Enzyme-containing detergent composition

Abstract

The invention relates to the technical field of detergents, and discloses an enzyme-containing detergent composition. The enzyme-containing detergent composition comprises the following components: an enzyme stabilizer, a surfactant and an enzyme, the enzyme stabilizer comprises triethanolamine citrate and vitamin C glucoside. The triethanolamine citrate and the vitamin C glucoside adopted by the invention can improve the stability of enzyme in the detergent to a large extent, are wide in application range, are applicable to surfactant types and enzyme types commonly used in the detergent, and can still play a good role when the content of the surfactant is high.

Description

Technical Field

[0001] The present invention relates to the technical field of detergents, and particularly to an enzyme-containing detergent composition. Background Art

[0002] Surfactants are the main dirt-removing components in detergents. When only surfactants are used in detergents for washing and dirt removal, only a part of the dirt can be removed, and a satisfactory effect cannot be achieved. Enzymes are a class of proteins that can efficiently catalyze specific reactions and have good cleaning effects on specific stains. When surfactants and enzymes are used in combination, the catalytic hydrolysis effect of the enzymes can be utilized to improve the dirt-removing effect of the surfactants in the detergents on dirt such as proteins, starches, and fats, achieving efficient dirt removal. However, there are the following problems: Components in the detergents, such as certain surfactants, free water, certain auxiliaries, and oxidizing substances, are very likely to react with enzyme proteins, causing the dissociation of enzyme proteins or the denaturation of peptide chains, and thus causing the enzymes to lose their activity. The stability problem of enzymes in detergents restricts their application in detergents.

[0003] Currently, the methods for improving enzyme stability mainly include enzyme molecule modification, enzyme molecule modification, enzyme molecule immobilization, and the addition of stabilizers. Compared with improving enzyme molecules, adding enzyme stabilizers to detergents is a relatively simple method to improve the stability of enzymes in detergents, but it is difficult to obtain suitable stabilizers or composite stabilizers. Borates and aryl borates have good stabilizing effects on enzymes, but they have greater irritation and environmental hazards and have been gradually prohibited in detergents in recent years. Other enzyme stabilizers often have problems such as poor stabilizing effects or limited application ranges. For example, in Patent CN109135960B, ethoxylated polyethyleneimine is used as a protease stabilizer in detergents. This stabilizer is mainly used to enhance the dirt-removing performance of proteases, and the improvement of enzyme stability is limited. Compared with the blank group, the enzyme activity retention rate is only increased by 5-10%; in Patent CN117625322A, benzisothiazolinone is used to improve the stability of enzyme preparations in the dishwashing liquid composition system, and the effect is better in the system where the dosage of sodium alkylbenzene sulfonate does not exceed 4% of the total weight of the dishwashing liquid composition. The effect becomes worse in the system with a higher dosage of sodium alkylbenzene sulfonate. If the dosage of benzisothiazolinone is increased, it will bring irritation to the dishwashing liquid. Therefore, it is of great practical significance to extensively and deeply study the influence of enzyme stabilizers on the activity stability of enzymes in detergents and develop enzyme stabilizers with good stabilizing effects and wide application ranges. Summary of the Invention

[0004] In order to solve the technical problems of the existing enzyme stabilizers with poor stabilizing effects and limited application ranges, the present invention provides an enzyme-containing detergent composition. Triethanolamine citrate and vitamin C glucoside are used as enzyme stabilizers in this enzyme-containing detergent composition, which can greatly improve the stability of enzymes in detergents and have a wide application range.

[0005] The specific technical solution of the present invention is as follows: An enzyme-containing detergent composition, comprising the following components: an enzyme stabilizer, a surfactant, and an enzyme; the enzyme stabilizer comprises triethanolamine citrate and glucosyl ascorbate.

