Enzyme-containing detergent composition and high-temperature stable dishwashing liquid

Abstract

The invention relates to the technical field of detergents, and provides an enzyme-containing detergent composition and a high-temperature stable dishwashing liquid, the enzyme-containing detergent composition comprises an inclusion compound formed by a cyclodextrin-polyethylene glycol graft copolymer and an enzyme, and a surfactant; the surfactant contains sorbitan ester and an EO / PO (Ethylene Oxide / Propylene Oxide) block copolymer. By optimizing the composition of the enzyme-containing clathrate compound and the surfactant, the cleaning ability of the detergent composition is improved from multiple angles, high cleaning ability for stubborn stains is achieved, and the enzyme activity retention rate of the enzyme-containing detergent composition is stable and far exceeds that of a traditional formula (generally lower than 50%) after 20 rounds of tests in a high-temperature environment of a dish-washing machine. And the performance of the product can be well maintained in the whole shelf life and service cycle.

Description

Technical Field

[0001] This invention relates to the field of detergent technology, and more particularly to enzyme-containing detergent compositions and high-temperature stable dishwashing liquids. Background Technology

[0002] Currently, automatic detergent dispensing has become a mainstream feature in high-end dishwashers due to its convenience. This function automatically dispenses detergent through an intelligent pumping system, but this requires the detergent to be pre-stored in the dishwasher's dispenser, which places stringent demands on the system's stability during long-term storage and under complex environments.

[0003] In existing technologies, detergents using only high-alkali, high-chelating-agent systems have the advantage of good stability. However, these detergents are ineffective at removing dried proteins (such as steamed eggs), caramelized starch (such as rice crust), and easily sticky vegetable particles (such as spinach), and cannot inhibit their secondary deposition, resulting in poor cleaning power. Furthermore, existing enzyme-containing dishwashing liquids experience a rapid decline in enzyme activity due to the self-digestion and thermal denaturation of proteases and amylases under storage and high-temperature washing conditions, leading to a significant decrease in cleaning power in the later stages of the product's life cycle. Summary of the Invention

[0004] This invention aims to at least solve one of the technical problems existing in related technologies. To this end, this invention proposes an enzyme-containing detergent composition, which, through the combined use of an inclusion complex formed by a cyclodextrin-polyethylene glycol graft copolymer and an enzyme, as well as a specific surfactant, constructs a multi-dimensional enzyme activity protection system, significantly improving the enzyme activity retention rate after high temperature.

[0005] The present invention also proposes a dishwashing liquid.

[0006] The enzyme-containing detergent composition provided according to the present invention comprises a cyclodextrin-polyethylene glycol graft copolymer, an enzyme-formed inclusion complex, and a surfactant; The surfactant contains dehydrated sorbitan ester and EO / PO block copolymer.

[0007] According to the enzyme-containing detergent composition provided by the present invention, the mass ratio of sorbitan ester to EO / PO block copolymer is 1:(1~5); the mass ratio of sorbitan ester to cyclodextrin-polyethylene glycol graft copolymer is 1:(10~15).

[0008] According to the enzyme-containing detergent composition provided by the present invention, the cyclodextrin-polyethylene glycol graft copolymer is obtained by reacting β-cyclodextrin and activated polyethylene glycol monomethyl ether in a molar ratio of 1:(2~4); the activated polyethylene glycol monomethyl ether is obtained by activating the terminal hydroxyl groups of polyethylene glycol monomethyl ether to imidazolium carbamate; preferably, the molecular weight of the polyethylene glycol monomethyl ether is 2000~5000 Da.

[0009] According to the enzyme-containing detergent composition provided by the present invention, the viscosity of the EO / PO block copolymer is 1200~1400 mPa·s.

[0010] According to the enzyme-containing detergent composition provided by the present invention, the pH value of the enzyme-containing detergent composition is 8 or higher; preferably 8 to 10.

[0011] Preferably, the enzyme-containing detergent composition further includes an alkaline auxiliaries; More preferably, the alkaline additive is selected from one or more of sodium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and sodium bicarbonate.

[0012] According to the enzyme-containing detergent composition provided by the present invention, the enzyme-containing detergent composition further includes a chelating agent in a mass ratio of 1 to 30%; Preferably, the chelating agent is selected from one or a combination of two or more of sodium citrate, aminocarboxylate, and tetrasodium ethylenediaminetetraacetate.

