Long-lasting fragrance-locked coated detergent and method for preparing the same

Abstract

The application belongs to the technical field of daily chemical washing composition, and provides a long-acting fragrance-locked coated detergent and a preparation method thereof. Covalent fragrance microcapsules are constructed by using quaternary ammonium oxidized cellulose nanofiber and amino-beta-cyclodextrin through an amide bond, and are compounded with sodium dodecyl benzene sulfonate, cocamidopropyl betaine, trisodium citrate and 1,2-propanediol to form a detergent system, so that high core material loading, shear stability and controllable fragrance release are realized, the problem that long-acting fragrance locking, low viscosity and wide processing window are difficult to be considered together in the existing coated detergent is solved, and the application is suitable for daily chemical scenes such as fabric washing.

Description

Technical Field

[0001] This invention relates to the field of daily chemical detergent technology, specifically to a long-lasting fragrance-locking encapsulated detergent and its preparation method. Background Technology

[0002] As fabric washing products increasingly evolve from simple stain removal to a synergistic development of cleaning, care, and sensory experience, consumers' expectations for detergents are no longer limited to cleaning power. They are now paying closer attention to the comfort of the scent on washed clothes, the longevity of the fragrance, and the overall user experience. For liquid or semi-liquid detergents, fragrances can be affected by the aqueous environment, surfactants, mechanical shear, and interfacial migration during storage, filling, transportation, dilution, rinsing, and drying. Therefore, the system needs to effectively retain the fragrance components while achieving appropriate release during actual use, ensuring that the fragrance performance is coordinated with the stain removal function. Simultaneously, as a compound system, detergents must also consider the fluidity of the base liquid, formulation compatibility, dispersion stability, and processing window width to avoid affecting the preparation and usage effects due to excessive thickening, shell instability, or premature release of the core material. Therefore, constructing a stable and responsive fragrance system based on the synergistic relationship between the fragrance core material, the coating structure, and the detergent base liquid has become an important direction in the development of daily chemical washing products.

[0003] Existing research on fragrance-retaining laundry detergent systems mainly focuses on microencapsulation, formulation dispersion, or sustained-release carriers, but there are still shortcomings in addressing all these aspects. For example, Chinese patent CN111808694A discloses a stable, long-lasting fragrance laundry pod and its preparation method. It improves the stratification and instability of microencapsulated fragrances in the laundry pod liquid by constructing a stable suspension system. However, based on its disclosure, the technical focus is mainly on the stable existence of the material itself, and there is still room for further optimization in balancing shell strength, shear resistance, and controlled fragrance release during use under high core material load conditions. Similarly, Chinese patent CN110845629A discloses a reactive fragrance-releasing nanocrystalline cellulose and its preparation method. It improves the stability of fragrance release through reactive fixation and is applicable to liquid systems. However, based on its disclosure, the focus is still on the sustained-release carrier itself, and the synergistic design of low viscosity, wide processing window, and high perceived release efficiency in detergent compounding systems has not been fully explored. Summary of the Invention

[0004] The purpose of this invention is to provide a long-lasting fragrance-locking encapsulated detergent and its preparation method, thereby solving the problem that current encapsulated detergents struggle to balance high core material load, long-lasting fragrance lock, low viscosity, wide processing window, high shell strength, shear stability, and controllable fragrance release and high perceived release efficiency during use.

[0005] Quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin are activated to form a shell system that combines stable coating and inclusion. On the one hand, this improves the coating stability and processing tolerance of the fragrance core material, and on the other hand, it preserves the fragrance release channels during the use stage, so that the dispersion stability, long-lasting fragrance retention and perceived release efficiency in the detergent base liquid can be synergistically balanced.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A long-lasting fragrance-locking encapsulated detergent, by weight, comprises the following components: 0.30–3.00 parts by weight of covalently encapsulated fragrance microcapsules (dry basis), 8.0–20.0 parts by weight of sodium dodecylbenzenesulfonate (active ingredient), 3.0–12.0 parts by weight of cocamidopropyl betaine (active ingredient), 1.0–6.0 parts by weight of trisodium citrate, 1.0–8.0 parts by weight of 1,2-propanediol, and deionized water to a total of 100 parts by weight; The core material of the covalently coated flavor microcapsule is composed of linalool, 2-phenylethanol and benzyl salicylate, and the shell is formed by quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin connected by amide bonds. The quaternized oxidized cellulose nanofibers are prepared by oxidizing cellulose with 2,2,6,6-tetramethylpiperidine-1-oxy free radical, sodium bromide and sodium hypochlorite and then reacting it with glycidyltrimethylammonium chloride. The amino-β-cyclodextrin is prepared by β-cyclodextrin, p-toluenesulfonyl chloride and ethylenediamine.

