Long-acting enzyme-stable washing composition and preparation method thereof

Abstract

The invention discloses a long-acting enzyme-stable washing composition and a preparation method thereof, and belongs to the field of washing products. The washing composition comprises the following raw materials in parts by weight: 15-29 parts of a film-forming agent; 37 to 55 parts of a total surfactant; 0.5 to 5 parts of a shape promoting agent; 0.5-4 parts of a chelating agent; 0.1-6 parts of an enzyme preparation; the total surfactant comprises an anionic surfactant, the anionic surfactant comprises C12-C18 alpha-olefin sulfonate and C8-C22 fatty alcohol sulfate, and the mass ratio of the C12-C18 alpha-olefin sulfonate to the C8-C22 fatty alcohol sulfate is (1.9-15): 1. The detergent provided by the invention has the effect that a washing product can still keep good dirt-removing power after being stored for a long time.

Description

Technical Field

[0001] This application relates to the field of detergent products, and in particular to a long-acting enzyme-stabilized detergent composition and its preparation method. Background Technology

[0002] Detergent products often contain enzymes to enhance their stain-removing ability and thus improve cleaning power. The mechanism of enzymes is mainly through enzymatic catalysis, which breaks down stains into smaller molecules. These smaller molecules are more easily rinsed away by water, thereby effectively removing stains.

[0003] However, after adding enzyme preparations, the activity of the enzyme preparations is affected due to long-term storage, which in turn makes the detergent's lasting cleaning power more vulnerable.

[0004] The activity of enzyme preparations in detergent products is mainly affected by the following factors: First, the high temperature environment during transportation causes partial loss of enzyme activity; Second, the surfactants that are indispensable in detergent products can also affect enzyme activity. For example, the charge carried by the ions ionized by ionic surfactants can cause changes in the spatial structure of enzyme protein, thereby affecting enzyme activity. Especially after long-term storage, the reduced enzyme activity can easily lead to a loss of detergency. Summary of the Invention

[0005] In order to enable detergent products to maintain good detergency after long-term storage, this application provides a long-acting enzyme-stabilized detergent composition and its preparation method.

[0006] Firstly, the washing composition provided in this application adopts the following technical solution: A washing composition comprising the following raw materials in parts by weight: Film-forming agent 15-29 parts; total surfactant 37-55 parts; forming agent 0.5-5 parts; chelating agent 0.5-4 parts; enzyme preparation 0.1-6 parts; The total surfactant comprises anionic surfactants, which include sodium C12-C18 α-alkenyl sulfonate and C8-C22 fatty alcohol sulfate, with a mass ratio of sodium C12-C18 α-alkenyl sulfonate to C8-C22 fatty alcohol sulfate of (1.9-15):1.

[0007] By adopting the above technical solutions, sodium α-alkenylsulfonate and fatty alcohol sulfate are anionic surfactants with strong detergency. Among them, fatty alcohol sulfate has a greater impact on enzyme activity than sodium α-alkenylsulfonate. In addition, sodium α-alkenylsulfonate has a weaker denaturing effect on skin proteins and is less likely to damage the sebum membrane barrier. In transdermal irritation tests, it performs better than traditional sulfate surfactants such as fatty alcohol sulfate. However, the strong hygroscopicity of sodium α-alkenylsulfonate can capture environmental moisture, which increases the water content of the detergent sheets and reduces their stability.

[0008] This application, in the presence of an enzyme preparation in the detergent composition, uses a combination of C12-C18 α-alkenylsulfonate and C8-C22 fatty alcohol sulfate as an anionic surfactant, preferably with the carbon chain range and ratio of α-alkenylsulfonate and fatty alcohol sulfate, to improve the detergency of the detergent composition after long-term storage and to improve the stability of the detergent sheets subsequently produced.

[0009] Sodium α-alkenylsulfonate is a branched olefin with a loosely packed micelle core, resulting in weak insertion force into the hydrophobic regions of enzymes. It also contains amphiphilic groups, leading to a thicker hydration layer on the micelle surface, further reducing hydrophobic contact with the enzyme. The critical micelle concentration (CMC) of sodium α-alkenylsulfonate is lower than that of fatty alcohol sulfate. At the same concentration, sodium α-alkenylsulfonate forms more micelles and has a lower concentration of free monomers. When laundry detergent sheets dissolve in water, a mixture of fatty alcohol sulfate and sodium α-alkenylsulfonate micelles preferentially forms, significantly reducing the CMC and further decreasing the concentrations of both free monomers. The surface charge density of the fatty alcohol sulfate and sodium α-alkenylsulfonate micelles is lower than that of pure fatty alcohol sulfate or sodium α-alkenylsulfonate micelles, weakening electrostatic repulsion with the enzyme and preventing enzyme inactivation due to micelle encapsulation. The formation of a homogeneous solid blend between fatty alcohol sulfate and sodium α-alkenylsulfonate avoids the localized enrichment of fatty alcohol sulfate during storage, preventing the formation of highly active monomer regions that could affect enzyme activity.