[0006] The general structural formula of the above-mentioned triethanolamine citrate is as follows:

[0007] The general structural formula of the above-mentioned glucosyl ascorbate is as follows:

[0008] The present invention uses the compound of triethanolamine citrate and glucosyl ascorbate as an enzyme stabilizer. They cooperate with each other to produce effective synergy, and can have a better stabilizing effect on the enzyme in the detergent. The specific mechanism is as follows: Each triethanolamine citrate molecule contains four hydroxyl groups, and each glucosyl ascorbate molecule contains seven hydroxyl groups. On the one hand, both can form multiple hydrogen bonds with the enzyme, increasing the rigidity of the protein, maintaining the stability of the enzyme molecular conformation, and inhibiting enzyme inactivation; on the other hand, these two enzyme stabilizers can also form hydrogen bonds with water, reducing the number of hydrogen bonds between the enzyme molecule and water molecules, changing the solvation layer around the enzyme molecule, increasing the stability of the enzyme, and preventing the enzyme from hydrolyzing and inactivating itself.

[0009] In addition, enzyme inactivation is also related to the oxidation of some amino acids in the enzyme. Although polyhydroxy compounds can show the effect of protecting the enzyme from hydrolysis, they cannot overcome the inactivation effect of oxidation. The glucosyl ascorbate molecule contains both multiple hydroxyl groups and the structure of vitamin C. When binding to the enzyme through the hydroxyl group, it can bring the vitamin C structure close to the enzyme molecule, and then make better use of the antioxidant effect of vitamin C to protect the enzyme from oxidation; at the same time, triethanolamine citrate can chelate metal ions well, inhibit the catalytic oxidation reaction of metal ions, and prevent glucosyl ascorbate from being oxidized. Through the above methods, the glucosyl ascorbate molecule and triethanolamine citrate cooperate with each other to prevent the oxidation of amino acids in the enzyme, thereby improving the stability of the enzyme in the detergent to a greater extent.

[0010] In the above manner, the enzyme stabilizer of the present invention has a stabilizing effect on the enzyme that is not affected by the surfactant in the detergent, and has low irritation, so it has a wide application range and is applicable to the common surfactant types and enzyme types in the detergent, and can still play a good role when the surfactant content is relatively high.

[0011] Preferably, the mass ratio of the triethanolamine citrate to the glucosyl ascorbate is 0.4-1.4:1.

[0012] Under the above-mentioned ratio, the enzyme in the detergent can have better stability. Among triethanolamine citrate and glucosyl ascorbate, when the proportion of the former is too high, since the hydroxyl content in triethanolamine citrate is less than that in glucosyl ascorbate and it does not carry the vitamin C structure with antioxidant property, the stabilizing effect on the enzyme will be weak; when the proportion of the latter is too high, the effect of triethanolamine citrate in inhibiting the metal ion-catalyzed oxidation reaction is weak, so the stability of the enzyme in the detergent will also be relatively poor.

[0013] Preferably, the mass percentage of the enzyme stabilizer in the enzyme-containing detergent composition is 0.02 - 1.2%; the mass ratio of the enzyme to the enzyme stabilizer is 1:0.02 - 1.2.

[0014] Further, the mass percentage of the enzyme stabilizer in the enzyme-containing detergent composition is 0.02 - 1%; the mass ratio of the enzyme to the enzyme stabilizer is 1:0.02 - 1.

[0015] Preferably, the mass percentage of the surfactant in the enzyme-containing detergent composition is 1 - 45%.

[0016] Preferably, the mass percentage of the enzyme in the enzyme-containing detergent composition is 0.01 - 5%.

[0017] Preferably, the surfactant includes one or more of an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.

[0018] Further, the anionic surfactant includes one or more of sodium alkylbenzenesulfonate, sodium laureth sulfate, sodium lauryl sulfate, sodium methyl ester sulfonate, secondary alkyl sulfonate, olefin sulfonate, disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, disodium cocoyl glutamate, and diisooctyl sulfosuccinate. 10～16 sodium alkylbenzenesulfonate, C 10～16 sodium laureth sulfate, C 8～16 sodium lauryl sulfate, C 12～18 sodium methyl ester sulfonate, C 10～18 secondary alkyl sulfonate, C 14～16 olefin sulfonate, disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, disodium cocoyl glutamate, and diisooctyl sulfosuccinate.

