A high-efficiency detergent containing dodecylbenzenesulfonic acid and its preparation method

Abstract

The present application relates to the field of daily chemical products, and specifically discloses a high-efficiency detergent containing dodecylbenzenesulfonic acid and a preparation method thereof. A high-efficiency detergent containing dodecylbenzenesulfonic acid, including the following raw materials in parts by weight: 5-8 parts of dodecylbenzenesulfonic acid; 4-7 parts of fatty alcohol polyoxyethylene ether; 5-6 parts of alkyl dimethyl betaine; 3-8 parts of coconut oil fatty acid diethanolamide; 3-5 parts of hydrophobically modified adsorbent filler; 3-6 parts of chelating agent; 1-3 parts of defoamer; 4-8 parts of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles; 80-95 parts of water; its preparation method is: after mixing the above components according to the formula, stirring is carried out to prepare the high-efficiency detergent. The high-efficiency detergent of the present application has the advantages of strong stain removal ability, preventing stains from secondary deposition on clothes and having antibacterial effect.

Description

Technical Field

[0001] The present application relates to the technical field of daily chemical products, and in particular to a high-efficiency detergent containing dodecylbenzenesulfonic acid and a preparation method thereof. Background Art

[0002] Detergents mainly include washing powder, soap and laundry liquid, etc. Detergents can quickly break down dirt and have become a necessary consumer product for people's lives.

[0003] According to the existing relevant technology, Chinese patent application CN201210578246.8 discloses a high-efficiency detergent, which is made from the following raw materials in parts by weight: 15-25 parts of sweet clover, 15-20 parts of fatty alcohol polyoxyethylene ether, 15-20 parts of polyoxyethylene ether sulfate, 2-6 parts of sodium silicate, 3-5 parts of a mixture of monoethanolamine and triethanolamine, 1-3 parts of a mixture of pectinase and oxidase, 20-25 parts of glycerol and 25-30 parts of ethanol.

[0004] This type of detergent can quickly and efficiently remove oil, sweat, and other contaminants from clothing, improving the cleaning performance of ordinary clothes. However, while detergents can quickly remove stains and have a certain cleaning effect, they cannot absorb the stains after washing, causing them to adhere to clothing again, significantly reducing the cleaning effect. Furthermore, they lack antibacterial properties during washing, allowing bacteria to easily adhere to and colonize clothing, causing damage to the skin.

[0005] In view of the above-mentioned related technologies, the inventors found that it is necessary to provide a high-efficiency detergent that can effectively remove oil stains and has antibacterial effects. Summary of the Invention

[0006] In order to improve the ability of a detergent to remove grease, prevent secondary deposits of stains, and provide antibacterial properties, the present application provides a high-efficiency detergent containing dodecylbenzenesulfonic acid and a preparation method thereof.

[0007] In a first aspect, the present application provides a high-efficiency detergent containing dodecylbenzenesulfonic acid, which adopts the following technical solution:

[0008] A high-efficiency detergent containing dodecylbenzenesulfonic acid, comprising the following raw materials in parts by weight: 5-8 parts of dodecylbenzenesulfonic acid; 4-7 parts of fatty alcohol polyoxyethylene ether; 5-6 parts of alkyl dimethyl betaine; 3-8 parts of coconut oil fatty acid diethanolamide; 3-5 parts of adsorption filler; 3-6 parts of chelating agent; 1-3 parts of defoaming agent; 4-8 parts of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles; and 80-95 parts of water.

[0009] The carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles include the following raw materials: 1-2 parts of carboxymethyl chitosan, 1-2 parts of polyethyleneimine, and 0.2-0.4 parts of silica gel particles.

[0010] By adopting the above technical solution, surfactants such as dodecylbenzenesulfonic acid, fatty alcohol polyoxyethylene ether, alkyl dimethyl betaine, coconut oil fatty acid diethanolamide, etc. are oriented on the liquid surface, which reduces the surface tension of the liquid, weakens the cohesive force between water molecules, and makes it easier for water to wet clothes; during the washing process, the hydrophobic end of the surfactant adsorbs oil stains, thereby forming emulsion droplets and wrapping the stains, making them dispersed in water, which helps to peel the oil stains from clothes; in the carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles, carboxymethyl chitosan has antibacterial properties, and the addition of carboxymethyl chitosan can form a protective layer on the surface of clothes, which is not easily eroded by pathogens; polyethyleneimine can destroy bacterial membranes, further enhancing the antibacterial effect; the carboxylmethyl introduced in carboxymethyl chitosan dissociates into hydrogen ions in the aqueous solution, and polyethyleneimine Amines are rich in amino groups with a large number of positive charges, so polyethyleneimine can form a hydrogel of a polyelectrolyte complex with carboxymethyl chitosan through electrostatic attraction. The hydrogel formed by the two has strong water flow resistance and viscosity, so when washing clothes, it can make silica gel particles adhere to the clothes. Silica gel particles have a relatively smooth touch. Therefore, the hydrogel not only makes the detergent have a strong antibacterial ability, but also can adhere to silica gel particles, thereby improving the smoothness of the clothing surface and playing an auxiliary role in smoothing clothes; when the hydrophobic modified adsorbent filler comes into contact with the stain, due to the hydrophobicity of the filler, it is easy to combine with the hydrophobic stain, thereby separating the stain from the clothes and reducing the residue of the stain on the clothes. In addition, the hydrophobic modified adsorbent filler can be evenly distributed in the detergent, increasing the contact area with the stain and improving the washing efficiency.

