Biological enzyme synergistic natural laundry detergent and preparation method thereof

Abstract

This invention provides a bio-enzyme synergistic natural laundry detergent and its preparation method, comprising the following components: a plant-derived surfactant compound system, fatty acids, a compound bio-enzyme preparation, a natural alkaline neutralizer, functional additives, and water; wherein the plant-derived surfactant compound system includes plant-derived anionic surfactants and plant-derived nonionic surfactants. This invention constructs a core stain-removing system through a precise compounding of plant-derived anionic and nonionic surfactants with specific structural formulas, achieving a dual synergistic effect of surfactants and bio-enzymes through targeted catalytic decomposition of multiple enzyme systems. Simultaneously, the optimized preparation process ensures the activity of the enzyme preparation. The resulting laundry detergent possesses high naturalness, excellent stability, and strong targeted stain removal capabilities. Even at low concentrations, it exhibits excellent removal effects on various common and stubborn stains, while being gentle on clothes and easily biodegradable, overcoming the shortcomings of traditional natural laundry detergents.

Description

Technical Field

[0001] This invention relates to the field of daily chemical products technology, and in particular to a natural laundry detergent with synergistic effects of bio-enzymes and its preparation method. Background Technology

[0002] With consumers' increasing demands for both health and environmental protection as well as washing performance, natural laundry detergents have become the mainstream in the market. However, existing natural laundry detergents still have significant technical shortcomings: On the one hand, traditional natural laundry detergents rely solely on the single detergency of plant-derived surfactants, lacking the ability to target and remove different types of stubborn stains. They are ineffective at removing stubborn stains such as protein, fat, and starch. Furthermore, many products blindly increase the amount of surfactants added to enhance detergency, resulting in residues after washing and difficulty in rinsing. On the other hand, although some natural laundry detergents add single biological enzymes, they do not consider the synergistic compatibility between surfactants and enzymes. The emulsification and penetration of surfactants do not effectively assist the catalytic decomposition of enzymes, and some surfactants may even inhibit enzyme activity, failing to achieve enhanced detergency. In addition, the surfactants in existing natural laundry detergents are mostly simply stacked together without precise formulation based on the molecular structure of plant-derived surfactants, resulting in poor system stability, easy stratification at low temperatures, and low synergistic detergency of surfactants.

[0003] Currently, existing research on natural laundry detergents mainly focuses on the naturalization of raw materials, without exploring the synergistic relationship between surfactant molecular structure, enzyme type, and detergency. For example, some products add long-chain surfactants, which have strong detergency but poor penetration, failing to deliver the enzyme preparation to the stains inside the fabric fibers. Some products add a single type of enzyme preparation, which can only decompose a certain type of stain, and the enzyme activity ratio is not controlled, resulting in the failure of the synergistic effect with the surfactant. In addition, the manufacturing process of some products does not consider the temperature sensitivity of the enzyme preparation, and the process of dissolving surfactants at high temperatures can easily cause enzyme inactivation, thus losing the detergency-enhancing effect of the biological enzyme.

[0004] In summary, developing a natural laundry detergent based on a specific plant-derived surfactant compound, combined with the precise synergy of multiple complex enzyme systems, and achieving dual stain-removing enhancement through surfactants and bio-enzymes, to solve the technical problems of traditional natural laundry detergents such as weak stain removal targeting, poor removal of stubborn stains, and poor synergy between surfactants and enzymes, and to achieve a dual improvement in naturalness and washing performance, is a key issue that urgently needs to be addressed in this field.

[0005] Therefore, it is necessary to provide a new technical solution to overcome the defects existing in the prior art. Summary of the Invention

[0006] Based on this, the present invention provides a natural laundry detergent with synergistic effects of bio-enzymes and its preparation method. The core stain removal system is constructed by precisely compounding plant-derived anionic nonionic surfactants with specific structures. The dual synergistic effect of surfactants and bio-enzymes is achieved by combining the targeted catalytic decomposition of multiple enzyme systems. At the same time, the activity of enzyme preparation is ensured by optimizing the preparation process. The final laundry detergent has the characteristics of high naturalness, excellent stability and strong targeted stain removal ability. It has excellent removal effect on various common stains and stubborn stains at low concentrations. It is also gentle on clothes and easy to degrade, overcoming the defects of traditional natural laundry detergents.

