Highly efficient detergent and its preparation method

Abstract

The application provides a high-efficiency detergent and a preparation method thereof, and relates to the technical field of daily chemical products.The detergent comprises microencapsulated composite enzymes, chelating agents, surfactants, additives and water; the active ingredients of the microencapsulated composite enzymes are composed of lipase, protease and amylase, and are prepared by sodium alginate-chitosan microencapsulation embedding, so that the enzyme activity is effectively protected, the stability of the enzymes in the detergent system is improved, and the targeted decomposition of composite stains is realized; the chelating agents are composed of tetrasodium iminodisuccinate and maleic acid-acrylic acid copolymer sodium salt, and can synergistically improve the hard water resistance and the stain removal efficiency; the surfactants are composed of sodium fatty acid methyl ester sulfonate, alkyl polyglycoside and cocamide propyl betaine, and have strong emulsifying and stain removing power and mildness.The detergent is suitable for cleaning tableware and fruits and vegetables, and has the characteristics of high stability, strong stain removing power, easy rinsing, mildness and environmental protection.

Description

Technical Field

[0001] This invention relates to the field of daily necessities chemical technology, specifically to a highly effective detergent and its preparation method. Background Technology

[0002] As a core product for kitchen cleaning, dishwashing liquid's cleaning performance and user experience directly impact daily cleaning efficiency and safety. Traditional dishwashing liquid formulas often use high-content anionic surfactants combined with phosphates as their core system, which has revealed numerous technical shortcomings in practical applications, making it difficult to meet diverse cleaning needs. In hard water environments, the ingredients in traditional formulas easily react with calcium and magnesium ions in the water, not only significantly reducing their cleaning power but also producing soap scum residue on tableware surfaces, increasing rinsing difficulty and water consumption. For common kitchen stains involving protein, starch, and grease, traditional dishwashing liquids lack targeted decomposition capabilities, relying solely on the emulsifying and dispersing effects of surfactants. This results in low efficiency in breaking down stubborn stains, requiring repeated scrubbing, making the cleaning process time-consuming and laborious.

[0003] Meanwhile, while high-concentration surfactant systems can enhance detergency, they can easily damage the skin's lipid barrier, causing skin irritation. They struggle to balance strong detergency with gentleness, and long-term exposure may pose potential health risks. Furthermore, the use of single chelating agents in traditional formulas results in poor rinsing, easily leading to redeposition of stain particles, affecting cleaning effectiveness and tableware maintenance. Additionally, the excessive use of phosphates can cause eutrophication pollution in aquatic environments.

[0004] To address these issues, the industry has attempted to adjust surfactant ratios or add single enzyme preparations, but problems remain, such as poor stability of enzyme preparations in high-surfactant and metal ion environments, limited improvement in hard water resistance, and poor simultaneous decomposition of multiple types of stains. Therefore, developing a dishwashing liquid that can achieve highly efficient stain removal in complex environments such as hard water, low temperatures, and heavy oil stains, while also being easy to rinse, has become an urgent need in the kitchen cleaning industry. This is of great significance for improving cleaning efficiency, optimizing the user experience, and practicing environmental protection principles. Summary of the Invention

[0005] The purpose of this invention is to provide a highly efficient detergent and its preparation method. The detergent provided by this invention has the characteristics of excellent stability, strong detergency, and easy rinsing.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a highly efficient detergent, comprising, by weight percentage: 0.8%-1.2% microencapsulated complex enzyme, 0.5%-1% chelating agent, 10%-15% surfactant, 1%-3% additives, and the balance being water; the active ingredient of the microencapsulated complex enzyme is composed of lipase, protease, and amylase; the chelating agent is composed of tetrasodium iminodisuccinate and sodium salt of maleic acid acrylate copolymer.

[0007] Preferably, the mass ratio of the tetrasodium iminodisuccinate to the sodium salt of the maleic acrylate copolymer is (1-3):1.

[0008] Preferably, the microencapsulated complex enzyme is composed of microencapsulated lipase, microencapsulated protease and microencapsulated amylase in a mass ratio of 1:(1-1.5):(0.5-1).

[0009] More preferably, the preparation method of the microencapsulated complex enzyme includes: mixing lipase, protease, and amylase with sodium alginate aqueous solution to obtain an aqueous suspension; mixing Span 80 with vegetable oil to obtain an oil phase; emulsifying the aqueous suspension and oil phase to obtain an emulsion; adding calcium chloride solution and chitosan acetate solution for solidification; filtering; drying the precipitate to obtain microencapsulated lipase, microencapsulated protease, and microencapsulated amylase, and mixing them.

[0010] More preferably, the mass ratio of the Span 80 to the vegetable oil is 1:(5-10).

[0011] More preferably, the volume ratio of the aqueous suspension to the oil phase is 1:(4-6).

[0012] Preferably, the surfactant comprises at least one of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214, and cocamidopropyl betaine.

[0013] Preferably, the additives include at least one of thickeners, preservatives, fragrances, and humectants.

