deionized water, add them to the above solution and stir evenly. Then, add the Sapindus mukorossi extract, Citrus aurantium extract and Grape arvensis seed extract in sequence and stir evenly. Finally, add the modified nano titanium dioxide and stir at a medium speed of 1000~1500 rpm for 10~20 min to ensure that it is evenly dispersed in the system. S3. Turn on the cooling circulating water to reduce the temperature inside the reactor to below 30°C, and slowly add multiple plant enzymes and preservatives in sequence, stirring at low speed of 500~800 rpm for 20~40 minutes. S4. Detect the pH value, adjust the pH value to 7-8 with citric acid, continue stirring for 5-15 minutes until the system is homogeneous and stable, let stand to defoam, and obtain the herbal food-grade dishwasher detergent composition.

[0015] The beneficial effects of this invention are: This invention utilizes a combination of three herbal surfactants—grape seed, tangerine peel, and soapberry—with multiple plant enzymes to construct a food-grade dishwasher detergent composition. This composition poses no safety risks, allowing dishes to directly contact food after washing. Soapberry peel is rich in natural saponins, an excellent nonionic surfactant that effectively reduces the surface tension of water and emulsifies grease. It provides moderate foaming, rinses easily, and possesses mild antibacterial properties, making it the primary surfactant in the formula responsible for basic cleaning. Grape seeds are rich in proanthocyanidins, a highly effective natural antioxidant. In detergents, it prevents the oxidation and deterioration of active ingredients, extending product shelf life. Simultaneously, it forms a protective film on the surface of dishes, helping to inhibit bacterial growth. Tangerine peel is rich in citrus essential oils (terpenoids) and natural fruit acids. Citrus essential oils are natural solvents and deodorizers, effectively dissolving heavy grease and removing odors; while fruit acids help break down limescale and mineral deposits. Multiple plant enzymes (enzymes) precisely break down specific food stains. Proteases specifically break down proteins in food residues, such as milk stains, egg stains, meat gravy, and chocolate, breaking down large protein molecules into smaller peptides or amino acids that are easily rinsed away. Amylases target starchy stains, such as those from noodles, rice, mashed potatoes, and sauces, breaking down starch chains to prevent these stains from gelatinizing and hardening on the tableware. Lipases target animal and vegetable oils, deeply hydrolyzing stubborn oil films and stains, especially in cold water or low-temperature washing environments, where their effectiveness far surpasses that of simple surfactants. Cellulase in dishwashing detergents primarily prevents redeposition of dirt; it subtly polishes the surface and fibers of tableware (such as dishwasher filters), making it difficult for dirt to re-adhere, while also leaving glassware sparkling clean after washing. To further enhance the cleaning power, safety, and stability of the detergent composition, modified cellulose microcrystals and modified nano-titanium dioxide were added. The modified cellulose microcrystals significantly improve grease removal and prevent dirt redeposition, while the modified nano-titanium dioxide imparts highly efficient antibacterial properties to the detergent polymer, while protecting enzyme activity and extending product shelf life. Together with herbal surfactants and a multi-plant enzyme system, these components create a comprehensive, high-performance detergent system encompassing physical cleaning, biodegradation, surface protection, and antibacterial preservation.

[0016] This invention achieves asymmetric grafting of lipophilic and hydrophilic segments on the surface of cellulose nanocrystals, giving them a Janus structure. One side is lipophilic to anchor oil stains, while the other side is hydrophilic to stably disperse them. During washing, the lipophilic segments (long-chain alkyl groups) actively anchor to the surface of emulsified oil droplets or oil films, while the hydrophilic segments (carboxymethyl / polyacrylamide) extend outward, forming stable steric hindrance. The anchored oil stains are encapsulated by the cellulose microcrystals, forming micron-sized composite particles that are stably suspended in the washing liquid and completely carried away with the drainage, fundamentally preventing redeposition of oil stains. The rigid structure of the cellulose microcrystals exerts a physical prying effect on the fixed dirt under mechanical force, forming a synergistic effect with the chemical emulsification of surfactants.

