An enzyme preparation for laundry detergent that can effectively improve the washing effect

Abstract

The present invention provides an enzyme preparation for laundry detergent that can effectively improve the washing effect. The enzyme preparation for laundry detergent includes a protease component, a lipase component, and polyethylene glycol. The protease component includes a protease and a protease carrier for immobilizing the protease. The protease carrier includes a porous nanomaterial and polydopamine formed on the surface of the porous nanomaterial. The lipase component includes a lipase and sodium polyoxyalkylene sulfosuccinate. In the enzyme preparation for laundry detergent provided in this solution, the protease and the lipase can maintain good activity for a long time. Therefore, when the enzyme preparation for laundry detergent provided in this solution is applied to the preparation of laundry detergent, the washing effect of the laundry detergent can be effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of washing products, and particularly relates to an enzyme preparation for laundry detergent that can effectively improve the washing effect. Background Art

[0002] The effective decontamination components in traditional laundry detergents are usually surfactants. However, the main components of complex mixtures such as body fluid stains are fats, proteins, and inorganic substances such as dust in the environment. Ordinary surfactants are difficult to effectively remove such stains. To improve the washing effect of laundry detergent, bioenzymes can be introduced into the laundry detergent. In the formulation design of laundry detergent containing bioenzymes, common bioenzymes include protease and lipase. Based on the characteristic of the single degradation effect of enzymes, protease is mainly used to decompose protein stains such as blood stains and sweat stains, while lipase is mainly used to decompose fat stains such as oil stains. Therefore, if it is necessary to comprehensively improve the detergency of laundry detergent against stains with complex components, multiple different bioenzymes need to be added to the laundry detergent.

[0003] However, the stability of both protease and lipase is a challenge in the formulation design of laundry detergent using bioenzymes. In a liquid medium, protease can degrade lipase. On the other hand, the stability of protease in laundry detergent is also poor and it is easily inactivated by other additives in the laundry detergent. If the bioenzymes cannot maintain good activity in the laundry detergent, the application of bioenzymes is still difficult to effectively improve the washing effect of the laundry detergent. Summary of the Invention

[0004] The present invention provides an enzyme preparation for laundry detergent that can effectively improve the washing effect. The components in this laundry detergent enzyme preparation can coexist stably for a long time. The protease and lipase contained therein can play their targeted decontamination roles without interfering with each other, and it can effectively improve the washing effect of the laundry detergent by using it.

[0005] According to one aspect of the present invention, there is provided an enzyme preparation for laundry detergent that can effectively improve the washing effect. The enzyme preparation for laundry detergent includes a protease component, a lipase component, and polyethylene glycol; the protease component includes protease and a protease carrier for immobilizing the protease. The protease carrier includes a porous nanomaterial and polydopamine formed on the surface of the porous nanomaterial; the lipase component includes lipase and polyoxyalkylene type sulfosuccinate. In the protease component of the enzyme preparation for laundry detergent provided in this solution, the protease component is adsorbed and immobilized by the porous nanomaterial, and the polydopamine attached to the surface of the porous nanomaterial can enhance the immobilization effect of the protease. Under the action of the above immobilization treatment, the protease is enriched on the surface of the protease carrier. On the one hand, the structural stability of the protease is improved, thereby reducing the degradation of the protease before normal use. On the other hand, it can to a certain extent avoid the degradation of other protein-based effective detergency active ingredients (such as lipase) by the protease free in the laundry detergent. In addition, based on the certain viscosity of polydopamine, the polydopamine attached to the surface of the porous nanomaterial can also promote the adhesion of the protease component to the stain surface, which is beneficial to the contact between the protease component and the protease target substrate and improves the detergency ability of the protease component. In the lipase component of the enzyme preparation for laundry detergent provided in this solution, the polyoxyalkylene type sulfosuccinate includes a polyoxyalkylene chain segment, which makes the above polyoxyalkylene type sulfosuccinate have the characteristics of a non-ionic surfactant. When the polyoxyalkylene type sulfosuccinate is compounded with the contained lipase, the two can coexist stably. At the same time, the polyoxyalkylene type sulfosuccinate has a certain adsorption effect on polyethylene glycol. When the above lipase component is mixed with polyethylene glycol, the polyethylene glycol is adsorbed by the polyoxyalkylene type sulfosuccinate and enriched on the surface of the lipase component, and the polyethylene glycol chain segment stretches, which can to a certain extent prevent the lipase and the protease component from approaching each other, reducing the possibility of the lipase being degraded by the protease, thereby effectively protecting the lipase. In summary, in this solution, by matching protease and lipase with different materials respectively to form a protease component and a lipase component, and combining the application of polyethylene glycol, the protease and the lipase can maintain a certain distance even in the same dispersion liquid phase, avoiding the two from contacting and reacting with each other and causing premature inactivation. Since in the enzyme preparation for laundry detergent provided in this solution, the protease and the lipase can maintain good activity for a long time, when the enzyme preparation for laundry detergent provided in this solution is applied to the preparation of laundry detergent, it can effectively improve the washing effect of the laundry detergent, enabling the laundry detergent to have a high detergency effect on protein stains and fat stains simultaneously within the normal shelf life.

[0006] Preferably, the porous nanomaterial includes at least one of mesoporous carbon, mesoporous graphite, and mesoporous silica. The above two porous nanomaterials have the characteristics of stable structure, safety and non-toxicity, large specific surface area, and good adsorption performance, and can effectively adsorb protease.

[0007] Preferably, the porous nanomaterial includes mesoporous graphite. Using mesoporous graphite as the porous nanomaterial participating in the protease carrier is beneficial to further improve the immobilization effect of the protease carrier on protease, improve the structural stability of protease, and thus enable the enzyme preparation for laundry provided by this solution to maintain high-efficiency protein stain removal ability for a long time.

[0008] Preferably, the porous nanomaterial further includes mesoporous ZIF-8. Calculated by mass ratio, protease: mesoporous ZIF-8 = (100 - 500): 1. When the protease component contains mesoporous ZIF-8, the activity and stability of protease can be significantly improved, and thus the protein stain removal ability of the enzyme preparation for laundry is enhanced.

[0009] Preferably, the protease includes at least one of subtilisin alkaline protease, trypsin, and papain.

[0010] Preferably, the protease includes papain.

[0011] Preferably, the polyoxyalkylene type sodium sulfosuccinate includes at least one of di-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate and di-(2-ethylhexyl polyoxypropylene) sodium sulfosuccinate.

[0012] Preferably, the polyoxyalkylene type sodium sulfosuccinate includes di-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate and di-(2-ethylhexyl polyoxypropylene) sodium sulfosuccinate. Calculated by the amount of substance ratio, di-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate: di-(2-ethylhexyl polyoxypropylene) sodium sulfosuccinate = 3 - 5: 1. By using di-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate and di-(2-ethylhexyl polyoxypropylene) sodium sulfosuccinate in combination, the structural strength of the coating formed by the polyoxyalkylene type sodium sulfosuccinate on the surface of lipase and the adsorption effect of the polyoxyalkylene type sodium sulfosuccinate on polyethylene glycol can be improved, thereby strengthening the isolation effect on lipase and protease and improving the coexistence stability of the two.