[0014] The present invention also provides a method for preparing the above-mentioned dishwashing liquid, comprising: mixing a chelating agent with water, and then sequentially adding a surfactant, an auxiliary agent and a microencapsulated complex enzyme to obtain the dishwashing liquid.

[0015] The present invention also provides an application of the above-mentioned dishwashing liquid, wherein the dishwashing liquid is applied to the cleaning of tableware and fruits and vegetables.

[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention provides a highly efficient detergent, comprising: a microencapsulated complex enzyme, a chelating agent, a surfactant, an additive, and water. The complex enzyme is composed of microencapsulated lipase, protease, and amylase in a specific ratio. The chelating agent is a compound of tetrasodium iminodisuccinate and sodium salt of maleic acid acrylate copolymer. The surfactant is preferably a compound of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214, and cocamidopropyl betaine. This detergent utilizes the microencapsulated complex enzyme to target and decompose complex stains. The compound chelating agent achieves complementary synergistic effects of chelation and dispersion. The compound surfactant balances detergency and gentleness. The synergistic effect of all components results in strong detergency even in complex environments such as hard water, excellent high and low temperature stability, easy rinsing, and a superior sensory experience. Furthermore, it is phosphorus-free and environmentally friendly, reducing surfactant usage and rinsing water consumption, thus combining cleaning efficiency with safety. Detailed Implementation

[0017] This invention provides a highly efficient detergent, comprising, by weight percentage: 0.8%-1.2% microencapsulated complex enzyme, 0.5%-1% chelating agent, 10%-15% surfactant, 1%-3% additives, and the balance being water; the active ingredient of the microencapsulated complex enzyme is composed of lipase, protease, and amylase; the chelating agent is composed of tetrasodium iminodisuccinate and sodium salt of maleic acid acrylate copolymer.

[0018] In this invention, the preferred mass ratio of the tetrasodium iminodisuccinate and the sodium salt of the maleic acrylate copolymer is (1-3):1, and more preferably 2:1.

[0019] The tetrasodium iminodisuccinate described in this invention has a strong chelating ability for heavy metal ions such as calcium, magnesium, iron, and copper ions. It can quickly form stable water-soluble complexes with scale-forming ions in hard water, efficiently soften water quality, eliminate the complexation and consumption of surfactants by metal ions, and fully release the emulsifying and detergency performance of surfactants.

[0020] The sodium maleic acid-acrylic acid copolymer described in this invention functions as a chelating agent and dispersant in dishwashing liquid. On one hand, it has a certain chelating ability for calcium and magnesium ions, making it more suitable for medium to high concentrations of hard water; on the other hand, its polymer chains can adsorb onto the surface of tiny dirt particles and soap scum, stably dispersing them in water through steric hindrance, completely solving the problem of dirt redeposition that easily occurs with single chelating agents, avoiding soap scum residue on tableware, and significantly improving rinsing efficiency.

[0021] This invention combines tetrasodium iminodisuccinate with sodium maleate-acrylate copolymer to achieve rapid chelation and efficient dispersion, significantly improving the detergent's resistance to hard water and its detergency. The former's rapid and strong chelating properties with metal ions quickly reduce the concentration of free calcium and magnesium ions in water, while the latter disperses existing precipitates or particles encapsulated in oil stains, stabilizing them in water for rinsing away. This prevents secondary deposition of soap scum on tableware, thus avoiding the problem of poor rinsing effect when using a single chelating agent. Under hard water conditions, while tetrasodium iminodisuccinate alone can soften water, its chelating capacity is consumed quickly. Sodium maleate-acrylate copolymer, through its dispersion effect, reduces the instantaneous impact of excessive local hardness on surfactants, allowing surfactants to focus more on reducing oil-water interfacial tension, thereby significantly improving the detergent's degreasing speed and foam stability.

[0022] The preferred method for preparing the microencapsulated complex enzyme of the present invention includes: mixing lipase, protease, and amylase with sodium alginate aqueous solution to obtain an aqueous suspension; mixing Span 80 with vegetable oil to obtain an oil phase; emulsifying the aqueous suspension and oil phase to obtain an emulsion; adding calcium chloride solution and chitosan acetate solution for solidification; filtering; drying the precipitate; and mixing the obtained microencapsulated lipase, microencapsulated protease, and microencapsulated amylase at a mass ratio of 1:(1-1.5):(0.5-1) to obtain the microencapsulated complex enzyme; the mass ratio is more preferably 1:1.2:0.8; the mass ratio of Span 80 to vegetable oil is preferably 1:(5-10), more preferably 1:8; and the volume ratio of the aqueous suspension to the oil phase is preferably 1:(4-6), more preferably 1:5.

[0023] This invention's microencapsulated complex enzyme can target and decompose stubborn stains composed of grease, protein, and starch on kitchen tableware. Combined with surfactants, it achieves rapid stain removal, reducing the need for scrubbing. The microencapsulation process protects the enzyme from degradation by surfactants and metal ions in the detergent system, enhancing its stability and shelf life. This complex enzyme maintains a stable catalytic effect during use, is suitable for complex cleaning scenarios such as hard water and low temperatures, and, when combined with chelating agents and surfactants, can further improve the overall cleaning efficacy of detergents, meeting the safe cleaning needs of tableware and fruits and vegetables.