[0011] Optionally, the preparation method of the carboxymethyl chitosan-polyethyleneimine hydrogel modified silica particles is:

[0012] S1: stirring and mixing an aqueous solution of carboxymethyl chitosan and an aqueous solution of polyethyleneimine, immersing the mixture in liquid nitrogen for 20-30 minutes, freeze-drying the mixture, and grinding the mixture to obtain a hydrogel powder;

[0013] S2: Add the hydrogel powder to PBS buffer, add silica gel particles, and stir until gelation to prepare carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles.

[0014] By adopting the above technical solution, carboxymethyl chitosan not only has excellent water solubility, but also has excellent biocompatibility and biodegradability, thereby enhancing the antibacterial performance of clothing; and carboxymethyl chitosan and polyethyleneimine form a composite hydrogel with adhesion, good resistance to water impact and strong antibacterial ability through electrostatic interaction. When the hydrogel powder is mixed and stirred with silica gel particles until gelation, the hydrogel can be wrapped on the surface of the silica gel particles. When washing clothes, the adhesion of the hydrogel can attach the silica gel particles to the surface of the clothes, and the water flow resistance makes the silica gel particles not easily washed away during the washing process, thereby attaching a layer of silica gel particles to the surface of the clothes, increasing the smoothness of the clothes, and making the washed clothes have a smoother touch.

[0015] Optionally, the silica gel particles are treated as follows:

[0016] Using silica gel particles as the receiving substrate, a chitosan solution with a concentration of 0.4-0.6wt% was electrosprayed and then dried. During the electrospray treatment, the voltage was 6.5-7.5kV, the liquid flow rate was 2-4μL / min, and the receiving distance was 5-6cm.

[0017] By adopting the above technical solution, the chitosan solution is formed into microparticles after electro-atomization treatment. Since chitosan has special film-forming properties and bio-friendliness, it has a good finishing effect on fabrics. After the chitosan is wrapped on the surface of the silica gel particles, it is then mixed with the hydrogel powder and stirred until gelation. Under the adhesion of the hydrogel, it adheres to the surface of the clothing, further improving the smoothness of the clothing and reducing the pilling and pilling of the clothing; and chitosan has cationic properties and can inhibit bacterial growth. Therefore, the chitosan electro-atomized microparticles are adsorbed on the surface of the silica gel particles, which not only makes the clothing smoother and increases wearing comfort, but also further enhances the antibacterial effect of the detergent.

[0018] Optionally, the hydrophobically modified adsorption filler is prepared by the following method:

[0019] The adsorption filler is treated with acid, mixed evenly with the silane coupling agent solution by ultrasonication, filtered, dried, and then immersed in a gallic acid solution, stirred evenly, filtered and dried.

[0020] By adopting the above technical solution, under acidic conditions, the active groups on the surface of the adsorption filler are activated, and the introduced hydroxyl groups serve as anchoring points for the silane coupling agent; 3-aminopropyltriethoxysilane (APTES) is used as a silane coupling agent to modify the surface of the adsorption filler and amino the adsorption filler; gallic acid is added to covalently couple with the amino adsorption filler, and the carboxyl group of gallic acid and the amino group on the surface of the adsorption filler form an amide bond. Gallic acid contains polyphenol groups and is a natural polyphenol compound. It has antioxidant and antibacterial abilities as well as certain hydrophobicity. Therefore, gallic acid can improve the antibacterial ability of the adsorption filler while increasing the dispersibility and stability of the adsorption filler. After adsorbing stains, the adsorption filler can be better detached from the clothing, avoiding the redeposition of the stains washed off the clothing.

[0021] Optionally, the adsorption filler is one or more of clay, bentonite and activated carbon.

