Cleaning composition and preparation method thereof

Abstract

The invention discloses a cleaning composition and a preparation method thereof, and belongs to the technical field of daily chemical detergents. The cleaning composition disclosed by the invention is prepared from the following components in percentage by mass: 20 to 30 percent of a ternary compound surfactant, 8 to 10 percent of an oil stain directional cleaning agent, 2 to 3 percent of a color fixative composition, 1 to 5 percent of a solvent synergist, 0.8 to 1.2 percent of a bactericide, 1.5 to 3 percent of a microcapsule coated enzyme preparation, 0.2 to 0.5 percent of a pH regulator, 0.1 to 0.3 percent of a preservative and the balance of deionized water. The cleaning composition solves the technical problem that an existing cleaning agent is difficult to meet efficient decontamination, long-acting color protection and component compatibility at the same time.

Description

Technical Field

[0001] This invention belongs to the field of daily chemical detergent technology, specifically relating to a cleaning composition and its preparation method. Background Technology

[0002] Cleaning compositions are widely used in industry and households. Their core function is to synergistically remove stains and protect the substrate through surfactants and additives. In industry, equipment and tooling in machining and mining environments are prone to stubborn oil stains such as kerosene and coal dust. Incomplete cleaning can affect equipment precision and even pose safety hazards. In households, such oil stains on kitchen surfaces and clothing are also difficult to remove. Today, in addition to their stain-removing power, cleaning products are increasingly demanding in terms of color protection for clothing and colored parts. Furthermore, the need for sterilization in food processing and other fields is growing due to increased health awareness, making sterilizing ingredients a crucial component of formulations.

[0003] Traditional cleaning methods present significant challenges. To remove stubborn oil stains, products often rely on high concentrations of strong alkalis (such as sodium hydroxide) or organic solvents (such as petroleum ether), which, while effective at removing stains, readily react with dyes, causing fading. In terms of sterilization, commonly used quaternary ammonium compounds (QACs, nitrogen-containing cationic surfactants) can disrupt the spatial structure of enzymes (such as proteases), rendering them inactive. Furthermore, residues of strong alkalis and organic solvents can interfere with industrial processing or irritate the skin, triggering allergies.

[0004] Existing technologies have made attempts to improve the problem: In terms of color protection, physical color protection uses polymers (such as PVP) to form a protective film, but it is easy to fall off; chemical color protection uses metal chelating agents to stabilize dyes, but it is not resistant to strong alkalis; the residue problem is solved by reducing the concentration of chemical substances and compounding surfactants to make up for the detergency; the compatibility problem is solved by using microcapsule spatial isolation or step-by-step release technology to avoid the action of quaternary ammonium salts and enzyme preparations.

[0005] However, existing solutions still have limitations: color-protecting technologies have short-lived effects or poor adaptability, concentration-reducing solutions sacrifice cleaning power for heavy oil stains, and microencapsulation technology is complex, costly, and results in insufficient ingredient release. Current formulations consistently struggle to balance high-efficiency cleaning, long-lasting color protection, ingredient compatibility, and low residue, making the development of cleaning compositions that meet multiple needs a pressing challenge for the industry. Summary of the Invention

[0006] The purpose of this invention is to provide a cleaning composition and its preparation method, in order to solve the technical problem that existing cleaning agents cannot simultaneously meet the requirements of high-efficiency stain removal, long-lasting color protection, and ingredient compatibility.

[0007] To achieve the above objectives, the present invention employs the following technical solution: This invention discloses a cleaning composition, wherein the components of the cleaning composition, by weight percentage, comprise: The mixture consists of 20-30% ternary compound surfactant, 8-10% oil stain targeted cleaner, 2-3% color protectant combination, 1-5% solvent synergist, 0.8-1.2% bactericide, 1.5-3% microencapsulated enzyme preparation, 0.2-0.5% pH adjuster, and 0.1-0.3% preservative, with the balance being deionized water.

[0008] Furthermore, the ternary compound surfactant comprises nonionic surfactants, anionic surfactants, and amphoteric surfactants; The oil stain targeted cleaner is polypropylene terephthalate modified with siloxane groups; The color-protecting agent composition comprises polyvinylpyrrolidone and an acrylic acid copolymer; the acrylic acid copolymer is an acrylic acid / maleic anhydride copolymer.

[0009] Furthermore, the nonionic surfactant is an alkyl glycoside; the anionic surfactant is sodium fatty alcohol polyoxyethylene ether sulfate; and the amphoteric surfactant is cocamidopropyl betaine. In the ternary compound surfactant, the mass ratio of nonionic surfactant, anionic surfactant and amphoteric surfactant is (10~18):(5~10):(3~5).

[0010] Furthermore, the molecular weight of the siloxane-modified polypropylene terephthalate is 2000~5000 Da; In the color-protecting agent combination, the mass ratio of polyvinylpyrrolidone to acrylic copolymer is (0.5~1):(1.5~2).