[0024] The surfactant of the present invention preferably includes at least one of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine, more preferably including sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine; the mass ratio of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine is (3-5):(1.5-2.5):1, and more preferably 4:2:1.

[0025] This invention utilizes surfactants in dishwashing liquids to perform core cleaning functions such as emulsification, wetting, and dispersion. Sodium methyl ester sulfonate, an anionic surfactant, possesses strong emulsifying power, quickly encapsulating grease and oil stains to form micelles, achieving the removal and dissolution of oil. Alkyl glycoside 1214, a nonionic surfactant, exhibits excellent detergency and solubilization properties, is resistant to hard water, and has good compatibility with other surfactants, enhancing the system's dispersion ability for complex stains while reducing overall surfactant irritation. Cocamidopropyl betaine, an amphoteric surfactant, provides excellent foaming properties with fine, easily rinsed foam, enhancing the system's wetting and spreading properties, assisting in the removal of adhesive stains from tableware and fruit / vegetable surfaces, and neutralizing the irritation of anionic surfactants, thus improving gentleness. The combination of these three surfactants balances strong detergency with low irritation, making it suitable for complex scenarios such as hard water. When used in conjunction with chelating agents and complex enzymes, it further enhances the overall cleaning efficacy of the dishwashing liquid.

[0026] The additives of this invention include at least one of a thickener, a preservative, a fragrance, and a humectant; the thickener is preferably xanthan gum, and the amount of xanthan gum used is preferably 0.2%-0.4%, more preferably 0.3%; the preservative is preferably phenoxyethanol, and the amount of phenoxyethanol used is preferably 0.4%-0.6%, more preferably 0.5%; the fragrance is preferably lemon fragrance, sweet orange fragrance, and grapefruit fragrance, and the amount of the fragrance is preferably 0.1%-0.2%, more preferably 0.15%; the humectant is preferably glycerin or betaine, and the amount of the humectant is preferably 0.5%-1.2%, more preferably 1%.

[0027] The present invention also provides a method for preparing the above-mentioned dishwashing liquid, comprising: mixing a chelating agent with water, and then sequentially adding a surfactant, an auxiliary agent and a microencapsulated complex enzyme to obtain the dishwashing liquid.

[0028] The present invention also provides an application of the above-mentioned dishwashing liquid, wherein the dishwashing liquid is applied to the cleaning of tableware and fruits and vegetables.

[0029] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0030] Unless otherwise specified, the following embodiments are all conventional methods.

[0031] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0032] In both the examples and comparative examples, the water used in the preparation of the detergent was deionized water.

[0033] The lipase was sourced from Shandong Haimu Detergent & Daily Chemical Co., Ltd., with an enzyme activity of 200,000 U / g; the protease was an alkaline protease sourced from Jinan Xinhe Chemical Technology Co., Ltd., with an enzyme activity of 200,000 U / g; the amylase was sourced from Ningxia Xiasheng Industrial Group Co., Ltd., with an enzyme activity of 10,000 U / mL; the sodium alginate was sourced from Qingdao Mingyue Algae Group Co., Ltd., with a viscosity of 600-800 mPa·s at 20℃; the chitosan was sourced from Henan Bangrun Chemical Products Co., Ltd., CAS No. 9012-76-4, item number BR-024; the sodium maleic acid-acrylic acid copolymer was sourced from Wuhan Jushun Chemical Co., Ltd., CAS No. 52255-49-9; and the sodium fatty acid methyl ester sulfonate was sourced from Wuhan Pushida Biotechnology Co., Ltd., CAS No. 93348-22-2.

[0034] Example 1 (1) Preparation of microencapsulated complex enzymes Lipase, protease, and amylase were each mixed with a 2.5% sodium alginate aqueous solution at a mass ratio of 1:18 to obtain an aqueous suspension. Span 80 and rapeseed oil were mixed at a mass ratio of 1:8 to obtain an oil phase. The aqueous suspension was added dropwise to the oil phase, and emulsified at 30℃ and 350 r / min for 28 min to obtain an emulsion. The emulsion was added dropwise to a 2% calcium chloride solution, and after gel solidification for 23 min, it was filtered, the precipitate was collected, washed three times with deionized water, and then immersed in chitosan acetate solution for solidification for 18 min. After filtration, the precipitate was collected, washed three times with deionized water, and dried at 40℃ to a moisture content of 3 ± 0.5 wt% to obtain microencapsulated lipase, microencapsulated protease, and microencapsulated amylase. The obtained microencapsulated lipase, microencapsulated protease, and microencapsulated amylase were then mixed at a mass ratio of 1:1.2:0.8 to obtain a microencapsulated complex enzyme. The mass ratio of the aqueous suspension to the oil phase is 1:5; the chitosan in the chitosan acetic acid solution is dissolved in a 1% (w / w) acetic acid solution, and the mass fraction of chitosan is 0.8%.