[0019] Further, the nonionic surfactant includes one or more of alkyl glucoside, coconut oil methyl glucamide, C 8～16 alkyl glucoside, coconut oil methyl glucamide, C 12～18 fatty alcohol polyoxyethylene ether, C 9～11 fatty alcohol polyoxyethylene ether, C 12～14 secondary alcohol ethoxylate, and polyglycerol fatty acid ester.

[0020] Further, the amphoteric surfactant includes one or more of cocamidopropyl betaine, C 12～14 alkyl dimethyl betaine, cocamidopropyl hydroxysulfobetaine, cocamidopropyl amine oxide, and coconut oil-based dimethyl amine oxide.

[0021] Preferably, the enzyme includes one or more of protease, cellulase, amylase, lipase, cutinase, catalase, and mannanase.

[0022] Further, the enzyme includes one or more of protease, amylase, and lipase.

[0023] Preferably, the enzyme-containing detergent composition further includes auxiliaries; the auxiliaries include one or more of chelating agents, preservatives, organic solvents, pH regulators, hydrotropes, antioxidants, functional auxiliaries, fragrances, and pigments.

[0024] Further, the chelating agent includes one or more of tetrasodium glutamate diacetate, trisodium N,N-bis(carboxymethyl)alanine, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, aminotris(methylenephosphonic acid), diethylenetriamine penta(methylenephosphonic acid), hexamethylenediamine tetra(methylenephosphonic acid), bis(hexamethylenetriamine) pentamethylenephosphonic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid.

[0025] Further, the preservative includes one or more of phenoxyethanol, sodium benzoate, potassium sorbate, methylisothiazolinone, methylchloroisothiazolinone, benzisothiazolinone, and methylparaben.

[0026] Further, the organic solvent includes one or more of ethanol, propylene glycol, glycerol, diethylene glycol butyl ether, diethylene glycol ethyl ether, dipropylene glycol butyl ether, acetone glycerol, and isohexylene glycol.

[0027] Further, the pH regulator includes one or more of lactic acid, oxalic acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and monoethanolamine.

[0028] Further, the hydrotrope includes one or more of sodium xylene sulfonate, sodium isopropylbenzene sulfonate, and sodium p-toluenesulfonate.

[0029] Further, the antioxidant includes one or more of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant AT76), 2,6-di-tert-butyl-4-methylphenol (BHT), tert-butyl-4-hydroxyanisole (BHA), tert-butylhydroquinone (TBHQ), and tea polyphenols.

[0030] Furthermore, the efficacy aids include one or more of polymers, bacteriostatic agents, ultraviolet absorbers, softeners, and optical brighteners.

[0031] Preferably, the mass percentage of the aids in the enzyme-containing detergent composition is 0.001-10%.

[0032] Compared with the prior art, the present invention has the following advantages: (1) The present invention uses the compound of triethanolamine citrate and glucoside of vitamin C as an enzyme stabilizer. The two can cooperate with each other to produce a synergistic effect, so that the enzyme in the detergent has high stability, and thus the detergency of the detergent can be maintained stable for a long time.

[0033] (2) The enzyme stabilizer adopted in the present invention has a wide application range in detergents and is applicable to common surfactant types and enzyme types in detergents, and can still play a good role when the surfactant content is high. Detailed implementation manners

[0034] The present invention will be further described below in conjunction with embodiments.

[0035] General embodiment An enzyme-containing detergent composition comprises the following components: an enzyme stabilizer, a surfactant, and an enzyme; the enzyme stabilizer comprises triethanolamine citrate and glucoside of vitamin C.

[0036] In some specific implementation manners, the mass ratio of triethanolamine citrate to glucoside of vitamin C is 0.4-1.4:1.

[0037] In some specific implementation manners, the mass percentages of the enzyme stabilizer, the surfactant, and the enzyme in the enzyme-containing detergent composition are 0.02-1.2%, 1-45%, and 0.01-5% respectively; the mass ratio of the enzyme to the enzyme stabilizer is 1:0.02-1.2.