[0013] Preferably, the preparation of the protease component includes the following operations: Step A1. Prepare a protease solution containing protease and a porous nanomaterial dispersion containing porous nanomaterials respectively; Step A2. Mix the protease solution and the porous nanomaterial dispersion so that the porous nanomaterials adsorb the protease; Step A3. Add a hydrochloric acid dopamine solution to the mixture obtained after completion of Step A2 to form polydopamine on the surface of the porous material particles. In the above Step A2, the adsorption of the protease by the porous nanomaterials realizes the pre-fixation of the protease, and in the subsequent Step A3, hydrochloric acid dopamine is converted into polydopamine by self-crosslinking on the surface of the porous nanomaterials, and the polydopamine adheres to the surface of the porous nanomaterials. Through the above operations, the protease can be made to extend into the pores of the porous nanomaterials as much as possible. The polydopamine will not overly occupy the interior of the pores of the porous nanomaterials, but play a strengthening role in fixing the protease on the surface of the porous nanomaterials. The fixation effect of the protease on the protease carrier in the protease component obtained thereby is good, and the activity and stability of the protease can be further improved.

[0014] Preferably, the preparation of the lipase component includes the following operations: Step B1. Prepare a lipase solution containing lipase and a polyoxyalkylene sulfosuccinate solution containing polyoxyalkylene sulfosuccinate respectively; Step B2. Mix the lipase solution and the polyoxyalkylene sulfosuccinate solution to obtain a premixed solution. In the premixed solution, the molar concentration of the polyoxyalkylene sulfosuccinate solution is not less than 8 mM, and the premixed solution is placed at a temperature of 30 °C and incubated for 45 - 90 minutes.

[0015] Preferably, the pH of the protease solution is 7.4 ± 0.2, and the pH of the hydrochloric acid dopamine solution is 7.4 ± 0.2.

[0016] Preferably, the mass concentration of hydrochloric acid dopamine in the hydrochloric acid dopamine solution is 3 wt% - 6 wt%; in Step A3, the reaction temperature for forming polydopamine on the surface of the porous material particles is 28 °C ± 1 °C. Thereby, a uniform polydopamine layer can be formed on the surface of the porous nanomaterials, optimizing the immobilization effect of the protease and improving the protein decontamination ability of the laundry detergent using the enzyme preparation of this solution.

[0017] Preferably, the weight-average molecular weight of the polyethylene glycol is 1000 - 4000. Selecting polyethylene glycol with a weight-average molecular weight falling within this numerical range as the raw material of the laundry detergent enzyme preparation provided by this solution can optimize the adsorption effect of polyoxyalkylene sulfosuccinate on polyethylene glycol, thereby strengthening the barrier effect of polyethylene glycol between the lipase component and the protease component and improving the coexistence stability of lipase and protease.

[0018] Preferably, the preparation method of the enzyme preparation for laundry detergent includes the following operations: Step 1, mix the lipase component and polyethylene glycol at 30°C ± 2°C and keep warm for 45 - 90 minutes; Step 2, lower the temperature of the mixed solution obtained after Step 1 to below 28°C, and then add the protease component thereto. During the process of Step 1 above, under the adsorption of the lipase component, polyethylene glycol is evenly arranged on the surface of the lipase component, and in the subsequent Step 2, when adding the protease component, the polyethylene glycol arranged on the surface of the lipase component constructs a barrier that effectively prevents the contact between the lipase combination and the protease component. Detailed implementation mode

[0019] In order to enable those skilled in the art to better understand the solution of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments.

[0020] The CAS numbers of the enzyme preparations used in the following examples and comparative examples are as follows: papain, CAS 9001 - 73 - 4; subtilisin, CAS 9014 - 01 - 1; trypsin, CAS 9002 - 07 - 7; lipase, CAS 9001 - 62 - 1.

[0021] The mesoporous ZIF - 8 used in the following examples and comparative examples refers to 2 - methylimidazole zinc MOF, CAS 59061 - 53 - 9.

[0022] Example 1

[0023] In this example, a laundry detergent containing an enzyme preparation is prepared, and the production process is carried out in two parts, specifically the preparation of the enzyme preparation for laundry and the preparation of the laundry detergent.

[0024] 1. Preparation of the enzyme preparation for laundry detergent

[0025] (1) Preparation of the protease component

[0026] Step A1, preparation of materials:

[0027] In this example, papain is used as the protease for preparing the protease component. The porous nanomaterials used in this example include mesoporous graphite and mesoporous ZIF - 8. The above three materials are taken according to the mass ratio of mesoporous graphite: mesoporous ZIF - 8: papain = 4:0.005:1;

[0028] Mix papain with a phosphate buffer solution with pH = 7.4 to prepare a protease solution with a papain mass concentration of 5 mg / mL;

[0029] Add the porous nanomaterial to a 15 wt% ethanol solution. Determine the amount of the ethanol solution according to the mass of the mesoporous graphite: the volume of the ethanol solution = 20 mg: 1 mL, and perform ultrasonic dispersion to obtain a porous nanomaterial dispersion;

[0030] Dissolve dopamine hydrochloride in a phosphate buffer solution with pH = 7.4 to obtain a dopamine hydrochloride solution with a mass content of dopamine hydrochloride of 0.5 wt%.

[0031] Step A2, adsorption pre-fixation of protease:

[0032] Fully mix the protease solution and the porous nanomaterial dispersion, and place the resulting mixture under a temperature condition of 25 °C and stir for 2 hours.

[0033] Step A3, polymerization of dopamine hydrochloride:

[0034] Add the dopamine hydrochloride solution to the mixture obtained after completion of Step A2. The feeding amount of the dopamine hydrochloride solution satisfies that the mass ratio of the above mixture to the dopamine hydrochloride solution = 1:1. After mixing the above two solutions, continuously stir it at 28 °C (mark this temperature as "reaction temperature T1") for 10 hours. Dopamine hydrochloride generates polydopamine through self-crosslinking and adheres to the surface of the porous nanomaterial, thereby completing the preparation of the protease component.

[0035] (2) Preparation of the lipase component

[0036] Step B1. Preparation of materials:

[0037] The sodium polyoxyalkylene succinate sulfonate used in this example includes sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate and sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate. Calculated according to the molar ratio, sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate: sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate = 4:1;

[0038] Weigh sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate and sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate by amount, then mix the two to obtain a compound sodium polyoxyalkylene succinate sulfonate, and then dissolve the above compound sodium polyoxyalkylene succinate sulfonate in a phosphate buffer solution with pH = 7.4 to obtain a sodium polyoxyalkylene succinate sulfonate solution with a total molar concentration of sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate and sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate of 20 mM;

[0039] Mix the lipase with a phosphate buffer solution with pH = 7.4 to prepare a lipase solution with a mass concentration of the lipase of 5 mg / mL.

