Washing machine tank cleaning agent wrapped by water-soluble film and preparation process thereof

Abstract

The invention relates to a washing machine tank cleaning agent wrapped by a water-soluble film and a preparation process thereof, and belongs to the technical field of cleaning agents. The cleaning agent is prepared from the following components in percentage by weight: 0.1 to 0.3 percent of a sterilizing agent, 0.25 to 0.5 percent of an enzyme preparation, 0.4 to 0.5 percent of a chelating agent, 0.9 to 1.2 percent of a penetrating agent, 1.2 to 1.8 percent of a surfactant, 0.15 to 0.22 percent of an anti-redeposition agent, 0.4 to 0.6 percent of colored particles, 0.2 to 0.3 percent of essence and the balance of sodium percarbonate, according to the penetrant, ethylene glycol diglycidyl ether and diallylamine are subjected to ring opening, then quaternization is carried out through 3-iodopropanol, and finally, 3-sulfydryl-1-sodium propanesulfonate is subjected to click addition to introduce a branched sodium sulfonate-terminated structure for modification; the introduction of the penetrant realizes targeted permeation, rapid softening and deep removal of dirt in the interlayer of the washing machine tank, and solves the industrial pain points of'surface cleaning and interlayer residue 'of a traditional cleaning agent.

Description

Technical Field

[0001] The present invention belongs to the technical field of cleaning agents, and in particular relates to a washing machine tub cleaner wrapped in a water-soluble film and a preparation process thereof. Background Art

[0002] As washing machines age, complex dirt such as clothing fibers, soap scum, and biofilm easily accumulates on the inner walls and interlayer areas of the washing machine tub. Existing washing machine tub cleaners are primarily divided into liquid and solid types. While liquid cleaners are convenient for adding functional components, the coating process is complex: on the one hand, liquid contents easily penetrate the water-soluble membrane, causing the membrane to swell and rupture. On the other hand, liquid formulations require the addition of thickeners to maintain the integrity of the coating, which in turn weakens the release efficiency of the active ingredients. In comparison, solid detergents coated with water-soluble membranes offer the advantage of quantitative packaging and are highly favored in the market.

[0003] However, existing cleaning agents mainly rely on oxidative decomposition to remove dirt, and the overall decontamination strength is insufficient. In addition, the inner wall structure of the washing machine tub is complex, and the decontamination depth relying on oxidative decomposition and physical flushing is insufficient. In the existing technology, the cleaning efficiency can be improved to a certain extent by compounding penetrants. However, conventional penetrants only serve as wetting carriers and lack the chemical softening function for the dirt matrix, resulting in low oxidative decomposition efficiency, making it difficult to improve the cleaning efficiency. Summary of the Invention

[0004] In order to solve the technical problems mentioned in the background technology, the purpose of the present invention is to provide a washing machine tank cleaner wrapped with a water-soluble film and a preparation process thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A washing machine tub cleaner wrapped in a water-soluble film comprises the following components: 0.1-0.3 wt% of a bactericide, 0.25-0.5 wt% of an enzyme preparation, 0.4-0.5 wt% of a chelating agent, 0.9-1.2 wt% of a penetrant, 1.2-1.8 wt% of a surfactant, 0.15-0.22 wt% of an anti-redeposition agent, 0.4-0.6 wt% of colored particles, 0.2-0.3 wt% of an essence, and the balance being sodium percarbonate.

[0007] Wherein, the penetrant is prepared by the following method:

[0008] Step A1: Diallylamine, triethylamine, and acetone were mixed, and nitrogen was introduced. Ethylene glycol diglycidyl ether was slowly added at room temperature and stirred for 2-3 hours. The reaction was then continued in a water bath at 40-50°C for 1-1.5 hours. After the reaction was completed, the acetone was evaporated in vacuo to obtain Intermediate 1.