[0013] More preferably, the aminocarboxylate is selected from methylglycine diacetate (MGDA) and / or glutamic acid diacetate (GLDA).

[0014] According to the enzyme-containing detergent composition provided by the present invention, the enzyme-containing detergent composition further includes a polymer dispersant in a mass ratio of 0.5-10%; Preferably, the polymer dispersant is selected from acrylic homopolymers and / or acrylic-maleic acid copolymers; more preferably, acrylic-maleic acid copolymers are used.

[0015] According to the enzyme-containing detergent composition provided by the present invention, the enzyme-containing detergent composition comprises, by mass percentage: 1-15% surfactant, 0.5-10% polymer dispersant, 0.1-10% enzyme, 1-15% alkaline auxiliaries, 1-30% chelating agent, 1-20% enzyme protectant, 5-50% solvent, 0-5% other auxiliaries, and water as balance; The other additives are selected from one or more combinations of defoamers, fragrances, pH adjusters, corrosion inhibitors, and thickeners; Preferably, the enzyme is selected from one or a combination of two or more of protease, amylase, lipase, and pectinase.

[0016] According to the enzyme-containing detergent composition provided by the present invention, the enzyme protectant and the enzyme are premixed in water and then mixed with the remaining components to obtain the enzyme-containing detergent composition; preferably, the mass ratio of the enzyme protectant and the enzyme in the mixture is (1~20):(0.1~10).

[0017] The present invention also provides a dishwashing liquid comprising the enzyme-containing detergent composition described above.

[0018] This invention provides an enzyme-containing detergent composition and a high-temperature stable dishwashing liquid. By optimizing the composition of the enzyme inclusion complex and surfactant, and improving the cleaning power of the detergent composition from multiple angles, it not only achieves high cleaning power against stubborn stains, but also ensures that the enzyme-containing detergent composition maintains a stable enzyme activity retention rate after 20 rounds of testing in a dishwasher's high-temperature environment, far exceeding that of traditional formulas (usually below 50%), thus ensuring that the product maintains good performance throughout its shelf life and usage cycle.

[0019] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Detailed Implementation

[0020] The embodiments of the present invention will be described in further detail below with reference to examples. These examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.

[0021] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above 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 one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0022] In a specific embodiment of the present invention, an enzyme-containing detergent composition is first provided, comprising a cyclodextrin-polyethylene glycol graft copolymer, an enzyme-formed inclusion complex, and a surfactant; The surfactant contains dehydrated sorbitan ester and EO / PO block copolymer.

[0023] To enhance the high-temperature resistance and activity of enzyme molecules, this invention combines an inclusion complex formed by a cyclodextrin-polyethylene glycol graft copolymer and the enzyme with a compound surfactant capable of forming a protective film at the interface. The cyclodextrin structure in the inclusion complex precisely encapsulates the active site or vulnerable hydrophobic regions of the enzyme molecule, directly inhibiting proteolytic digestion. Simultaneously, its long-chain PEG structure forms a barrier around the enzyme molecule, effectively blocking the impact of high-temperature water molecules and other harmful substances. The synergistic effect of dehydrated sorbitan ester and EO / PO block copolymer forms a protective film that ensures stable enzyme activity retention in the enzyme-containing detergent composition after 20 rounds of high-temperature dishwasher testing, significantly exceeding that of traditional formulations (typically below 50%), thus ensuring good performance maintenance throughout the product's shelf life and usage cycle.

[0024] Among them, the cyclodextrin-polyethylene glycol graft copolymer and other polymer components in the system, due to their strong steric hindrance effect, can effectively suspend the detached dirt particles, improving the problem of secondary deposition of easily re-sticky stains such as spinach. The cyclodextrin-polyethylene glycol graft copolymer can also encapsulate oil and pigment molecules, making them easier to remove.

[0025] The system of this invention avoids the use of highly irritating strong alkalis or strong oxidants as the main means of cleaning. The overall formula is milder, safer for tableware materials, and more environmentally friendly.

[0026] In some specific embodiments of the present invention, the mass ratio of dehydrated sorbitan ester to EO / PO block copolymer is 1:(1~5). As an example, it can be any value or a range of values ​​from 1:1, 1:2, 1:3, 1:4, 1:5.

