Enzyme-containing detergent compositions and dishwashing liquid

Abstract

This invention relates to the field of detergent technology, providing an enzyme-containing detergent composition and dishwashing liquid. The enzyme-containing detergent composition includes a surfactant and a polymer dispersant; the surfactant contains N-octyl-2-pyrrolidone and fatty alcohol polyoxyethylene ether; the fatty alcohol polyoxyethylene ether has a cloud point of 49-54 and an HLB value of 11-12; the polymer dispersant contains hydrophilically modified polyethyleneimine. This invention, through the combined use of specific surfactants and polymer dispersants, constructs a multi-dimensional enzyme activity protection system, enabling the detergent composition to maintain a stable retention rate of over 85% for both core protease and amylase activities after 20 standard washes at high temperatures in a dishwasher, far exceeding that of traditional formulations (typically below 60%). This ensures that the product maintains strong biological detergency in the high-temperature washing environment of a dishwasher, providing users with a stable and reliable cleaning experience.

Description

Technical Field

[0001] This invention relates to the field of detergent technology, and more particularly to enzyme-containing detergent compositions and 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] While enzyme-free detergents with high alkalinity and high chelating agent systems exhibit good stability, their ability to break down and remove stubborn stains such as protein (e.g., steamed egg custard), caramelized starch (e.g., rice crust), and vegetable residues rich in fiber and pigment (e.g., spinach) is limited, making thorough cleaning difficult. Meanwhile, enzyme-containing detergents are highly susceptible to degradation and deactivation under the high temperatures generated during summer transportation or dishwasher operation, leading to a sharp decline in cleaning power towards the end of their lifespan. 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 that, through the combined use of specific surfactants and polymer dispersants, 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 includes a surfactant and a polymer dispersant; The surfactant contains N-octyl-2-pyrrolidone and fatty alcohol polyoxyethylene ether; the fatty alcohol polyoxyethylene ether has a cloud point of 49-54 and an HLB value of 11-12. The polymer dispersant contains hydrophilic modified polyethyleneimine.

[0007] According to the enzyme-containing detergent composition provided by the present invention, the hydrophilic modified polyethyleneimine has a hydroxyl value greater than or equal to 61 mg KOH / g; Preferably, the molecular weight of the hydrophilic modified polyethyleneimine is 2000~100000.

[0008] In the enzyme-containing detergent composition provided by the present invention, the mass ratio of N-octyl-2-pyrrolidone to fatty alcohol polyoxyethylene ether is 1:(1~3).

[0009] According to the enzyme-containing detergent composition provided by the present invention, the total mass ratio of the N-octyl-2-pyrrolidone and fatty alcohol polyoxyethylene ether to the mass ratio of the hydrophilic modified polyethyleneimine is 8:(5~10).

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

[0011] 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 more combinations of sodium citrate, methylglycine diacetate (MGDA), and glutamic acid diacetate (GLDA).

[0012] According to the enzyme-containing detergent composition provided by the present invention, the enzyme-containing detergent composition further includes an enzyme stabilizer at a mass ratio of 0.1-20%; Preferably, the enzyme stabilizer is selected from one or more of glycerol, propylene glycol, borax, sodium formate, and calcium chloride; more preferably, it is calcium chloride.

[0013] According to the enzyme-containing detergent composition provided by the present invention, the enzyme in the enzyme-containing detergent composition is selected from one or more combinations of protease, amylase, lipase, and pectinase.

[0014] 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 preparation, 1-15% alkaline additive, 1-30% chelating agent, 0.1-20% enzyme stabilizer, 5-50% solvent, 0-5% other additives, and water as the balance; The other additives are selected from one or more combinations of defoamers, fragrances, pH adjusters, corrosion inhibitors, and thickeners.

[0015] The present invention also provides a dishwashing liquid comprising the enzyme-containing detergent composition described above.

[0016] The present invention provides an enzyme-containing detergent composition and dishwashing liquid, which, through the combined use of specific surfactants and polymer dispersants, jointly constructs a multi-dimensional enzyme activity protection system, significantly improving the enzyme activity retention rate after high temperature.

[0017] 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

[0018] 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.

[0019] 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.

[0020] In a specific embodiment of the present invention, an enzyme-containing detergent composition is first provided, comprising a surfactant and a polymer dispersant; The surfactant contains N-octyl-2-pyrrolidone and fatty alcohol polyoxyethylene ether; the fatty alcohol polyoxyethylene ether has a cloud point of 49-54 and an HLB value of 11-12. The polymer dispersant contains hydrophilic modified polyethyleneimine.

[0021] To ensure superior cleaning power against various stains, this invention first designed an enzyme-containing detergent system. Research revealed a reversible binding relationship between the hydrophilic modified polyethyleneimine and the enzyme. Furthermore, the synergistic effect of N-octyl-2-pyrrolidone and the aforementioned specifically structured fatty alcohol polyoxyethylene ether creates a shielding effect on the enzyme surface. The combined surfactant and hydrophilic modified polyethyleneimine further enhance the synergistic effect, resulting in excellent stability of the enzyme under long-term storage and complex environments. Consequently, the detergent composition of this invention exhibits a stable retention rate of over 85% for both the core protease and amylase after 20 standard washes at high temperatures in a dishwasher, significantly higher than traditional formulations (typically below 60%). This ensures the product maintains strong biological detergency in the high-temperature washing environment of a dishwasher, providing users with a stable and reliable cleaning experience.