[0007] One object of the present invention is to provide a bio-enzyme synergistic natural laundry detergent, wherein the bio-enzyme synergistic natural laundry detergent comprises the following components by mass fraction: Plant-derived surfactant compound system 15-70% Fatty acids 1-5% Compound biological enzyme preparation 0.1-5% Natural alkaline neutralizer 0.01-1% Functional additives 0.1-10% Water balance; in, The plant-derived surfactant compound system includes plant-derived anionic surfactants and plant-derived nonionic surfactants.

[0008] Furthermore, the plant-derived nonionic surfactant includes polyglycerol fatty acid esters.

[0009] Preferably, the fatty acid is palmitic acid; the polyglycerol fatty acid ester is polyglycerol palmitate.

[0010] Furthermore, the plant-derived nonionic surfactant also includes C8-C 14 One or more of alkyl glycosides, fatty alcohol alkoxylates, and fatty alcohol polyoxyethylene ethers.

[0011] Preferably, the C8-C 14 The structural formula of alkyl glycosides is shown below: RO-(C6H 10 O5) n H Where R is C8-C 14 Plant-derived straight-chain alkyl groups, n=1-3, average degree of polymerization 1.2-1.8; The structural formula of the fatty alcohol alkoxylate is shown below: RO-(EO) x (PO) y H Where R is C 12 -C 18Plant-derived straight-chain alkyl groups, where EO is ethylene oxide and PO is propylene oxide, x=1-16, y=0-16, and both EO and PO are plant-derived; The structural formula of the fatty alcohol polyoxyethylene ether (preferably a natural AEOX series derived from corn / sugarcane fermentation) is shown below: RO-(CH2CH2O) n H Where R is C 12 -C 14 Corn / sugarcane fermentation is derived from all-natural straight-chain alkyl groups, where n is an integer from 3 to 12.

[0012] Furthermore, the plant-derived anionic surfactant includes one or more of cocoyl glycinate, fatty acid methyl ester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfate.

[0013] Preferably, the structural formula of the cocoyl glycinate is as follows: RCO-NH-CH2-COOM Where R is C8-C 18 Plant-derived straight-chain alkyl group, M is Na + K + NH4 + One of them; The structural formula of the fatty acid methyl ester sulfonate (MES) is shown below: RCH(SO3M)COOCH3 Where R is C8-C 16 Plant-derived straight-chain alkyl group, M is Na + K + One of them; The structural formula of the sodium fatty alcohol polyoxyethylene ether sulfate (AES) is shown below: RO-(CH2CH2O) n -SO3M Where R is C 12 -C 14 Plant-derived straight-chain alkyl group, n is 2-3 (i.e., AES 2EO-3EO), M is Na + K + One of them, and the AES is a natural anionic surfactant obtained by sulfonation of plant-derived fatty alcohols and plant-derived ethylene oxide.

[0014] Furthermore, the mass ratio of the plant-derived anionic surfactant to the plant-derived nonionic surfactant is 1:1-5.

[0015] Furthermore, the compound bio-enzyme preparation is selected from one or more of protease, lipase, amylase, cellulase, mannanase, and pectinase. The compound bio-enzyme preparation can specifically decompose various stubborn stains and forms a synergistic cleaning effect with the plant-derived surfactant compound system.

[0016] Furthermore, the natural alkaline neutralizing agent is selected from one or more of sodium hydroxide, sodium carbonate, and potassium bicarbonate. The mixed system after the alkaline neutralizing agent reacts with fatty acids preferably has a pH of 6.5-9.0, which can more fully activate the detergency activity of surfactants and biological enzymes.

[0017] Furthermore, the functional additives are selected from one or more of plant-derived chelating agents, natural preservatives, pH adjusters, colorants, color stabilizers, and liquid fragrances.