[0017] This invention modifies nano-titanium dioxide by using plant polyphenols as a biological template and surface modifier to synthesize nano-TiO2 under mild conditions, and then firmly grafts polyphenol molecules onto the TiO2 surface. The surface-bonded polyphenols endow the material with dual functions: under weak light, it absorbs photon energy and generates photogenerated electrons (electrons). - ) and holes (h + ); Surface-grafted plant polyphenols (such as EGCG) contain multiple phenolic hydroxyl groups, which can act as highly efficient trapping agents and transfer media for holes and electrons, inhibiting the rapid recombination of electrons and holes, and promoting their reaction with surface-adsorbed water and oxygen to generate hydroxyl radicals (·OH) and superoxide anions (·O2). - It contains reactive oxygen species (ROS) such as phenols; these ROS can damage bacterial cell membranes and oxidize proteins and nucleic acids, thus achieving highly efficient sterilization. Polyphenols themselves also have the effect of damaging bacterial cell membranes, and the two work synergistically. During storage, dissolved oxygen and trace metal ions in the formula can induce the generation of free radicals, which attack the sensitive structural domains of enzyme proteins, leading to enzyme inactivation. It is a powerful free radical scavenger and antioxidant. Its ortho-phenolic hydroxyl groups can preferentially react with free radicals to form stable semiquinone free radicals, thereby blocking the oxidative attack of free radicals on enzymes. The microenvironment provided by the TiO2 surface also helps stabilize the enzyme conformation and prevent its denaturation.

[0018] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] This invention's herbal-derived food-grade dishwasher detergent composition strictly prohibits the addition of: phosphorus, fluorescent whitening agents, artificial fragrances, artificial colors, preservatives, heavy metals, synthetic surfactants (such as LAS and AES), formaldehyde releasers, etc., ensuring that the product poses no safety hazard when in contact with food. Dishware can directly contact food after washing without secondary rinsing. Simultaneously, it guarantees the natural compatibility of modified additives, active enzymes, and herbal ingredients, without damaging enzyme activity or producing harmful byproducts. The herbal extracts are prepared using low-temperature extraction to preserve activity, and other raw materials are commercially available chemical raw materials.

[0021] Sapindus mukorossi extract is obtained by selecting wild Sapindus mukorossi fruit peel, removing impurities, drying at low temperature (45℃, 3h), pulverizing to 80 mesh, adding deionized water (material-liquid ratio 1:15), extracting at low temperature of 40℃ for 2h, filtering to remove residue, concentrating to a viscous state, vacuum drying (50℃, 4h), pulverizing to 100 mesh, and obtaining Sapindus mukorossi extract (saponin content ≥35%), which is then sealed and stored for later use.

[0022] The extract of tea branch mandarin orange was obtained by washing and drying the peel of Xinhui tea branch mandarin orange, drying it at low temperature (40℃, 2h), pulverizing it to 80 mesh, adding food-grade ethanol (material-liquid ratio 1:10), extracting it at low temperature of 35℃ for 1.5h, filtering, concentrating, removing ethanol, and vacuum drying (48℃, 3h) to obtain tea branch mandarin orange volatile oil extract, which was sealed and stored for later use.

[0023] The green grape seed extract is made from high-quality green grape seeds, which are pulverized to 60 mesh, added to deionized water (material-to-liquid ratio 1:20), extracted at 50℃ for 2.5 hours, filtered, concentrated, vacuum dried (52℃, 4 hours), and pulverized to 100 mesh to obtain green grape seed extract (proanthocyanidin content ≥20%), which is then sealed and stored for later use.

[0024] Example 1

[0025] A modified cellulose microcrystal is prepared by brominating the surface of cellulose nanocrystals and then polymerizing them via SI-ATRP at the Pickering emulsion interface, simultaneously grafting lipophilic long-chain hydrophobic alkyl chains and hydrophilic carboxymethyl chains. The preparation method includes the following steps: (1) 5g of cellulose nanocrystals were ultrasonically dispersed in 200mL of N,N-dimethylformamide to obtain a uniform suspension. 1.5g of catalyst 4-dimethylaminopyridine and 3.5mL of triethylamine were added. The mixture was stirred for 30min under ice bath conditions. 6mL of a mixture of bromoisobutyryl bromide and 20mL of N,N-dimethylformamide was slowly added dropwise. After the addition was completed, the mixture was reacted for 24h under nitrogen protection at room temperature. After the reaction was completed, the mixture was washed 3-5 times by centrifugation with ethanol and deionized water, and then freeze-dried to obtain brominated cellulose nanocrystals. (2) 2g of cellulose bromide nanocrystals were ultrasonically dispersed in 100mL of deionized water, and 5g of hydrophilic monomer N-isopropylacrylamide was added. The mixture was stirred evenly to obtain an aqueous phase. 100mL of liquid paraffin was mixed with 5g of hydrophobic monomer styrene and ultrasonically degassed to obtain an oil phase. The oil phase was slowly added to the aqueous phase and emulsified at 10000rpm for 5min using a high-shear emulsifier to form a stable oil-in-water Pickering emulsion. (3) Transfer the emulsion to a three-necked flask, purge with nitrogen for 30 min to remove oxygen, add 0.5 g of catalyst cuprous bromide and 1.2 mL of ligand pentamethyldiethylenetriamine under nitrogen protection, stir in a water bath at 30 °C for 12 h, add a large amount of methanol to break the emulsion after the reaction, collect the solid product by centrifugation, wash with tetrahydrofuran, ethanol and deionized water 2 to 4 times in sequence, and freeze dry to obtain modified cellulose microcrystals.