[0027] In some specific embodiments of the present invention, the mass ratio of dehydrated sorbitan ester to cyclodextrin-polyethylene glycol graft copolymer is 1:(10~15). As an example, it can be any value or a range of values ​​from 1:10, 1:11, 1:12, 1:13, 1:14, 1:15.

[0028] In some specific embodiments of the present invention, the cyclodextrin-polyethylene glycol graft copolymer is obtained by reacting β-cyclodextrin and activated polyethylene glycol monomethyl ether in a molar ratio of 1:(2~4); the activated polyethylene glycol monomethyl ether is obtained by activating the terminal hydroxyl groups of polyethylene glycol monomethyl ether to imidazolium carbamate; preferably, the molecular weight of the polyethylene glycol monomethyl ether is 2000~5000 Da.

[0029] Studies have found that the number of PEG chains attached to the β-cyclodextrin molecule in the cyclodextrin-polyethylene glycol graft copolymer needs to be controlled within a reasonable range, which is more conducive to obtaining more stable enzyme activity in the enzyme-containing detergent composition.

[0030] In some specific embodiments of the present invention, the activated polyethylene glycol monomethyl ether is prepared by mixing polyethylene glycol monomethyl ether with an excess of 1,1'-carbonyldiimidazole to activate the terminal hydroxyl groups of mPEG into imidazolium carbamate. Generally, the amount of 1,1'-carbonyldiimidazole used is 1 to 1.5 molar equivalents of polyethylene glycol monomethyl ether.

[0031] In some specific embodiments of the present invention, the preparation method of the cyclodextrin-polyethylene glycol graft copolymer includes: A mixture of polyethylene glycol monomethyl ether and anhydrous DMSO was prepared. 1,1'-carbonyldiimidazole was added to the mixture and reacted at 25~30℃ for 4~6h to obtain an activated mPEG solution. The activated mPEG solution was added to a DMSO solution containing β-cyclodextrin, and DMAP (catalyst) was added. The mixture was reacted at 40-50°C for 24-48 hours to obtain a mixed system containing cyclodextrin-polyethylene glycol graft copolymer.

[0032] The cyclodextrin-polyethylene glycol graft copolymer in the mixed system was separated and purified.

[0033] Generally, the separation and purification process includes: mixing the mixture with a sufficient amount of ice-cold diethyl ether to precipitate the cyclodextrin-polyethylene glycol graft copolymer as a white solid or viscous substance, collecting the precipitate by centrifugation, washing it 2-3 times with fresh diethyl ether, dialysis with water to completely remove unreacted mPEG and β-cyclodextrin, and finally freeze-drying to obtain the cyclodextrin-polyethylene glycol graft copolymer.

[0034] As an example, dialysis using dialysis bags and dialysis for 48-72 hours, with water changed every 8 hours, can completely remove unreacted mPEG and β-cyclodextrin. The molecular weight cutoff of the dialysis bag can be determined based on the molecular weights of the mPEG and β-cyclodextrin used.

[0035] In some specific embodiments of the present invention, the viscosity of the EO / PO block copolymer is 1200~1400 mPa·s. As an example, it can be any value or a range of values ​​among 1200 mPa·s, 1250 mPa·s, 1300 mPa·s, 1350 mPa·s, and 1400 mPa·s.

[0036] The EO / PO block copolymer in this invention can be purchased from commercial channels. Experiments have shown that Clariant Genapole ED3060 has the best effect.

[0037] To further enhance the cleaning power of the enzyme-containing detergent composition, in some specific embodiments of the present invention, the pH value of the enzyme-containing detergent composition is 8 or higher; to avoid the decrease in enzyme activity under strongly alkaline conditions, the pH value of the enzyme-containing detergent composition is preferably 8 to 10.

[0038] In some specific embodiments of the present invention, the enzyme-containing detergent composition further includes an alkaline additive.

[0039] In some specific embodiments of the present invention, the alkaline additive is selected from one or more combinations of sodium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and sodium bicarbonate.

[0040] To further enhance the cleaning power of the enzyme-containing detergent composition, in some specific embodiments of the present invention, the enzyme-containing detergent composition further includes a chelating agent at a mass ratio of 1-30%. As an example, it can be any value or a range of values ​​from 1%, 6%, 11%, 16%, 21%, 26%, and 30%.

[0041] In some specific embodiments of the present invention, the chelating agent is selected from one or more combinations of sodium citrate, aminocarboxylic acids, and tetrasodium ethylenediaminetetraacetate.