[0009] In the above step A1 reaction, the ratio of ethylene glycol diglycidyl ether, diallylamine, triethylamine and acetone is 10 mmol: 20 mmol: 1-1.5 mL: 20-30 mL. The ethylene glycol diglycidyl ether and diallylamine undergo ring opening. The specific reaction process is as follows:

[0010]

[0011] Step A2: Mix the intermediate 1, 3-iodopropanol, potassium carbonate, and isopropanol, and purge with dry air. Heat to 75°C and reflux for 8-10 hours. After the reaction is complete, filter and remove isopropanol from the filtrate by rotary evaporation. Wash the substrate with cyclohexane and dry it to obtain the intermediate 2.

[0012] In the above step A2 reaction, the ratio of the intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol is 10 mmol: 22-24 mmol: 3.5-4.5 g: 60-70 mL. The intermediate 1 and 3-iodopropanol are subjected to a quaternization reaction. The specific reaction process is as follows:

[0013]

[0014] Step A3: Dissolve the intermediate sodium 2,3-mercapto-1-propanesulfonate and dimethylformamide aqueous solution, add the photoinitiator and mix well, and then conduct the photoinitiator at 600-800 mW / cm 2 The mixture was stirred and reacted under ultraviolet irradiation for 10-13 hours. After the reaction was completed, dimethylformamide was removed by vacuum rotary evaporation to obtain a penetrant.

[0015] In the above step A3 reaction, the amount ratio of intermediate 2, sodium 3-mercapto-1-propanesulfonate, photoinitiator and dimethylformamide aqueous solution is 10 mmol:40 mmol:55-70 mg:45-55 mL, and sodium 3-mercapto-1-propanesulfonate and intermediate 2 undergo addition reaction. The specific reaction process is as follows:

[0016]

[0017] Preferably, the bactericide is one of menthol and sodium hypochlorite.

[0018] Preferably, the enzyme preparation is alkaline protease.

[0019] Preferably, the surfactant is fatty alcohol polyoxyethylene ether.

[0020] A preparation method of a washing machine tank cleaner wrapped with a water-soluble film comprises the following steps: uniformly mixing the components, quantitatively packaging the components, and then packaging the components by pressing the water-soluble film to obtain the washing machine tank cleaner wrapped with the water-soluble film.

[0021] Beneficial effects of the present invention:

[0022] The cleaning agent of the present invention uses sodium percarbonate as an active ingredient and adds a self-developed penetrant to improve cleaning efficiency and cleaning depth. The penetrant is prepared by ring-opening ethylene glycol diglycidyl ether and diallylamine to prepare intermediate 1, which is then quaternized with 3-iodopropanol to prepare intermediate 2. Finally, sodium 3-mercapto-1-propanesulfonate is subjected to double-bond click addition to intermediate 2 to introduce a branched end sodium sulfonate structure modification. By designing a penetrant with a multi-level functional structure and combining it with water-soluble film coating technology, the core defects of the existing technology are solved. The specific advantages are as follows:

[0023] 1. The penetrant has a quaternary ammonium structure and a sodium sulfonate dual structure, excellent water dispersibility, and excellent compatibility with water-soluble membranes (such as polyvinyl alcohol), which prevents premature dissolution of the membrane material or aggregation of the penetrant, ensuring the stability of the detergent during storage;

[0024] 2. Polybranched sodium sulfonate imparts low surface tension to the molecule, allowing it to quickly wet the washing machine tub interlayer. The quaternary ammonium structure adsorbs onto the negatively charged dirt surface through electrostatic action, neutralizing the charge and destroying the dirt-substrate interface. The sodium sulfonate group chelates with calcium and magnesium ions, breaking down the soap scum crystal structure and enhancing the hydrophilicity of the dirt. This allows the active oxygen released by sodium percarbonate to penetrate deeper into the dirt, improving the efficiency of oxidative decomposition.

[0025] 3. The sulfur, nitrogen and oxygen atoms in the molecule form a three-dimensional network chelating site, which has a strong coordination effect on the metal ions in the soap scum, so that the penetrant forms a directional surface chelation on the inner wall of the washing machine, significantly improving the efficiency of soap scum removal.