[0018] Furthermore, the plant-derived chelating agent is selected from one or more of sodium citrate, sodium phytate, sodium malate, sodium pectate, sodium alginate, disodium glutamate, and sodium aspartate; the preservative is selected from one or more of phenoxyethanol, benzyl alcohol, benzoic acid, potassium sorbate, sodium benzoate, sodium lactate, and sodium dehydroacetate; and the pH adjuster includes citric acid.

[0019] Our research revealed that short-chain fatty alcohol alkyl glycosides exhibit strong solubilizing effects in highly concentrated surfactant systems, forming homogeneous and stable laundry detergents with other surfactants. However, after prolonged low-temperature storage, these detergents often exhibit severe stratification. Combining a certain proportion of cocoyl glycinate and polyglycerol fatty acid esters with a specific amount of short-chain fatty alcohol alkyl glycosides effectively improves the storage performance of the laundry detergent. Furthermore, all of these surfactants can be produced from naturally sourced raw materials, thus achieving the goal of replacing traditional petrochemical-derived organic solvents with naturally sourced surfactants.

[0020] Another object of the present invention is to provide a method for preparing the above-mentioned bio-enzyme synergistic natural laundry detergent, wherein the method for preparing the bio-enzyme synergistic natural laundry detergent includes the following steps: S1. Add natural alkaline neutralizer and water to the preparation container and stir to obtain an alkaline aqueous phase; S2. Add fatty acids to the alkaline aqueous phase, stir, and obtain a neutralized premixed solution. S3. Add the plant-derived surfactant compound system to the neutralized premixed liquid, stir, add the remaining ingredients, stir until homogeneous, and obtain the bio-enzyme synergistic natural laundry detergent.

[0021] The present invention has the following beneficial effects: This invention discloses a bio-enzyme synergistic natural laundry detergent, with natural amino acid-type anionic surfactants and plant-derived fatty acid soap surfactants as the core, synergistically combined with natural alkyl glycosides, polyglycerol fatty acid esters, and natural fatty alcohol polyoxyethylene ether nonionic surfactants. A stable system is constructed through the complementary molecular structures and synergistic functions of the anionic and nonionic surfactants. The various anionic surfactants of this invention lay the foundation for its strong cleaning power with their strong penetration and gentle emulsification properties, while the nonionic surfactants optimize system compatibility with their excellent solubilizing and wetting properties, reducing the aggregation of anionic surfactants. Simultaneously, through charge complementarity and HLB value matching, the stability of the laundry detergent is significantly improved over a wide temperature and concentration range, without issues such as stratification or gelation during long-term storage. More importantly, the surfactant compound system of this invention forms a highly efficient targeted synergistic effect with the composite bio-enzyme preparation. The emulsifying and penetrating action of the surfactants can quickly remove stains from the fabric surface and inside the fibers, while simultaneously creating a stable microenvironment for the enzyme preparation, promoting full contact between the enzyme and the stain. The composite enzyme specifically decomposes various stubborn stains, resulting in a significant improvement in cleaning power compared to traditional natural laundry detergents.

[0022] All the core surfactants in this invention are derived from natural plant materials. The formula is gentle and non-irritating, with a pH value suitable for human skin and various fabrics. It leaves no residue after washing, making it suitable for use in sensitive situations such as baby clothes and underwear, while avoiding damage to fabric fibers. It achieves the characteristics of high stability, strong detergency, and gentle care for clothes.

[0023] It is worth mentioning that the present invention obtains a soap-based system by reacting palmitic acid with an alkaline neutralizing agent. When compounded with polyglycerol fatty acid esters, not only is there good compatibility between alkyl chains, which is beneficial for miscibility and adjustment of system stability, thereby avoiding phase separation, flocculation and other phenomena; but also, polyglycerol fatty acid esters can effectively disperse soap scum in hard water and can synergistically exert chelating effects with other surfactants to achieve a significant reduction in scum, further enhancing the cleaning and washing effect. Detailed Implementation

[0024] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0025] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0026] It should be understood that, except in any operational instance or otherwise indicated, all figures representing the amounts of ingredients used, for example, in the specification and claims, should be understood to be modified in all cases by the term "about". Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximations varying with the desired performance to be obtained according to the invention.