[0011] Furthermore, the solvent synergist is propylene glycol; The bactericide is a composition of tea tree oil, pine needle oil, and cedarwood oil; The microcapsule-encapsulated enzyme preparation is formed by encapsulating a complex enzyme in sodium alginate-chitosan / hydroxypropyl methylcellulose bilayer microcapsules; the complex enzyme is composed of protease, lipase, amylase and other enzymes; the other enzymes are a combination of cellulase, mannanase, pectinase and laccase; The pH adjuster is a mixture of sodium citrate and sodium hydroxide; the preservative is phenoxyethanol.

[0012] Furthermore, in the complex enzyme, the mass ratio of the protease, lipase, amylase and other enzymes is (15~25):(10~20):(5~10):(5~15).

[0013] The present invention also discloses a method for preparing the above-mentioned cleaning composition, comprising the following steps: S1: After heating water, add ternary compound surfactant, oil stain targeted cleaner and solvent synergist in sequence, stir to obtain solution A; S2: Then, add the color-protecting agent combination to solution A, stir, and obtain solution B; S3: Add the enzyme preparation encapsulated in microcapsules to solution B, and adjust the pH value with a pH adjuster to obtain solution C; S4: Add bactericide and preservative to solution C, stir, and obtain solution D; S5: The solution D is subjected to high-pressure homogenization to obtain a clean composition.

[0014] Furthermore, the water heating temperature is 40~50℃; the stirring speed is 200~300rpm, and the time is 20~30min; In S2, solution A is cooled to below 30°C, and then a color-protecting agent combination is added; the stirring speed is 100~150 rpm; In S3, the pH value is adjusted to 7-9 using a pH adjuster; In S5, the pressure of the high-pressure homogenization process is 20~30MPa, and the number of cycles is 2~3.

[0015] Furthermore, the method for preparing the microcapsule-encapsulated enzyme preparation includes the following steps: The complex enzyme was dissolved in phosphate buffer to obtain an enzyme solution; then the enzyme solution was mixed with sodium alginate solution to obtain an enzyme-sodium alginate mixture; then the enzyme-sodium alginate mixture was homogenized and emulsified and dropped into CaCl2 solution for cross-linking and solidification to obtain calcium alginate gel microspheres. Calcium alginate gel microspheres were placed in a chitosan solution, and the chitosan layer was coated by electrostatic adsorption to obtain gel microspheres coated with chitosan layer. The obtained chitosan-coated gel microspheres were added to a hydroxypropyl methylcellulose solution, followed by the addition of anhydrous ethanol for separation and deposition. After solidification and washing, microcapsules were obtained. The microcapsules were pre-frozen and freeze-dried sequentially to obtain the enzyme preparation encapsulated in microcapsules.

[0016] Furthermore, the pH value of the phosphate buffer solution is 6-7; the mass concentration of the enzyme solution is 10-15%. The mass ratio of the enzyme solution to the sodium alginate solution is 1:(2.5~3.5); the mass concentration of the sodium alginate solution is 1.8%~2.2%; the mass concentration of the CaCl2 solution is 1.3%~1.7%; and the volume ratio of the enzyme-sodium alginate mixture to the CaCl2 solution is 1:(3~5). The mass ratio of calcium alginate gel microspheres to chitosan solution is 1:(4~6); the chitosan solution has a pH of 5.0~5.5 and a mass concentration of 0.7%~0.9%. The mass ratio of the chitosan-coated gel microspheres to the hydroxypropyl methylcellulose solution is 1:(3~5); the mass concentration of the hydroxypropyl methylcellulose solution is 2.5~3.5%. The anhydrous ethanol is added at a rate ≤5 mL / min; the volume of anhydrous ethanol added is 1.8 to 2.2 times the volume of the chitosan-coated gel microspheres; the separation and deposition temperature is 28 to 32 °C. The pre-freezing temperature is -42 to -38°C, and the time is 3.5 to 4.5 hours; the freeze-drying parameters are freeze-drying at -52 to -48°C and 0.08 to 0.12 mbar for 23 to 25 hours.

[0017] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a cleaning composition comprising a system including a ternary compound surfactant, an oil-specific cleaner, a color-protecting agent combination, a solvent synergist, a bactericide, a microencapsulated enzyme preparation, a pH adjuster, and a preservative. The ternary compound surfactant and the nonionic polyester oil-specific cleaner work synergistically to effectively embed stain molecules into the hydrophobic core of micelles, improving the emulsification efficiency of hydrophobic stains. The color-protecting agent combination stabilizes the color-protecting agent structure through a dynamic charge cross-linking network, enabling the color-protecting agent to effectively exert its dual mechanism of adsorbing dyes and chelating metal ions. It also works synergistically with the ternary compound surfactant and the nonionic polyester oil-specific cleaner to prevent color-protecting agent migration and micelle stability degradation, maintaining a three-phase balance between micelles, stains, and fabric. The microencapsulated enzyme preparation uses a physical barrier to block enzyme degradation and delay premature enzyme inactivation, solving the technical problem that existing cleaners cannot simultaneously meet the requirements of high-efficiency stain removal, long-lasting color protection, and component compatibility.

[0018] Furthermore, according to relevant experimental results, it has been proven that by using alkyl glycosides, sodium fatty alcohol polyoxyethylene ether sulfate and cocamidopropyl betaine to form a ternary compound surfactant, the final cleaning composition has a micelle size of 40±2nm, a high specific surface area to enhance the oil adsorption capacity, and a comprehensive decontamination index Pi value of 1.55.