[0022] At the same time, the aforementioned surfactants also have excellent penetration capabilities, which can help enzymes quickly enter the interface between stains and tableware. The hydrophilic modified polyethylene imide also plays a role in preventing secondary pollution and deposition after the stains are dispersed, greatly improving the cleaning power.

[0023] In some specific embodiments of the present invention, the hydroxyl value of the hydrophilic modified polyethyleneimine is greater than or equal to 61 mg KOH / g.

[0024] In some specific embodiments of the present invention, the molecular weight of the hydrophilic modified polyethyleneimine is 2000~100000. Studies have found that hydrophilic modified polyethyleneimine in this molecular weight range can effectively adsorb onto the stain particles after enzymatic decomposition, forming steric hindrance and preventing them from being electrostatically adsorbed onto the surface of tableware again in high-temperature water flow.

[0025] In some specific embodiments of the present invention, the mass ratio of N-octyl-2-pyrrolidone to fatty alcohol polyoxyethylene ether is 1:(1~3).

[0026] In some specific embodiments of the present invention, the surfactant further includes a fatty alcohol alkoxylate, preferably a block copolymer of ethylene oxide and propylene oxide.

[0027] In some specific embodiments of the present invention, the surfactant comprises, by weight, 2 to 4 parts of N-octyl-2-pyrrolidone, 4 to 6 parts of fatty alcohol polyoxyethylene ether, and 3 to 6 parts of ethylene oxide and propylene oxide block copolymer.

[0028] In some specific embodiments of the present invention, the total mass ratio of the N-octyl-2-pyrrolidone and fatty alcohol polyoxyethylene ether to the mass ratio of the hydrophilic modified polyethyleneimine is 8:(5~10).

[0029] In some specific embodiments of the present invention, the polymer dispersant may further include acrylic homopolymer, acrylic-maleic acid copolymer, etc.

[0030] In order to further improve 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 above. In order to avoid the decrease of enzyme activity under strongly alkaline conditions, the pH value of the enzyme-containing detergent composition is preferably 8 to 10.

[0031] In some specific embodiments of the present invention, the enzyme-containing detergent composition further includes an alkaline additive.

[0032] 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 metasilicate.

[0033] Studies have found that sodium metasilicate not only provides alkalinity to help remove grease, but also acts as a corrosion inhibitor synergist, protecting the glaze of tableware and dishwasher pipes during high-temperature washing. Therefore, it is a preferred material in this invention.

[0034] 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%.

[0035] 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.

[0036] Preferably, the aminocarboxylate is selected from methylglycine diacetate (MGDA) and / or glutamic acid diacetate (GLDA).

[0037] In some specific embodiments of the present invention, the enzyme-containing detergent composition further includes an enzyme stabilizer at a mass ratio of 0.1% to 20%.

[0038] In some specific embodiments of the present invention, the enzyme stabilizer is selected from one or more combinations of glycerol, propylene glycol, borax, sodium formate, and calcium chloride.

[0039] In some specific embodiments of the present invention, the enzyme stabilizer includes a first stabilizer and a second stabilizer; wherein the first stabilizer is selected from one or more combinations of glycerol, propylene glycol, polyethylene glycol, and sorbitol; and the second stabilizer is selected from one or more combinations of borax, boric acid, sodium formate, calcium chloride, and calcium citrate. The stability of the enzyme can be further optimized through a composite stabilization system.

[0040] In some specific embodiments of the present invention, the enzyme in the enzyme-containing detergent composition is selected from one or more combinations of protease, amylase, lipase, and pectinase.

[0041] In some specific embodiments of the present invention, the enzyme-containing detergent composition comprises, by weight parts: 5-15 parts surfactant; 10-20 parts chelating agent; 3-6 parts alkaline additive; 5-15 parts polymer dispersant; 0.1~0.5 parts enzyme stabilizer; 0.5 to 5 parts enzyme.

[0042] 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.

[0043] In some specific embodiments of the present invention, the chelating agent is a mixture of methylglycine diacetate (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.

[0044] In some specific embodiments of the present invention, the enzyme-containing detergent composition comprises, by weight percentage: 1-15% surfactant, 0.5-10% polymer dispersant, 0.1-10% enzyme preparation, 1-15% alkaline auxiliaries, 1-30% chelating agent, 1-20% enzyme stabilizer, 5-50% solvent, 0-5% other auxiliaries, and water as the balance. The other additives are selected from one or more combinations of defoamers, fragrances, pH adjusters, corrosion inhibitors, and thickeners.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] In a specific embodiment of the present invention, a dishwashing liquid is also provided, comprising the enzyme-containing detergent composition described above.