[0027] The following raw materials are used in the embodiments of the present invention: Natural AEO9, purchased from CLARIANT, brand name Genapol LA 090 SG Vita.

[0028] Sodium cocoyl glycinate, purchased from Nanjing Huashi New Materials Co., Ltd., brand name EverSoftTM YCS-30S.

[0029] C8-C 14 Alkyl glycosides: purchased from Shanghai Fakai Chemical Co., Ltd., GreenAPG 0814B46.

[0030] C8-C 10 Alkyl glycoside: Purchased from Yangzhou Chenhua New Materials Co., Ltd., brand name APG 0810, effective content approximately 50%.

[0031] C 12 -C 14 Alkyl glycoside: purchased from BASF Ltd., brand name Glucopon® 600 CSUP.

[0032] Preservative: Purchased from Guangdong Dimei New Material Technology Co., Ltd., brand name Antimicro C230.

[0033] Protease: Purchased from Novozymes (China) Biotechnology Co., Ltd., brand name Progress Uno 101 L.

[0034] Lipase: Purchased from Novozymes (China) Biotechnology Co., Ltd., brand name Lipex 100 L.

[0035] Amylase: Purchased from Novozymes (China) Biotechnology Co., Ltd., brand name Amplify Prime 100 L.

[0036] Fragrance: Purchased from Guangzhou Fenhao Fragrance Co., Ltd., fragrance type YKL019 Eucalyptus.

[0037] The components and their corresponding mass fractions of the bio-enzyme synergistic natural laundry detergents in Examples 1-3 are shown in Table 1.

[0038] Table 1 Mass fraction of Examples 1-3 The preparation method of the bio-enzyme synergistic natural laundry detergent in Examples 1-3 includes the following steps: S1. Add sodium hydroxide and water to the preparation tank according to the above mass fraction, stir and dissolve to obtain an alkaline aqueous phase; S2. Add palmitic acid to the alkaline aqueous phase and stir until the system is homogeneous to obtain the neutralized premixed solution. S3. Add natural AEO9, sodium cocoyl glycinate, and C8-C to the neutralized premixed solution. 14 Alkyl glycosides, C8-C 10 Alkyl glycosides, C 12 -C 14 Alkyl glycosides and polyglycerol-10 palmitate were dissolved by stirring. Citric acid was added, and the temperature of the mixture was adjusted to 30-35℃. The remaining ingredients were added, and the mixture was stirred until it was evenly dispersed and the system was homogeneous, thus obtaining a natural laundry detergent with synergistic effects of bio-enzymes.

[0039] Comparative Examples 1-3 are set up based on Example 1: The difference between Comparative Example 1 and Example 1 is that polyglycerol-10 palmitate was replaced with an equal mass of polyglycerol-10 laurate, while the other components and preparation methods were the same as in Example 1.

[0040] The difference between Comparative Example 2 and Example 1 is that polyglycerol-10 palmitate was replaced with an equal mass of C. 12 -C 14 The alkyl glycosides, other components, and preparation methods are the same as in Example 1.

[0041] The difference between Comparative Example 3 and Example 1 is that C8-C 14 Alkyl glycosides, C8-C 10 Alkyl glycosides were replaced with an equal mass of C 12 -C 14 The alkyl glycosides, other components, and preparation methods are the same as in Example 1.

[0042] Test Example 1 Stability tests were performed on the samples prepared in the examples and comparative examples.

[0043] Test method: Low temperature stability: After sealing the laundry detergent in separate bottles, place them in an environment of 0±2℃ and keep them at a constant temperature for 1 month. Observe whether there is any obvious discoloration, layering or precipitation in the appearance of the laundry detergent. If there is no obvious discoloration, layering or precipitation, it is judged to be qualified for low temperature stability.