[0040] Step B2. Preparation of lipase-polyoxyalkylene sodium sulfosuccinate complex:

[0041] The lipase solution and the polyoxyalkylene sodium succinate solution were mixed at a volume ratio of 1:1, and the resulting mixture was placed at a temperature of 30° C. and stirred for 1 hour. The resulting mixture was used as a lipase component.

[0042] (3) Preparation of enzyme preparations for laundry detergent

[0043] Step 1: Mix the lipase component and polyethylene glycol (weight average molecular weight of polyethylene glycol is 2000) at 30°C ± 2°C and keep warm for 60 minutes;

[0044] Step 2: Lower the temperature of the mixed solution obtained after step 1 to 25° C., and then add the protease component thereto.

[0045] In the above process of preparing the enzyme preparation for laundry detergent, the usage ratio of each material is calculated according to the mass ratio, protease component: lipase component: polyethylene glycol = 1:1:0.2.

[0046] 2. Preparation of laundry detergent

[0047] The enzyme preparation for laundry detergent is vacuum-dried to remove moisture, thereby producing enzyme granules. The following laundry detergent formulation is prepared: 0.5% enzyme granules, 25% coconut oil fatty acid diethanolamide, 12.5% sodium lauroyl sarcosinate, 5%-10% anhydrous sodium citrate, and the balance deionized water. These ingredients are mixed thoroughly to produce a laundry detergent. The specific amount of anhydrous sodium citrate is determined to achieve a pH of 7.4 ± 0.2 for the finished laundry detergent.

[0048] Example 2

[0049] This example follows Example 1, using the raw material composition used to prepare the protease component as a variable. Different treatment groups were set up to prepare laundry detergents. The correspondence between the treatment group numbers, the type of protease used, and the porous material composition is shown in Table 1. Aside from the variable settings shown in Table 1, the other materials and process steps used in preparing the laundry detergents in each treatment group in this example remained strictly consistent with those in Example 1.

[0050] Table 1. Variable settings between treatment groups in Example 1 and Example 2

[0051]

[0052] Example 3

[0053] This example refers to Example 1. Taking the mass concentration of dopamine hydrochloride in the dopamine hydrochloride solution prepared for preparing the protease component (prepared in step A1) and the reaction temperature T1 involved in step A3 as variables, different treatment groups are set respectively to prepare laundry detergent. The corresponding relationship between the numbers of each treatment group and the mass concentration of the dopamine hydrochloride solution and the reaction temperature T1 is shown in Table 2. Except for the variable settings shown in Table 2, other materials and process steps used by each treatment group in this example during the preparation of laundry detergent are strictly the same as those in Example 1.

[0054] Table 2. Variable settings between each treatment group in Example 1 and Example 3

[0055] Group Mass concentration of dopamine hydrochloride Reaction temperature T1 of step A3 Example 1 0.5wt% 28℃ Treatment group 1 of Example 3 0.3wt% 27℃ Treatment group 2 of Example 3 0.6wt% 29℃ Treatment group 3 of Example 3 0.1wt% 28℃ Treatment group 4 of Example 3 0.8wt% 28℃ Treatment group 5 of Example 3 0.5wt% 25℃ Treatment group 6 of Example 3 0.5wt% 30℃

[0056] Example 4

[0057] This example refers to Example 1. Taking sodium polyoxyalkylene sulfosuccinate included in the raw materials for preparing the lipase component as a variable, different treatment groups are set respectively to prepare laundry detergent. The corresponding relationship between the numbers of each treatment group and the sodium polyoxyalkylene sulfosuccinate used is shown in Table 3. Except for the variable settings shown in Table 3, other materials and process steps used by each treatment group in this example during the preparation of laundry detergent are strictly the same as those in Example 1.

[0058] As shown in Table 3, among the treatment groups set in this example, the sodium polyoxyalkylene sulfosuccinate used in treatment groups 1-3 is composed of a compound of sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate and sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate. The molar ratios of sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate and sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate taken by the above treatment groups are shown in Table 3. The sodium polyoxyalkylene sulfosuccinate used in treatment group 4 is only sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate, and the sodium polyoxyalkylene sulfosuccinate used in treatment group 5 is only sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate.

[0059] Table 3. Variable settings between each treatment group in Example 1 and Example 4

[0060]

[0061]

[0062] Example 5

[0063] This example refers to Example 1. Taking polyethylene glycol used for preparing enzyme preparations for laundry detergent as a variable, different treatment groups were set up respectively to prepare laundry detergent. The numbers of each treatment group and the corresponding weight-average molecular weight of polyethylene glycol used are shown in Table 4. Except for the variable settings shown in Table 4, other materials and process steps used in each treatment group of this example in the process of preparing laundry detergent are exactly the same as those in Example 1.

[0064] Table 4. Variable settings between each treatment group in Example 1 and Example 5

[0065] Group Weight-average molecular weight of polyethylene glycol Example 1 2000 Treatment group 1 of Example 5 1000 Treatment group 2 of Example 5 4000 Treatment group 3 of Example 5 500 Treatment group 4 of Example 5 5000

[0066] Example 6

[0067] This example refers to Example 1 to prepare laundry detergent. The raw materials used in this example for preparing laundry detergent are the same as those in Example 1. However, according to different specific production processes, different treatment groups are set up. For details, please refer to the following description of this example.

[0068] Treatment group 1

[0069] The difference between Treatment group 1 and Example 1 lies in the preparation of the protease component. The specific operation for preparing the protease component in Treatment group 1 is as follows:

[0070] Step A1, preparation of materials:

[0071] The material preparation operation involved in Treatment group 1 is exactly the same as that in Example 1.

[0072] Step A2, immobilization of protease:

[0073] At 25°C, the protease solution, the porous nanomaterial dispersion, and the hydrochloric acid dopamine solution were mixed together, and the dosages of the three were exactly the same as those of the corresponding materials in Example 1; then the resulting mixed slurry was heated to 28°C and continuously stirred at 28°C for 10 hours to complete the preparation of the protease component.

[0074] Except for the above differences in the preparation of the protease component, other materials and process steps used in Treatment group 1 in the process of preparing laundry detergent are exactly the same as those in Example 1.

[0075] Treatment group 2:

[0076] The difference between Treatment group 2 and Example 1 lies in the preparation operation of the enzyme preparation for laundry detergent. The specific operation for preparing the enzyme preparation for laundry detergent in Treatment group 1 is as follows:

[0077] At 25 °C, the lipase component, polyethylene glycol (the weight-average molecular weight of polyethylene glycol is 2000), and the protease component were mixed and incubated for 60 minutes to obtain the enzyme preparation for laundry detergent of Treatment Group 2. In the process of preparing the enzyme preparation for laundry detergent described above, the dosage relationship between the various materials was calculated by mass ratio: protease component: lipase component: polyethylene glycol = 1:1:0.2.

[0078] Except for the above differences in the preparation of the enzyme preparation for laundry detergent, the other materials and process steps used in Treatment Group 2 in the process of preparing the laundry detergent were exactly the same as those in Example 1.