[0010] Optionally, the total surfactant comprises anionic surfactant, nonionic surfactant and softening antistatic agent, wherein the content of anionic surfactant in the total surfactant is 50-85% by mass, the content of nonionic surfactant is 10-35% and the content of softening antistatic agent is 5-20%.

[0011] By adopting the above technical solution, anionic surfactants and nonionic surfactants achieve synergistic detergency, and together with softening and antistatic agents, they achieve antistatic properties in fabrics, thereby enhancing the overall performance of the washing composition.

[0012] Optionally, the nonionic surfactant includes at least one of secondary alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkyl glycoside, alcohol ether glycoside, modified oil ethoxylate, and EO / PO block polyether.

[0013] By adopting the above technical solution, the nonionic surfactant has good solubilizing and wetting effects. When anionic surfactant is used as the main surfactant, the surface activity of the washing system can be further improved, and the washing function can be better.

[0014] Optionally, the softening and antistatic agent includes at least one of methyl sulfate [ethoxylated cocoyl di(hydroxyethyl)formate ammonium] salt, hydrolyzed wheat protein / PVP copolymer, and hydrolyzed wheat protein / silicone copolymer.

[0015] By adopting the above technical solutions, static electricity in fabrics can be reduced, improving the wearing comfort of fabrics after washing.

[0016] Optionally, the enzyme preparation includes at least one of protease, cellulase, amylase, mannanase, pectinase, phosphodiesterase, and lipase.

[0017] By adopting the above technical solutions, the enzyme preparations promote the decomposition of organic matter in stains under catalysis. Through the synergistic effect of different types of enzyme preparations, precise removal of various types of stains is achieved, improving the detergency of the washing composition. Furthermore, in this application, the use of a compound of C12-C18 α-olefin sulfonate and C8-C22 fatty alcohol sulfate as an anionic surfactant extends the activity period of the enzyme preparations, allowing them to maintain their catalytic and detergency effects even after long-term storage.

[0018] Optionally, the film-forming agent includes polyvinyl alcohol.

[0019] Optionally, the molecular weight of the polyvinyl alcohol is 84,000-130,000.

[0020] Optionally, the forming agent includes at least one of glycerol, propylene glycol, butylene glycol, hexanediol, octyl glycol, and sorbitol.

[0021] By adopting the above technical solution, the stability of the washing sheet is improved after the washing composition is formed into a washing sheet.

[0022] Optionally, the chelating agent includes at least one of sodium citrate, tetrasodium glutamate diacetate, trisodium methylglycine diacetate, and sodium ethylenediamine disuccinate.

[0023] By adopting the above technical solution, the chelating agent can chelate with metal ions in hard water or tap water, form a synergistic effect with plant polysaccharides to achieve better water softening, and the chelating agent can also play a role in adjusting the pH of the slurry.

[0024] Optional ingredients may also include one or more of dyes, fragrances, and plant extracts.

[0025] By adopting the above technical solutions, plant extracts can be added to achieve antibacterial or natural fragrance retention, dyes can be added to give the washing composition a specific color, and fragrances can be added to give the washing composition a scent, depending on the product requirements.

[0026] Secondly, the method for preparing a washing composition provided in this application adopts the following technical solution: A method for preparing a detergent composition includes the following steps: Polyvinyl alcohol is mixed with water under heating conditions until the mixture dissolves. Add anionic and nonionic surfactants and stir to dissolve; Stop heating, add softening and antistatic agent, shaping agent and chelating agent, and continue stirring; Add the enzyme preparation and continue stirring to obtain a slurry; The slurry is dried, shaped into sheets, and a washing composition is obtained.