[0044] Room temperature stability: After sealing the laundry detergent in separate bottles, place them in an environment of 25±2℃ for 1 month. Observe whether there is any obvious discoloration, layering or precipitation in the appearance of the laundry detergent. If there is no obvious discoloration, layering or precipitation, it is judged to be qualified for room temperature stability.

[0045] High-temperature stability: After sealing the laundry detergent in separate bottles, place them in an environment of 45±2℃ for one month. Observe whether there is any obvious discoloration, layering or precipitation in the appearance of the laundry detergent. If there is no obvious discoloration, layering or precipitation, it is judged to be qualified for high-temperature stability.

[0046] The test results are shown in Table 2.

[0047] Table 2 Stability Test Results As shown in Table 2, the laundry detergents in Examples 1-3, through the compounding of various anionic and nonionic surfactants, achieved a stable mixed system with good stability under the specified conditions. In Comparative Example 2, polyglycerol fatty acid esters were replaced with alkyl glycosides. The large amount of alkyl glycosides lacked compatibility with fatty acid soaps, resulting in a lack of the crystallization-inhibiting and emulsifying effects of polyglycerol fatty acid esters, leading to stratification at both high and low temperatures. Furthermore, Comparative Example 3, lacking the compounding of alkyl glycosides with different carbon chain distributions and using only a single alkyl glycoside, caused an imbalance in the micelle aggregation state and disruption of the hydrophilic-lipophilic balance at high temperatures, resulting in high-temperature turbidity and poor homogeneity.

[0048] Test Example 2 The samples prepared in the examples and comparative examples were subjected to a decontamination test.

[0049] Test method: The detergency test was conducted in accordance with GB / T 13174-2008, "Determination of detergency and recycle performance of detergents for clothing". In the detergency test, the sample dosage was in accordance with the requirements of QB / T 1224, "Liquid detergents for clothing".

[0050] The results are shown in Table 3, where the R value represents the stain removal value and the P value represents the stain removal ratio. Generally, a standard laundry detergent is used as a reference sample, and its stain removal ratio is set to 1.00. The P value is obtained by dividing the R value of other detergents by the R value of the standard laundry detergent. The higher the P value, the better the cleaning power. Since the surfactant content in Examples 2 and 3 meets the concentrated standard, the stain removal test was conducted according to the concentrated detergent standard.

[0051] The test results are shown in Table 3.

[0052] Table 3. Results of Decontamination Performance Test As shown in Table 3, the laundry detergent prepared in the examples has a significantly better cleaning effect on carbon black, protein, and sebum than the standard laundry detergent. Comparative Example 1, using polyglycerol-10 laurate as a component, showed a reduced compatibility with palmitic acid soap, resulting in a slight decrease in cleaning effectiveness. Comparative Example 2, using alkyl glycosides instead of polyglycerol fatty acid esters, further reduced the compatibility with the carbon chain arrangement and micelle structure of the fatty acid soap, leading to unsatisfactory emulsification and penetration, reduced synergistic cleaning ability with enzymes and other components, and decreased soap scum dispersion, thus exhibiting significantly poor cleaning performance. Comparative Example 3, using a single alkyl glycoside with a narrow carbon chain distribution, could not form a mixed micelle system highly compatible with other surfactants, resulting in insufficient synergistic cleaning performance with the complex enzyme. Its emulsification and dispersion efficiency for carbon black and protein stains, as well as its ability to remove sebum stains, were weaker than the compound system, failing to achieve optimal cleaning effect.

[0053] Test Example 3 Anti-redeposition tests were conducted on laundry detergent samples.

[0054] Test method: First wash: A yellow soil stain suspension was prepared by mixing 75% deionized water, 20% standard yellow dust, and 5% oil stains according to the specified mass ratio. This yellow soil stain suspension, along with the laundry detergent to be tested and five standard 6 cm × 6 cm white cotton cloths, were placed in a vertical stain remover. The washing process was performed according to GB / T13174-2021 standard. The detergent concentration was 1 g / L, and the yellow soil stain suspension concentration was 10 g / L. After washing, the white cloths were air-dried, and the whiteness value after the first wash was recorded.