[0042] In some specific embodiments of the present invention, the aminocarboxylate is selected from methylglycine diacetate (MGDA) and / or glutamic acid diacetate (GLDA).

[0043] In some specific embodiments of the present invention, the chelating agent is a mixture of methylglycine diacetic acid (MGDA) and tetrasodium ethylenediaminetetraacetate (EDTA), preferably, the mass ratio of MGDA to EDTA is 14:(1~2). Studies have found that using a compound chelating agent helps to avoid the reduction in enzyme activity caused by an overly strong chelating agent system. As an example, it can be any value or a range of values ​​from 14:1.0, 14:1.2, 14:1.4, 14:1.6, 14:1.8, 14:2.0.

[0044] In some specific embodiments of the present invention, the enzyme-containing detergent composition further includes a polymer dispersant at a mass ratio of 0.5% to 10%. As an example, it can be any value or a range of values ​​from 0.5%, 2.0%, 3.5%, 5.0%, 6.5%, 8.0%, 9.5%, and 10.0%.

[0045] In some specific embodiments of the present invention, the polymer dispersant is selected from acrylic homopolymers and / or acrylic-maleic acid copolymers; more preferably acrylic-maleic acid copolymers.

[0046] In this invention, stains are removed from multiple angles, such as by decomposing specific stains with biological enzymes, alkalis, and chelating agents, while effectively avoiding the reduction of biological enzyme activity. The overall advantages of the resulting enzyme-containing detergent composition are significantly increased.

[0047] In some specific embodiments of the present invention, the enzyme-containing detergent composition comprises, by weight percentage: 1-15% surfactant, 1-30% chelating agent, 1-15% alkaline additive, 0.5-10% polymer dispersant, 1-20% enzyme protectant, 0.1-10% enzyme, 5-50% solvent, 0-5% other additives, and water as the balance.

[0048] The other additives are selected from one or more combinations of defoamers, fragrances, pH adjusters, corrosion inhibitors, and thickeners.

[0049] The solvent is selected from one or more of glycerol, propylene glycol, and ethanol.

[0050] In some specific embodiments of the present invention, the enzyme is selected from one or more combinations of protease, amylase, lipase, and pectinase.

[0051] Preferably, the composition of the enzyme-containing detergent composition is as follows, by weight percentage: Surfactant 8-13%, chelating agent 14-15%, alkaline additive 1-5%, polymer dispersant 6-7%, enzyme protectant 8-12%, enzyme 1-5%, solvent 5-10%, other additives 0.1-0.5%, water balance.

[0052] In some specific embodiments of the present invention, the surfactant further includes alkyl glycoside surfactants.

[0053] In some specific embodiments of the present invention, the surfactant comprises, by weight, 0.5 to 2 parts of dehydrated sorbitan ester, 2 to 5 parts of EO / PO block copolymer and 2 to 4 parts of alkyl glycoside surfactant.

[0054] Considering that dishwashers use high-pressure spray arms for cleaning, excessive foam can reduce spray pressure, affecting cleaning power and potentially causing overflow. Furthermore, traditional strong defoamers may disrupt the three-dimensional structure of enzymes, leading to inactivation. In this invention, the defoamer is selected from one or more combinations of silicone-based defoamers, polyether-based defoamers, and mineral oil-based defoamers. Silicone-based defoamers include, but are not limited to, polydimethylsiloxane (PDMS), polyether-modified polysiloxane (polyether silicone oil), mixtures of hydrophobic fumed silica and silicone oil, or emulsified silicone oil. Non-silicone defoamers include, but are not limited to, fatty alcohol alkoxylates (terminally capped low-foaming surfactants), oxidized paraffin, branched fatty alcohols, or fatty acid ester complexes.

[0055] In this invention, the pH adjuster is not only used to directly adjust the pH value of the enzyme-containing detergent composition and adjust the conformation of the enzyme, but also to construct a buffer system for the enzyme-containing detergent composition and promote the improvement of enzyme activity retention. Preferably, the pH adjuster includes citric acid.

[0056] In order to achieve powerful cleaning while avoiding negative effects on the surface of tableware, the enzyme-containing detergent composition of the present invention also includes the corrosion inhibitor, such as benzotriazole.