[0079] Comparative Example 1

[0080] This comparative example used Example 1 as a reference to prepare a laundry detergent.

[0081] The difference from Example 1 was that in the process of preparing the enzyme preparation for laundry detergent in this comparative example, the feeding operation of polyethylene glycol was omitted. That is, the enzyme preparation for laundry detergent obtained in this comparative example consisted only of the protease component and the lipase component. In the process of preparing the laundry detergent, the addition amount of the enzyme preparation for laundry detergent in this comparative example in the laundry detergent was equal to the addition amount of the enzyme preparation for laundry detergent obtained in Example 1 in the laundry detergent minus the proportion of polyethylene glycol (calculated according to the raw material addition amount of polyethylene glycol), that is, to ensure that the amounts of protease and lipase used for preparing the laundry detergent were basically the same as those in Example 1.

[0082] Except for the above differences, the other materials and process steps used in this comparative example to prepare the laundry detergent were exactly the same as those in Example 1.

[0083] Comparative Example 2

[0084] This comparative example used Example 1 as a reference to prepare a laundry detergent.

[0085] The difference from Example 1 is that in the process of preparing the enzyme preparation for laundry detergent in this comparative example, the application of the porous nanomaterial is omitted, that is, the protease is not immobilized with the porous nanomaterial. The specific operation for preparing the protease component in this comparative example is as follows: (1) Prepare a protease solution and a hydrochloric acid dopamine solution. The materials and operation steps used to prepare the above two solutions are strictly the same as the corresponding content in Example 1. (2) Add the hydrochloric acid dopamine solution to the protease solution. The dosages of the two are the same as the corresponding materials in Example 1. After mixing, continuously stir the mixture at 28 °C for 10 hours to complete the preparation of the protease component. In the process of preparing the laundry detergent, the addition amount of the enzyme preparation for laundry detergent in this comparative example in the laundry detergent is equal to the addition amount of the enzyme preparation for laundry detergent obtained in Example 1 in the laundry detergent minus the proportion of the porous nanomaterial (calculated according to the raw material addition amount of the porous nanomaterial), that is, to ensure that the dosages of protease and lipase used for preparing the laundry detergent are basically the same as those in Example 1.

[0086] Except for the above differences, the other materials and process steps used in this comparative example to prepare the laundry detergent are strictly the same as those in Example 1.

[0087] Comparative Example 3

[0088] This comparative example uses Example 1 as a reference to prepare the laundry detergent.

[0089] The difference from Example 1 is that in the process of preparing the enzyme preparation for laundry detergent in this comparative example, the application of hydrochloric acid dopamine is omitted, that is, the protease component does not contain polydopamine. The specific operation for preparing the protease component in this comparative example is as follows: (1) Prepare a protease solution and a porous nanomaterial dispersion. The materials and operation steps used to prepare the above two solutions are strictly the same as the corresponding content in Example 1. (2) Thoroughly mix the protease solution and the porous nanomaterial dispersion, and place the resulting mixture under the temperature condition of 25 °C and stir for 2 hours to complete the preparation of the protease component. In the process of preparing the laundry detergent, the addition amount of the enzyme preparation for laundry detergent in this comparative example in the laundry detergent is equal to the addition amount of the enzyme preparation for laundry detergent obtained in Example 1 in the laundry detergent minus the proportion of polydopamine (calculated by extrapolating according to the raw material addition amount of hydrochloric acid dopamine), that is, to ensure that the dosages of protease and lipase used for preparing the laundry detergent are basically the same as those in Example 1.

[0090] Except for the above differences, the other materials and process steps used in this comparative example to prepare the laundry detergent are strictly the same as those in Example 1.

[0091] Comparative Example 4

[0092] This comparative example uses Example 1 as a reference to prepare the laundry detergent.

[0093] What differentiates this comparative example from Example 1 is that in the process of preparing the enzyme preparation for laundry detergent, chitosan of equal mass is used to replace dopamine hydrochloride in the raw materials for preparing the protease component.

[0094] Except for the above differences, all other materials and process steps used in preparing the laundry detergent in this comparative example are strictly the same as those in Example 1.

[0095] Comparative Example 5

[0096] This comparative example uses Example 1 as a reference to prepare laundry detergent. What differentiates this comparative example from Example 1 is that in the process of preparing the enzyme preparation for laundry detergent, the feeding operation of polyoxyalkylene type sulfosuccinate is omitted. Except for the above differences, all other materials and process steps used in preparing the laundry detergent in this comparative example are strictly the same as those in Example 1.

[0097] Comparative Example 6

[0098] This comparative example uses Example 1 as a reference to prepare laundry detergent. What differentiates this comparative example from Example 1 is that in the process of preparing the enzyme preparation for laundry detergent, sulfosuccinic acid bis(2-ethylhexyl) ester of equal amount of substance is used to replace polyoxyalkylene type sulfosuccinate in the raw materials for preparing the enzyme preparation for laundry detergent in Example 1. Except for the above differences, all other materials and process steps used in preparing the laundry detergent in this comparative example are strictly the same as those in Example 1.

[0099] Comparative Example 7

[0100] This comparative example prepares a laundry detergent containing an enzyme preparation, and the production process is carried out in two parts, specifically the preparation of the enzyme preparation for laundry and the formulation of the laundry detergent.

[0101] 1. Preparation of the enzyme preparation for laundry detergent

[0102] (1) Preparation of the protease component

[0103] Step A1. Preparation of materials:

[0104] This comparative example uses papain as the protease for preparing the protease component. The polyoxyalkylene type sulfosuccinate used in this example includes bis(2-ethylhexyl polyoxyethylene) sulfosuccinate and bis(2-ethylhexyl polyoxypropylene) sulfosuccinate. Calculated by molar ratio, bis(2-ethylhexyl polyoxyethylene) sulfosuccinate: bis(2-ethylhexyl polyoxypropylene) sulfosuccinate = 4:1;

[0105] Weigh sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate and sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate by weight, then mix the two to obtain a compound polyoxyalkylene type sulfosuccinate sodium salt. Then dissolve the above compound polyoxyalkylene type sulfosuccinate sodium salt in a phosphate buffer solution with pH = 7.4 to obtain a polyoxyalkylene type sulfosuccinate sodium salt solution with a total molar concentration of 20 mM of sodium bis(2-ethylhexyl polyoxyethylene) sulfosuccinate and sodium bis(2-ethylhexyl polyoxypropylene) sulfosuccinate;

[0106] Mix protease with a phosphate buffer solution with pH = 7.4 to prepare a protease solution with a mass concentration of protease of 5 mg / mL.

[0107] Step A2. Preparation of protease-polyoxyalkylene type sulfosuccinate sodium salt complex:

[0108] Mix the above protease solution and polyoxyalkylene type sulfosuccinate sodium salt solution in a volume ratio of 1:1, place the resulting mixture under a temperature condition of 30 °C, and stir for 1 hour, using the resulting mixture as the protease component.