[0019] Furthermore, according to relevant experimental results, the use of polyvinylpyrrolidone-acrylic acid / maleic anhydride copolymer color-protecting agent combination can maintain the three-phase balance of micelles-stains-fabric and achieve a color difference ΔE=2.4 after 50 washes, thus overcoming the color-protecting failure problem caused by the competitive adsorption of surfactants in traditional color-protecting agents.

[0020] Furthermore, according to relevant experimental results, the use of sodium alginate-chitosan / hydroxypropyl methylcellulose bilayer microcapsule technology to encapsulate the complex enzyme resulted in an activity retention rate of up to 94% after storage at 40℃ for 6 months, an improvement of 108.9% compared to the unencapsulated system. The bilayer microcapsule encapsulation technology extended the enzyme's action time, improved stain decomposition efficiency, and increased the overall stain removal index (Pi) by 53.5% compared to the unencapsulated system. Detailed Implementation

[0021] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0022] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0023] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0024] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0025] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0026] This invention provides a cleaning composition, which, by mass percentage, comprises: 20-30% ternary compound surfactant, 8-10% oil stain targeted cleaner, 2-3% color protection agent combination, 1-5% solvent synergist, 0.8-1.2% bactericide, 1.5-3% microencapsulated enzyme preparation, 0.2-0.5% pH adjuster, 0.1-0.3% preservative, and the balance being deionized water.

[0027] Preferably, the ternary compound surfactant comprises a nonionic surfactant, anionic surfactant, and amphoteric surfactant; the oil stain targeted cleaner is siloxane-modified polypropylene terephthalate; the color-protecting agent combination comprises a copolymer of polyvinylpyrrolidone and acrylic acid; the solvent synergist is propylene glycol; the bactericide is a combination of tea tree oil, pine needle oil, and cedarwood oil; the microcapsule-encapsulated enzyme preparation is formed by encapsulating a complex enzyme in sodium alginate-chitosan / hydroxypropyl methylcellulose bilayer microcapsules, the complex enzyme being composed of protease, lipase, amylase, and other enzymes, wherein the other enzymes are a combination of cellulase, mannanase, pectinase, and laccase; the pH adjuster is a mixture of sodium citrate and sodium hydroxide; and the preservative is phenoxyethanol.

[0028] Preferably, the nonionic surfactant is an alkyl glycoside, the anionic surfactant is sodium fatty alcohol polyoxyethylene ether sulfate, and the amphoteric surfactant is cocamidopropyl betaine; wherein the mass ratio of the nonionic surfactant, the anionic surfactant, and the amphoteric surfactant is 10~18:5~10:3~5.

[0029] Preferably, the molecular weight of the siloxane-modified polypropylene terephthalate is 2000~5000 Da.

[0030] Preferably, in the color-protecting agent combination, the mass ratio of polyvinylpyrrolidone to acrylic copolymer is 0.5~1:1.5~2; the acrylic copolymer is an acrylic acid / maleic anhydride copolymer.

[0031] Preferably, in the complex enzyme, the mass ratio of protease, lipase, amylase, and other enzymes is 15~25:10~20:5~10:5~15.

[0032] Preferably, the microcapsule-encapsulated enzyme preparation is prepared by the following steps: S1. Dissolve the complex enzyme in a phosphate buffer solution with pH 6-7 to prepare a 10-15% enzyme solution, and mix it with a 1.8%-2.2% sodium alginate solution at a mass ratio of 1:(2.5-3.5) to obtain an enzyme-sodium alginate mixture; then, after homogenization and emulsification, the enzyme-sodium alginate mixture is dropped into a 1.3%-1.7% CaCl2 solution for cross-linking and solidification to form calcium alginate gel microspheres. The volume ratio of the enzyme-sodium alginate mixture to the CaCl2 solution is 1:(3-5). S2. The calcium alginate gel microspheres obtained in S1 are placed in a 0.7-0.9% chitosan solution with pH=5.0-5.5, and the chitosan layer is coated by electrostatic adsorption. The mass ratio of the calcium alginate gel microspheres to the chitosan solution is 1:(4-6). S3. The chitosan-coated gel microspheres obtained in S2 were added to a 2.5-3.5% hydroxypropyl methylcellulose solution at a mass ratio of 1:(3-5). Anhydrous ethanol, 1.8-2.2 times the volume of the microspheres, was added at a rate of ≤5 mL / min. The hydroxypropyl methylcellulose solution was induced to separate and deposit at 28-32℃. After solidification, the residual solvent was washed away. S4. The microcapsules obtained in S3 are pre-frozen at -42~-38℃ for 3.5~4.5h, freeze-dried at -52~-48℃ and 0.08~0.12mbar for 23~25h, and then passed through an 80~120 mesh sieve to obtain the microcapsule-encapsulated enzyme preparation.