[0057] In some specific embodiments of the present invention, the enzyme protectant and the enzyme are premixed in water and then mixed with the remaining components to obtain the enzyme-containing detergent composition; preferably, the mass ratio of the enzyme protectant and the enzyme in the mixture is (1~20):(0.1~10).

[0058] In the enzyme-containing detergent composition, the cyclodextrin-polyethylene glycol graft copolymer is coated on the enzyme surface, thereby protecting the enzyme.

[0059] To avoid reducing enzyme activity, the premixing temperature is 4–10°C. As an example, it can be any value from 4°C, 6°C, 8°C, and 10°C, or a range of values.

[0060] To allow sufficient time for cyclodextrin molecules to encapsulate with hydrophobic amino acid residues or specific peptides on the surface of enzyme molecules, the premixing time is preferably 2-4 hours.

[0061] The premixed solution is used directly in the enzyme-containing detergent composition, that is, it is mixed as a whole with the other components.

[0062] Studies have found that the enzyme-containing detergent composition of the present invention also has low foaming properties and good pumping stability, making it particularly suitable for use in automatic dishwashers and other equipment. In a specific embodiment of the present invention, a dishwashing liquid is also provided, comprising the enzyme-containing detergent composition as described above.

[0063] The enzyme-containing detergent composition and high-temperature stable dishwashing liquid of the present invention will be described in detail below with reference to specific implementation examples.

[0064] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels. The sources of some raw materials are as follows: Alkyl glycoside surfactant: APG 0810 from China National Light Industry Chemical Group.

[0065] Acrylic acid-maleic acid copolymer: Degree of polymerization: 3000~4000.

[0066] Dehydrated sorbitan ester: Evonik's SD-100.

[0067] EO / PO block copolymer: Clariant Genapol ED3060.

[0068] In the embodiments of this invention, the enzymes of the same type used were selected from the same batch for the experiment.

[0069] Preparation Example 1 A method for preparing a cyclodextrin-polyethylene glycol graft copolymer, comprising the following steps: (1) Polyethylene glycol monomethyl ether with a molecular weight of 2000 Da was dried under high vacuum at 60°C for 2 hours to completely remove moisture.

[0070] (2) Under nitrogen protection, the polyethylene glycol monomethyl ether obtained in step (1) was dissolved in anhydrous DMSO. The system was kept at 25°C. 1,1'-carbonyldiimidazole was slowly added to the solution at 1.2 molar equivalents. The reaction was carried out for 5 hours to obtain an activated mPEG solution.

[0071] (3) Dissolve β-cyclodextrin in anhydrous DMSO. Add the activated mPEG solution obtained in step (2) slowly to the DMSO solution containing cyclodextrin through a constant pressure dropping funnel. The molar ratio of mPEG to β-cyclodextrin is 3:1. Add a catalytic amount of DMAP and raise the reaction temperature to 45°C. React for 36 hours under nitrogen protection and stirring.

[0072] (4) Slowly pour the reaction solution obtained in step (3) into 10 times the volume of ice-cold ether. The cyclodextrin-polyethylene glycol graft copolymer will precipitate out as a white solid or viscous substance. Centrifuge to collect the precipitate and wash it 2-3 times with fresh ether to remove DMSO and imidazole byproducts, and obtain the crude product.

[0073] (5) The crude product obtained in step (4) is redissolved in deionized water and placed in a dialysis bag with a molecular weight cutoff of 7000~8000 Da. Dialyze with deionized water for 72 hours, changing the water every 8 hours, to completely remove unreacted small molecules mPEG and β-CD. The final solution in the dialysis bag is freeze-dried to obtain a white flocculent or powdery purified product.

[0074] Preparation Example 2 The preparation method is basically the same as in Example 1, except that the polyethylene glycol monomethyl ether with a molecular weight of 2000 Da is replaced with polyethylene glycol monomethyl ether with a molecular weight of 5000 Da, and dialysis is performed in step (5) using a dialysis bag with a molecular weight of MWCO 14000~20000 Da.

[0075] Preparation Example 3 The preparation method is basically the same as that in Example 1, except that the molar ratio of mPEG to β-cyclodextrin in step (3) is 1:1.

[0076] Example 1 This embodiment provides an enzyme-containing detergent composition, the raw material composition of which is shown in the table below by mass percentage.