[0049] The enzyme-containing detergent composition and dishwashing liquid of the present invention will be described in detail below with reference to specific implementation examples.

[0050] 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: Ethylene oxide and propylene oxide block copolymer: Genapol EP 2484.

[0051] Acrylic acid-maleic acid copolymer: BASF polymer sucralose CP-5.

[0052] N-Octyl-2-pyrrolidone: Surfadone LP-100.

[0053] Fatty alcohol polyoxyethylene ether: BEROL 840.

[0054] Hydrophilic modified polyethyleneimine: Sokalan HP 20.

[0055] In the embodiments of this invention, the enzymes of the same type used were selected from the same batch for the experiment.

[0056] 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.

[0057] Table 1

[0058] This embodiment also provides a method for preparing the above-mentioned enzyme-containing detergent composition, which is to mix the above-mentioned raw materials evenly.

[0059] Example 2 It is basically the same as Example 1, except that: The mass percentage of N-octyl-2-pyrrolidone is 4%.

[0060] The mass percentage of fatty alcohol polyoxyethylene ether is 4%.

[0061] Example 3 It is basically the same as Example 1, except that: The mass percentage of hydrophilic modified polyethyleneimine is 5%.

[0062] Example 4 It is basically the same as Example 1, except that: The mass percentage of hydrophilic modified polyethyleneimine is 7%.

[0063] Example 5 It is basically the same as Example 1, except that: The mass percentage of hydrophilic modified polyethyleneimine is 3%.

[0064] Example 6 It is basically the same as Example 1, except that: The mass percentage of N-octyl-2-pyrrolidone is 1%.

[0065] The mass percentage of fatty alcohol polyoxyethylene ether is 7%.

[0066] Example 7 It is basically the same as Example 1, except that: The mass percentage of N-octyl-2-pyrrolidone is 6%.

[0067] The mass percentage of fatty alcohol polyoxyethylene ether is 2%.

[0068] Comparative Example 1 It is basically the same as Example 1, except that: The hydrophilic modified polyethyleneimine was replaced by an equal mass of acrylic-maleic acid copolymer.

[0069] Comparative Example 2 It is basically the same as Example 1, except that: The mass of N-octyl-2-pyrrolidone was replaced with water.

[0070] Comparative Example 3 It is basically the same as Example 1, except that: Replace 6% by weight of fatty alcohol polyoxyethylene ether with 4% by weight of AEO9, and make up the remainder with water.

[0071] 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.

[0072] The test results (cleaning power scores) are shown in Tables 2-1 to 2-2 below.

[0073] Table 2-1

[0074] Table 2-2

[0075] 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%.

[0076] The results are shown in Tables 3-1 to 3-2 below.

[0077] Table 3-1

[0078] Table 3-2

[0079] The data above demonstrates that this invention, through the use of specific surfactants and polymer dispersants, 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.

[0080] 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, Including surfactants and polymer dispersants; The surfactant contains N-octyl-2-pyrrolidone and fatty alcohol polyoxyethylene ether; the fatty alcohol polyoxyethylene ether has a cloud point of 49-54 and an HLB value of 11-12. The polymer dispersant contains hydrophilic modified polyethyleneimine.

2. The enzyme-containing detergent composition according to claim 1, characterized in that, The hydrophilic modified polyethyleneimine has a hydroxyl value greater than or equal to 61 mg KOH / g; Preferably, the molecular weight of the hydrophilic modified polyethyleneimine is 2000~100000.

3. The enzyme-containing detergent composition according to claim 1 or 2, characterized in that, The mass ratio of N-octyl-2-pyrrolidone to fatty alcohol polyoxyethylene ether is 1:(1~3).

4. The enzyme-containing detergent composition according to any one of claims 1 to 3, characterized in that, The total mass ratio of the N-octyl-2-pyrrolidone and fatty alcohol polyoxyethylene ether to the mass ratio of the hydrophilic modified polyethyleneimine is 8:(5~10).

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 above 8; Preferably, the enzyme-containing detergent composition further includes an alkaline auxiliaries; More preferably, the alkaline additive is selected from one or a combination of two or more of sodium hydroxide, sodium carbonate, potassium carbonate, and sodium silicate.

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, methylglycine diacetate, and 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 an enzyme stabilizer at a mass ratio of 0.1% to 20%. Preferably, the enzyme stabilizer is selected from one or more of glycerol, propylene glycol, borax, sodium formate, and calcium chloride; more preferably, it is calcium chloride.

8. The enzyme-containing detergent composition according to any one of claims 1 to 7, characterized in that, The enzymes in the enzyme-containing detergent composition are selected from one or more combinations 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 enzyme-containing detergent composition comprises, by weight percentage: 1-15% surfactant, 0.5-10% polymer dispersant, 0.1-10% enzyme preparation, 1-15% alkaline additive, 1-30% chelating agent, 0.1-20% enzyme stabilizer, 5-50% solvent, 0-5% other additives, and water as the balance. The other additives are selected from one or more combinations of defoamers, fragrances, pH adjusters, corrosion inhibitors, and thickeners.

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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