[0033] The present invention also discloses a method for preparing the above-mentioned cleaning composition, comprising the following steps: Step 1: Heat deionized water to 40~50℃, add ternary compound surfactant, oil stain targeted cleaner and solvent synergist, stir until completely dissolved to obtain solution A; Step 2: Cool solution A to below 30°C, add the color-protecting agent combination, stir at low speed until well mixed, and obtain solution B; Step 3: Add the microencapsulated enzyme preparation to solution B, and then adjust the pH to 7-9 with a pH adjuster to obtain solution C; Step 4: Add bactericide and preservative to solution C, stir for 5 minutes to obtain solution D; Step 5: Process solution D through a high-pressure homogenizer to form nanomicelles with a particle size ≤50nm, and cool to room temperature to obtain a clean composition.

[0034] Preferably, the stirring speed in step one is 200~300 rpm and the time is 20~30 min; the stirring speed in step two is 100~150 rpm; and the pressure of the high-pressure homogenizer in step five is 20~30 MPa, and the number of cycles is 2~3.

[0035] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0036] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0037] The specific components and corresponding mass percentages of the cleaning compositions in Examples 1 to 7 of the present invention are shown in Tables 1 and 2. Table 1 shows the components and corresponding mass percentages of each cleaning composition in Examples 1 to 5; Table 2 shows the differences between the components and corresponding mass percentages of the cleaning compositions in Examples 6 and 7 and those in Example 1.

[0038] Table 1. Components and corresponding mass percentages of each cleaning composition in Examples 1-5.

[0039] Table 2. Differences between the components and corresponding mass percentages of the cleaning compositions in Examples 6 and 7 and those in Example 1.

[0040] The preparation methods for the cleaning compositions of Examples 1 to 3, according to the components and percentages in Table 1, include the following steps: Step 1: Heat deionized water to 45°C, add ternary compound surfactant, oil stain targeted cleaner and solvent synergist, stir until completely dissolved to obtain solution A; wherein, the oil stain targeted cleaner is polypropylene terephthalate modified with siloxane groups, and the molar percentage of siloxane groups therein is 5%; Step 2: Cool solution A to below 30°C, add the color-protecting agent combination, stir at low speed until well mixed, and obtain solution B; Step 3: Add the microencapsulated enzyme preparation to solution B, and then adjust the pH to 8 with a pH adjuster to obtain solution C; Step 4: Add bactericide and preservative to solution C, stir for 5 minutes to obtain solution D; Step 5: Process solution D through a high-pressure homogenizer to form nanomicelles with a particle size ≤50nm, and cool to room temperature to obtain a clean composition; In step 1, the stirring speed is 250 rpm and the time is 25 min; in step 2, the stirring speed is 125 rpm; in step 5, the pressure of the high-pressure homogenizer is 25 MPa and the number of cycles is 3. The microcapsule-encapsulated enzyme preparation in step 3 is prepared through the following steps: Step 1: Under conditions of ≤25℃, mix the compound enzymes according to the mass ratio and dissolve them in phosphate buffer solution with pH=6.5 to prepare a 13% enzyme solution; mix the enzyme solution with 2.0% sodium alginate solution at a mass ratio of 1:3, homogenize and emulsify at 2000rpm for 10min, and add the resulting emulsion dropwise to 1.5% CaCl2 solution at a volume ratio of 1:4, and stir at 300rpm for 30min to form calcium alginate gel microspheres; Step 2: Place the calcium alginate gel microspheres obtained in Step 1 into a 0.8% chitosan solution (solvent is 1% acetic acid) at pH=5.3 and stir at 150 rpm for 40 min to coat the chitosan layer by electrostatic adsorption. The mass ratio of the calcium alginate gel microspheres to the chitosan solution is 1:5. Step 3: Add the chitosan-coated gel microspheres obtained in Step 2 to a 3% hydroxypropyl methylcellulose solution prepared at 60℃ and cooled to 30℃ at a mass ratio of 1:4, and mix thoroughly at 500 rpm; then add anhydrous ethanol at a rate of ≤5 mL / min, 2 times the volume of the microspheres, and induce phase separation and deposition of the hydroxypropyl methylcellulose solution at 30℃, and continue stirring for 60 min. After filtration, wash three times with deionized water pre-cooled at 4℃. Step 4: Pre-freeze the microcapsules obtained in Step 3 at -40℃ for 4 hours, freeze-dry them at -50℃ and 0.1mbar for 24 hours, and pass them through an 80~120 mesh sieve to obtain the double-layer microcapsule enzyme preparation.