[0077] Table 1

[0078] This embodiment also provides a method for preparing the above-mentioned enzyme-containing detergent composition, including: According to the dosages in Table 1 above, add the cyclodextrin-polyethylene glycol graft copolymer to water, and slowly add protease, amylase, lipase, and pectinase under 5°C and gentle stirring conditions. Continue stirring for 3 hours to obtain the pretreated solution; The pretreatment solution is mixed with the other components in Table 1 above to obtain the final product.

[0079] Example 2 It is basically the same as Example 1, except that: The mass percentage of the cyclodextrin-polyethylene glycol graft copolymer is 10%.

[0080] Example 3 It is basically the same as Example 1, except that: The mass percentage of dehydrated sorbitan ester is 3%.

[0081] The EO / PO block copolymer has a mass percentage of 3%.

[0082] Example 4 It is basically the same as Example 1, except that: The cyclodextrin-polyethylene glycol graft copolymer prepared in Preparation Example 1 was replaced by an equal mass of the cyclodextrin-polyethylene glycol graft copolymer prepared in Preparation Example 2.

[0083] Example 5 It is basically the same as Example 1, except that: The cyclodextrin-polyethylene glycol graft copolymer prepared in Preparation Example 1 was replaced by an equal mass of the cyclodextrin-polyethylene glycol graft copolymer prepared in Preparation Example 3.

[0084] Example 6 It is basically the same as Example 1, except that: The mass percentage of the EO / PO block copolymer is 0.5%.

[0085] The mass percentage of dehydrated sorbitan ester is 5.5%.

[0086] Example 7 It is basically the same as Example 1, except that: The EO / PO block copolymer has a mass percentage of 2%.

[0087] The mass percentage of dehydrated sorbitan ester is 4%.

[0088] Example 8 It is basically the same as Example 1, except that: The EO / PO block copolymer has a mass percentage of 4%.

[0089] The mass percentage of dehydrated sorbitan ester is 2%.

[0090] Comparative Example 1 It is basically the same as Example 1, except that: The cyclodextrin-polyethylene glycol graft copolymer was replaced with water by mass.

[0091] Comparative Example 2 It is basically the same as Example 1, except that: The EO / PO block copolymer was replaced with water by mass.

[0092] Comparative Example 3 It is basically the same as Example 1, except that: The mass of dehydrated sorbitan esters was replaced with water.

[0093] Comparative Example 4 It is basically the same as Example 1, except that: The cyclodextrin-polyethylene glycol graft copolymer was replaced with water by mass.

[0094] The mass of dehydrated sorbitan esters was replaced with water.

[0095] Comparative Example 5 It is basically the same as Example 1, except that: The EO / PO block copolymer was replaced with water by mass.

[0096] The mass of dehydrated sorbitan esters was replaced with water.

[0097] Comparative Example 6 It is basically the same as Example 1, except that: The cyclodextrin-polyethylene glycol graft copolymer was replaced with water by mass.

[0098] The EO / PO block copolymer was replaced with water by mass.

[0099] Test Example 1: Cleaning Power Test Test Method: Several stubborn stains were selected, including spinach, minced meat, and oatmeal porridge. The staining method followed GB 38383-2019 "Energy Efficiency and Water Efficiency Limits and Grades for Dishwashers". After staining, the dishes were aged in an 80℃ oven for 3 hours. Dishwasher Model: RX600; Detergent Usage: 33.75g; Test Program: Extra Strong Wash; Loading Capacity: 15 place settings.

[0100] The test results (cleaning power scores) are shown in Tables 2-1 to 2-2 below.

[0101] Table 2-1

[0102] Table 2-2

[0103] Test Example 2: Thermoresistant Enzyme Activity Test Test method: Select Midea automatic dispensing dishwasher (model S65pro), fill the dispensing device with detergent (do not dispense), and after the dishwasher runs 20 standard washes, test the enzyme activity retention rate. Enzyme activity retention rate (%) = enzyme activity value / initial enzyme activity value × 100%.

[0104] The results are shown in Tables 3-1 to 3-2 below.

[0105] Table 3-1

[0106] Table 3-2

[0107] The data above demonstrates that this invention, through optimized formulation, significantly improves the tolerance of the enzyme-containing detergent composition to the high-temperature dishwasher operating environment, with minimal decrease in enzyme activity. Furthermore, the enzyme-containing detergent composition exhibits excellent cleaning power against various types of stains.