[0038] In some specific implementation manners, the surfactant includes one or more of an anionic surfactant, a non-ionic surfactant, and an amphoteric surfactant. The above surfactants will be further described below, but the surfactants applicable in the present invention are not limited thereto: Anionic surfactants include but are not limited to: C 10～16 sodium alkylbenzene sulfonate, C 10～16 sodium fatty alcohol polyoxyethylene ether sulfate, C 8～16 sodium fatty alcohol sulfate, C 12～18 sodium fatty acid methyl ester sulfonate, C 10～18 secondary alkyl sulfonate, C 14～16One or more of sodium alkenyl sulfonate, disodium lauryl sulfosuccinate, disodium laureth sulfosuccinate, disodium cocoyl glutamate, and diisooctyl sulfosuccinate sodium.

[0039] Nonionic surfactants include but are not limited to: C 8～16 Alkyl glucoside, coconut oil methyl glucamide, C 12～18 Fatty alcohol polyoxyethylene ether, C 9～11 Fatty alcohol polyoxyethylene ether, C 12～14 One or more of secondary alcohol ethoxylate and polyglycerol fatty acid ester.

[0040] Amphoteric surfactants include but are not limited to: one or more of coconut oil amide propyl betaine, C 12～14 Alkyl dimethyl betaine, coconut oil amide propyl hydroxysulfobetaine, coconut oil amide propyl amine oxide, and coconut oil dimethyl amine oxide.

[0041] In some specific embodiments, the enzyme includes one or more of protease, cellulase, amylase, lipase, cutinase, catalase, and mannanase.

[0042] In some specific embodiments, the enzyme-containing detergent composition further includes auxiliaries, and the mass percentage of the auxiliaries in the enzyme-containing detergent composition is 0.001-10%; the auxiliaries include one or more of chelating agents, preservatives, organic solvents, pH regulators, hydrotropes, antioxidants, functional auxiliaries, fragrances, and pigments. The above auxiliaries are further described below, but the auxiliaries applicable in the present invention are not limited thereto: Chelating agents include but are not limited to: one or more of tetrasodium glutamate diacetate, trisodium N,N-bis(carboxymethyl)alanine, disodium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, aminotris(methylenephosphonic acid), diethylenetriamine penta(methylenephosphonic acid), hexamethylenediamine tetra(methylenephosphonic acid), bis(hexamethylenetriamine pentamethylenephosphonic acid), and 1-hydroxyethylidene-1,1-diphosphonic acid. If a chelating agent is used, the mass percentage of the chelating agent in the enzyme-containing detergent composition is usually 0.01-5%, preferably 0.1-2%.

[0043] Preservatives include but are not limited to: one or more of phenoxyethanol, sodium benzoate, potassium sorbate, methylisothiazolinone, methylchloroisothiazolinone, benzisothiazolinone, and methyl paraben. If a preservative is used, the mass percentage of the preservative in the enzyme-containing detergent composition is usually 0.01-5%, preferably 0.02-2%.

[0044] Organic solvents include, but are not limited to, one or more of ethanol, propylene glycol, glycerol, diethylene glycol butyl ether, diethylene glycol ethyl ether, dipropylene glycol butyl ether, acetone glycerol, and isohexylene glycol. When using an organic solvent, the mass percentage of the organic solvent in the enzyme-containing detergent composition is generally 0.01-10%, preferably 0.05-10%.

[0045] pH regulators include, but are not limited to, one or more of lactic acid, oxalic acid, hydrochloric acid, sulfamic acid, methanesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and monoethanolamine. When using a pH regulator, the mass percentage of the pH regulator in the enzyme-containing detergent composition is generally 0.01-10%, preferably 0.01-5%.

[0046] Hydrotrope agents include, but are not limited to, one or more of sodium xylene sulfonate, sodium isopropylbenzene sulfonate, and sodium p-toluenesulfonate. When using a hydrotrope agent, the mass percentage of the hydrotrope agent in the enzyme-containing detergent composition is generally 0.1-10%, preferably 1-10%.

[0047] Antioxidants include, but are not limited to, one or more of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant AT76), 2,6-di-tert-butyl-4-methylphenol (BHT), tert-butyl-4-hydroxyanisole (BHA), tert-butylhydroquinone (TBHQ), and tea polyphenols. When using an antioxidant, the content of these antioxidants in the detergent composition is generally 0.001-1% by mass, preferably 0.001-0.5%.