[0041] The preparation methods of the cleaning compositions of Examples 4 and 5, according to the components and percentages in Table 1, include the following steps: Step 1: Heat deionized water to 40°C, add ternary compound surfactant, oil stain targeted cleaner, and solvent synergist, and stir until completely dissolved to obtain solution A; wherein, the oil stain targeted cleaner is polypropylene terephthalate modified with siloxane groups, and the molar percentage of siloxane groups therein is 5%; Step 2: Cool solution A to below 30°C, add the color-protecting agent combination, stir at low speed until well mixed, and obtain solution B; Step 3: Add the microencapsulated enzyme preparation to solution B, and then adjust the pH to 7 with a pH adjuster to obtain solution C; Step 4: Add bactericide and preservative to solution C, stir for 5 minutes to obtain solution D; Step 5: Process solution D through a high-pressure homogenizer to form nanomicelles with a particle size ≤50nm, and cool to room temperature to obtain a clean composition; In step 1, the stirring speed is 200 rpm and the time is 20 min; in step 2, the stirring speed is 100 rpm; in step 5, the pressure of the high-pressure homogenizer is 20 MPa and the number of cycles is 2. The microcapsule-encapsulated enzyme preparation in step 3 is prepared through the following steps: Step 1: Under conditions of ≤25℃, mix the compound enzymes according to the mass ratio and dissolve them in phosphate buffer solution with pH=6 to prepare a 10% enzyme solution; mix the enzyme solution with 1.8% sodium alginate solution at a mass ratio of 1:2.5, homogenize and emulsify at 2000rpm for 10min, and add the resulting emulsion dropwise to 1.3% CaCl2 solution at a volume ratio of 1:3, and stir at 300rpm for 30min to form calcium alginate gel microspheres; Step 2: Place the calcium alginate gel microspheres obtained in Step 1 into a 0.7% chitosan solution (solvent is 1% acetic acid) at pH=5 and stir at 150 rpm for 40 min to coat the chitosan layer by electrostatic adsorption. The mass ratio of the calcium alginate gel microspheres to the chitosan solution is 1:4. Step 3: Add the chitosan-coated gel microspheres obtained in Step 2 to a 2.5% hydroxypropyl methylcellulose solution prepared at 60℃ and cooled to 30℃ at a mass ratio of 1:3, and mix thoroughly at 500 rpm; then add 1.8 times the volume of anhydrous ethanol of the microspheres at a rate of ≤5 mL / min, induce phase separation and deposition of the hydroxypropyl methylcellulose solution at 28℃, and continue stirring for 60 min. After filtration, wash three times with deionized water pre-cooled at 4℃. Step 4: Pre-freeze the microcapsules obtained in Step 3 at -42℃ for 3.5h, freeze-dry them at -52℃ and 0.08mbar for 23h, and pass them through an 80~120 mesh sieve to obtain the double-layer microcapsule enzyme preparation.

[0042] The preparation method of the cleaning compositions of Examples 6 and 7, according to the components and percentages in Table 2, includes the following steps: Step 1: Heat deionized water to 50°C, add a ternary compound surfactant, an oil stain-specific cleaner, and a solvent synergist, and stir until completely dissolved to obtain solution A; wherein, the oil stain-specific cleaner is polypropylene terephthalate modified with siloxane groups, and the molar percentage of siloxane groups therein is 5%; Step 2: Cool solution A to below 30°C, add the color-protecting agent combination, stir at low speed until well mixed, and obtain solution B; Step 3: Add the microencapsulated enzyme preparation to solution B, and then adjust the pH to 9 with a pH adjuster to obtain solution C; Step 4: Add bactericide and preservative to solution C, stir for 5 minutes to obtain solution D; Step 5: Process solution D through a high-pressure homogenizer to form nanomicelles with a particle size ≤50nm, and cool to room temperature to obtain a clean composition; In step 1, the stirring speed is 300 rpm and the time is 30 min; in step 2, the stirring speed is 150 rpm; in step 5, the pressure of the high-pressure homogenizer is 30 MPa and the number of cycles is 3. The microcapsule-encapsulated enzyme preparation in step 3 is prepared through the following steps: Step 1: Under conditions of ≤25℃, mix the compound enzymes according to the mass ratio and dissolve them in phosphate buffer solution with pH=7 to prepare a 15% enzyme solution; mix the enzyme solution with 2.2% sodium alginate solution at a mass ratio of 1:3.5, homogenize and emulsify at 2000rpm for 10min, and add the resulting emulsion dropwise to 1.7% CaCl2 solution at a volume ratio of 1:5, and stir at 300rpm for 30min to form calcium alginate gel microspheres; Step 2: Place the calcium alginate gel microspheres obtained in Step 1 into a 0.9% chitosan solution (solvent is 1% acetic acid) at pH=5.5 and stir at 150 rpm for 40 min to coat the chitosan layer by electrostatic adsorption. The mass ratio of the calcium alginate gel microspheres to the chitosan solution is 1:6. Step 3: Add the chitosan-coated gel microspheres obtained in Step 2 to a 3.5% hydroxypropyl methylcellulose solution prepared at 60℃ and cooled to 30℃ at a mass ratio of 1:5, and mix thoroughly at 500 rpm; then add anhydrous ethanol at a rate of ≤5 mL / min, 2.2 times the volume of the microspheres, and induce phase separation and deposition of the hydroxypropyl methylcellulose solution at 32℃, and continue stirring for 60 min. After filtration, wash three times with deionized water pre-cooled at 4℃. Step 4: Pre-freeze the microcapsules obtained in Step 3 at -38℃ for 4.5h, freeze-dry them at -48℃ and 0.12mbar for 25h, and pass them through an 80~120 mesh sieve to obtain the double-layer microcapsule enzyme preparation.

[0043] The differences between Comparative Examples 1 to 10 and Embodiment 1 of the present invention are shown in Table 3.

[0044] Table 3 clearly indicates the differences between Comparative Examples 1 to 10 and Example 1.

[0045] The cleaning compositions of Comparative Examples 1 to 10 were prepared using the same method as in Example 1.