[0108] In this system, cyclodextrin-polyethylene glycol graft copolymer, dehydrated sorbitan ester, and EO / PO block copolymer play a key synergistic role, constructing a high-temperature and high-humidity resistant enzyme protection system. This results in excellent removal of protein (minced meat), starch (oatmeal), and mixed stains (spinach / butter) thanks to highly active enzymes. The formulation in Example 2 is even better, maintaining high performance while also offering cost advantages.

[0109] Finally, it should be noted that the above embodiments are only for illustrating the present invention and not for limiting the present invention. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art should understand that various combinations, modifications, or equivalent substitutions of the technical solutions of the present invention do not depart from the spirit and scope of the technical solutions of the present invention and should be covered within the scope of the claims of the present invention.

Claims

1. An enzyme-containing detergent composition, characterized in that, This includes cyclodextrin-polyethylene glycol graft copolymers, enzyme-formed inclusion complexes, and surfactants; The surfactant contains dehydrated sorbitan ester and EO / PO block copolymer.

2. The enzyme-containing detergent composition according to claim 1, characterized in that, The mass ratio of dehydrated sorbitan ester to EO / PO block copolymer is 1:(1~5); the mass ratio of dehydrated sorbitan ester to cyclodextrin-polyethylene glycol graft copolymer is 1:(10~15).

3. The enzyme-containing detergent composition according to claim 1 or 2, characterized in that, The cyclodextrin-polyethylene glycol graft copolymer is obtained by reacting β-cyclodextrin and activated polyethylene glycol monomethyl ether in a molar ratio of 1:(2~4); the activated polyethylene glycol monomethyl ether is obtained by activating the terminal hydroxyl groups of polyethylene glycol monomethyl ether to imidazolium carbamate; preferably, the molecular weight of the polyethylene glycol monomethyl ether is 2000~5000 Da.

4. The enzyme-containing detergent composition according to any one of claims 1 to 3, characterized in that, The viscosity of the EO / PO block copolymer is 1200~1400 mPa·s.

5. The enzyme-containing detergent composition according to any one of claims 1 to 4, characterized in that, The pH value of the enzyme-containing detergent composition is 8 or higher; preferably 8 to 10. Preferably, the enzyme-containing detergent composition further includes an alkaline auxiliaries; More preferably, the alkaline additive is selected from one or more of sodium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and sodium bicarbonate.

6. The enzyme-containing detergent composition according to any one of claims 1 to 5, characterized in that, The enzyme-containing detergent composition further includes a chelating agent at a mass ratio of 1-30%; Preferably, the chelating agent is selected from one or a combination of two or more of sodium citrate, aminocarboxylate, and tetrasodium ethylenediaminetetraacetate; More preferably, the aminocarboxylate is selected from methylglycine diacetate and / or glutamic acid diacetate.

7. The enzyme-containing detergent composition according to any one of claims 1 to 6, characterized in that, The enzyme-containing detergent composition further includes a polymer dispersant at a mass ratio of 0.5-10%; Preferably, the polymer dispersant is selected from acrylic homopolymers and / or acrylic-maleic acid copolymers.

8. The enzyme-containing detergent composition according to any one of claims 1 to 7, characterized in that, The enzyme-containing detergent composition comprises, by weight percentage: 1-15% surfactant, 0.5-10% polymer dispersant, 0.1-10% enzyme, 1-15% alkaline additive, 1-30% chelating agent, 1-20% enzyme protectant, 5-50% solvent, 0-5% other additives, and water as balance; The other additives are selected from one or more combinations of defoamers, fragrances, pH adjusters, corrosion inhibitors, and thickeners; The enzyme protectant contains the cyclodextrin-polyethylene glycol graft copolymer; Preferably, the enzyme is selected from one or a combination of two or more of protease, amylase, lipase, and pectinase.

9. The enzyme-containing detergent composition according to any one of claims 1 to 8, characterized in that, The cyclodextrin-polyethylene glycol graft copolymer and the enzyme are premixed in water and then mixed with the remaining components to obtain the enzyme-containing detergent composition; preferably, the mass ratio of the cyclodextrin-polyethylene glycol graft copolymer and the enzyme in the mixture is (1~20):(0.1~10).

10. A dishwashing liquid, characterized in that, Includes the enzyme-containing detergent composition according to any one of claims 1 to 9.

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