[0048] Functional aids include, but are not limited to, one or more of polymers, bacteriostatic agents, ultraviolet absorbers, softeners, and optical brighteners. Among them: Polymers include, but are not limited to, one or more of salts of homopolymers and / or copolymers of acrylic acid, cellulose derivatives, homopolymers and / or copolymers of vinylpyrrolidone, polyethyleneimine derivatives, polyethylene terephthalate glycol esters and / or their derivatives, and polyethylene glycol and / or its derivatives. Polymers can endow the enzyme-containing detergent composition with the efficacy of anti-soil redeposition, or promote the dissociation of dirt from the substrate surface, or improve the appearance of the detergent composition and other beneficial effects.

[0049] The bacteriostatic agents include, but are not limited to, one or more of parachlorometaxylenol, parachlorometacresol, dichlorophene, trichlorophene, triclocarban, o-phenylphenol, dodecyldimethylbenzylammonium chloride, dodecyltrimethylammonium chloride, tetradecyldimethylbenzylammonium chloride, tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride, octadecyltrimethylammonium chloride, ditridecyldimethylammonium chloride, polyhexamethylene biguanide hydrochloride, 1-hexadecylpyridinium chloride, zinc pyrithione and pyrithione ethanolamine salt. The bacteriostatic agents can endow the enzyme-containing detergent composition with antibacterial and antifungal effects.

[0050] The ultraviolet absorbers include, but are not limited to, one or more of phenyl salicylate, UV-P, UV-O, UV-9, UV-531, UVP-327, RMB and triazine ultraviolet absorbers. The ultraviolet absorbers can endow the enzyme-containing detergent composition with anti-ultraviolet effects.

[0051] The softeners include, but are not limited to, one or more of dioctadecyl sulfosuccinate, sorbitan fatty acid esters, fatty acid diethanolamides, modified silicone softeners, quaternary ammonium salt softeners and imidazoline softeners. The softeners can endow the detergent with fabric softening effects.

[0052] The brighteners can be fluorescent brighteners, including but not limited to: stilbenyl biphenyl compounds and / or bis-triazinyl amino stilbene compounds. The brighteners can endow the detergent with the effects of whitening and brightening clothes.

[0053] The enzyme-containing detergent composition of the present invention can be directly used as a detergent, or added to a conventional detergent in an amount of 1-60 wt%. The above detergents can be fabric detergents, dishwashing detergents, fruit and vegetable detergents, hard surface detergents, range hood detergents, shower gels or hand sanitizers, but are not limited thereto.

[0054] The enzyme-containing detergent composition of the present invention can be prepared by conventional means well-known to those skilled in the art. Specifically, appropriate processing temperatures and processing times can be selected according to the state and function of the components in the solution, as well as the stability and thermal stability of the components. Specific Examples The present invention will be described below through specific examples. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. Without departing from the spirit and scope of the inventive concept, changes and advantages that can be conceived by those skilled in the art are included in the present invention, and the scope of protection of the present invention is defined by the appended claims and any equivalents thereof.

[0056] In the following examples and comparative examples, the contents involved are all mass percentages, and the contents of all components are calculated based on the content of the active substance.

[0057] In the following examples and comparative examples, the performance test methods for the enzyme-containing detergent compositions are as follows: (1) Enzyme stability test: Enzyme stability refers to the change in the content of the enzyme preparation after the sample undergoes an aging test. The less the change in the content of the enzyme preparation, the better the stability of the components of the sample. The enzyme activity retention rate E is used to quantitatively characterize the stability of the enzyme preparation in the components before and after the aging test. The specific steps are as follows: The sample is placed in a sealed container and stored at a constant temperature of 37 ± 1 °C for a period of time. After 4 weeks and 8 weeks, the ratio of the residual standard stain detergency (R1) of the sample to the initial standard stain detergency (R0) of the sample without being stored under the above specific conditions is calculated. The enzyme activity retention rate E is calculated according to the following formula: R0: The initial standard stain detergency of the sample before undergoing the aging test of the enzyme preparation; R1: The residual standard stain detergency of the sample after undergoing the aging test of the enzyme preparation; E: The enzyme activity retention rate, with the unit of %.