[0026] Example 2

[0027] A modified nano-titanium dioxide, synthesized via a sol-gel method, is a nano-titanium dioxide with a surface modified by green tea polyphenols. The preparation method includes the following steps: A. Dissolve 10g of tea polyphenol extract in a mixture of 100mL of deionized water and 50mL of anhydrous ethanol, filter through a 0.45μm filter membrane to remove insoluble matter, and obtain a clear tea polyphenol solution. Adjust the pH to 5.0~6.0. B. Slowly add 50 mL of tetrabutyl titanate to 100 mL of anhydrous ethanol and stir magnetically for 30 min to obtain solution A. Add 5 mL of glacial acetic acid to 150 mL of the above tea polyphenol solution as a hydrolysis inhibitor and stir evenly to obtain solution B. Under vigorous stirring, slowly add solution A to solution B at a rate of 1~2 drops / second. After the addition is complete, continue stirring for 2 h to form a uniform sol system. C. Transfer the sol to a hydrothermal reactor and hydrothermally treat it at 120℃ for 12 hours. After the hydrothermal reaction is completed, cool it naturally to room temperature, centrifuge to collect the precipitate, and wash it 2-4 times alternately with deionized water and anhydrous ethanol to remove the physically adsorbed free polyphenols. Dry the product under vacuum at 60℃ for 12 hours and grind it to obtain modified nano-titanium dioxide.

[0028] Example 3

[0029] A herbal-derived food-grade dishwasher detergent composition comprises the following raw materials in parts by weight: 150 parts of Sapindus mukorossi extract, 50 parts of Citrus aurantium extract, 5 parts of Grapeseed extract, 60 parts of modified cellulose microcrystals, 40 parts of sodium bicarbonate, 60 parts of sodium citrate, 20 parts of vegetable glycerin, 5 parts of xanthan gum, 10 parts of protease, 20 parts of amylase, 5 parts of lipase, 10 parts of cellulase, 15 parts of modified nano-titanium dioxide, 3 parts of potassium sorbate, 10 parts of citric acid, and 550 parts of deionized water; wherein the modified cellulose microcrystals are prepared in Example 1, and the modified nano-titanium dioxide is prepared in Example 2.

[0030] The preparation method of the above-mentioned herbal-derived food-grade dishwasher detergent composition includes the following steps: S1. Add deionized water to the reactor, and slowly add chelating agent and sodium bicarbonate while stirring. Stir until completely dissolved, then add thickener and stabilizer, and stir at high speed until completely dispersed and uniform to form a transparent viscous base. S2. After pre-dispersing the modified cellulose microcrystals with a small amount of deionized water, add them to the above solution and stir evenly. Then, add the Sapindus mukorossi extract, Citrus aurantium extract and Grape arvensis seed extract in sequence and stir evenly. Finally, add the modified nano titanium dioxide and homogenize at 1000 rpm for 20 minutes to ensure that it is evenly dispersed in the system. S3. Turn on the cooling circulating water to reduce the temperature inside the reactor to below 30°C, and slowly add multiple plant enzymes and preservatives in sequence, stirring at low speed of 5000 rpm for 40 minutes. S4. Detect the pH value, adjust the pH value to 7-8 with citric acid, continue stirring for 5 minutes until the system is homogeneous and stable, let stand to defoam, and obtain the herbal food-grade dishwasher detergent composition.