[0109] (2) Preparation of lipase component

[0110] Step B1, Preparation of materials:

[0111] The porous nanomaterials used in this comparative example include mesoporous graphite and mesoporous ZIF-8, and the above three materials are taken in a mass ratio of mesoporous graphite: mesoporous ZIF-8: lipase = 4:0.005:1;

[0112] Mix lipase with a phosphate buffer solution with pH = 7.4 to prepare a lipase solution with a lipase mass concentration of 5 mg / mL;

[0113] Add the porous nanomaterials to a 15 wt% ethanol solution, determine the amount of ethanol solution according to the mass of mesoporous graphite: volume of ethanol solution = 20 mg: 1 mL, and ultrasonically disperse to obtain a porous nanomaterial dispersion;

[0114] Dissolve dopamine hydrochloride in a phosphate buffer solution with pH = 7.4 to obtain a dopamine hydrochloride solution with a mass content of dopamine hydrochloride of 0.5 wt%.

[0115] Step B2, Adsorption pre-fixation of lipase:

[0116] Fully mix the lipase solution and the porous nanomaterial dispersion, and place the resulting mixture under a temperature condition of 25 °C and stir for 2 hours.

[0117] Step B3, Polymerization of dopamine hydrochloride:

[0118] To the mixed solution obtained after step B2 is added dopamine hydrochloride solution, the amount of dopamine hydrochloride solution added is satisfied, the mass ratio of the mixed solution to the dopamine hydrochloride solution is 1:1, and after the two solutions are mixed, they are continuously stirred at 28 ° C for 10 hours. Dopamine hydrochloride is self-crosslinked to generate polydopamine and attached to the surface of the porous nanomaterial, thereby completing the preparation of the lipase component.

[0119] (3) Preparation of enzyme preparations for laundry detergent

[0120] Step 1: Mix the protease component and polyethylene glycol (weight average molecular weight of polyethylene glycol is 2000) at 30°C ± 2°C and keep warm for 60 minutes;

[0121] Step 2: Lower the temperature of the mixed solution obtained after step 1 to 25° C., and then add the lipase component thereto.

[0122] In the above process of preparing the enzyme preparation for laundry detergent, the usage ratio of each material is calculated according to the mass ratio, protease component: lipase component: polyethylene glycol = 1:1:0.2.

[0123] 2. Preparation of laundry detergent

[0124] The enzyme preparation for the laundry detergent is vacuum dried to remove moisture therefrom to obtain enzyme preparation granules. The following laundry detergent formula is prepared: 0.5% enzyme preparation granules, 25% coconut oil fatty acid diethanolamide, 12.5% sodium lauroyl sarcosinate, 5%-10% anhydrous sodium citrate, and the balance deionized water. The above materials are mixed thoroughly to obtain a laundry detergent. The specific amount of anhydrous sodium citrate is determined so that the pH value of the finished laundry detergent reaches 7.4±0.2.

[0125] Test Case

[0126] 1. Test subjects

[0127] This test example uses the laundry detergents prepared in Examples 1-6 and Comparative Examples 1-6 as test objects.

[0128] 2. Detergency test

[0129] Using 250 mg / kg of hard water, prepare the standard laundry detergent into a 0.2 wt% sample and the test object into a 0.3 wt% sample respectively. Conduct the detergency test on the above samples according to the provisions of GB / T 13174-2021 "Determination of Detergency and Recycling Washing Performance of Detergents for Clothing". Statistically analyze the detergency ratios of the samples for two types of stained cloths, namely protein (JB-02) and sebum (JB-03). As a reference, the above standard laundry detergent is prepared according to the provisions in GB / T 13174-2021, and a reference protease is added to the standard laundry detergent according to the regulations in this standard.

[0130] The sampling times for the above detergency test include sampling the freshly prepared finished laundry detergent (detergency test of freshly prepared sample) and sampling the laundry detergent after 3 months of storage (detergency test of long-term stored sample, the sample storage temperature is 25-30 °C, and the storage conditions of the test samples are kept consistent).

[0131] 3. Test Results

[0132] For easy comparison, organize the test results of this test example in Table 5-10 below for grouped display.

[0133] The test results of this test example show that the laundry detergents separately prepared in Examples 1-6 can effectively remove the protein stains and fat stains on the soiled cloth used for the detergency test. Examples 1-6 are the protease components of the laundry detergent enzyme preparation, and all use porous nanomaterials and involve the application of dopamine hydrochloride. The porous nanomaterials can play a good adsorption role on the protease, and dopamine hydrochloride can be self-polymerized into sticky polydopamine through self-polymerization. The polydopamine adheres to the surface of the porous nanomaterials. On the one hand, it can strengthen the connection stability between the porous nanomaterials and the protease. On the other hand, it is also beneficial to the contact between the protease component and the stains, improving the reaction efficiency of the protease with the target substrate. With the mutual cooperation of the porous nanomaterials and polydopamine, the protease can be firmly fixed on the surface of the protease carrier jointly composed of the two, thereby improving the structural stability of the protease and also reducing the amount of free protease through the immobilization of the protease, so that the stability of the protease in the laundry detergent system can be improved. And the raw materials for preparing the lipase component in Examples 1-6 all include lipase and polyoxyalkylene type sulfosuccinate. The molecular structure of polyoxyalkylene type sulfosuccinate contains a polyoxyalkylene type chain segment, so that it has the characteristics of a non-ionic surfactant and can coexist stably with lipase and protease. Mixing polyoxyalkylene type sulfosuccinate with lipase to obtain the lipase component, the structure and properties of the lipase component are stable, and the polyoxyalkylene type sulfosuccinate can have a certain adsorption effect on polyethylene glycol. Therefore, when the lipase component and polyethylene glycol are mixed, the polyethylene glycol will be enriched on the surface of the lipase component due to the adsorption of the polyoxyalkylene type sulfosuccinate. Thus, it is equivalent to setting a separation barrier between the lipase component and the protease component, hindering the mutual contact between the protease and the lipase. In summary, in the laundry detergent enzyme preparation prepared in Examples 1-6, the protease and the lipase can maintain good activity for a long time. Therefore, when the laundry detergent enzyme preparation is applied to the preparation of laundry detergent, it can effectively improve the washing effect of the laundry detergent, so that the laundry detergent shows good detergency for protein stains and fat stains.

[0134] Table 5. Detergency test of the laundry detergents separately prepared in Example 1 and each comparative example

[0135]

[0136] Compared with the laundry detergents separately prepared in Examples 1-6, the laundry detergents separately prepared in Comparative Examples 1-6 all have a significantly lower detergency under the same test conditions. The following combines the test result data shown in Table 5 to analyze the detergency of the laundry detergents separately prepared in Example 1 and Comparative Examples 1-6.