[0022] By adopting the above technical solution, as an adsorption filler, it has a large specific surface area and a suitable pore structure, has a strong adsorption force in the liquid, does not chemically react with the adsorbate and the medium, and can quickly achieve substance separation.

[0023] Optionally, the chelating agent is one or more of ethylenediaminetetraacetic acid, nitrilotriacetic acid and sodium citrate.

[0024] By adopting the above technical solution, the chelating agent can adsorb hard water ions such as calcium and magnesium in water to form a stable complex, so that the surfactant in the detergent can play a more effective role and improve the washing effect of the detergent.

[0025] Optionally, the defoaming agent is polyethylene glycol ether.

[0026] By adopting the above technical solution, polyethylene glycol ether, as a suspending and dispersing agent, has a good ability to suspend and disperse dirt. When polyethylene glycol ether is combined with a surfactant, it can significantly improve the cleaning effect of the detergent, destroy the stability of the foam, reduce the generation of foam when washing clothes, and increase the rinsing effect.

[0027] In a second aspect, the present application provides a method for preparing a high-efficiency detergent containing dodecylbenzenesulfonic acid, using the following technical solution:

[0028] A method for preparing a high-efficiency detergent containing dodecylbenzenesulfonic acid comprises the following steps: mixing water, dodecylbenzenesulfonic acid, fatty alcohol polyoxyethylene ether, alkyl dimethyl betaine, coconut oil fatty acid diethanolamide, hydrophobically modified adsorption filler, carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles, a chelating agent, and a defoaming agent according to a formula, and then stirring the mixture to prepare the high-efficiency detergent.

[0029] By adopting the above technical solution, the raw materials are fully mixed and stirred, so that the components of the detergent are more uniform, and a high-efficiency detergent with good antibacterial and decontamination effects that prevents stains from staining clothes again is obtained, and makes clothes softer and smoother.

[0030] In summary, this application has the following beneficial effects:

[0031] 1. Since the present application uses raw materials such as dodecylbenzenesulfonic acid, fatty alcohol polyoxyethylene ether, alkyl dimethyl betaine, coconut oil fatty acid diethanolamide, adsorbent filler, carboxymethyl chitosan-polyethyleneimine hydrogel modified silica particles to prepare a high-efficiency detergent, the surfactants such as dodecylbenzenesulfonic acid used can reduce the surface tension of the liquid and weaken the intermolecular cohesion, so that the oil stains on the clothes form emulsion droplets and then peel off from the clothes. The carboxymethyl chitosan-polyethyleneimine hydrogel complex has a certain adhesion and antibacterial effect, which makes the detergent have a better bactericidal effect. At the same time, it can also combine the silica particles with the surface of the clothes, increase the smoothness of the clothes surface, and increase the wearing comfort.

[0032] 2. In this application, chitosan electrosprayed microparticles modified silica gel particles are preferably used. Chitosan has excellent film-forming properties and bio-friendliness. After being wrapped with chitosan, the smoothness of clothes can be improved and pilling of clothes can be reduced. In addition, chitosan has a good bactericidal effect, which enhances the antibacterial effect of detergent on clothes.

[0033] 3. In the present application, the adsorption filler is pretreated with gallic acid. The addition of gallic acid can be covalently coupled with the amino adsorption filler. Gallic acid has antibacterial and antioxidant capabilities. At the same time, it also increases the dispersibility and stability of the adsorption filler after pretreatment, avoiding secondary contamination of clothes when washing clothes. DETAILED DESCRIPTION

[0034] The following examples further illustrate the present application in detail.

[0035] Preparation Examples 1-6 of Carboxymethyl Chitosan-Polyethyleneimine Hydrogel Modified Silica Gel Particles

[0036] Preparation Example 1: 2 g of carboxymethyl chitosan was added to 38 g of water to prepare a carboxymethyl chitosan aqueous solution; 2 g of polyethyleneimine was added to 38 g of water to prepare a polyethyleneimine aqueous solution; the carboxymethyl chitosan solution and the polyethyleneimine solution were stirred and mixed, immersed in liquid nitrogen for 20 minutes, freeze-dried, and ground to obtain a hydrogel powder; the hydrogel powder was added to 10 times its mass of PBS buffer, 0.4 g of silica gel particles were added, and stirred until gelation occurred to obtain carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles, wherein the silica gel particles were obtained by grinding silica gel particles through a 200-mesh sieve, and the silica gel particles were selected from Shenzhen Jialong Plastic Raw Materials, item number TE-35A.