[0027] In summary, this application has the following beneficial effects: 1. This application, in the presence of enzyme preparations in the detergent composition, uses a combination of C12-C18 α-alkenylsulfonate sodium and C8-C22 fatty alcohol sulfate as an anionic surfactant. The preferred carbon chain range and ratio of α-alkenylsulfonate sodium and fatty alcohol sulfate enhance the detergency of the detergent composition after long-term storage and improve the stability of the subsequently produced detergent sheets. When the detergent sheets dissolve in water, fatty alcohol sulfate and α-alkenylsulfonate mixed micelles preferentially form, significantly reducing the critical mixed micelle concentration and further reducing the concentrations of the two free monomers. The surface charge density of the fatty alcohol sulfate and α-alkenylsulfonate mixed micelles is lower than that of pure fatty alcohol sulfate or α-alkenylsulfonate micelles, weakening the electrostatic repulsion with the enzyme and preventing the enzyme from being encapsulated and inactivated.

[0028] 2. The fatty alcohol sulfate and sodium α-olefin sulfonate form a homogeneous solid blend, which can prevent the local enrichment of fatty alcohol sulfate during storage, thus avoiding the formation of highly active monomeric regions that would affect enzyme activity. Attached Figure Description

[0029] Figure 1 This is a graph showing the trend of protein detergency of detergent tablets at a temperature of (25±2)℃.

[0030] Figure 2 This is a graph showing the trend of the sebum-removing performance of the detergent sheets at a temperature of (25±2)℃.

[0031] Figure 3 This is a graph showing the trend of protein detergency of detergent tablets at a temperature of (45±2)℃.

[0032] Figure 4 This is a graph showing the trend of the sebum-removing performance of the detergent sheets at a temperature of (45±2)℃. Detailed Implementation

[0033] The following is in conjunction with the appendix Figure 1-4 This application will be described in further detail.

[0034] Example 1 A washing composition comprising the following raw materials in parts by weight: Film-forming agent 25 parts; total surfactant 53 parts; forming agent 2 parts; chelating agent 3 parts; enzyme preparation 2 parts.

[0035] The film-forming agent is specifically polyvinyl alcohol, with a molecular weight of 85,000.

[0036] The total surfactant consists of anionic surfactants, nonionic surfactants, and softening and antistatic agents. By mass percentage, the total surfactant contains 79.2% anionic surfactants, 13.2% nonionic surfactants, and 7.6% softening and antistatic agents.

[0037] The anionic surfactant is specifically formulated from sodium C12-C18 α-alkenyl sulfonate and C8-C22 fatty alcohol sulfate, with a mass ratio of sodium C12-C18 α-alkenyl sulfonate to C8-C22 fatty alcohol sulfate of 2:1, and more specifically, sodium C12 α-alkenyl sulfonate and sodium C8 fatty alcohol sulfate; the nonionic surfactant is specifically formulated from alkyl glycosides and modified oil ethoxylates; the softening and antistatic agent is specifically methyl sulfate [ethoxylated coconut oil alkyl di(hydroxyethyl)formate ammonium] salt.

[0038] The specific growth promoter is glycerol.

[0039] The chelating agent is sodium citrate.

[0040] The enzyme preparation is specifically a liquid enzyme preparation, which is a compound of protease, amylase and lipase.

[0041] A method for preparing a detergent composition includes the following steps: Polyvinyl alcohol is mixed with 100 parts of water at a temperature of 80°C until the mixture swells and dissolves completely. Keep the temperature at 80℃, add anionic and nonionic surfactants, and stir to dissolve for 30 minutes; Stop heating, add softening and antistatic agent, shaping agent and chelating agent, and continue stirring for 30 minutes; Add the enzyme preparation and continue stirring for 5 minutes to obtain a slurry; The slurry is dried, molded into sheets, and a washing composition is obtained, specifically a washing sheet.

[0042] Example 2-Example 12 The difference between Examples 2 to 12 of the washing composition and Example 1 is that the raw materials of the washing composition are different, as shown in Table 1.

[0043] Table 1 Specifically, the C12-C18 α-alkenyl sulfonate in Examples 2, 4-7, and 9-11 is C12 α-alkenyl sulfonate; the C12-C18 α-alkenyl sulfonate in Examples 3, 8, and 12 is C18 α-alkenyl sulfonate; the C8-C22 fatty alcohol sulfate in Examples 2-5 and 9-11 is C8 fatty alcohol sulfate; and the C8-C22 fatty alcohol sulfate in Examples 6-8 and 12 is C22 fatty alcohol sulfate.