[0026] The introduction of penetrants enables targeted penetration, rapid softening and deep removal of dirt in the interlayer of the washing machine tub, solving the industry pain points of "surface cleaning and interlayer residue" of traditional cleaners, while being both highly efficient and environmentally friendly. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0028] Example 1, preparation of penetrant, the specific implementation process is as follows:

[0029] Step A1: Diallylamine, triethylamine, and acetone were mixed, nitrogen was introduced, and stirring was performed at 120 rpm. Ethylene glycol diglycidyl ether was slowly added at room temperature and stirred for 3 h. The reaction was then continued in a water bath at 40°C for 1.5 h. The ratio of ethylene glycol diglycidyl ether, diallylamine, triethylamine, and acetone was 10 mmol:20 mmol:1 mL:20 mL. After the reaction was completed, the acetone was evaporated in vacuo to obtain Intermediate 1.

[0030] Step A2: Take intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol, mix them, pass dry air protection, raise the temperature to 75°C (steam temperature) and reflux for 10 hours, wherein the amount ratio of intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol is 10mmol:22mmol:3.5g:60mL. After the reaction is completed, filter to remove potassium carbonate, and remove isopropanol by rotary evaporation of the filtrate. The substrate is washed with cyclohexane and dried to obtain intermediate 2.

[0031] Step A3: Mix the intermediate 2,3-mercapto-1-propanesulfonic acid sodium and dimethylformamide aqueous solution, then add the photoinitiator and mix well. Stir at 60 rpm and use 600 mW / cm 2 The reaction was carried out under ultraviolet irradiation for 13 hours, wherein the amount ratio of the intermediate 2, 3-mercapto-1-propanesulfonic acid sodium, the photoinitiator and the dimethylformamide aqueous solution was 10 mmol: 40 mmol: 55 mg: 45 mL, the photoinitiator used was photoinitiator 1173, and the mass fraction of the dimethylformamide aqueous solution was 50%. After the reaction was completed, the dimethylformamide was removed by vacuum rotary evaporation to obtain the penetrant.

[0032] Example 2, preparation of penetrant, the specific implementation process is as follows:

[0033] Step A1: Diallylamine, triethylamine, and acetone were mixed, nitrogen was introduced, and stirring was performed at 150 rpm. Ethylene glycol diglycidyl ether was slowly added at room temperature and stirred for 2 h. The reaction was then continued in a water bath at 50°C for 1 h. The ratio of ethylene glycol diglycidyl ether, diallylamine, triethylamine, and acetone was 10 mmol:20 mmol:1.5 mL:30 mL. After the reaction was completed, the acetone was evaporated in vacuo to obtain Intermediate 1.

[0034] Step A2: Take intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol, mix them, pass dry air protection, raise the temperature to 75°C and reflux for 8 hours, wherein the amount ratio of intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol is 10mmol:24mmol:4.5g:70mL. After the reaction is completed, filter to remove potassium carbonate, and remove isopropanol by rotary evaporation of the filtrate. The substrate is washed with cyclohexane and dried to obtain intermediate 2.

[0035] Step A3: Mix the intermediate 2,3-mercapto-1-propanesulfonic acid sodium and dimethylformamide aqueous solution, then add the photoinitiator and mix well. Stir at 90 rpm and use 800 mW / cm 2 The reaction was carried out under ultraviolet irradiation for 10 hours, wherein the amount ratio of the intermediate 2, 3-mercapto-1-propanesulfonic acid sodium, the photoinitiator and the dimethylformamide aqueous solution was 10 mmol: 40 mmol: 70 mg: 55 mL, the photoinitiator used was photoinitiator 1173, and the mass fraction of the dimethylformamide aqueous solution was 60%. After the reaction was completed, the dimethylformamide was removed by vacuum rotary evaporation to obtain the penetrant.