[0031] Example 4

[0032] A herbal-derived food-grade dishwasher detergent composition comprises the following raw materials in parts by weight: 200 parts of Sapindus mukorossi extract, 20 parts of Citrus aurantium extract, 20 parts of Grape arugula seed extract, 30 parts of modified cellulose microcrystals, 80 parts of sodium bicarbonate, 30 parts of sodium citrate, 50 parts of vegetable glycerin, 1 part of xanthan gum, 25 parts of protease, 10 parts of amylase, 15 parts of lipase, 5 parts of cellulase, 40 parts of modified nano-titanium dioxide, 1 part of potassium sorbate, 15 parts of citric acid, and 500 parts of deionized water; wherein the modified cellulose microcrystals are prepared in Example 1, and the modified nano-titanium dioxide is prepared in Example 2.

[0033] The preparation method of the above-mentioned herbal-derived food-grade dishwasher detergent composition includes the following steps: S1. Add deionized water to the reactor, and slowly add chelating agent and sodium bicarbonate while stirring. Stir until completely dissolved, then add thickener and stabilizer, and stir at high speed until completely dispersed and uniform to form a transparent viscous base. S2. After pre-dispersing the modified cellulose microcrystals with a small amount of deionized water, add them to the above solution and stir evenly. Then, add the Sapindus mukorossi extract, Citrus aurantium extract and Grape arguta seed extract in sequence and stir evenly. Finally, add the modified nano titanium dioxide and homogenize at 1500 rpm for 10 minutes to ensure that it is evenly dispersed in the system. S3. Turn on the cooling circulating water to reduce the temperature inside the reactor to below 30°C, and slowly add multiple plant enzymes and preservatives in sequence, stirring at low speed of 800 rpm for 20 minutes. S4. Detect the pH value, adjust the pH value to 7-8 with citric acid, continue stirring for 15 minutes until the system is homogeneous and stable, let stand to defoam, and obtain the herbal food-grade dishwasher detergent composition.

[0034] Example 5

[0035] A herbal-derived food-grade dishwasher detergent composition comprises the following raw materials in parts by weight: 175 parts of Sapindus mukorossi extract, 35 parts of Citrus aurantium extract, 12 parts of Grapefruit seed extract, 45 parts of modified cellulose microcrystals, 60 parts of sodium bicarbonate, 45 parts of sodium citrate, 35 parts of vegetable glycerin, 3 parts of xanthan gum, 18 parts of protease, 15 parts of amylase, 10 parts of lipase, and 8 parts of cellulase, 30 parts of modified nano-titanium dioxide, 2 parts of potassium sorbate, 12 parts of citric acid, and 520 parts of deionized water; wherein the modified cellulose microcrystals are prepared in Example 1, and the modified nano-titanium dioxide is prepared in Example 2.

[0036] The preparation method of the above-mentioned herbal-derived food-grade dishwasher detergent composition includes the following steps: S1. Add deionized water to the reactor, and slowly add chelating agent and sodium bicarbonate while stirring. Stir until completely dissolved, then add thickener and stabilizer, and stir at high speed until completely dispersed and uniform to form a transparent viscous base. S2. After pre-dispersing the modified cellulose microcrystals with a small amount of deionized water, add them to the above solution and stir evenly. Then, add the Sapindus mukorossi extract, Citrus aurantium extract and Grape arvensis seed extract in sequence and stir evenly. Finally, add the modified nano titanium dioxide and homogenize at 1250 rpm for 15 min to ensure that it is evenly dispersed in the system. S3. Turn on the cooling circulating water to reduce the temperature inside the reactor to below 30°C, and slowly add multiple plant enzymes and preservatives in sequence, stirring at low speed of 650 rpm for 30 minutes. S4. Detect the pH value, adjust the pH value to 7-8 with citric acid, continue stirring for 10 minutes until the system is homogeneous and stable, let stand to defoam, and obtain the herbal food-grade dishwasher detergent composition.

[0037] Comparative Example 1 A herbal-derived food-grade dishwasher detergent composition comprises the following raw materials in parts by weight: 175 parts of Sapindus mukorossi extract, 35 parts of Citrus aurantium extract, 12 parts of Grapeseed extract, 60 parts of sodium bicarbonate, 45 parts of sodium citrate, 35 parts of vegetable glycerin, 3 parts of xanthan gum, 18 parts of protease, 15 parts of amylase, 10 parts of lipase, 8 parts of cellulase, 30 parts of modified nano-titanium dioxide, 2 parts of potassium sorbate, 12 parts of citric acid, and 520 parts of deionized water; wherein the modified nano-titanium dioxide is prepared in Example 2.