[0137] In Comparative Example 1, polyethylene glycol was not contained in the raw materials for preparing the laundry detergent enzyme preparation. Therefore, it was impossible to rely on polyethylene glycol to set up a barrier between the lipase component and the protease component of the laundry detergent enzyme preparation. However, the test sample provided in Comparative Example 1 still had good detergency performance in the in-situ sample detergency test. This shows that although polyethylene glycol was not present in the test sample, there was still a material that effectively blocked between the protease and the lipase. In the sample in which the polyalkylene oxide type sodium sulfosuccinate and the lipase jointly constituted the lipase component, the polyalkylene oxide type sodium sulfosuccinate would play a certain role in encapsulating the lipase, thereby to a certain extent avoiding the contact between the lipase and the protease, enabling the lipase and the protease in the laundry detergent to stably coexist in a short time. However, according to the test results of the detergency of the long-term stored sample measured for the laundry detergent of Comparative Example 1, after being placed for a period of time, the protein stain detergency and the fat stain detergency of the laundry detergent of Comparative Example 1 decreased significantly. The reason for the above test results was that relying solely on the polyalkylene oxide type sodium sulfosuccinate could not form an isolation barrier with good structural strength. After being placed for a period of time, the coating layer composed of the polyalkylene oxide type sodium sulfosuccinate might be damaged, thus unable to effectively block the contact between the lipase and the protease in the laundry detergent, resulting in the inactivation of both due to mutual reaction. In Examples 1-6, due to the use of polyethylene glycol, after the polyalkylene oxide type sodium sulfosuccinate in the lipase component adsorbed polyethylene glycol, the structural strength of the coating layer formed by the polyalkylene oxide type sodium sulfosuccinate was improved. Moreover, the extension of polyethylene glycol on the surface of the lipase component also prevented the lipase component and the protease component from approaching each other, so that the laundry detergents provided in these examples could maintain good lipase activity and protease activity for a long time.

[0138] In Comparative Example 2, the raw materials for preparing the protease component did not contain porous nanomaterials. In the process of the protease component, the hydrochloric acid dopamine mixed with the protease could be converted into polydopamine through self-crosslinking. As described above, polydopamine had a certain viscosity, thus being able to play a certain role in encapsulating and fixing the protease. However, polydopamine was not sufficient to provide a fixation carrier for the protease to achieve a good fixation effect. Therefore, as the storage time prolonged, the amount of protease free from the protease component increased. The free protease had poor structural stability and was more likely to diffuse in the laundry detergent. If there was also a situation where part of the lipase was free from the lipase component, there was a possibility that the free protease and the lipase would react with each other and become inactivated.

[0139] The main operation for preparing the protease component in Comparative Example 3 lies in adsorbing the protease by using porous nanomaterials to achieve the immobilization of the protease. Since the raw materials used for preparing the protease component in this comparative example do not contain dopamine hydrochloride, there is no polydopamine on the surface of the porous nanomaterials in the obtained protease component. Relying solely on the porous nanomaterials is also difficult to stably immobilize the protease for a long time. As the storage time prolongs, more and more proteases fall off from the protease carrier. Referring to the analysis of Comparative Example 2, the failure of protease immobilization will reduce the coexistence stability of protease and lipase in the laundry detergent, and increase the possibility of their inactivation by reacting when they come into contact with each other. From the test results of the detergency of the long-term stored samples measured for the test object provided in Comparative Example 3, it can be seen that after long-term storage, the detergency of the laundry detergent prepared in Comparative Example 3, especially the detergency for protein stains, has significantly decreased. In the process of preparing the lipase component of the enzyme preparation for laundry detergent in Comparative Example 4, chitosan was used to replace dopamine hydrochloride. Although chitosan can also undergo a self-crosslinking reaction to transform into a self-crosslinked product similar to hydrogel, chitosan is difficult to coexist stably with the protease. Therefore, in the process of preparing the protease component, it is difficult to effectively form the chitosan self-crosslinked product. That is, in the protease component prepared in Comparative Example 4, the immobilization of the protease is mainly achieved by using porous nanomaterials, which is similar to Comparative Example 3. From the detergency test results corresponding to Comparative Example 3 and Comparative Example 4, the detergency levels of the two are close.

[0140] Among the test objects of this test example, the detergency for protein stains and the detergency for fat stains measured for the test object provided in Comparative Example 5 are the lowest values compared with the same period. In the process of preparing the lipase component of the enzyme preparation for laundry detergent in Comparative Example 5, the addition of polyalkylene oxide type sulfosuccinate was omitted, resulting in the lack of materials that can adsorb polyethylene glycol, and thus unable to form an orderly arranged polyethylene glycol barrier around the lipase. The lipase in this laundry detergent enzyme preparation can contact the protease extending from the surface of the protease carrier in the protease component, and the two are inactivated after reaction, resulting in a rapid decrease in the activity of the active materials that can effectively degrade protein stains and fat stains in the laundry detergent, leading to poor detergency for protein stains and fat stains of the laundry detergent. The activities of the protease and lipase in the laundry detergent provided in Comparative Example 5 decrease rapidly as the storage time prolongs. Therefore, after long-term storage, the above laundry detergent basically does not contain protease and lipase with effective detergency activity, and basically relies on the surfactants contained therein to play a detergency role. Since the surfactants contained in this laundry detergent are mainly non-ionic surfactants, their detergency ability is weak, resulting in the detergency of the long-term stored sample measured for the laundry detergent provided in Comparative Example 5 being even inferior to that of the standard laundry detergent used as the reference for calculating the detergency in this test example.

[0141] Compared with Example 1, in the process of preparing the enzyme preparation for laundry detergent, Comparative Example 6 uses sodium sulfosuccinate that does not contain a polyoxyalkylene chain structure instead of polyoxyalkylene sodium sulfosuccinate as a raw material for preparing the lipase component, and further prepares the lipase component. The test results of this test example show that the protein stain removal and fat stain removal corresponding to the freshly prepared sample of the test object prepared in Comparative Example 6 are higher than the year-on-year test results of the other comparative examples. However, the protein stain removal and fat stain removal corresponding to the long-term sample of the test object prepared in Comparative Example 6 are not superior to the year-on-year test results of the other comparative examples, and its measured fat substance removal is even lower than that of some comparative examples. This shows that the laundry detergent prepared in Comparative Example 6 has a significant loss of protein stain removal active substances and fat stain removal active substances after long-term storage. In the freshly prepared sample provided in Comparative Example 6, the lipase component composed of sodium sulfosuccinate and lipase can adsorb polyethylene glycol, thereby allowing the lipase and protease in the freshly prepared sample to remain undisturbed for a short period of time. However, sodium sulfosuccinate and lipase are difficult to coexist stably for a long time. As the storage time increases, the sodium sulfosuccinate and lipase consume each other. The content of sodium sulfosuccinate is low, and although the sodium sulfosuccinate contained in the lipase component is insufficient to completely consume the lipase, as the content of sodium sulfosuccinate decreases, the free lipase in the lipase component increases, and the free lipase diffuses in the laundry detergent until it contacts the protease component, where the free lipase interacts with the protease in the protease component and is inactivated.