[0037] Preparation Example 2: 1 g of carboxymethyl chitosan was added to 19 g of water to prepare a carboxymethyl chitosan aqueous solution; 1 g of polyethyleneimine was added to 19 g of water to prepare a polyethyleneimine aqueous solution; the carboxymethyl chitosan solution and the polyethyleneimine solution were stirred and mixed, immersed in liquid nitrogen for 20 minutes, freeze-dried, and ground to obtain a hydrogel powder; the hydrogel powder was added to 10 times its mass of PBS buffer, 0.2 g of silica gel particles were added, and stirred until gelation occurred. The silica gel particles were obtained by grinding silica gel particles through a 200-mesh sieve. The silica gel particles were selected from Shenzhen Jialong Plastic Raw Materials, item number TE-35A.

[0038] Preparation Example 3: The difference from Preparation Example 1 is that the added silica gel particles are pretreated using the following method:

[0039] ① Preparation of 0.4 wt% chitosan solution: 0.4 g of chitosan was weighed using an electronic balance and placed in a round-bottom flask. 99.6 g of 1.0% dilute acetic acid was added and stirred to dissolve until clear to prepare a 0.4 wt% chitosan solution.

[0040] ② Electrospray 0.4wt% chitosan solution: After aspirating 4mL of chitosan solution into the syringe, fix it on the propulsion pump with a voltage of 7.5kV and a liquid flow rate of 4μL / min. When the atomization state is stable, place the silica gel particles directly below the metal capillary needle tip with a receiving distance of 6cm and a receiving time of 1h. Dry after the receiving is completed.

[0041] Preparation Example 4: The difference from Preparation Example 3 is that the parameters for silica gel particle pretreatment are different. The specific method is as follows:

[0042] ① Preparation of 0.6 wt% chitosan solution: 0.6 g of chitosan was weighed using an electronic balance and placed in a round-bottom flask. 99.4 g of 1.0% dilute acetic acid was added and stirred to dissolve until clear to prepare a 0.6 wt% chitosan solution.

[0043] ② Electrospray 0.6wt% chitosan solution: After aspirating 4mL of chitosan solution into the syringe, fix it on the propulsion pump with a voltage of 7.5kV and a liquid flow rate of 4μL / min. When the atomization state is stable, place the silica gel particles directly below the metal capillary needle tip with a receiving distance of 6cm and a receiving time of 1h. Dry after the receiving is completed.

[0044] Preparation Example 5: The difference from Preparation Example 3 is that the parameters for silica gel particle pretreatment are different. The specific method is as follows:

[0045] ① Preparation of 0.2 wt% chitosan solution: 0.2 g of chitosan was weighed using an electronic balance and placed in a round-bottom flask. 99.8 g of 1.0% dilute acetic acid was added and stirred to dissolve until clear to prepare a 0.2 wt% chitosan solution.

[0046] ② Electrospray 0.2wt% chitosan solution: After aspirating 4mL of chitosan solution into the syringe, fix it on the propulsion pump with a voltage of 7.5kV and a liquid flow rate of 4μL / min. When the atomization state is stable, place the silica gel particles directly below the metal capillary needle tip with a receiving distance of 6cm and a receiving time of 1h. Dry after the receiving is completed.

[0047] Preparation Example 6: The difference from Preparation Example 3 is that the parameters for silica gel particle pretreatment are different. The specific method is as follows:

[0048] ① Preparation of 0.8 wt% chitosan solution: 0.8 g of chitosan was weighed using an electronic balance and placed in a round-bottom flask. 100.0 g of 1.0% dilute acetic acid was added and stirred to dissolve until clear to prepare a 0.8 wt% chitosan solution.

[0049] ② Electrospray 0.8wt% chitosan solution: After aspirating 4mL of chitosan solution into the syringe, fix it on the propulsion pump with a voltage of 7.5kV and a liquid flow rate of 4μL / min. When the atomization state is stable, place the silica gel particles directly below the metal capillary needle tip with a receiving distance of 6cm and a receiving time of 1h. Dry after the receiving is completed.

[0050] Example 1: A high-efficiency detergent containing dodecylbenzenesulfonic acid, the raw material dosage of which is shown in Table 1, carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles are prepared according to Preparation Example 1, and the preparation method of the hydrophobically modified adsorption filler is as follows: slowly adding activated carbon to a concentrated nitric acid solution, stirring at 60°C for 24 hours, filtering and drying; dispersing the dried adsorption filler in anhydrous toluene and mixing evenly, adding 3-aminopropyltriethoxysilane, ultrasonicating for 30 minutes, filtering and drying to obtain the adsorption filler, the amount of 3-aminopropyltriethoxysilane is 0.1 of the filler mass; dodecylbenzenesulfonic acid is selected from Shandong Zhenglian Chemical Co., Ltd., with the item number 07, fatty alcohol polyoxyethylene ether is selected from Guangzhou Maituo Biotechnology, with the model number AEO-9, coconut oil fatty acid diethanolamide is selected from Hubei Langbowan Biomedicine, with the item number EF234243, alkyl dimethyl betaine is octadecyl dimethyl betaine, selected from Jinan Xiangfeng Weiye Chemical, with the model number BS-18, the chelating agent is ethylenediaminetetraacetic acid, and the defoaming agent is polyethylene glycol ether, selected from Guangzhou Bolun Chemical, with the model number peg400.