[0038] The preparation method of the above-mentioned herbal food-grade dishwasher detergent composition is the same as that in Example 5, except that modified cellulose microcrystals are not added in step S2.

[0039] Comparative Example 2 A herbal-derived food-grade dishwasher detergent composition comprises the following raw materials in parts by weight: 175 parts of Sapindus mukorossi extract, 35 parts of Citrus aurantium extract, 12 parts of Grapeseed extract, 45 parts of modified cellulose microcrystals, 60 parts of sodium bicarbonate, 45 parts of sodium citrate, 35 parts of vegetable glycerin, 3 parts of xanthan gum, 18 parts of protease, 15 parts of amylase, 10 parts of lipase, 8 parts of cellulase, 2 parts of potassium sorbate, 12 parts of citric acid, and 520 parts of deionized water; wherein the modified cellulose microcrystals are prepared in Example 1.

[0040] The preparation method of the above-mentioned herbal food-grade dishwasher detergent composition is the same as that in Example 5, except that modified nano-titanium dioxide is not added in step S2.

[0041] Performance testing The performance of the herbal food-grade dishwasher detergent compositions prepared in Examples 3-5 and Comparative Examples 1 and 2 above was tested.

[0042] (1) Decontamination performance test Referring to GB / T 24692-2023, protein stains, starch stains, and grease stains were prepared and evenly coated onto cleaned, dried, and weighed ceramic plates. After aging at room temperature for 2 hours, the contaminated plates were placed in a household dishwasher with 5 mL of detergent sample added. The standard washing program was run: 65℃ main wash + 45℃ rinse. After washing, the plates were removed and dried at room temperature for 24 hours. They were then weighed, and the stain removal rate (%) was calculated. Stain removal rate = (plate weight before coating - plate weight after washing) / (plate weight before coating) × 100%. Each sample was measured in parallel 6 times, and the average value was taken. (2) Antibacterial performance test Referring to QB / T 5484-2020 and QB / T 2850-2023, dilute the detergent sample with sterile hard water to the working concentration. Add the diluted sample and bacterial suspension (final concentration approximately 1×10⁻⁶) sequentially to a sterile conical flask. 5 The samples (CFU / mL) and nutrient broth were placed in a constant temperature shaking incubator and cultured at 37℃ and 150 rpm for 18–24 h. The viable count was determined by plate counting method, and the antibacterial rate (%) was calculated. Antibacterial rate = viable count of blank control group - viable count of sample group / viable count of blank control group × 100%; (3) Anti-redeposition performance test Add standard artificial dirt (a mixture of grease, protein, and carbon black) to hard water (250 mg / kg CaCO3) to prepare a 0.1% dirt suspension. Place a clean glass slide (pre-weighed and its whiteness measured) in a dishwasher, add a detergent sample, run a complete washing program, and repeat the above steps 10 times (simulating multiple uses). Use a whiteness meter to measure the whiteness change of the glass slide before and after washing and calculate the whiteness retention rate. Weigh the glass slide before and after washing and calculate the weight gain rate. (4) Place the detergent sample in a 40℃ constant temperature incubator and store it for 4 weeks. Determine the protease activity using the Folin method (GB / T 23527-2009) and calculate the enzyme activity retention rate (%). Enzyme activity retention rate = enzyme activity after aging / initial enzyme activity × 100%; The obtained data is shown in Table 1 below.

[0043] Table 1 Performance test results of herbal food-grade dishwasher detergent composition

[0044] As shown in Table 1, the herbal-derived food-grade dishwasher detergent compositions in Examples 3-5 exhibited excellent cleaning effects on all three types of stains, especially grease stains. This indicates that the synergistic effect of the herbal surfactants and multiple enzymes was fully utilized. In Comparative Example 1, the grease removal rate decreased significantly, and the protein and starch removal rates also slightly decreased. This demonstrates that the modified cellulose microcrystals played a crucial role in the washing process. Their asymmetric oleophilic and hydrophilic amphiphilic structure actively anchored emulsified oil droplets, preventing their redeposition on the tableware surface, thus significantly improving the grease removal effect. The glass slide weight gain rate increased to 0.21%, directly demonstrating its anti-redeposition function. The cleaning rate in Comparative Example 2 was slightly lower than that of the examples but still above 97%, indicating that the modified nano-titanium dioxide had a limited impact on immediate cleaning power.