[0142] Compared with Example 1, Comparative Example 7 interchanges the materials used with protease and lipase, respectively. Based on this, in the laundry detergent enzyme preparation prepared in Comparative Example 7, protease and polyoxyalkylene sodium succinate sulfonate jointly constitute the protease component, while the lipase component is composed of lipase, porous nanomaterials, and polydopamine. Specifically, the porous nanomaterial with polydopamine attached to the surface serves as a lipase carrier to immobilize the lipase. However, as can be seen from the test results, compared with the test samples provided in Example 1, the protein stain detergency and fat stain detergency measured for the test samples provided in Comparative Example 7 are both on the low side. On the one hand, Comparative Example 7 does not use a protease carrier with good structural stability to achieve protease immobilization. On the other hand, polyoxyalkylene sodium succinate sulfonate is difficult to provide a relatively good coating effect on the protease. Therefore, in the laundry detergent prepared in Comparative Example 7, a considerable amount of free proteases are free in the laundry detergent. When these free proteases diffuse through the laundry detergent and come into contact with the lipase component, side reactions easily occur, resulting in the inactivation of the protease and lipase, causing the protein stain removal ability and fat stain removal ability of the laundry detergent provided in Comparative Example 7 to show a significant decrease.

[0143] As described above, the test samples provided in Examples 1-6 respectively all have good protein stain detergency and fat stain detergency. However, due to the still existing differences among the laundry detergent enzymes prepared in the above-mentioned examples respectively, there are still certain gaps in the protein stain detergency and fat stain detergency corresponding to the test samples provided in the above-mentioned examples respectively. The following will further analyze the laundry detergent enzymes prepared in Examples 1-6 respectively and their corresponding detergency test results.

[0144] Table 6 shows the test results of the test objects provided by each treatment group in Example 1 and Example 2. The test results of the laundry detergents provided by Treatment Group 6 of Example 1, Treatment Group 7 of Example 2, and Example 2 were compared: in the test of the detergency of freshly prepared samples, the detergency of protein stains measured for the above three laundry detergents showed relatively obvious differences, while the detergency effects on fat stains were comparable. This shows that choosing different types of porous nanomaterials to construct protease carriers mainly affects the effect of proteases. Among the three different porous nanomaterials, mesoporous graphite, mesoporous carbon, and mesoporous silica, choosing mesoporous graphite as the main porous nanomaterial for preparing protease carriers is beneficial to improving the activity of proteases; in the test of the detergency of stored samples, the above three laundry detergents can still maintain excellent detergency, but the difference in the detergency of fat stains among the three laundry detergents increases. The reason is that using mesoporous graphite and mesoporous carbon as the main porous nanomaterials can better immobilize proteases, while in the laundry detergent prepared in Treatment Group 7 with mesoporous silica as the main porous nanomaterial, the immobilization effect of proteases is slightly worse. As the storage time prolongs, some proteases in the protease component fall off from the protease carrier, and the free proteases react with lipases in the laundry detergent, resulting in the consumption of lipases, thus making the detergency of fat stains in the stored samples measured in Treatment Group 7 of Example 2 slightly weaker. In Treatment Groups 3, 4, and 5 of Example 2, mesoporous ZIF-8 was not used, and only mesoporous graphite, a kind of mesoporous nanomaterial, was used to prepare the protease component. From the test results of the detergency of the laundry detergents provided by the above treatment groups, it can be seen that when ZIF-8 is not contained in the protease carrier, choosing subtilisin alkaline protease as the active protease of the protease component results in the best detergency of protein stains for the corresponding test samples. Further comprehensively examining the test results of Example 1, Treatment Group 1 of Example 2, and Treatment Group 2 of Example 2, the test results show that for laundry detergents using subtilisin alkaline protease, trypsin, and papain as active proteases respectively, adding a small amount of mesoporous ZIF-8 to the porous nanomaterials used to make protease carriers can all improve the detergency of protein stains of the laundry detergents. However, it is worth noting that for the case of choosing papain as the active protease of the laundry detergent, the introduction of mesoporous ZIF-8 has the most significant effect on improving the detergency of protein stains of the laundry detergent. When mesoporous ZIF-8 and mesoporous graphite are used in combination, the detergency of protein stains measured in Example 1 using papain as the active protease of the laundry detergent is significantly higher than that in Treatment Group 1 and Treatment Group 2 of Example 2 using subtilisin alkaline protease and trypsin as the active proteases of the laundry detergent respectively.

[0145] Table 6. Detergency Test of Laundry Detergents Prepared in Example 1 and Example 2

[0146]

[0147] As described above, in the process of preparing the enzyme preparation for laundry detergent in Examples 1-6, dopamine hydrochloride was used as a raw material to generate polydopamine on the surface of the porous nanomaterial, and polydopamine was used to enhance the immobilization effect of protease. Between the treatment groups in Examples 1 and 3, the mass concentration of the dopamine hydrochloride solution and the polymerization reaction temperature of polydopamine were used as experimental variables for preparing the enzyme preparation for laundry detergent to prepare the enzyme preparation for laundry detergent. From the experimental results of this test example, there were differences in the protein stain detergency test results of the laundry detergents provided by the treatment groups in Examples 1 and 3 respectively. By adjusting the mass concentration of the dopamine hydrochloride solution and the polymerization reaction temperature of dopamine hydrochloride, the yield of polydopamine and the attachment state of polydopamine on the surface of the porous nanomaterial were controlled. When the mass concentration of the dopamine hydrochloride solution reached 3wt%-6wt%, dopamine hydrochloride underwent a polymerization reaction at a temperature of 28°C ± 1°C, whereby the conversion rate of dopamine hydrochloride to polydopamine was appropriate, and the generated polydopamine could be evenly attached to the surface of the porous nanomaterial, which could not only effectively strengthen the immobilization of protease but also not block the active sites of protease, enabling the laundry detergent containing protease components to efficiently exert its protein stain detergency.

[0148] Table 7. Detergency test of the laundry detergents separately prepared in Examples 1 and 3

[0149]

[0150] Table 8 shows the test results of the test objects provided by each treatment group in Example 1 and Example 4. The difference among these test objects lies in the types of polyoxyalkylene-type sodium sulfosuccinates used to prepare the lipase component. From the data shown in Table 8, when using bis-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate or bis-(2-ethylhexyl polyoxypropylene) sodium sulfosuccinate alone as the polyoxyalkylene-type sodium sulfosuccinate for preparing the lipase component, or using the mixture of bis-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate and bis-(2-ethylhexyl polyoxypropylene) sodium sulfosuccinate as the polyoxyalkylene-type sodium sulfosuccinate for preparing the lipase component, a barrier with an effective blocking effect can be formed outside the lipase component. Thus, in a system where the protease component and the lipase component coexist, it can play a certain protective role for the lipase. By comparing the detergency test results of the test objects provided by Treatment Group 3 and Treatment Group 4 in Example 4, it can be seen that when using only one material as the polyoxyalkylene-type sodium sulfosuccinate for preparing the lipase component, the laundry detergent prepared with bis-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate has a better detergency effect on fatty stains than the laundry detergent prepared with bis-(2-ethylhexyl polyoxypropylene) sodium sulfosuccinate. However, when bis-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate and bis-(2-ethylhexyl polyoxypropylene) sodium sulfosuccinate are compounded in a certain proportion, the detergency effect that can be achieved by the laundry detergent using the compounded polyoxyalkylene-type sodium sulfosuccinate is even better than that of the laundry detergent prepared with bis-(2-ethylhexyl polyoxyethylene) sodium sulfosuccinate alone.