[0058] If the enzyme activity retention rate after 4 weeks of aging is greater than 80% and the enzyme activity retention rate after 8 weeks of aging is greater than 65%, it is determined as "no obvious change in the enzyme preparation". If the enzyme activity retention rate after 4 weeks of aging is greater than 80% and the enzyme activity retention rate after 8 weeks of aging is less than or equal to 65%, it is determined as "obvious change in the enzyme preparation". If the enzyme activity retention rate after 4 weeks of aging is less than or equal to 80%, it is determined as "obvious change in the enzyme preparation". "No obvious change in the enzyme preparation" indicates good stability of the enzyme preparation.

[0059] When the enzyme-containing detergent composition contains more than one enzyme preparation, E is calculated separately for each enzyme preparation, and only the E result of the enzyme preparation with the lowest retention rate is taken as the enzyme activity retention rate of the total enzyme preparation.

[0060] (2) Standard stain detergency test: The steps for conducting the standard stain detergency test are as follows: (2.1) Standard stain preparation: Protein standard stain: Separate the egg yolk from the whole egg, place the egg yolk in a glass beaker and stir evenly with a manual egg beater, and filter the egg yolk liquid through a sieve to remove coarser egg yolk particles and eggshell particles.

[0061] Starch standard stain: Mix potato starch and water at a mass ratio of 1:25, place it on an electric stove and heat and stir until boiling, and let it cool naturally for later use.

[0062] Fat standard stain: Mixed oil in Appendix B of GB / T 9985.

[0063] (2.2) Preparation of soiled pieces: Protein soiled piece: Accurately weigh the washed and dried glass slides (76 mm × 26 mm × 2 mm) and number them. Apply the protein standard stain evenly on the glass slides, leave them to dry overnight (more than 12 h) in an incubator at 25 °C, then age them in an oven at 120 °C for 1 h. After the temperature returns to room temperature, accurately weigh the mass of each soiled piece with an analytical balance. Group every 4 pieces together, and control the soiling amount of each piece at 0.20 ± 0.05 g.

[0064] Starch soiled piece: Accurately weigh the washed and dried glass slides (76 mm × 26 mm × 2 mm) and number them. Apply the starch standard stain evenly on the glass slides, and leave them to dry overnight (more than 12 h) at room temperature. Accurately weigh the mass of each soiled piece with an analytical balance. Group every 4 pieces together, and control the soiling amount of each piece at 0.09 ± 0.005 g.

[0065] Fat soiled piece: Accurately weigh the washed and dried glass slides (76 mm × 26 mm × 2 mm) and number them. Apply the fat standard stain evenly on the glass slides, and leave them to dry for 3 h at room temperature. Accurately weigh the mass of each soiled piece with an analytical balance. Group every 4 pieces together, and control the soiling amount of each piece at 0.13 ± 0.02 g.

[0066] (2.3) Detergency test: Insert the glass slides with known soiling amounts into the corresponding washing racks for preparation of washing. Connect the decontamination machine to the power supply, set the washing temperature to 30 °C, the rotation speed to 160 r / min, and the washing time to 15 min. Prepare 1000 mL of a test sample solution with a certain concentration (1%) and pour it into the washing bucket of the vertical decontamination machine. Quickly place the soiled pieces with known weights and the corresponding washing racks into the washing bucket. Start counting the soaking time when the last washing rack is placed in the washing bucket. At the same time, quickly install the stirrer. When the soaking time reaches 10 min, start the decontamination machine. When the washing time reaches 15 min, the machine will automatically stop. Quickly remove the stirrer, take out the washing racks, and rinse them once with clean water. After rinsing, dry the glass slides at room temperature and weigh them to calculate the detergency of the standard stain. The detergency of the standard stain is the mass fraction of the washed standard stain, expressed in %, and is calculated according to the following formula: m0: Mass of the glass slide before soiling, in g; m1: Mass of the glass slide after soiling, in g; m2: Mass of the glass slide after washing, in g; R: Detergency of the standard stain, in %

[0067] Examples 1 - 6 and Comparative Example 1: Effects of Enzyme Stabilizers and Their Dosages The formulations of the enzyme-containing detergent compositions of Examples 1 - 6 and Comparative Example 1 are shown in Table 1.