[0045] In Examples 3-5, the antibacterial rates against *Escherichia coli* and *Staphylococcus aureus* were all ≥90%, meeting the standards for antibacterial detergents. Comparative Example 1 showed a slight decrease in antibacterial rate, still near the acceptable level. This may be because the cellulose microcrystals themselves do not have direct antibacterial activity; the slight decrease in antibacterial rate may be due to residual dirt on the tableware surface providing a partial refuge for bacteria. Comparative Example 2 showed a sharp decrease in antibacterial rate, far below the standard requirements, proving that modified nano-titanium dioxide is the core component in the formulation that achieves antibacterial function. Under the weak light irradiation inside the dishwasher, the TiO2 in this complex generates photogenerated electron-hole pairs, which synergistically interact with the surface-grafted polyphenols to produce reactive oxygen species (ROS), thereby effectively killing bacteria. Without this complex, the base antibacterial activity of *Citrus reticulata* essential oil and green grape seed extract alone is insufficient to achieve a highly efficient antibacterial level.

[0046] In Examples 3-5, the proteases retained over 84.3% of their activity after storage at 40°C for 4 weeks. The enzyme activity retention rate in Comparative Example 1 was comparable to that in the examples, indicating that cellulose microcrystals had no significant effect on enzyme activity. The enzyme activity retention rate in Comparative Example 2 was much lower than that in the examples, demonstrating the strong antioxidant effect of the polyphenolic component in the modified nano-titanium dioxide. Although green grape seed extract also provides antioxidant properties, the polyphenols grafted onto the TiO2 surface in the modified nano-titanium dioxide bind tightly to the surface, continuously scavenging free radicals and dissolved oxygen during storage, effectively protecting the fragile enzyme proteins from oxidative inactivation.

[0047] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0048] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A herbal-derived food-grade dishwasher detergent composition, characterized in that, The ingredients include the following parts by weight: 150-200 parts of Sapindus mukorossi extract, 20-50 parts of Citrus aurantium extract, 5-20 parts of green grape seed extract, 30-60 parts of modified cellulose microcrystals, 40-80 parts of sodium bicarbonate, 30-60 parts of chelating agent, 20-50 parts of thickener, 1-5 parts of stabilizer, 30-70 parts of multiple plant enzymes, 15-40 parts of modified nano titanium dioxide, 1-3 parts of preservative, 10-15 parts of citric acid, and 500-550 parts of deionized water; The modified cellulose microcrystals are cellulose nanocrystals that have been brominated on the surface and then polymerized by atom transfer radical polymerization at the Pickering emulsion interface, while simultaneously grafting lipophilic long-chain hydrophobic alkyl chains and hydrophilic carboxymethyl chains; the modified nano-titanium dioxide is nano-titanium dioxide with surface modification of green tea polyphenols synthesized by the sol-gel method.

2. The herbal-derived food-grade dishwasher detergent composition according to claim 1, characterized in that, The multiple plant enzymes include 10-25 parts of protease, 10-20 parts of amylase, 5-15 parts of lipase and 5-10 parts of cellulase.

3. The herbal-derived food-grade dishwasher detergent composition according to claim 1, characterized in that, The chelating agent is sodium citrate, the thickener is vegetable glycerin, the stabilizer is xanthan gum, and the preservative is potassium sorbate.