[0007] Furthermore, the quaternized oxidized cellulose nanofibers have a carboxyl content of 0.60–1.50 mmol / g, a degree of quaternization of 0.05–0.40, and an amino substitution degree of 0.05–0.25 mmol / g for amino-β-cyclodextrin. The weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin is 100:20–120. The median particle size of the covalently coated fragrance microcapsules is 2–25 μm, the shell thickness is 80–500 nm, and the core material loading is 40.0 wt%–75.0 wt%.

[0008] Furthermore, quaternized oxidized cellulose nanofibers are prepared through the following steps: A1. Disperse 100 parts by weight of cellulose, 0.5-3 parts by weight of 2,2,6,6-tetramethylpiperidine-1-oxy free radical and 5-20 parts by weight of sodium bromide in 800-2000 parts by weight of deionized water at a dispersion temperature of 15-30℃ and a dispersion time of 0.5-2h. A2. Add 30-120 parts by weight of sodium hypochlorite at 0-10℃ and pH 9.5-10.5 and react for 1-4 hours. Adjust the pH of the system to and maintain it at 9.5-10.5 using a sodium hydroxide aqueous solution with a concentration of 0.5-2 mol / L. Sodium hypochlorite is added based on available chlorine. A3. Oxidation was terminated when the cellulose carboxyl content reached 0.60–1.80 mmol / g, and the mixture was washed until the pH value was 6.5–7.5. A4. Add 20-80 parts by weight of glycidyltrimethylammonium chloride and 2-10 parts by weight of sodium hydroxide to the oxidized cellulose obtained in A3, and react at 55-70℃ for 3-8 hours; A5. After homogenization under high pressure of 40-100 MPa for 2-6 times, quaternized oxidized cellulose nanofibers with a carboxyl content of 0.60-1.50 mmol / g and a degree of quaternization of 0.05-0.40 were obtained.

[0009] Furthermore, amino-β-cyclodextrin is prepared by the following steps: B1. Dissolve 100 parts by weight of β-cyclodextrin in an aqueous sodium hydroxide solution with a concentration of 0.30-1.00 mol / L and a total volume of 500-1500 mL, add 40-90 parts by weight of p-toluenesulfonyl chloride at 0-5℃ and react for 0.5-2 h; B2. Separate the obtained p-toluenesulfonated β-cyclodextrin and wash it until the pH of the filtrate is 7-8; B3. React the product obtained in B2 with 100-500 parts by weight of ethylenediamine at 35-50°C for 12-24 hours; B4. Precipitate with acetone and wash, then dry at 35–50 °C for 8–16 h to obtain amino-β-cyclodextrin with an amino substitution degree of 0.05–0.25 mmol / g.

[0010] Furthermore, amino-β-cyclodextrin is first reacted with at least one of linalool, 2-phenylethanol, and benzyl salicylate to form an inclusion unit, which is prepared by the following steps: C1. Add 100 parts by weight of amino-β-cyclodextrin and 10 to 60 parts by weight of at least one of linalool, 2-phenylethanol and benzyl salicylate to a mixed solvent composed of deionized water and ethanol, wherein the volume fraction of deionized water is 70 vol% to 95 vol% and the balance is ethanol. C2. Stir at 35–50℃ for 2–8 hours; C3. Remove the solvent under reduced pressure and dry at 40–60 °C for 6–12 h to obtain inclusion units with an inclusion weight of 5.0 wt%–25.0 wt%.