[0051] The preparation method of the above-mentioned high-efficiency detergent containing dodecylbenzenesulfonic acid comprises the following steps:

[0052] The high-efficiency detergent is prepared by mixing water, dodecylbenzenesulfonic acid, fatty alcohol polyoxyethylene ether, alkyl dimethyl betaine, coconut oil fatty acid diethanolamide, adsorption filler, carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles, chelating agent and defoaming agent and stirring.

[0053] Table 1 Amount of raw materials used for high efficiency detergents in Examples 1-5

[0054]

[0055] Example 2: A high-efficiency detergent containing dodecylbenzenesulfonic acid, the raw material dosages of which are shown in Table 1, carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles are prepared according to Preparation Example 2, and the preparation method of the hydrophobically modified adsorption filler is as follows: slowly adding activated carbon to a concentrated nitric acid solution, stirring at 60°C for 24 hours, filtering and drying; dispersing the dried adsorption filler in anhydrous toluene and mixing uniformly, adding 3-aminopropyltriethoxysilane, ultrasonicating for 30 minutes, filtering and drying to obtain the adsorption filler, and the amount of silane coupling agent is: The amount is 0.1; dodecylbenzenesulfonic acid is selected from Shandong Zhenglian Chemical Co., Ltd., the item number is 07, fatty alcohol polyoxyethylene ether is selected from Guangzhou Maituo Biotechnology, the model is AEO-9, coconut oil fatty acid diethanolamide is selected from Hubei Langbowan Biomedicine, the item number is EF234243, alkyl dimethyl betaine is octadecyl dimethyl betaine, selected from Jinan Xiangfeng Weiye Chemical, the model is BS-18, the chelating agent is ethylenediaminetetraacetic acid, the defoaming agent is polyethylene glycol ether, selected from Guangzhou Bolun Chemical, the model is peg400.

[0056] The preparation method of the above-mentioned high-efficiency detergent containing dodecylbenzenesulfonic acid comprises the following steps:

[0057] The high-efficiency detergent is prepared by mixing water, dodecylbenzenesulfonic acid, fatty alcohol polyoxyethylene ether, alkyl dimethyl betaine, coconut oil fatty acid diethanolamide, adsorption filler, carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles, chelating agent and defoaming agent and stirring.

[0058] Example 3: A high-efficiency detergent containing dodecylbenzenesulfonic acid. The difference from Example 1 is that the amounts of raw materials used are different. The amounts of raw materials used are shown in Table 1.

[0059] Example 4: A high-efficiency detergent containing dodecylbenzenesulfonic acid. The difference from Example 1 is that the amounts of raw materials used are different. The amounts of raw materials used are shown in Table 1.

[0060] Example 5: A high-efficiency detergent containing dodecylbenzenesulfonic acid. The difference from Example 1 is that the amounts of raw materials used are different. The amounts of raw materials used are shown in Table 1.

[0061] Example 6: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which differs from Example 1 in that the carboxymethyl chitosan-polyethyleneimine hydrogel-modified silica gel particles used are prepared by Preparation Example 3.

[0062] Example 7: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which is different from Example 6 in that the carboxymethyl chitosan-polyethyleneimine hydrogel-modified silica gel particles used are prepared by Preparation Example 4.

[0063] Example 8: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which differs from Example 6 in that the carboxymethyl chitosan-polyethyleneimine hydrogel-modified silica gel particles used are prepared by Preparation Example 5.

[0064] Example 9: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which is different from Example 6 in that the carboxymethyl chitosan-polyethyleneimine hydrogel-modified silica gel particles used are prepared by Preparation Example 6.

[0065] Example 10: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which differs from Example 6 in that the hydrophobically modified adsorbent filler used is prepared by the following method:

[0066] ① Slowly add activated carbon to concentrated nitric acid solution, stir at 60°C for 24 hours, filter and dry; ② Disperse the dried adsorption filler in anhydrous toluene and mix evenly, add 3-aminopropyltriethoxysilane, ultrasonicate for 30 minutes, filter and dry, the mass of 3-aminopropyltriethoxysilane is 0.1 of the mass of activated carbon; ③ Weigh an appropriate amount of gallic acid solid, dissolve it in distilled water, slowly add the activated carbon obtained in ② to the gallic acid solution, stir evenly and dry, the mass of gallic acid is 0.5 of the mass of activated carbon, and the activated carbon material is selected from Henan Yunlan Water Treatment Materials Co., Ltd., with a particle size of 200 mesh.