[0055] Circulating washing: Without adding loess stain suspension, wash the white cloth after the first wash with the corresponding detergent according to GB / T13174-2021 standard. The detergent concentration is 1 g / L. After each wash, dry the white cloth and wash it again. Repeat the washing cycle 10 times and record the whiteness value after washing.

[0056] The test results are shown in Table 4.

[0057] Table 4 Results of Redeposition Resistance Test As shown in Table 4, the anti-redeposition effect of the embodiments is better than that of the comparative examples, indicating that it can effectively remove dirt, disperse soap scum, chelate metal ions, and effectively inhibit the formation and deposition of scum. The anti-redeposition effect of comparative examples 1-3, which replaced the formulation components, decreased to varying degrees, proving that the various components of the present invention can form a good synergistic effect, avoiding dirt adhesion and deposition, and demonstrating significant advantages in both decontamination and anti-redeposition.

[0058] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0059] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A natural laundry detergent with synergistic effects of bio-enzymes, characterized in that, The bio-enzyme synergistic natural laundry detergent comprises the following ingredients by mass fraction: Plant-derived surfactant compound system 15-70% Fatty acids 1-5% Compound biological enzyme preparation 0.1-5% Natural alkaline neutralizer 0.01-1% Functional additives 0.1-10% Water balance; in, The plant-derived surfactant compound system includes plant-derived anionic surfactants and plant-derived nonionic surfactants.

2. The bio-enzyme synergistic natural laundry detergent according to claim 1, characterized in that, The plant-derived nonionic surfactants include polyglycerol fatty acid esters.

3. The bio-enzyme synergistic natural laundry detergent according to claim 2, characterized in that, The plant-derived nonionic surfactant also includes C8-C. 14 One or more of alkyl glycosides, fatty alcohol alkoxylates, and fatty alcohol polyoxyethylene ethers.

4. The bio-enzyme synergistic natural laundry detergent according to claim 1, characterized in that, The plant-derived anionic surfactants include one or more of the following: cocoyl glycinate, fatty acid methyl ester sulfonate, and sodium fatty alcohol polyoxyethylene ether sulfate.

5. The bio-enzyme synergistic natural laundry detergent according to claim 1, characterized in that, The mass ratio of the plant-derived anionic surfactant to the plant-derived nonionic surfactant is 1:1-5.

6. The bio-enzyme synergistic natural laundry detergent according to claim 1, characterized in that, The compound bio-enzyme preparation is selected from one or more of the following: protease, lipase, amylase, cellulase, mannanase, and pectinase.

7. The bio-enzyme synergistic natural laundry detergent according to claim 1, characterized in that, The natural alkaline neutralizing agent is selected from one or more of sodium hydroxide, sodium carbonate, and potassium bicarbonate.

8. The bio-enzyme synergistic natural laundry detergent according to claim 1, characterized in that, The functional additives are selected from one or more of plant-derived chelating agents, natural preservatives, pH adjusters, colorants, color stabilizers, and liquid fragrances.

9. The bio-enzyme synergistic natural laundry detergent according to claim 8, characterized in that, The plant-derived chelating agent is selected from one or more of sodium citrate, sodium phytate, sodium malate, sodium pectate, sodium alginate, disodium glutamate, and sodium aspartate; the preservative is selected from one or more of phenoxyethanol, benzyl alcohol, benzoic acid, potassium sorbate, sodium benzoate, sodium lactate, and sodium dehydroacetate; and the pH adjuster includes citric acid.

10. The method for preparing the bio-enzyme synergistic natural laundry detergent according to any one of claims 1-9, characterized in that, The preparation method of the bio-enzyme synergistic natural laundry detergent includes the following steps: S1. Add natural alkaline neutralizer and water to the preparation container and stir to obtain an alkaline aqueous phase; S2. Add fatty acids to the alkaline aqueous phase, stir, and obtain a neutralized premixed solution. S3. Add the plant-derived surfactant compound system to the neutralized premixed liquid, stir, add the remaining ingredients, stir until homogeneous, and obtain the bio-enzyme synergistic natural laundry detergent.

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