[0036] Example 3, preparation of penetrant, the specific implementation process is as follows:

[0037] Step A1: Diallylamine, triethylamine, and acetone were mixed, nitrogen was introduced, and stirring was performed at 150 rpm. Ethylene glycol diglycidyl ether was slowly added at room temperature and stirred for 2.5 h. The reaction was then continued in a water bath at 40°C for 1.3 h. The ratio of ethylene glycol diglycidyl ether, diallylamine, triethylamine, and acetone was 10 mmol:20 mmol:1.3 mL:25 mL. After the reaction was completed, the acetone was evaporated in vacuo to obtain Intermediate 1.

[0038] Step A2: Mix the intermediate 1, 3-iodopropanol, potassium carbonate, and isopropanol, introduce dry air protection, and heat to 75°C for reflux reaction for 9 hours. The ratio of the intermediate 1, 3-iodopropanol, potassium carbonate, and isopropanol is 10 mmol:23 mmol:4 g:65 mL. After the reaction is completed, the potassium carbonate is filtered to remove the potassium carbonate, and the filtrate is evaporated to remove the isopropanol. The substrate is washed with cyclohexane and dried to obtain intermediate 2.

[0039] Step A3: Mix the intermediate 2,3-mercapto-1-propanesulfonic acid sodium and dimethylformamide aqueous solution, then add the photoinitiator and mix well. Stir at 90 rpm and use 700 mW / cm 2 The reaction was carried out under ultraviolet irradiation for 11 hours, wherein the amount ratio of the intermediate 2, 3-mercapto-1-propanesulfonic acid sodium, the photoinitiator and the dimethylformamide aqueous solution was 10 mmol: 40 mmol: 65 mg: 50 mL, the photoinitiator used was photoinitiator 1173, and the mass fraction of the dimethylformamide aqueous solution was 50%. After the reaction was completed, the dimethylformamide was removed by vacuum rotary evaporation to obtain the penetrant.

[0040] Example 4, preparation of penetrant, the specific implementation process is as follows:

[0041] Step A1: Diallylamine, triethylamine, and acetone were mixed, nitrogen was introduced, and stirring was performed at 150 rpm. Ethylene glycol diglycidyl ether was slowly added at room temperature and stirred for 2.2 h. The reaction was then continued in a water bath at 45°C for 1.5 h. The ratio of ethylene glycol diglycidyl ether, diallylamine, triethylamine, and acetone was 10 mmol:20 mmol:1.5 mL:25 mL. After the reaction was completed, the acetone was evaporated in vacuo to obtain Intermediate 1.

[0042] Step A2: Take intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol, mix them, pass dry air protection, raise the temperature to 75°C and reflux for 9.5 hours, wherein the amount ratio of intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol is 10mmol:23mmol:4.5g:70mL. After the reaction is completed, filter to remove potassium carbonate, and remove isopropanol by rotary evaporation of the filtrate. The substrate is washed with cyclohexane and dried to obtain intermediate 2.

[0043] Step A3: Mix the intermediate 2,3-mercapto-1-propanesulfonic acid sodium and dimethylformamide aqueous solution, then add the photoinitiator and mix well. Stir at 90 rpm and use 800 mW / cm 2 The reaction was carried out under ultraviolet irradiation for 12 hours, wherein the amount ratio of the intermediate 2, 3-mercapto-1-propanesulfonic acid sodium, the photoinitiator and the dimethylformamide aqueous solution was 10 mmol: 40 mmol: 60 mg: 50 mL, the photoinitiator used was photoinitiator 1173, and the mass fraction of the dimethylformamide aqueous solution was 50%. After the reaction was completed, the dimethylformamide was removed by vacuum rotary evaporation to obtain the penetrant.