[0035] (2) Weighing Accurately weigh the following per 100 parts by weight: 1 part microencapsulated complex enzyme, 0.8 parts chelating agent, 12 parts surfactant, 1.95 parts auxiliary agent, with the remainder being water; The chelating agent is composed of tetrasodium iminodisuccinate and sodium salt of maleic acrylate copolymer, with a weight ratio of 2:1. The surfactant is composed of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine, with a weight ratio of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine of 4:2:1. The additives consist of xanthan gum, phenoxyethanol, lemon flavoring and betaine, with a weight ratio of 0.3:0.5:0.15:1.

[0036] (3) Preparation of dishwashing liquid Tetrasodium iminodisuccinate and sodium salt of maleic acid acrylate copolymer were stirred with water at 120 rpm for 12 min. While maintaining the speed of 120 rpm, xanthan gum, sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214, cocamidopropyl betaine, phenoxyethanol, lemon flavor and betaine were added in sequence. The speed was adjusted to 80 rpm, and microencapsulated complex enzyme was added and stirred for 12 min to obtain highly effective detergent S1.

[0037] Example 2 (1) Preparation of microencapsulated complex enzymes Lipase, protease, and amylase were each mixed with a 2% sodium alginate aqueous solution at a mass ratio of 1:15 to obtain an aqueous suspension. Span 80 and peanut oil were mixed at a mass ratio of 1:6 to obtain an oil phase. The aqueous suspension was added dropwise to the oil phase, and emulsified at 28℃ and 320 r / min for 30 min to obtain an emulsion. The emulsion was added dropwise to a 1.8% calcium chloride solution, and after gel solidification for 25 min, it was filtered, the precipitate was collected, washed three times with deionized water, and then immersed in a chitosan acetate solution for solidification for 20 min. After filtration, the precipitate was collected, washed three times with deionized water, and dried at 38℃ to a moisture content of 3 ± 0.5 wt% to obtain microencapsulated lipase, microencapsulated protease, and microencapsulated amylase. The obtained microencapsulated lipase, microencapsulated protease, and microencapsulated amylase were then mixed at a mass ratio of 1:1:0.5 to obtain a microencapsulated composite enzyme. The mass ratio of the aqueous suspension to the oil phase is 1:4; the chitosan in the chitosan acetic acid solution is dissolved in a 1% (w / w) acetic acid solution, and the mass fraction of chitosan is 0.6%.

[0038] (2) Weighing Accurately weigh the following per 100 parts by weight: 0.8 parts microencapsulated complex enzyme, 1 part chelating agent, 10 parts surfactant, 1.9 parts auxiliary agent, with the remainder being water; The chelating agent is composed of tetrasodium iminodisuccinate and sodium salt of maleic acrylate copolymer, with a weight ratio of 1:1. The surfactant is composed of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine, with a weight ratio of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine of 3:1.5:1. The additives consist of xanthan gum, phenoxyethanol, sweet orange flavoring, and glycerin, with a weight ratio of 0.2:0.4:0.1:1.2.

[0039] (3) Preparation of dishwashing liquid Tetrasodium iminodisuccinate and sodium salt of maleic acid acrylate copolymer were stirred with water at 100 rpm for 15 min. While maintaining the speed of 100 rpm, xanthan gum, sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214, cocamidopropyl betaine, phenoxyethanol, sweet orange flavor, and glycerin were added in sequence. The speed was adjusted to 60 rpm, and microencapsulated complex enzyme was added and stirred for 15 min to obtain highly effective detergent S2.

[0040] Example 3 (1) Preparation of microencapsulated complex enzymes Lipase, protease, and amylase were each mixed with a 3% sodium alginate aqueous solution at a mass ratio of 1:20 to obtain an aqueous suspension. Span 80 and rapeseed oil were mixed at a mass ratio of 1:10 to obtain an oil phase. The aqueous suspension was added dropwise to the oil phase, and emulsified at 32℃ and 380 r / min for 25 min to obtain an emulsion. The emulsion was added dropwise to a 2.2% calcium chloride solution, gelled for 20 min, filtered, and the precipitate was collected. After washing three times with deionized water, the precipitate was immersed in a chitosan acetate solution for 15 min, filtered, and the precipitate was collected. After washing three times with deionized water, the precipitate was dried at 42℃ to a moisture content of 3 ± 0.5 wt% to obtain microencapsulated lipase, microencapsulated protease, and microencapsulated amylase. The obtained microencapsulated lipase, microencapsulated protease, and microencapsulated amylase were then mixed at a mass ratio of 1:1.5:1 to obtain a microencapsulated complex enzyme. The mass ratio of the aqueous suspension to the oil phase is 1:6; the chitosan in the chitosan acetic acid solution is dissolved in a 1% (w / w) acetic acid solution, and the mass fraction of chitosan is 1%.