[0046] The cleaning compositions of Examples 1 to 7 and Comparative Examples 1 to 10 were subjected to performance index tests, and the test methods involved are as follows: 1) Detergent strength test (Pi value) Standard basis: GB / T 13174-2021 "Determination of detergency and recycle performance of detergents for clothing" Equipment and reagents: Stain removal tester: Model QW-12, speed 120r / min, temperature 40±1℃; Artificial soiled cloths: carbon black soiled cloth (JB-01), protein soiled cloth (JB-03), sebum soiled cloth (JB-05), purchased from China Daily Chemical Research Institute; Water quality: Hardness (150±5) ppm (calculated as CaCO3); Operating steps: 1. Cut the soiled cloth into 5cm×5cm samples and weigh them (accurate to 0.1mg). 2. Prepare a 0.2% cleaning composition solution (150 ppm hard water) with a bath ratio of 1:30; 3. Immerse the soiled cloth in the solution and mechanically stir at 40°C for 20 minutes; 4. After rinsing and drying, measure the reflectance (R value) using a WSB-3A whiteness meter. 5. Calculate the detergency value Pi: Pi = (R1 – R0) / (R2 – R0), where R0 is the reflectance of the unwashed soiled cloth, R1 is the reflectance of the sample after washing, and R2 is the reflectance of the standard laundry detergent (the reference material specified in GB / T13174) after washing. The weights for carbon black soiled cloths are set to 0.50, protein soiled cloths to 0.25, and sebum soiled cloths to 0.25. The overall detergency value is the weighted average of the detergency values ​​of each soiled cloth.

[0047] 2) Color difference test (ΔE) Standard based on: ISO 105-C06:2023 "Textiles – Tests for color fastness – Part C06: Color fastness to domestic and commercial washing" Equipment and parameters: Spectrophotometer: Datacolor 650, D65 light source, 10° observation angle; Washing equipment: Launder-Ometer type color fastness tester for washing; Operating steps: 1. Cut a 10cm × 4cm sample of dark-colored cotton fabric (dyed with CI Direct Black 38); 2. Prepare a 0.2% cleaning composition solution (40℃) with a liquor ratio of 1:50; 3. Place the sample in a stainless steel container, add 25 stainless steel balls, seal and place in the testing machine, wash at 45℃ for 30 minutes; 4. Repeat the washing-drying cycle 50 times; 5. Use a colorimeter to measure the L (light / dark), a (red / green), and b (yellow / blue) values ​​before and after washing, and calculate the color difference. .

[0048] 3) Enzyme activity retention rate test Standard basis: Taking lipase as an example, GB / T 23535-2009 "Lipase Preparations"; Equipment and reagents: Spectrophotometer: UV-2600, λ=410nm; Substrate: p-nitrophenol ester (p-NPP) solution (5 mmol / L, pH 8.0 Tris-HCl buffer); Operating steps: 1. Take 0.1 mL of enzyme preparation solution (diluted to a suitable concentration), add 2.9 mL of substrate solution, and react at 37℃ for 10 min; 2. Immediately add 0.5 mL of 0.5 mol / L NaOH to terminate the reaction; 3. Measure the absorbance at 410 nm and calculate the enzyme activity (U / mL) based on the standard curve. 4. Calculate the retention rate: Enzyme activity retention rate (%) = (activity after storage / initial activity) × 100 (storage conditions: 40℃, 6 months).

[0049] 4) Nanomicelle particle size stability test Equipment and parameters: Dynamic light scattering instrument: Malvern Zetasizer Nano ZS90; Sample cell: polystyrene cuvette, optical path 10mm; Operating steps: 1. Dilute the cleaning composition to 0.1% (deionized water) and ultrasonically disperse for 10 min (40 kHz, 100 W). 2. Pour the sample into a cuvette and equilibrate at 25°C for 2 minutes; 3. Set the scattering angle to 173°, the measurement time to 120 seconds, and repeat 3 times; 4. Use software (Zetasizer Software 7.13) to analyze the particle size distribution and obtain the Z-average value.

[0050] The detergency and color-protection test data are shown in Table 4. As can be seen from the data in Table 4, the overall detergency index of Examples 1 to 7 of the present invention is ≥1.43, the micelle size is ≤45±3nm, and the color protection ΔE is ≤3.0. The hydroxyl groups of alkyl glycosides and the siloxane groups of nonionic polyester form a directional adsorption network, which significantly improves the emulsification efficiency of hydrophobic stains. At the same time, it avoids charge competition with the color-protecting agent polyvinylpyrrolidone, so that the color-protecting agent can effectively exert the dual mechanism of adsorbing dyes and chelating metal ions. All examples show excellent overall detergency and color protection effects.

[0051] Table 4. Data from stain removal power test and color protection function test.

[0052] Based on the data in Table 4, Example 1 exhibits the best overall performance among all embodiments. Therefore, the following comparative examples were set up based on Example 1, and tests were conducted on detergency and color protection effects. The test data are shown in Table 5.