[0011] Furthermore, the covalently coated flavor microcapsules are prepared through the following steps: D1. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 2-20 parts by weight of polyvinyl alcohol in 500-2000 parts by weight of deionized water, wherein the quaternized oxidized cellulose nanofibers are folded on a dry basis. D2. Add 10-60 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 5-30 parts by weight of N-hydroxysuccinimide, adjust the pH of the system to 4.5-6.0 with hydrochloric acid or buffer solution, and activate at 15-35℃ for 0.5-2h. D3. Add 20-120 parts by weight of amino-β-cyclodextrin and 100-400 parts by weight of an oil phase composed of linalool, 2-phenylethanol and benzyl salicylate, or add 20-120 parts by weight of an inclusion unit formed by amino-β-cyclodextrin and at least one of linalool, 2-phenylethanol and benzyl salicylate and 100-400 parts by weight of an oil phase composed of linalool, 2-phenylethanol and benzyl salicylate, and emulsify at 3000-12000 r / min for 2-10 min; D4. Adjust the pH of the system to 6.0–7.5 using an alkaline solution and react for 1–4 hours. Then wash with deionized water 3–6 times and ultrafilter using an ultrafiltration membrane with a molecular weight cutoff of 50–300 kDa until the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the obtained covalently coated flavor microcapsules is no more than 500 mg / kg, thus obtaining covalently coated flavor microcapsules.

[0012] Furthermore, the mass ratio of linalool, 2-phenylethanol, and benzyl salicylate in the core material, normalized to their total weight, is (20–60):(10–40):(10–40). The weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin is 100:20–120. The long-lasting fragrance-locking encapsulated detergent has a pH of 6.8–7.8 and a viscosity of [missing information]. .

[0013] As a concept of this invention, a shell is formed by linking quaternized oxidized cellulose nanofibers with amino-β-cyclodextrin via amide bonds, and then coating linalool, 2-phenylethanol, and benzyl salicylate. This design is primarily used to enhance the long-lasting fragrance-locking performance, shear stability, and controlled fragrance release of long-acting fragrance-coated detergents. Quaternized oxidized cellulose nanofibers provide stable shell support and carboxyl reaction sites. Amino-β-cyclodextrin can both form inclusion units with fragrances and participate in the formation of covalently coated fragrance microcapsules, thus allowing for the control of core material loading, shell thickness, and median particle size. Combining the resulting covalently coated fragrance microcapsules with sodium dodecylbenzenesulfonate, cocamidopropyl betaine, trisodium citrate, and 1,2-propanediol facilitates a balance between long-lasting fragrance lock, low viscosity, and a wide processing window.

[0014] This invention also discloses a method for preparing a long-lasting fragrance-locking detergent, comprising the following steps: S1. Provides pre-prepared quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin; S2. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 2-20 parts by weight of polyvinyl alcohol in 500-2000 parts by weight of deionized water, add 10-60 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 5-30 parts by weight of N-hydroxysuccinimide, and activate for 0.5-2 hours at a pH of 4.5-6.0 and a temperature of 15-35°C; then add 20-120 parts by weight of amino-β-cyclodextrin and 100-400 parts by weight of an oil phase composed of linalool, 2-phenylethanol and benzyl salicylate, or add at least one of the following components: amino-β-cyclodextrin and linalool, 2-phenylethanol and benzyl salicylate. A mixture of 20-120 parts by weight of an encapsulating unit and 100-400 parts by weight of an oil phase composed of linalool, 2-phenylethanol, and benzyl salicylate is emulsified at 3000-12000 r / min for 2-10 min. The pH of the system is then adjusted to 6.0-7.5 and reacted for 1-4 h. The mixture is washed and ultrafiltered until the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the obtained covalently encapsulated fragrance microcapsules is no more than 500 mg / kg, thus obtaining covalently encapsulated fragrance microcapsules. S3. Add 8.0–20.0 parts by weight of sodium dodecylbenzenesulfonate, 3.0–12.0 parts by weight of cocamidopropyl betaine, 1.0–6.0 parts by weight of trisodium citrate, and 1.0–8.0 parts by weight of 1,2-propanediol to deionized water and mix at 20–35°C to form a detergent base solution; S4. Add the covalently coated fragrance microcapsules obtained in S2 to the detergent base solution obtained in S3 at a speed of 100-300 r / min, adjust the pH value to 6.8-7.8, defoam, and then fill to obtain a long-lasting fragrance-locking coated detergent.

[0015] Furthermore, the components used in S3 and S4, based on the weight parts of the resulting long-lasting fragrance-locking encapsulated detergent, include: 0.30–3.00 parts by weight of covalently encapsulated fragrance microcapsules on a dry basis, 8.0–20.0 parts by weight of sodium dodecylbenzenesulfonate on an active ingredient basis, 3.0–12.0 parts by weight of cocamidopropyl betaine on an active ingredient basis, 1.0–6.0 parts by weight of trisodium citrate, 1.0–8.0 parts by weight of 1,2-propanediol, and deionized water to a total of 100 parts by weight.