[0044] Methyl sulfate [ethoxylated cocoyl di(hydroxyethyl)formate ammonium] salt was purchased from Evonik Specialty Chemicals (Shanghai) Co., Ltd., model REWOQ UAT CPEM; hydrolyzed wheat protein / silicone copolymer was purchased from Croda Chemicals (Shanghai) Co., Ltd., Coltide HSI; hydrolyzed wheat protein / PVP copolymer was purchased from Croda Chemicals (Shanghai) Co., Ltd., Coltide HPVP.

[0045] Comparative Example 1 The difference from Example 1 is that the raw materials used to prepare the washing composition are different.

[0046] The amount of C8-C22 fatty alcohol sulfate added is 42 parts, and the amount of C12-C18 α-olefin sulfonate sodium added is 0.

[0047] Comparative Example 2 The difference from Example 1 is that the raw materials used to prepare the washing composition are different.

[0048] The amount of C8-C22 fatty alcohol sulfate added is 21 parts, and the amount of C12-C18 α-alkenyl sulfonate added is 21 parts. The mass ratio of C8-C22 fatty alcohol sulfate to C12-C18 α-alkenyl sulfonate is 1:1.

[0049] Comparative Example 3 The difference from Example 1 is that the raw materials used to prepare the washing composition are different.

[0050] The addition amount of C8-C22 fatty alcohol sulfate is 0, and the addition amount of C12-C18 α-olefin sulfonate sodium is 42 parts.

[0051] Comparative Example 4 The difference from Example 1 is that the raw materials used to prepare the washing composition are different.

[0052] The amount of C8-C22 fatty alcohol sulfate added is 2 parts, and the amount of C12-C18 α-alkenyl sulfonate added is 40 parts. The mass ratio of C12-C18 α-alkenyl sulfonate to C8-C22 fatty alcohol sulfate is 20:1.

[0053] The performance tests were conducted on the detergent sheets prepared in each example and comparative example as follows.

[0054] 1. Fabric stain removal test.

[0055] According to GB / T 13174-2021 "Determination of detergency and recycle performance of detergents for clothing", the washing water was hard water with 250 mg / kg CaCl2. The test fabrics were national standard carbon black JB-01 soiled fabric, national standard protein JB-02 soiled fabric, and national standard sebum JB-03 soiled fabric. The detergency was determined. The sample concentration was 0.025%, with 0.2% standard laundry detergent as a control, and the detergency ratio Pi was obtained. When Pi ≥ 1.0, it was qualified, and Pi < 1.0 was unqualified. The detergency was measured at day 0, week 1, week 4, and week 24 in an environment with a temperature of (25±2)℃ and a relative humidity of (45±5)%. The detergency was also measured at week 1, week 4, and week 24 in an environment with a temperature of (45±2)℃ and a relative humidity of (45±5)%. The detergency was measured after 7 days in an environment with a temperature of (25±2)℃ and a relative humidity of (75±5)%. The results are shown in Tables 2 and 3. Figure 1 , Figure 2 , Figure 3 and Figure 4 As shown.

[0056] Table 2. Decontamination test at (25±2)℃ storage Table 3. Decontamination test at (45±2)℃ storage Combination Figure 1 , Figure 2 , Figure 3 and Figure 4 It can be seen that, compared with Comparative Examples 1-4, the detergency performance of Examples 1-12 did not decrease significantly after 7 days of storage at room temperature; similarly, the detergency performance did not decrease significantly after 28 days of storage at 45°C.

[0057] 2. Moisture resistance stability Place a box of washing tablets (the washing tablets are stacked on top of each other inside) in a test environment with a temperature of (25 ± 2) °C and a relative humidity of (85 ± 5) %, for a test time of 48 h. Take it out, then separate two washing tablets, and observe whether there is any adhesion between the tablets. The results are shown in Table 4.

[0058] 3. Antistatic test The test is carried out according to GB / T6801 - 2013 "Determination of antistatic properties of fabric conditioners". The test concentration of the washing tablets to be tested is 2.5 g / L (the solvent is 250 mg / L hard water), and the logarithmic difference of the surface specific resistance △lgρs ≥ 2.5 is qualified. The test polyester cloth is purchased from the National Research Institute of Daily Chemical Industry. The results are shown in Table 4.