[0067] The preparation method of the above-mentioned high-efficiency detergent containing dodecylbenzenesulfonic acid comprises the following steps:

[0068] The high-efficiency detergent is prepared by mixing water, dodecylbenzenesulfonic acid, fatty alcohol polyoxyethylene ether, alkyl dimethyl betaine, coconut oil fatty acid diethanolamide, adsorption filler, carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles, chelating agent and defoaming agent and stirring.

[0069] Comparative Example 1: A high-efficiency detergent containing dodecylbenzenesulfonic acid. The difference from Example 1 is that silica gel particles are not added to the carboxymethyl chitosan-polyethyleneimine hydrogel. The preparation method of the carboxymethyl chitosan-polyethyleneimine hydrogel used is:

[0070] 2 g of carboxymethyl chitosan was added to 38 g of water to prepare a carboxymethyl chitosan aqueous solution; 2 g of polyethyleneimine was added to 38 g of water to prepare a polyethyleneimine aqueous solution; the carboxymethyl chitosan solution and the polyethyleneimine solution were stirred and mixed, immersed in liquid nitrogen for 20 minutes, freeze-dried, and ground to obtain a hydrogel powder; the hydrogel powder was added to 10 times its mass of PBS buffer and stirred until gelation occurred.

[0071] Comparative Example 2: A high-efficiency detergent containing dodecylbenzenesulfonic acid. The difference from Example 1 is that polyethyleneimine-modified silica gel particles are used in equal amounts to replace the carboxymethyl chitosan-polyethyleneimine hydrogel-modified silica gel particles. The polyethyleneimine-modified silica gel particles are prepared as follows:

[0072] 2 g of polyethyleneimine was added to 38 g of water to prepare a polyethyleneimine aqueous solution. 0.4 g of silica gel particles was slowly added to the polyethyleneimine aqueous solution, stirred at 60° C. for 30 min, filtered and dried.

[0073] Comparative Example 3: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which differs from Example 1 in that an equal amount of carboxymethyl chitosan-modified silica gel particles is used to replace the carboxymethyl chitosan-polyethyleneimine hydrogel-modified silica gel particles. The preparation method of the carboxymethyl chitosan-modified silica gel particles is as follows:

[0074] 2 g of carboxymethyl chitosan was added to 38 g of water to prepare a carboxymethyl chitosan aqueous solution. 0.4 g of silica gel particles was slowly added to the carboxymethyl chitosan aqueous solution, stirred at 60° C. for 30 min, filtered and dried.

[0075] Comparative Example 4: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which differs from Example 1 in that the amount of carboxymethyl chitosan-polyethyleneimine hydrogel-modified silica gel particles used is 2 kg.

[0076] Comparative Example 5: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which differs from Example 1 in that the amount of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles used is 10 kg.

[0077] Comparative Example 6: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which differs from Example 1 in that the amount of the hydrophobically modified adsorption filler used is 1 kg.

[0078] Comparative Example 7: A high-efficiency detergent containing dodecylbenzenesulfonic acid, which differs from Example 1 in that the amount of the hydrophobically modified adsorption filler added is 8 kg.

[0079] A high-efficiency detergent was prepared according to the methods in the examples and comparative examples, and its performance was tested according to the following methods:

[0080] Detergency testing: Detergency testing was conducted according to the method specified in GB / T 13174-2008, "Determination of detergency and wash cycle performance of detergents for clothing." Hard water preparation was based on GB / T 6367-1997. The detergency of the samples was determined by testing their performance on carbon black, protein, and sebum-stained cloths. The test conditions were a 0.2% detergent mass fraction in the aqueous solution, a water hardness of 250 mg / L, and a temperature of 40 ± 0.5°C. The results are shown in Table 2.

[0081] Table 2 Detergent cleaning performance test results

[0082]

[0083] Combined with the data in Table 2 and the amount of raw materials in Examples 1-9, the adsorption filler used in Example 10 is pretreated with a silane coupling agent and gallic acid. The pretreated adsorption filler has better dispersibility and stability and the best decontamination ability. The adsorption fillers used in Comparative Examples 1-4 are consistent with the adsorption fillers used in Example 1, so the decontamination performance is similar. However, due to the increase in the amount of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles in Comparative Example 5, the adhesion amount of silica gel particles on the clothes increases, affecting the decontamination effect of the clothes, resulting in a worse decontamination effect; the difference between Comparative Example 6 and Example 1 is that the amount of adsorption filler added is 1 kg. It can be seen from Table 2 that after the amount of adsorption filler decreases, the decontamination performance of the detergent decreases; the difference between Comparative Example 7 and Example 1 is that the amount of adsorption filler added is 8 kg. When the amount of adsorption filler increases, the decontamination effect does not increase accordingly.