[0041] (2) Weighing Accurately weigh the following per 100 parts by weight: 1.2 parts microencapsulated complex enzyme, 0.5 parts chelating agent, 15 parts surfactant, 2 parts auxiliary agent, with the remainder being water; The chelating agent is composed of tetrasodium iminodisuccinate and sodium salt of maleic acrylate copolymer, with a weight ratio of 3:1. The surfactant is composed of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine, with a weight ratio of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214 and cocamidopropyl betaine of 5:2.5:1. The additives consist of xanthan gum, phenoxyethanol, sweet orange flavor and betaine, with a weight ratio of 0.4:0.6:0.2:0.8.

[0042] (3) Preparation of dishwashing liquid Tetrasodium iminodisuccinate and sodium salt of maleic acid acrylate copolymer were stirred with water at 150 rpm for 10 min. While maintaining the speed of 150 rpm, xanthan gum, sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214, cocamidopropyl betaine, phenoxyethanol, sweet orange flavor and betaine were added in sequence. The speed was adjusted to 100 rpm, and microencapsulated complex enzyme was added and stirred for 10 min to obtain highly effective detergent S3.

[0043] Comparative Example 1 Unlike Example 1, the chelating agent was replaced with tetrasodium iminodisuccinate as a single chelating agent, while the total amount of chelating agent remained unchanged. The resulting detergent was denoted as D1.

[0044] Comparative Example 2 Unlike Example 1, the chelating agent was replaced with a single chelating agent, sodium maleate copolymer, while the total amount of chelating agent remained unchanged. The resulting detergent was designated as D2.

[0045] Comparative Example 3 Unlike Example 1, the chelating agent was composed of tetrasodium iminodisuccinate and sodium polyacrylate, with a mass ratio of tetrasodium iminodisuccinate to sodium polyacrylate of 2:01. The resulting detergent was designated as D3.

[0046] Comparative Example 4 Unlike Example 1, the surfactant is composed of sodium dodecylbenzenesulfonate, lauryl polyoxyethylene ether-9 and dodecyl dimethyl betaine, with a weight ratio of sodium dodecylbenzenesulfonate, lauryl polyoxyethylene ether-9 and dodecyl dimethyl betaine of 4:2:1. The resulting detergent is designated as D4.

[0047] Comparative Example 5 Unlike Example 1, the microencapsulated complex enzyme was replaced with an unencapsulated complex enzyme, which consisted of lipase, protease and amylase in a mass ratio of 1:1.2:0.8. The resulting detergent was designated as D5.

[0048] Experimental Example 1 Dishwashing liquid stability test This experiment tested the stability of the detergents prepared in Examples 1-3 (S1, S2, S3) and Comparative Examples 1-5 (D1, D2, D3, D4, D5).

[0049] The test method refers to the stability index in Table 1 of GB / T 9985-2022 Detergents for Hand Washing Dishwashing.

[0050] High temperature stability: Seal each sample and place it in a constant temperature chamber at 40℃±2℃. Let it stand for 24 hours. After it returns to room temperature, observe its appearance and check for phenomena such as layering, precipitation, odor, discoloration, and turbidity. Low temperature stability: Seal each sample and place it in a -5℃±2℃ refrigerator. Let it stand for 24 hours. After it returns to room temperature, observe its appearance and check for phenomena such as layering, precipitation, odor, discoloration, and turbidity. The high-temperature and low-temperature stability results of each sample are shown in Table 1.

[0051] Table 1. High-temperature and low-temperature stability of each sample The results in Table 1 show that S1, S2, and S3 detergents all remain uniform and transparent under high and low temperature environments, without any abnormal phenomena such as layering or precipitation. This proves that the detergents of the present invention have excellent temperature adaptability. The microencapsulated complex enzyme, compound chelating agent, and surfactant have good compatibility. The microencapsulation process effectively protects the enzyme preparation from the influence of temperature, while the compound chelating agent avoids the complexation or precipitation of components during temperature changes.

[0052] In the comparative examples, D1 used a single tetrasodium iminodisuccinate chelating agent, resulting in flocculent precipitation at high and low temperatures, and slight precipitation at low temperatures, indicating that a single chelating agent, when combined with other components in the system, easily produces trace amounts of insoluble matter during temperature fluctuations. D3, by replacing sodium maleate-acrylic acid copolymer with sodium polyacrylate, resulted in slight turbidity, confirming that sodium maleate-acrylic acid copolymer is more effective than sodium polyacrylate in improving the compatibility of the chelating agent with the system. D5 used an unencapsulated complex enzyme; since lipase and amylase are proteins, the protease decomposes some of them, leading to significant turbidity and substantial precipitation at high temperatures, and slight turbidity and precipitation at low temperatures. This indicates that microencapsulation protects the enzyme preparation, while unencapsulated enzymes are prone to inactivation and aggregation in the system. The single graft copolymer chelating agent in D2 and the modified surfactant system in D4 remained stable, indicating that these two types of components have good temperature stability and did not negatively impact the system. Overall, the design of the compound chelating agent and the microencapsulation process of the complex enzyme in this invention can improve the high and low temperature stability of detergents.