[0044] Example 5, preparation of penetrant, the specific implementation process is as follows:

[0045] Step A1: Diallylamine, triethylamine, and acetone were mixed, nitrogen was introduced, and stirring was performed at 120 rpm. Ethylene glycol diglycidyl ether was slowly added at room temperature and stirred for 3 h. The reaction was then continued in a water bath at 50°C for 1.1 h. The ratio of ethylene glycol diglycidyl ether, diallylamine, triethylamine, and acetone was 10 mmol:20 mmol:1.2 mL:30 mL. After the reaction was completed, the acetone was evaporated in vacuo to obtain Intermediate 1.

[0046] Step A2: Take intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol, mix them, pass dry air protection, raise the temperature to 75°C and reflux for 9 hours, wherein the amount ratio of intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol is 10mmol:24mmol:4g:70mL. After the reaction is completed, filter to remove potassium carbonate, and remove isopropanol by rotary evaporation of the filtrate. The substrate is washed with cyclohexane and dried to obtain intermediate 2.

[0047] Step A3: Mix the intermediate 2,3-mercapto-1-propanesulfonic acid sodium and dimethylformamide aqueous solution, then add the photoinitiator and mix well. Stir at 90 rpm and use 700 mW / cm 2 The reaction was carried out under ultraviolet irradiation for 11 hours, wherein the amount ratio of the intermediate 2, 3-mercapto-1-propanesulfonic acid sodium, the photoinitiator and the dimethylformamide aqueous solution was 10 mmol: 40 mmol: 65 mg: 55 mL, the photoinitiator used was photoinitiator 1173, and the mass fraction of the dimethylformamide aqueous solution was 60%. After the reaction was completed, the dimethylformamide was removed by vacuum rotary evaporation to obtain the penetrant.

[0048] The following implementation process is used to prepare the cleaning agent. The specific component and raw material information is disclosed as follows:

[0049] Sodium percarbonate, an industrial-grade raw material; bactericides, menthol and sodium hypochlorite, both industrial-grade raw materials; enzyme preparation, APG-1115 alkaline protease; chelating agent, ethylenediaminetetraacetic acid, an industrial-grade raw material; penetrant, prepared as described in Examples 1-5 above, respectively designated as samples 1-5; surfactant, AEO-9 fatty alcohol polyoxyethylene ether; anti-redeposition agent, ACUSOL445NG commercial preparation; colored particles, a mixture of commercially available green particles and blue particles of equal mass; flavor, a commercially available lavender solid flavor.

[0050] The following are the formula components in the specific test process as shown in Table 1-Table 2:

[0051] Table 1

[0052] Component / wt% Experimental group 1 Experimental Group 2 Experimental Group 3 Experimental Group 4 Experimental Group 5 Sodium percarbonate 95.68 95.35 95.15 95.47 95.07 Menthol 0.1 0.15 0.2 0.15 0.18 enzyme preparations 0.5 0.4 0.45 0.4 0.5 chelating agents 0.4 0.4 0.5 0.5 0.45 penetrants 0.9 (sample 1) 1.0 (Sample 2) 1.1(Sample 3) 1.1 (Sample 4) 1.2 (Sample 5) surfactants 1.5 1.8 1.7 1.6 1.7 Anti-redeposition agents 0.22 0.2 0.2 0.18 0.15 Colorful particles 0.5 0.5 0.4 0.4 0.5 essence 0.2 0.2 0.3 0.2 0.25

[0053] Table 2

[0054]

[0055]

[0056] Control group 1 refers to test group 5, except that no penetrant was added and the balance was supplemented to 100 wt % with sodium percarbonate. The rest of the process was exactly the same.

[0057] Control group 2, referring to experimental group 5, replaced the penetrant with OEP-70 alkali-resistant penetrant, and the rest of the implementation process was exactly the same.