[0084] Antibacterial testing: Detergents were tested for their antibacterial properties according to QB / T 2738-2005. The detergent stock solution was used as the test subject, and the suspension quantitative method was used to determine the antibacterial rate against Staphylococcus aureus for 30 minutes. The experiment was repeated three times, and the average value was used as the final result. The results are shown in Table 3.

[0085] Table 3 Antibacterial performance test results of detergents

[0086]

[0087] Combining the data in Table 3 and the raw material dosage of Example 1, carboxymethyl chitosan and polyethyleneimine have dual antibacterial properties, so Example 1 has obvious antibacterial effect. Examples 2-5 adjust the raw material dosage. It can be seen that the antibacterial effect of Examples 2-5 decreases with the decrease in dosage; the difference between Example 6 and Example 7 and Example 1 is that the carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles used are prepared in Preparation Example 3 and Preparation Example 4. After the silica gel particles are coated with chitosan particles, the antibacterial effect of chitosan further enhances the antibacterial effect of the detergent; the difference between Example 8 and Example 9 and Example 6 is that the carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles used are prepared in Preparation Example 5 and Preparation Example 6, and the concentration of the chitosan solution is reduced and increased. It can be seen from the table that the antibacterial ability of the detergent in Example 8 decreases slightly, but is still better than the antibacterial effect of Examples 1-5. The antibacterial effect of Example 9 does not decrease with the addition of chitosan on the surface of the silica gel particles. The difference between Comparative Example 1 and Example 1 is that no silica gel particles are added, and the antibacterial performance of the detergent is not much different; the difference between Comparative Example 2 and Example 1 is that no carboxymethyl chitosan is added. It can be seen from the data that the antibacterial performance of Comparative Example 2 is greatly reduced; the difference between Comparative Example 3 and Example 1 is that no polyethyleneimine is added. It can be seen from the data that Comparative Example 3 shows the same antibacterial performance decline as Comparative Example 2; the difference between Comparative Examples 4-5 and Example 1 is that the amount of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles used is adjusted. It can be seen from the data that whether the amount is increased or decreased, the antibacterial effect is not as good as the antibacterial effect of Example 6, and after reducing the amount of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles, the antibacterial effect of Comparative Example 4 is lower than that of Example 1, and after increasing the amount of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles in Comparative Example 5, the antibacterial effect is slightly higher than that of Example 1.

[0088] Softness and Smoothness Test: Place 3-5 test cotton towels in a drum washing machine, add 5ml of detergent, and wash under the same conditions for 30 minutes, 20 times in a row. Remove and air-dry on a clothes hanger. Ten testers (total) lay the standard and test towels flat on their palms. Rub them on both cheeks with moderate force, or use both hands to feel the softness and smoothness of the towels. Compare them to the standard towel and rate their softness and smoothness (10 = softest / smoothest, 1 = hardest / roughest). The sum of all 10 test scores is shown in Table 4.

[0089] Table 4 Softening / smoothness performance test results of detergents

[0090]

[0091] According to the data in Table 4 and the dosage in Example 1, the silica gel particles have a certain lubricating effect, while the carboxymethyl chitosan-polyethyleneimine hydrogel has an adhesive effect and water flow resistance. The silica gel particles are adhered to the surface of the clothing, and the clothing of Example 1 has high softness and smoothness. The difference between Examples 2-5 and Example 1 is that the dosage of the raw materials used is adjusted, and the softness and smoothness of the clothing also decreases slightly as the dosage of the raw materials is reduced.

[0092] The difference between Example 6-7 and Example 1 is that the carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles used are made from Preparation Example 3 and Preparation Example 4. It can be seen from the data that the silica gel particles are wrapped by chitosan, which further improves the softness of the clothes, and the smoothness of the clothes also increases due to the adhesion of the silica gel particles.

[0093] The difference between Examples 8-9 and Example 6 is that the carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles used are made from Preparation Examples 5 and 6, and the concentration of chitosan particles is reduced and increased, respectively. Compared with Example 6, the softness and smoothness of the clothing in Example 8 are slightly reduced, but are still slightly higher than those in Example 1. Compared with Example 6, the effect of Example 9 is not much different, indicating that the appropriate concentration of chitosan solution wrapped with silica gel particles can improve the smoothness of clothing.