[0053] Experimental Example 2 Hard water cleaning power test This experiment tested the hard water detergency of the detergents prepared in Examples 1-3 (S1, S2, S3) and Comparative Examples 1-5 (D1, D2, D3, D4, D5).

[0054] The oil removal rate was determined according to the oil removal rate method (arbitration method) in GB / T 9985-2022, which specifies the determination of detergency in detergents for hand washing dishes.

[0055] The method for testing detergency is as follows: 1. Preparation of standard dishwashing detergent Weigh out 14 parts (100%) of sodium alkylbenzene sulfonate, 1 part (100%) of sodium ethoxylated alkyl sulfate, 5 parts of anhydrous ethanol, and 5 parts of urea according to the mass ratio. Add water to 100 parts, mix well, and adjust the pH to 7.5±0.5 with hydrochloric acid or sodium hydroxide.

[0056] Preparation of mixed oil sludge Weigh out 5 parts butter, 5 parts lard, 10 parts vegetable oil, and 1 part glyceryl monostearate according to the specified mass ratio. Place them in a beaker and heat on an electric stove to 180°C to melt them. Maintain this temperature for 10 minutes with electromagnetic stirring. After natural cooling, refrigerate for later use.

[0057] 2. Preparation of the stained sheet Environmental conditions: The entire process of preparing the stained slide should be kept at a room temperature of 22±3℃ and a relative humidity of 50±10% (i.e., the selection or adjustment of environmental conditions during the test should be based on the principle of obtaining a stained glass slide that meets the requirements).

[0058] Preparing glass slides: Newly purchased glass slides need to be boiled in detergent solution for 15 minutes, washed with clean water until no water droplets remain, then soaked in chromic acid cleaning solution for 1 hour, rinsed with clean water and distilled water, and stored in a drying oven. Mark each glass slide with a serial number, and draw a line 10 mm from the top edge of the slide to indicate the area below which smearing is to be applied; draw a line 5 mm from the bottom edge of the slide to indicate where to wipe off excess oil below this line. Weigh each glass slide (accurate to 1 mg), and use the prepared clips to clip each slide above the top edge of the known-weight slide, then hang it on a slide drying rack, placing the drying rack in an enamel tray to prepare for smearing.

[0059] Slide contamination: Take an appropriate amount of the prepared mixed oil and place it in a constant temperature water bath to maintain the oil temperature at 50±2℃. Remove each slide, along with its clamp, from the drying rack. Holding the clamp, slowly immerse the slide in oil at 50±2℃ until it is 10mm below the top edge, then slowly remove it. Repeat this process three times. After the last coating, wait until the oil dripping speed slows down, then hang the coated slide back on the drying rack. Prepare the coated slides in sequence. After the oil on the slide solidifies, wipe the excess oil from the bottom edge and sides (5mm below the bottom edge) with filter paper or degreased cotton, then use tweezers to hold degreased cotton soaked in anhydrous ethanol or petroleum ether and wipe until clean. Allow the slides to dry for 3 hours under the conditions required for this experiment. Transfer the dried slides to a weighing rack and accurately weigh each coated slide using an analytical balance. The weight of each slide should be controlled at 0.13±0.02g. Four slides are grouped together, and the weight of each group of slides should be controlled at 0.50±0.05g.

[0060] 3. The test procedure shall be carried out according to the following steps: a) Stain remover settings: washing temperature 30℃, rotation speed 160r / min, washing time 3min.

[0061] b) Sample preparation: Weigh 4.0 g of the sample to be tested and dissolve it in 2000 mL of 250 mg / L hard water, shake well and set aside. Prepare a standard dishwashing detergent solution under the same conditions.

[0062] c) Insert the prepared soiled sheets into the washing rack in groups of four for washing.

[0063] d) Measure 800 mL of the test solution and place it into the washing tank of the vertical cleaning machine. Each pair of washing tanks corresponds to a set of parallel samples. When the temperature of the test solution rises to 30°C, quickly place the stained sheets of known mass along with the washing racks into the washing tanks. Start the soaking time when the last washing rack is placed. Install the stirrer. After soaking for 1 minute, start the cleaning machine to begin washing. After 3 minutes, the cleaning machine will automatically stop. Quickly remove the stirrer and take out the washing rack. Hang the washed stained sheets one by one on the drying rack and let them air dry for 2 hours under the environmental conditions required by this test before transferring them to the weighing rack for weighing.

[0064] Parallel tests were conducted on standard tableware detergent and dishwashing liquid samples on the same machine, with three parallel tests for each sample.

[0065] 4. Calculate the oil removal rate Expressed as mass fraction, the degreasing rate W and degreasing ratio R are calculated according to the formula.

[0066] W = (m1 - m2) ÷ (m1 - m0) × 100%; In the formula: W is the degreasing rate; m0 is the mass of the slide before coating, in grams (g); m1 is the mass of the slide after coating, in grams (g); m2 is the mass of the soiled slide after washing, in grams (g).

[0067] R = W1 / W2; In the formula, W1 is the oil removal rate of the sample, and W2 is the oil removal rate of the standard dishwashing detergent.