[0059] Table 4 Moisture resistance △lgρs Comparative Example 1 No adhesion 2.4 Comparative Example 2 No adhesion 2.5 Comparative Example 3 Severe adhesion 2.4 Comparative Example 4 Severe adhesion 2.3 Example 1 No adhesion 5.0 Example 2 No adhesion 4.9 Example 3 No adhesion 5.1 Example 4 No adhesion 5.2 Example 5 No adhesion 5.4 Example 6 No adhesion 4.5 Example 7 No adhesion 4.6 Example 8 No adhesion 5.3 Example 9 No adhesion 5.8 Example 10 No adhesion 5.7 Example 11 No adhesion 4.9 Example 12 No adhesion 5.3 4. Determination of critical micelle concentration (CMC) Prepare sample solutions with different concentrations (mass concentration percentage), and measure the surface tension of each sample solution at about 25 °C (instrument: Beijing Hake SFT - D6a). By measuring the surface tension of solutions with different concentrations, plot a graph of surface tension vs. concentration. When the surface adsorption reaches saturation, there will be a turning point in the curve, and the concentration at this point is the CMC. The results are shown in Table 5. (Surface tension of tap water on the day: 73.178 mN / m) Table 5 Combined with the test results, it can be seen that using the compound of C12 - C18 α - olefin sulfonate and C8 - C22 fatty alcohol sulfate as an anionic surfactant, and optimizing the ratio of C12 - C18 α - olefin sulfonate and C8 - C22 fatty alcohol sulfate, can reduce the impact on the activity of the enzyme preparation, so as to still maintain good detergency after long - term storage, and can resist the impact of high temperature on the activity of the enzyme preparation. After long - term and high - temperature storage, the detergency of the washing tablets is maintained.

[0060] In addition, using the compound of C12 - C18 α - olefin sulfonate and C8 - C22 fatty alcohol sulfate as an anionic surfactant, and optimizing the ratio of C12 - C18 α - olefin sulfonate and C8 - C22 fatty alcohol sulfate, can also better exert the antistatic effect of the fabric softening antistatic agent and improve the wet stability of the washing tablets.

[0061] This specific embodiment is only an interpretation of the present application, and it does not limit the present application. Those skilled in the art can make modifications without creative contributions to this specific embodiment according to needs after reading this specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A washing composition, characterized in that: Including the following parts by weight of raw materials: Film-forming agent: 15-29 parts; Total surfactant: 37-55 parts; Forming agent 0.5-5 parts; chelating agent 0.5-4 parts; enzyme preparation 0.1-6 parts; The total surfactant comprises anionic surfactants, which include sodium C12-C18 α-alkenyl sulfonate and C8-C22 fatty alcohol sulfate, with a mass ratio of sodium C12-C18 α-alkenyl sulfonate to C8-C22 fatty alcohol sulfate of (1.9~15):

1.

2. The washing composition according to claim 1, characterized in that: The total surfactant comprises anionic surfactants, nonionic surfactants, and softening and antistatic agents. By mass percentage, the total surfactant contains 50-85% anionic surfactants, 10-35% nonionic surfactants, and 5-20% softening and antistatic agents.

3. The washing composition according to claim 1, characterized in that: The nonionic surfactant includes at least one of secondary alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkyl glycoside, alcohol ether glycoside, modified oil ethoxylate, and EO / PO block polyether.

4. The washing composition according to claim 1, characterized in that: The softening and antistatic agent includes at least one of methyl sulfate [ethoxylated cocoyl di(hydroxyethyl)formate ammonium] salt, hydrolyzed wheat protein / PVP copolymer, and hydrolyzed wheat protein / silicone copolymer.

5. The washing composition according to claim 1, characterized in that: The enzyme preparation includes at least one of protease, cellulase, amylase, mannanase, pectinase, phosphodiesterase, and lipase.

6. The washing composition according to claim 1, characterized in that: The film-forming agent includes polyvinyl alcohol.

7. The washing composition according to claim 1, characterized in that: The shaping agent includes at least one of glycerol, propylene glycol, butylene glycol, hexanediol, octyl glycol, and sorbitol.

8. A washing composition according to claim 1, characterized in that: The chelating agent includes at least one of sodium citrate, tetrasodium glutamate diacetate, trisodium methylglycine diacetate, and sodium ethylenediamine disuccinate.

9. A washing composition according to claim 1, characterized in that: The raw materials also include one or more of dyes, fragrances, and plant extracts.

10. A method for preparing the detergent composition as described in claim 1, characterized in that: Includes the following steps: Polyvinyl alcohol is mixed with water under heating conditions until the mixture dissolves. Add anionic and nonionic surfactants and stir to dissolve; Stop heating, add softening and antistatic agent, shaping agent and chelating agent, and continue stirring; Add the enzyme preparation and continue stirring to obtain a slurry; The slurry is dried, shaped into sheets, and a washing composition is obtained.

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