4. The herbal-derived food-grade dishwasher detergent composition according to claim 1, characterized in that, The method for preparing the modified cellulose microcrystals includes the following steps: (1) Cellulose nanocrystals were ultrasonically dispersed in N,N-dimethylformamide to obtain a uniform suspension. 4-Dimethylaminopyridine and triethylamine were added and stirred for 20-40 min under ice bath conditions. 2-Bromoisobutyryl bromide in N,N-dimethylformamide solution was slowly added dropwise. After the addition was completed, the reaction was carried out at room temperature under nitrogen protection for 18-30 h. After the reaction was completed, the nanocrystals were washed 3-5 times by centrifugation with ethanol and deionized water, and then freeze-dried to obtain brominated cellulose nanocrystals. (2) Disperse cellulose bromide nanocrystals in deionized water by ultrasonication, add N-isopropylacrylamide, stir evenly to obtain an aqueous phase, mix liquid paraffin with styrene, degas by ultrasonication to obtain an oil phase, slowly add the oil phase to the aqueous phase, and emulsify for 4-6 minutes using a high-shear emulsifier to form a stable oil-in-water Pickering emulsion. (3) Transfer the emulsion to a three-necked flask, purge with nitrogen for 20-40 min to remove oxygen, add cuprous bromide and pentamethyldiethylenetriamine under nitrogen protection, stir in a water bath at 30°C for 8-16 h, add a large amount of methanol to break the emulsion after the reaction, collect the solid product by centrifugation, wash with tetrahydrofuran, ethanol and deionized water 2-4 times in sequence, and freeze dry to obtain modified cellulose microcrystals.

5. The herbal-derived food-grade dishwasher detergent composition according to claim 4, characterized in that, The mass ratio of cellulose nanocrystals, 2-bromoisobutyryl bromide, and 4-dimethylaminopyridine is 1:2.2:0.3, and the grafting rate of the brominated cellulose nanocrystals is 0.5~2.0 mmol / g.

6. The herbal-derived food-grade dishwasher detergent composition according to claim 4, characterized in that, The mass ratio of the brominated cellulose nanocrystals, N-isopropylacrylamide, styrene, cuprous bromide, and pentamethyldiethylenetriamine is 4:10:10:1:

2.

7. The herbal-derived food-grade dishwasher detergent composition according to claim 1, characterized in that, The preparation method of the modified nano-titanium dioxide includes the following steps: A. Dissolve the tea polyphenol extract in a mixture of deionized water and anhydrous ethanol, filter with a 0.4~0.5 μm filter membrane to remove insoluble matter, and obtain a clear tea polyphenol solution. Adjust the pH to 5.0~6.

0. B. Slowly add tetrabutyl titanate to anhydrous ethanol and stir magnetically for 20-40 minutes to obtain solution A. Add glacial acetic acid to the above tea polyphenol solution and stir until homogeneous to obtain solution B. Under vigorous stirring, slowly add solution A to solution B at a rate of 1-2 drops / second. After the addition is complete, continue stirring for 1.5-2.5 hours to form a homogeneous sol system. C. Transfer the sol to a hydrothermal reactor and treat it at 120℃ for 8-16 hours. After the hydrothermal reaction is completed, cool it naturally to room temperature, collect the precipitate by centrifugation, and wash it 2-4 times alternately with deionized water and anhydrous ethanol to remove the physically adsorbed free polyphenols. After vacuum drying, grind the product to obtain modified nano titanium dioxide.

8. The herbal-derived food-grade dishwasher detergent composition according to claim 7, characterized in that, The tea polyphenol extract contains ≥50% epigallocatechin gallate (EGCG).

9. The herbal-derived food-grade dishwasher detergent composition according to claim 7, characterized in that, The mass ratio of the tea polyphenol extract to tetrabutyl titanate is 1:5~10.

10. A method for preparing the herbal-derived food-grade dishwasher detergent composition according to any one of claims 1 to 9, characterized in that, Includes the following steps: S1. Add deionized water to the reactor, and slowly add chelating agent and sodium bicarbonate while stirring. Stir until completely dissolved, then add thickener and stabilizer, and stir at high speed until completely dispersed and uniform to form a transparent viscous base. S2. After pre-dispersing the modified cellulose microcrystals with a small amount of deionized water, add them to the above solution and stir evenly. Then, add the Sapindus mukorossi extract, Citrus aurantium extract and Grape arvensis seed extract in sequence and stir evenly. Finally, add the modified nano titanium dioxide and stir at a medium speed of 1000~1500 rpm for 10~20 min to ensure that it is evenly dispersed in the system. S3. Turn on the cooling circulating water to reduce the temperature inside the reactor to below 30°C, and slowly add multiple plant enzymes and preservatives in sequence, stirring at low speed of 500~800 rpm for 20~40 minutes. S4. Detect the pH value, adjust the pH value to 7-8 with citric acid, continue stirring for 5-15 minutes until the system is homogeneous and stable, let stand to defoam, and obtain the herbal food-grade dishwasher detergent composition.

Images