[0068] The detergency evaluation is based on the arithmetic mean of the ratio of the sample's oil removal rate to that of the standard dishwashing detergent. A ratio greater than 1.05 indicates that the detergency is greater than that of the standard dishwashing detergent, a ratio less than 0.95 indicates that the detergency is less than that of the standard dishwashing detergent, and a ratio greater than or equal to 0.95 and less than or equal to 1.05 indicates that the detergency is equal to that of the standard dishwashing detergent.

[0069] The test results of the hard water cleaning ability of each sample are shown in Table 2.

[0070] Table 2. Test results of hard water decontamination rate and decontamination ratio for each sample. Table 2 shows that detergents S1, S2, and S3 have high oil removal rates, significantly higher than the stain removal rates of standard detergents, and their stain removal ratios are significantly higher than 1.05, indicating that the detergents obtained by the technical solution of this invention have extremely strong hard water cleaning capabilities. This is due to the targeted decomposition of grease, protein, and starch stains by the microencapsulated complex enzymes, and the highly efficient chelating and dispersing ability of the compound chelating agent for calcium and magnesium ions in hard water, effectively protecting the cleaning efficacy of the surfactants.

[0071] In the comparative examples, D1 and D2, using a single chelating agent, showed a lower detergency ratio compared to S1. This indicates that the combination of tetrasodium iminodisuccinate and the graft copolymer achieves complementary chelation and dispersion functions. A single chelating agent cannot simultaneously achieve efficient water softening and prevention of redeposition of dirt, resulting in a decrease in detergency. In D3, replacing sodium maleic acrylate copolymer with sodium polyacrylate resulted in a lower detergency ratio than S1, indicating that sodium maleic acrylate copolymer is more effective in improving chelation efficiency and cannot achieve the same synergistic effect when combined with tetrasodium iminodisuccinate. In D4, changing the surfactant system resulted in a lower detergency ratio compared to S1, indicating that the surfactant selected in this invention has better emulsification and dispersion capabilities in hard water, making it more suitable for removing complex oil stains. D5, without encapsulated complex enzymes, had the lowest detergency ratio. This is because lipase and amylase are protein enzymes, and in the unencapsulated state, the protease will hydrolyze them, leading to a loss of activity and reducing the lipase's ability to decompose grease. This weakens the decomposition of grease stains, and relying solely on surfactants for cleaning significantly reduces detergency.

[0072] The above data demonstrates that this invention has a highly efficient cleaning effect under hard water conditions. Its core lies in the synergistic effect of microencapsulated complex enzymes, compound chelating agents, and surfactant systems, which achieves rapid decomposition of complex stains, effective shielding against hard water ions, and inhibition of dirt redeposition, significantly improving the overall cleaning performance of the detergent and meeting the cleaning needs in complex scenarios.

[0073] Experimental Example 3 Sensory evaluation test This experiment conducted sensory evaluation tests on the dishwashing liquids prepared in Examples 1-3 (S1, S2, S3) and Comparative Examples 1-5 (D1, D2, D3, D4, D5) from four perspectives: appearance, odor, foaming performance, and rinsing performance.

[0074] Twenty individuals with experience using dishwashing detergent (10 men and 10 women, aged 20-30) were selected, with no olfactory impairments, skin allergies, or other issues. They received standardized training on assessment criteria and procedures before the evaluation.

[0075] The weights and scoring details for the four evaluation dimensions are as follows: Total score = Appearance score + Odor score + Foam performance score + Rinse performance score. The higher the score, the better the sensory experience.

[0076] 1. Appearance (10 points) Evaluation conditions: The original sample solution was observed under natural light at a room temperature of 25℃.

[0077] 9-10 points: Uniform and transparent liquid, without layering, sediment, flocculent matter, or turbidity, and with uniform color; 6-8 points: Basically transparent, with slight flocculent matter / small amount of sediment, no layering, and basically uniform color; 0-5 points: Severely turbid, with a large amount of sediment / obvious layering, and uneven color.

[0078] 2. Odor (20 points) Evaluation criteria: Take 5 mL of sample into a beaker and gently smell the odor.

[0079] 18-20 points: The scent is fresh and gentle, without any pungent or unpleasant odors, and the fragrance lingers. 14-17 points: The scent is relatively fresh, slightly pungent / no odor, and the fragrance lasts for a moderate amount of time; 10-13 points: The scent is average, with a slight off-odor, and the fragrance is strong / weak. 0-9 points: The odor is pungent and has a distinct odor (such as rancid or chemical smell).

[0080] 3. Foam performance (30 points) Evaluation procedure: Dissolve 2g of sample in 500mL of 250mg / L hard water, stir with a glass rod at 200r / min for 30s, let stand for 1min and observe the foam height and fineness.

[0081] 27-30 minutes: Foam height ≥ 5cm, fine and dense foam, not easy to defoam; 21-26 points: Foam height 3-5cm, foam is relatively fine, slight defoaming; 15-20 minutes: Foam height 1-3cm, coarse foam, defoams quickly; 0-14 points: Foam height <1cm, basically no foam / rapid defoaming.