[0094] The difference between Comparative Example 1 and Example 1 is that no silica gel particles are added. It can be seen from the data that the softness and smoothness of the clothes in Comparative Example 1 are the lowest; the difference between Comparative Example 2 and Example 1 is that no carboxymethyl chitosan is added. It can be seen from the data that the softness and smoothness of the clothes in Comparative Example 2 are slightly lower than those in Example 1, but are still higher than those in Comparative Example 1.

[0095] The difference between Comparative Example 3 and Example 1 is that no polyethyleneimine is added. After washing with detergent, the softness and smoothness of the clothes are not high, but slightly higher than the softness and smoothness of Comparative Example 1, indicating that the lack of polyethyleneimine leads to a decrease in the amount of silica gel particles adhered, and the smoothness of the clothes after washing decreases.

[0096] The difference between Comparative Examples 4-5 and Example 1 is that the amount of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles is reduced and increased. It can be seen that after adjusting the amount, the softness and smoothness of the clothes in Comparative Example 4 are lower than those in Example 1, while the softness of the clothes in Comparative Example 5 is slightly lower than that in Example 1, and the smoothness is slightly higher than that in Example 1.

[0097] The difference between Comparative Examples 6-7 and Example 1 is that the amount of the hydrophobically modified adsorption filler is reduced or increased. It can be seen that the difference is not obvious compared with Example 1.

[0098] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A high-efficiency detergent containing dodecylbenzenesulfonic acid, characterized in that: The invention comprises the following raw materials in parts by weight: 5-8 parts of dodecylbenzenesulfonic acid; 4-7 parts of fatty alcohol polyoxyethylene ether; 5-6 parts of alkyl dimethyl betaine; 3-8 parts of coconut oil fatty acid diethanolamide; 3-5 parts of hydrophobically modified adsorption filler; 3-6 parts of chelating agent; 1-3 parts of defoaming agent; 4-8 parts of carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles; and 80-95 parts of water. The carboxymethyl chitosan-polyethyleneimine hydrogel modified silica particles include the following raw materials in parts by weight: 1-2 parts of carboxymethyl chitosan, 1-2 parts of polyethyleneimine, and 0.2-0.4 parts of silica particles; The preparation method of the carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles is as follows: S1: stirring and mixing an aqueous solution of carboxymethyl chitosan and an aqueous solution of polyethyleneimine, immersing the mixture in liquid nitrogen for 20-30 minutes, freeze-drying the mixture, and grinding the mixture to obtain a hydrogel powder; S2: Add the hydrogel powder to PBS buffer, add silica gel particles, and stir until gelation to prepare carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles.

2. The high-efficiency detergent containing dodecylbenzenesulfonic acid according to claim 1, wherein: The silica gel particles are treated as follows: Using silica gel particles as the receiving substrate, a chitosan solution with a concentration of 0.4-0.6wt% was electrosprayed and then dried. During the electrospray treatment, the voltage was 6.5-7.5kV, the liquid flow rate was 2-4μL / min, and the receiving distance was 5-6cm.

3. The high-efficiency detergent containing dodecylbenzenesulfonic acid according to claim 1, characterized in that: The hydrophobically modified adsorption filler is prepared by the following method: The adsorption filler is treated with acid, mixed evenly with the silane coupling agent solution by ultrasonication, filtered, dried, and then immersed in a gallic acid solution, stirred evenly, filtered and dried.

4. The high-efficiency detergent containing dodecylbenzenesulfonic acid according to claim 3, characterized in that: The adsorption filler is one or more of clay, bentonite and activated carbon.

5. The high-efficiency detergent containing dodecylbenzenesulfonic acid according to claim 1, characterized in that: The chelating agent is one or more of ethylenediaminetetraacetic acid, nitrilotriacetic acid and sodium citrate.

6. The high-efficiency detergent containing dodecylbenzenesulfonic acid according to claim 1, characterized in that: The defoaming agent is polyethylene glycol ether.

7. The method for preparing the high-efficiency detergent containing dodecylbenzenesulfonic acid according to any one of claims 1 to 6, characterized in that: The following steps are involved: According to the formula, water, dodecylbenzenesulfonic acid, fatty alcohol polyoxyethylene ether, alkyl dimethyl betaine, coconut oil fatty acid diethanolamide, hydrophobically modified adsorption filler, carboxymethyl chitosan-polyethyleneimine hydrogel modified silica gel particles, chelating agent and defoaming agent are mixed and stirred to prepare a high-efficiency detergent.

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