[0151] Table 8. Detergency Test of Laundry Detergents Prepared in Example 1 and Example 4

[0152]

[0153] Based on the test results of the test subjects provided by the respective treatment groups of Examples 1 and 5, Example 1, Example 5 Treatment Group 1, and Example 5 Treatment Group 2, which selected polyethylene glycol with a weight-average molecular weight of 1000-4000 as the raw material for the laundry detergent enzyme preparation, exhibited significantly superior detergency. The weight-average molecular weight of polyethylene glycol in the raw materials used to prepare the laundry detergent enzyme preparation provided in this solution affects the adsorption of polyethylene glycol by the polyoxyalkylene sodium succinate sulfonate in the lipase component. As described above, in this solution, by allowing the polyoxyalkylene sodium succinate sulfonate in the lipase component to adsorb polyethylene glycol, the polyethylene glycol is systematically enriched on the surface of the lipase component, thereby acting as a barrier to the lipase component and the protease component. Polyoxyalkylene sodium sulfosuccinate has a better adsorption effect on polyethylene glycol with a weight-average molecular weight of 1000-4000. Therefore, selecting polyethylene glycol with a weight-average molecular weight of 1000-4000 as the raw material for enzyme preparations for laundry detergents can improve the adsorption effect of polyoxyalkylene sodium sulfosuccinate on polyethylene glycol, thereby strengthening the barrier effect of polyethylene glycol between the lipase component and the protease component, and improving the coexistence stability of lipase and protease, which is reflected in the year-on-year improvement in the protein stain removal power and fat stain removal power of the corresponding test objects.

[0154] Table 9. Decontamination ability test of the laundry detergents prepared in Example 1 and Example 5

[0155]

[0156] In the process of preparing the protease component, embodiment 1 first utilizes porous nano material that protease is adsorbed pre-fixed, and then generates polydopamine on the surface of porous nano material. Yet, in the process of preparing the protease component, the treatment group 1 of embodiment 6, with the disposable mixing of protease, porous nano material, dopamine hydrochloride, thus, the polydopamine that dopamine hydrochloride transforms into may partly enter the pore content of porous nano material, has occupied the position that porous nano material is used to fix protease, makes the fixing effect of protease slightly poor. With respect to the laundry liquid that embodiment 1 makes, there should be more free proteases in the laundry liquid that embodiment 6 treatment group 1 makes, the stability and activity of these free proteases themselves are slightly poor with respect to immobilized protease, and free protease also can react with the lipase in the laundry liquid loss lipase simultaneously. Thus, by table 10, can see that the test result corresponding to the test object of embodiment 1 and embodiment 6 treatment group 1 is compared, and the test object that embodiment 1 provides records higher detergency.

[0157] Regarding the preparation of enzyme preparations for laundry detergents, in Example 1, the lipase component and polyethylene glycol were first mixed. After the polyethylene glycol was arranged on the surface of the lipase component under the adsorption action of the lipase component, the protease component was then added. Due to the regular arrangement of the polyethylene glycol, in the enzyme preparation for laundry detergents prepared in Example 1, the polyethylene glycol could provide an excellent barrier effect between the lipase component and the protease component, fully avoiding the mutual interference between the lipase component and the protease component. In treatment group 2 of Example 6, by mixing the lipase component, the protease component, and polyethylene glycol at one time to prepare the enzyme preparation for laundry detergents, since there was no step of pre-mixing the lipase component and polyethylene glycol, after mixing, some of the polyethylene glycol in the mixing system might not be adsorbed by the lipase component in time, and the lipase component and the protease component might contact and react with each other to become inactivated after mixing. Consistent with the above analysis, as shown in Table 10, when the test results corresponding to the test objects of Example 1 and treatment group 2 of Example 6 were compared, the test object provided by Example 1 had a higher detergency.

[0158] Table 10. Detergency test of laundry detergents prepared in Example 1 and Example 6 respectively

[0159]

[0160] The above examples are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the above examples, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced, but these modifications or replacements are all within the protection scope of the present invention.

Claims

1. A laundry detergent enzyme preparation that effectively improves the washing effect, characterized in that: The enzyme preparation for laundry detergent comprises a protease component, a lipase component and polyethylene glycol in a weight ratio of 1:1:0.2; The protease component includes a protease, a porous nanomaterial for adsorbing the protease, and dopamine hydrochloride for forming polydopamine on the surface of the porous nanomaterial adsorbed with the protease; the porous nanomaterial includes at least one of mesoporous carbon, mesoporous graphite, and mesoporous silica, and the porous nanomaterial:protease component is 4:1 according to the mass ratio; the porous nanomaterial also includes mesoporous ZIF-8, and the mass ratio of protease:mesoporous ZIF-8 is (100-500):1; The lipase component includes lipase and polyoxyalkylene sodium succinate sulfonate, and the amount is such that 5g of lipase is mixed with every 20mmol of polyoxyalkylene sodium succinate sulfonate; the polyoxyalkylene sodium succinate sulfonate includes at least one of di-(2-ethylhexyl polyoxyethylene) succinic acid diester sodium sulfonate and di-(2-ethylhexyl polyoxypropylene) succinic acid diester sodium sulfonate; The preparation method of the enzyme preparation for laundry detergent comprises the following operations: step 1, mixing the lipase component and the polyethylene glycol at 30°C±2°C and keeping the mixture warm for 45-90 minutes; step 2, lowering the temperature of the mixed solution obtained after step 1 to below 28°C, and then adding the protease component thereto.

2. The enzyme preparation for laundry detergent according to claim 1, characterized in that: The porous nanomaterial includes mesoporous graphite.

3. The enzyme preparation for laundry detergent according to claim 1, wherein: The protease comprises at least one of subtilisin, trypsin and papain.

4. The enzyme preparation for laundry detergent according to claim 1, wherein: The polyoxyalkylene sodium succinate sulfonate includes di-(2-ethylhexyl polyoxyethylene) sodium diester sulfonate of succinate and di-(2-ethylhexyl polyoxypropylene) sodium diester sulfonate of succinate. Calculated based on the ratio of the amount of substance, the di-(2-ethylhexyl polyoxyethylene) sodium diester sulfonate of succinate: the di-(2-ethylhexyl polyoxypropylene) sodium diester sulfonate of succinate is equal to 3-5:

1.

5. The enzyme preparation for laundry detergent according to claim 1, wherein: The pH of the protease solution is 7.4±0.2, and the pH of the dopamine hydrochloride solution is 7.4±0.

2.

6. The enzyme preparation for laundry detergent according to claim 1, characterized in that: The weight average molecular weight of the polyethylene glycol is 1000-4000.

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