[0082] 4. Rinsing performance (40 points) Evaluation procedure: Wash the standard porcelain bowl with mixed oil stains with the above diluted solution for 10 seconds, then rinse with tap water (flow rate 2L / min), and record the amount of rinsing water used when the bowl wall is free of foam and slippery feeling.

[0083] 36-40 points: Rinse with ≤200mL of water, no foam, no slippery feeling, and no residue on the bowl wall; 28-35 minutes: Use 200-300mL of water for rinsing. There should be a small amount of foam on the bowl wall. After rinsing lightly, there should be no slippery feeling. 20-27 minutes: Use 300-400mL of water for rinsing. There will be a lot of foam on the bowl wall. After rinsing several times, there will be no slippery feeling. 0-19 points: Rinse with more than 400mL of water, produce a lot of foam on the bowl wall, and still feel noticeably slippery after rinsing, with residue.

[0084] The evaluation results are the average scores of the 20 evaluators. The specific scores for each sample and the total score are shown in Table 3.

[0085] Table 3 Sensory evaluation results (scores) for each sample Table 3 shows that the dishwashing liquids prepared by S1, S2, and S3 of this invention have a far superior sensory experience compared to the comparative products. Furthermore, the scores of the samples from the three examples are similar, indicating excellent overall sensory quality. The dishwashing liquid of this invention is uniform, transparent, and free of impurities. It has a fresh, mild, and odorless scent, produces high-quality, fine, and dense foam, requires ≤200mL of rinsing water, and leaves no residue or slippery feeling. This is attributed to the anti-deposition properties of the compound chelating agent and the easy-rinsing characteristics of the surfactant.

[0086] D1-D3 showed slight impurities and decreased rinsing performance due to the replacement of a single chelating agent or sodium maleate copolymer with sodium polyacrylate, indicating that specific chelating agent combinations play a key role in the system's compatibility and rinsing effect. D4 showed a decline in odor, foam, and rinsing performance after changing the surfactant system, proving that the surfactant combination system selected in this invention is more suitable for sensory experience. D5 had the lowest appearance score due to turbidity and precipitation caused by the lack of encapsulation of the complex enzyme, and the enzyme inactivation affected the cleaning effect, resulting in the worst foam and rinsing performance, indicating that the microencapsulation process has a significant impact on the overall sensory experience of the product.

[0087] The above data demonstrates that the compound chelating agent, microencapsulated complex enzyme, and surfactant system of the present invention not only ensures the detergent's high cleaning efficiency but also achieves comprehensive improvements in appearance, odor, foaming performance, and rinsing performance.

[0088] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A highly effective stain-removing dishwashing liquid, characterized in that, By weight percentage, it contains the following components: 0.8%-1.2% microencapsulated complex enzyme, 0.5%-1% chelating agent, 10%-15% surfactant, 1%-3% auxiliary agent, and the balance is water; The active components of the microencapsulated complex enzyme consist of lipase, protease, and amylase. The chelating agent is composed of tetrasodium iminodisuccinate and sodium salt of maleic acid acrylate copolymer.

2. The detergent according to claim 1, characterized in that, The mass ratio of the tetrasodium iminodisuccinate to the sodium salt of the maleic acrylate copolymer is (1-3):

1.

3. The detergent according to claim 1, characterized in that, The microencapsulated complex enzyme is composed of microencapsulated lipase, microencapsulated protease and microencapsulated amylase in a mass ratio of 1:(1-1.5):(0.5-1).

4. The detergent according to claim 3, characterized in that, The preparation method of the microencapsulated complex enzyme includes: mixing lipase, protease, and amylase with sodium alginate aqueous solution to obtain an aqueous suspension; mixing Span 80 with vegetable oil to obtain an oil phase; emulsifying the aqueous suspension and oil phase to obtain an emulsion; adding calcium chloride solution and chitosan acetate solution for solidification; filtering; drying the precipitate to obtain microencapsulated lipase, microencapsulated protease, and microencapsulated amylase, which are then mixed.

5. The detergent according to claim 4, characterized in that, The mass ratio of Span 80 to vegetable oil is 1:(5-10).

6. The detergent according to claim 4, characterized in that, The volume ratio of the aqueous suspension to the oil phase is 1:(4-6).

7. The detergent according to claim 1, characterized in that, The surfactant includes at least one of sodium fatty acid methyl ester sulfonate, alkyl glycoside 1214, and cocamidopropyl betaine.

8. The detergent according to claim 1, characterized in that, The additives include at least one of thickeners, preservatives, fragrances, and humectants.

9. A method for preparing a dishwashing liquid according to any one of claims 1-8, characterized in that, include: After mixing the chelating agent with water, surfactants, additives, and microencapsulated complex enzymes are added in sequence to obtain dishwashing liquid.

10. An application of the detergent according to any one of claims 1-8, characterized in that, The dishwashing liquid is used for cleaning tableware and fruits and vegetables.

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