[0068] Table 1 Formulations of Enzyme-Containing Detergent Compositions (Examples 1 - 6 and Comparative Example 1) The performance test results of the enzyme-containing detergent compositions of Examples 1 - 6 and Comparative Example 1 are shown in Table 2.

[0069] Table 2 Performance Test Results of Enzyme-Containing Detergent Compositions (Examples 1 - 6 and Comparative Example 1) Analyzing the performance test results in Table 2, it can be seen that: (1) The protease stability of Comparative Example 1 is very poor; compared with Comparative Example 1, the protease stabilities of Examples 1 - 6 are significantly improved, and higher protease activities and protein stain detergency can be maintained after 4 weeks and 8 weeks of aging. This indicates that by adding triethanolamine citrate and ascorbyl glucoside, the present invention can effectively improve the protease stability in the enzyme-containing detergent composition, enabling the enzyme-containing detergent composition to maintain a good detergency effect for a long time. The reason is as follows: Both triethanolamine citrate and ascorbyl glucoside contain a large number of hydroxyl groups. On the one hand, they can form hydrogen bonds with the enzyme, increase the rigidity of the protein, maintain the conformational stability of the enzyme, and reduce the influence of harmful substances on the enzyme. On the other hand, they can form hydrogen bonds with water, reduce the interaction between the enzyme and water, exclude the solvation layer of the protein, and prevent the enzyme from self-hydrolysis; in addition, ascorbyl glucoside can also use the vitamin C structure therein to protect the enzyme from oxidation. At the same time, triethanolamine citrate can chelate metal ions well, inhibit the catalytic oxidation reaction of metal ions, and prevent ascorbyl glucoside from being oxidized, which can further enhance the enzyme stability in the detergent.

[0070] (2) It can be seen from Examples 1 - 6 that as the dosages of triethanolamine citrate and ascorbyl glucoside in the enzyme-containing detergent composition increase, the stabilizing effect on the enzyme is enhanced. When the dosage reaches a certain value, it may be due to the oversaturation of the number of hydroxyl groups in the stabilizer, and further increasing the dosage will no longer improve the enzyme stability.

[0071] Examples 7 - 9 and Comparative Examples 2 - 7: Effects of Enzyme Stabilizer Compositions The formulations of the enzyme-containing detergent compositions of Examples 7 - 9 and Comparative Examples 2 - 6 are shown in Table 3.

[0072] Table 3 Formulations of Enzyme-Containing Detergent Compositions (Examples 7 - 9 and Comparative Examples 2 - 6) The performance test results of the enzyme-containing detergent compositions of Examples 7 to 9 and Comparative Examples 2 to 6 are shown in Table 4.

[0073] Table 4 Performance test results of the enzyme-containing detergent compositions (Examples 7 to 9 and Comparative Examples 2 to 6) Analyzing the performance test results in Table 4, it can be seen that: (1) Compared with Comparative Example 2 and Comparative Example 6, the protease stability of Examples 7 to 9 is significantly improved. This indicates that when triethanolamine citrate and ascorbyl glucoside are used in combination, a synergistic effect can be produced between them, and the stabilizing effect on the enzyme is better than that of either of them used alone. The reason for the analysis is that: compared with triethanolamine citrate, ascorbyl glucoside contains more hydroxyl groups and contains the ascorbic acid structure, so the effect of improving enzyme stability is better; triethanolamine citrate can chelate metal ions well, inhibit the catalytic oxidation reaction of metal ions, and prevent ascorbyl glucoside from being oxidized. Therefore, on the basis of using ascorbyl glucoside, further adding triethanolamine citrate can improve enzyme stability to a greater extent.

[0074] (2) The protease activity retention rates of Comparative Examples 3 to 5 are higher than those of Comparative Examples 2 and 6, but lower than those of Examples 7 to 9. This shows that the ratio between triethanolamine citrate and ascorbyl glucoside will affect its stabilizing effect on the enzyme. When the mass ratio between them is in the range of 0.4 to 1.4:1, the stability of the enzyme in the detergent can be improved to a greater extent.