[0053] Table 5 Comparison of Stain Removal Power and Color Protection Test Data

[0054] According to the data in Table 5, in Comparative Example 1, the micelle size increased to 152±9 nm with the oil-free directional cleaner, and the Pi value dropped sharply from 1.55 to 0.65; in Comparative Example 2, when the alkyl glycoside was replaced with linear alkylbenzene sulfonate, the micelles became loose (206±15 nm), and the color protection ΔE value deteriorated to 5.3. This is due to the sulfonic acid group (-SO3) of the linear alkylbenzene sulfonate. - The alkyl groups of nonionic polyester lack chemical complementarity and exhibit charge repulsion with the color-protecting agent polyvinylpyrrolidone, thus disrupting the color-protecting system. In Comparative Example 3, replacing the alkyl glycoside with fatty alcohol polyoxyethylene ether resulted in a sharp drop in the Pi value to 0.81, a deterioration in the color-protecting ΔE to 5.1, and a micelle size of 103±6 nm. This phenomenon can be attributed to the lack of chemical complementarity between the ethoxy chain of fatty alcohol polyoxyethylene ether and nonionic polyester, as well as competition for hydrogen bonds with the color-protecting agent polyvinylpyrrolidone, disrupting the three-phase equilibrium of micelle-stain-fabric. In Comparative Example 4, excessive surfactant led to a decrease in micelle stability (138±8 nm), which was attributed to the excessive surfactant. The excessive amount of polyvinylpyrrolidone (PVP) leads to overloading of the micelle interface, an imbalance in the critical micelle concentration, and a loose structure. Comparative Example 5 shows a nonionic polyester with a molecular weight of 1000 Da, a micelle size of 181±10 nm, and a Pi value decreasing to 0.85. This is because the low molecular weight of the nonionic polyester results in short molecular chains, preventing the formation of stable hydrophobic-hydrophilic microregions and weakening the oil anchoring ability. Comparative Example 6 shows a lack of siloxane groups, resulting in a color-protecting ΔE value of 4.5 and a loose micelle structure (174±10 nm). This is because siloxane groups are the core sites for the directional adsorption of oil; their absence prevents stain molecules from effectively embedding into the hydrophobic core of the micelles and also causes the color-protecting agent to migrate. Comparative Example 7 shows an excess of PVP, resulting in poorer color protection and larger micelle size. This is because the excess PVP leads to competitive adsorption of color-protecting agent molecules, damaging dye stability. Simultaneously, the imbalance in the color-protecting agent ratio affects the synergistic effect of the surfactant-oil-targeting cleaning agent. All comparative data were significantly inferior to those of Example 1, demonstrating that the synergistic effect of the ternary compound surfactant and nonionic polyester, as well as the parameter boundaries of the color-protecting agent, are the core of the technical solution.

[0055] The test data for enzyme encapsulation technology are shown in Table 6.

[0056] Table 6. Test data for enzyme encapsulation technology

[0057] As shown in Table 6, the composite enzymes of Examples 1 and 6-7, encapsulated in sodium alginate-chitosan / hydroxypropyl methylcellulose bilayer microcapsules, exhibited an enzyme activity retention rate as high as 89-94%. The enzyme activity retention rate of Example 1 was 108.9% higher than that of the unencapsulated Comparative Example 8. This indicates that the bilayer microcapsules physically blocked enzyme degradation, delaying premature enzyme inactivation. The composite enzymes of Comparative Examples 9-10, encapsulated in sodium alginate-chitosan / hydroxypropyl methylcellulose bilayer microcapsules, had an unbalanced enzyme ratio, resulting in an enzyme activity retention rate of 75-80%, still lower than the examples. This demonstrates that encapsulation technology needs to work synergistically with optimized enzyme ratios to maximize the protective effect. The Pi values ​​(1.43-1.55) of Examples 1 and 6-7 were significantly higher than those of Comparative Examples 8-10 (1.01-1.19). Specifically, the Pi value of Example 1 was 53.5% higher than that of the unencapsulated Comparative Example 8. This phenomenon can be attributed to the encapsulation technology extending the enzyme's action time and improving stain decomposition efficiency. Rapid release without encapsulation leads to significant enzyme inactivation in the initial stages of washing, while the slow release in the examples maintains the effective enzyme concentration throughout the washing process. The micelle size (40-44 nm) in Examples 1 and 6-7 is significantly smaller than that in Comparative Examples 8-10 (88-113 nm). Smaller micelle size provides a larger specific surface area, enhancing oil adsorption efficiency and thus improving detergency. Encapsulating the enzyme at the micelle interface avoids competition for adsorption sites with alkyl glycosides, maintaining the synergistic stability of the micelle-enzyme system.

[0058] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A cleaning composition, characterized in that, The cleaning composition comprises, by weight percentage: The mixture consists of 20-30% ternary compound surfactant, 8-10% oil stain targeted cleaner, 2-3% color protectant combination, 1-5% solvent synergist, 0.8-1.2% bactericide, 1.5-3% microencapsulated enzyme preparation, 0.2-0.5% pH adjuster, and 0.1-0.3% preservative, with the balance being deionized water.