[0058] Samples were taken from the cleaning agent prepared as above to conduct relevant performance tests. The specific test results are shown in Table 3:

[0059] Table 3

[0060] Active ingredient content / % Active oxygen content / % Sterilization rate / % Cleaning power / % Experimental group 1 1.22 11.78 99.9 95 Experimental Group 2 1.18 11.56 99.8 96 Experimental Group 3 1.35 11.61 99.9 96 Experimental Group 4 1.25 11.35 99.8 97 Experimental Group 5 1.39 11.25 99.7 98 Experimental Group 6 1.28 11.21 99.8 97 Experimental Group 7 1.18 11.95 99.9 95 Experimental Group 8 1.33 11.59 99.9 97 Experimental Group 9 1.27 11.68 99.8 98 Experimental group 10 1.21 11.92 99.8 95 Control group 1 1.42 11.33 99.8 88 Control group 2 1.37 11.29 98.6 90

[0061] Note: The active matter content and active oxygen content are tested according to the method specified in GB / T13173-2021; the bactericidal rate is tested according to the method specified in Appendix 1 of QB / T 2850-2023; the cleaning power is tested according to the method specified in QB / T2117-1995.

[0062] From the test results in Table 3, it can be seen that the active substance and active oxygen content of the detergents in the experimental group and the control group are similar during the washing process, and both have good bactericidal functions. However, the cleaning power of the experimental group reaches more than 95%, with an efficient deep cleaning effect.

[0063] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0064] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A washing machine tank cleaner wrapped in a water-soluble film, characterized in that: The specific components are: bactericide 0.1-0.3wt%, enzyme preparation 0.25-0.5wt%, chelating agent 0.4-0.5wt%, penetrant 0.9-1.2wt%, surfactant 1.2-1.8wt%, anti-redeposition agent 0.15-0.22wt%, color particles 0.4-0.6wt% and flavor 0.2-0.3wt%, and the balance is sodium percarbonate; The penetrant is prepared by the following method: Step A1: Diallylamine, triethylamine, and acetone were mixed, and nitrogen was introduced. Ethylene glycol diglycidyl ether was slowly added at room temperature and stirred for 2-3 hours. The reaction was then continued in a water bath at 40-50°C for 1-1.5 hours to prepare Intermediate 1. Step A2: Intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol were mixed, and dry air was passed through the mixture. The mixture was heated to 75°C and refluxed for 8-10 hours to prepare Intermediate 2. Step A3: Dissolve the intermediate sodium 2,3-mercapto-1-propanesulfonate and dimethylformamide aqueous solution, add the photoinitiator and mix well, and then conduct the photoinitiator at 600-800 mW / cm 2 The mixture was stirred and reacted under ultraviolet irradiation for 10-13 hours to prepare a penetrant.

2. The water-soluble film-wrapped washing machine tank cleaner according to claim 1, characterized in that: The usage ratio of ethylene glycol diglycidyl ether, diallylamine, triethylamine and acetone is 10 mmol: 20 mmol: 1-1.5 mL: 20-30 mL.

3. The water-soluble film-wrapped washing machine tank cleaner according to claim 2, characterized in that: The usage ratio of intermediate 1, 3-iodopropanol, potassium carbonate and isopropanol is 10 mmol: 22-24 mmol: 3.5-4.5 g: 60-70 mL.

4. The water-soluble film-wrapped washing machine tank cleaner according to claim 3, characterized in that: The usage ratio of the intermediate 2, sodium 3-mercapto-1-propanesulfonate, the photoinitiator and the dimethylformamide aqueous solution is 10 mmol: 40 mmol: 55-70 mg: 45-55 mL.

5. The water-soluble film-wrapped washing machine tank cleaner according to claim 1, characterized in that: The bactericide is one of menthol and sodium hypochlorite.

6. The water-soluble film-wrapped washing machine tank cleaner according to claim 1, characterized in that: The enzyme preparation is alkaline protease.

7. The water-soluble film-wrapped washing machine tank cleaner according to claim 1, characterized in that: The surfactant is fatty alcohol polyoxyethylene ether.

8. A method for preparing a washing machine tank cleaner coated with a water-soluble film according to any one of claims 1 to 7, characterized in that: Specifically, the components are mixed evenly, quantitatively divided and packaged, and then the components are packaged by pressing a water-soluble film to obtain a washing machine tank cleaner wrapped with a water-soluble film.

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