[0075] The formulations of the enzyme-containing detergent compositions of Example 7 and Comparative Examples 7 to 9 are shown in Table 7.

[0076] Table 7 Formulations of the enzyme-containing detergent compositions (Example 7 and Comparative Examples 7 to 9) The performance test results of the enzyme-containing detergent compositions of Example 7 and Comparative Examples 7 to 9 are shown in Table 8.

[0077] Table 8 Performance test results of the enzyme-containing detergent compositions (Example 7 and Comparative Examples 7 to 9) Analyzing the performance test results in Table 8, it can be seen that: The protease stability of Example 7 is higher than that of Comparative Examples 7-9, which indicates that compared with using vitamin C and glucoside separately, the use of ascorbyl glucoside in the present invention can improve the enzyme stability in detergents to a greater extent. The reason for analysis is that: the ascorbyl glucoside molecule contains multiple hydroxyl groups and the structure of vitamin C at the same time. When binding to the enzyme through the hydroxyl group, the vitamin C structure can be brought closer to the enzyme molecule, and then the antioxidant effect of vitamin C can be better utilized to protect the enzyme from the influence of oxidation.

[0078] Examples 10-18: Stabilizing effects on different types of enzymes The formulations of the enzyme-containing detergent compositions of Examples 10-18 are shown in Table 9.

[0079] Table 9 Formulations of enzyme-containing detergent compositions (Examples 10-18) The performance test results of the enzyme-containing detergent compositions of Examples 10-18 are shown in Table 10.

[0080] Table 10 Performance test results of enzyme-containing detergent compositions (Examples 10-18) Analyzing the performance test results in Table 10, it can be seen that: Examples 16-24 all have good enzyme stability, indicating that the enzyme stabilizer in the present invention can act on protease, amylase and lipase, and is applicable to both single enzyme and mixed enzyme.

[0081] Unless otherwise defined, all technical terms and scientific terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the art to which the present disclosure belongs. The raw materials and equipment used in the present invention are conventional raw materials and equipment in the art and can be obtained from conventional commercial channels without special instructions; the methods used in the present invention are conventional methods in the art without special instructions.

[0082] The above are only the preferred embodiments of the present invention and do not impose any limitation on the present invention. Any simple modification, change and equivalent transformation made to the above embodiments according to the technical essence of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. An enzyme-containing detergent composition, characterized in that The invention comprises the following components: an enzyme stabilizer, a surfactant and an enzyme; the enzyme stabilizer comprises triethanolamine citrate and vitamin C glucoside.

2. The enzyme detergent composition according to claim 1, characterized in that The general structural formula of the triethanolamine citrate is as follows: The general structural formula of the vitamin C glucoside is as follows:

3. The enzyme detergent composition according to claim 1, characterized in that The mass ratio of the triethanolamine citrate to vitamin C glucoside is 0.4-1.4:

1.

4. The enzyme detergent composition according to claim 1 or 3, characterized in that The mass percentage of the enzyme stabilizer in the enzyme-containing detergent composition is 0.02-1.2%; the mass ratio of the enzyme to the enzyme stabilizer is 1:0.02-1.

2.

5. The enzyme detergent composition according to claim 1, characterized in that The mass percentage of the surfactant in the enzyme-containing detergent composition is 1 to 45%.

6. The enzyme detergent composition according to claim 1, characterized in that The mass percentage of the enzyme in the enzyme-containing detergent composition is 0.01-5%.

7. The enzyme detergent composition according to claim 1 or 5, characterized in that The surfactant includes one or more of anionic surfactants, nonionic surfactants and amphoteric surfactants.

8. The enzyme detergent composition according to claim 1 or 6, characterized in that The enzymes include one or more of proteases, cellulases, amylases, lipases, cutinases, catalases and mannanases.

9. The enzyme detergent composition according to claim 1, characterized in that The invention also includes auxiliary agents, which include one or more of chelating agents, preservatives, organic solvents, pH regulators, hydrotropes, antioxidants, functional auxiliary agents, flavors and pigments.

10. The enzyme detergent composition according to claim 9, characterized in that The mass percentage of the auxiliary agent in the enzyme-containing detergent composition is 0.001-10%.

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