2. The cleaning composition according to claim 1, characterized in that, The ternary compound surfactant includes nonionic surfactants, anionic surfactants, and amphoteric surfactants; The targeted oil stain cleaner is polypropylene terephthalate modified with siloxane groups; The color-protecting agent composition comprises polyvinylpyrrolidone and an acrylic copolymer; the acrylic copolymer is an acrylic acid / maleic anhydride copolymer.

3. The cleaning composition according to claim 2, characterized in that, The nonionic surfactant is an alkyl glycoside; the anionic surfactant is sodium fatty alcohol polyoxyethylene ether sulfate; the amphoteric surfactant is cocamidopropyl betaine; In the ternary compound surfactant, the mass ratio of nonionic surfactant, anionic surfactant and amphoteric surfactant is (10~18):(5~10):(3~5).

4. The cleaning composition according to claim 2, characterized in that, The molecular weight of the siloxane-modified polypropylene terephthalate is 2000~5000 Da; In the color-protecting agent combination, the mass ratio of polyvinylpyrrolidone to acrylic copolymer is (0.5~1):(1.5~2).

5. The cleaning composition according to claim 1, characterized in that, The solvent synergist is propylene glycol; The bactericide is a composition of tea tree oil, pine needle oil, and cedarwood oil; The microcapsule-encapsulated enzyme preparation is formed by encapsulating a complex enzyme in sodium alginate-chitosan / hydroxypropyl methylcellulose bilayer microcapsules; the complex enzyme is composed of protease, lipase, amylase and other enzymes; the other enzymes are a combination of cellulase, mannanase, pectinase and laccase; The pH adjuster is a mixture of sodium citrate and sodium hydroxide; the preservative is phenoxyethanol.

6. The cleaning composition according to claim 5, characterized in that, In the complex enzyme, the mass ratio of the protease, lipase, amylase and other enzymes is (15~25):(10~20):(5~10):(5~15).

7. A method for preparing a cleaning composition according to any one of claims 1 to 6, characterized in that, Includes the following steps: S1: After heating water, add ternary compound surfactant, oil stain targeted cleaner and solvent synergist in sequence, stir to obtain solution A; S2: Then, add the color-protecting agent combination to solution A, stir, and obtain solution B; S3: Add the enzyme preparation encapsulated in microcapsules to solution B, and adjust the pH value with a pH adjuster to obtain solution C; S4: Add bactericide and preservative to solution C, stir, and obtain solution D; S5: The solution D is subjected to high-pressure homogenization to obtain a clean composition.

8. A method for preparing a cleaning composition according to claim 7, characterized in that, In S1, the water is heated to a temperature of 40-50°C; the stirring speed is 200-300 rpm, and the stirring time is 20-30 min. In S2, solution A is cooled to below 30°C, and then a color-protecting agent combination is added; the stirring speed is 100~150 rpm; In S3, the pH value is adjusted to 7-9 using a pH adjuster; In S5, the pressure of the high-pressure homogenization process is 20~30MPa, and the number of cycles is 2~3.

9. A method for preparing a cleaning composition according to claim 7, characterized in that, The method for preparing the microcapsule-encapsulated enzyme preparation includes the following steps: The complex enzyme was dissolved in phosphate buffer to obtain an enzyme solution; then the enzyme solution was mixed with sodium alginate solution to obtain an enzyme-sodium alginate mixture; then the enzyme-sodium alginate mixture was homogenized and emulsified and dropped into CaCl2 solution for cross-linking and solidification to obtain calcium alginate gel microspheres. Calcium alginate gel microspheres were placed in a chitosan solution, and the chitosan layer was coated by electrostatic adsorption to obtain gel microspheres coated with chitosan layer. The obtained chitosan-coated gel microspheres were added to a hydroxypropyl methylcellulose solution, followed by the addition of anhydrous ethanol for separation and deposition. After solidification and washing, microcapsules were obtained. The microcapsules were pre-frozen and freeze-dried sequentially to obtain the enzyme preparation encapsulated in microcapsules.

10. A method for preparing a cleaning composition according to claim 9, characterized in that, The pH value of the phosphate buffer solution is 6-7; the mass concentration of the enzyme solution is 10-15%. The mass ratio of the enzyme solution to the sodium alginate solution is 1:(2.5~3.5); the mass concentration of the sodium alginate solution is 1.8%~2.2%; the mass concentration of the CaCl2 solution is 1.3%~1.7%; and the volume ratio of the enzyme-sodium alginate mixture to the CaCl2 solution is 1:(3~5). The mass ratio of calcium alginate gel microspheres to chitosan solution is 1:(4~6); the chitosan solution has a pH of 5.0~5.5 and a mass concentration of 0.7%~0.9%. The mass ratio of the chitosan-coated gel microspheres to the hydroxypropyl methylcellulose solution is 1:(3~5); the mass concentration of the hydroxypropyl methylcellulose solution is 2.5~3.5%. The anhydrous ethanol is added at a rate ≤5 mL / min; the volume of anhydrous ethanol added is 1.8 to 2.2 times the volume of the chitosan-coated gel microspheres; the separation and deposition temperature is 28 to 32 °C. The pre-freezing temperature is -42 to -38°C, and the time is 3.5 to 4.5 hours; the freeze-drying parameters are freeze-drying at -52 to -48°C and 0.08 to 0.12 mbar for 23 to 25 hours.

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