[0016] Furthermore, in the obtained long-lasting fragrance-locking encapsulated detergent, the residual amount of glycidyl trimethylammonium chloride is not greater than 1000 mg / kg and the residual amount of p-toluenesulfonyl chloride is not greater than 200 mg / kg, based on the total mass of the detergent. In addition, in the covalently encapsulated fragrance microcapsules contained in the obtained long-lasting fragrance-locking encapsulated detergent, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is not greater than 500 mg / kg, based on the mass of the covalently encapsulated fragrance microcapsules.

[0017] Furthermore, when adding covalently coated flavor microcapsules to S4, the system temperature is 20-30℃, the stirring speed is 100-300 r / min, and mixing continues for 10-40 min after addition.

[0018] Furthermore, the amount of deionized water used in A1 is 800–2000 parts by weight, the dispersion temperature is 15–30°C, and the dispersion time is 0.5–2 hours.

[0019] Furthermore, in A2, the pH value of the system is adjusted to and maintained at 9.5–10.5 using a sodium hydroxide aqueous solution with a concentration of 0.5–2 mol / L, and sodium hypochlorite is added based on available chlorine.

[0020] Furthermore, A3 is washed with deionized water 3 to 8 times until the pH of the filtrate is 6.5 to 7.5.

[0021] Furthermore, the oxidized cellulose obtained from A3 in A4 is a wet cellulose slurry, and glycidyl trimethylammonium chloride is added in the form of an aqueous solution, based on the effective ingredient.

[0022] Furthermore, before high-pressure homogenization in A5, the solid content of the system is adjusted to 0.5–3.0 wt%, and the homogenization temperature is 20–30 °C.

[0023] Furthermore, the total volume of the sodium hydroxide aqueous solution in B1 is 500–1500 mL, and the p-toluenesulfonyl chloride is added in batches or dropwise.

[0024] Furthermore, in B2, filtration or centrifugation is used for separation, and the sample is washed 3 to 6 times with deionized water or ice water.

[0025] Furthermore, in B3, ethylenediamine serves as both a reagent and a reaction medium, and the reaction is continuously stirred during the process.

[0026] Furthermore, the amount of acetone used in B4 is 5 to 15 times the volume of the reaction liquid, and it is vacuum dried at 35 to 50°C for 8 to 16 hours.

[0027] Furthermore, the total volume of the mixed solvent consisting of deionized water and ethanol in C1 is 300–1000 mL.

[0028] Furthermore, the stirring speed in C2 is 100–500 r / min; when kneading is used, the kneading conditions include the type of kneading equipment, the speed, and the time.

[0029] Furthermore, the amount of deionized water used in D1 is 500–2000 parts by weight, and the quaternized oxidized cellulose nanofibers are calculated on a dry basis.

[0030] Furthermore, in D2, the pH of the system is adjusted to 4.5–6.0 using hydrochloric acid or buffer solution.

[0031] Furthermore, when inclusion units are added to D3, the total amount of core material includes the fragrance contained in the inclusion units as well as the fragrance subsequently added to the oil phase.

[0032] Furthermore, D3 employs a high-speed shear emulsifier for emulsification.

[0033] Furthermore, in D4, the pH of the system is adjusted to 6.0–7.5 using an alkaline solution, followed by washing with deionized water 3–6 times, and ultrafiltration is performed using an ultrafiltration membrane with a molecular weight cutoff of 50–300 kDa.

[0034] Furthermore, the amount of covalently coated flavor microcapsules is calculated on a dry basis, and the amounts of sodium dodecylbenzenesulfonate and cocamidopropyl betaine are calculated on an active ingredient basis.

[0035] Furthermore, the mass ratio of linalool, 2-phenylethanol, and benzyl salicylate was calculated by normalizing the total weight of the three.

[0036] Furthermore, the core material loading is the percentage of the core material mass to the total mass of the dry-based covalently coated flavor microcapsules.

[0037] Furthermore, the median particle size was determined using a laser particle size analyzer, and the shell thickness was determined using an electron microscope.

[0038] Furthermore, the pH value of the detergent was measured at 25°C, and the viscosity was measured at 25°C using a rotational viscometer.

[0039] Furthermore, the residual amounts of glycidyl trimethylammonium chloride and p-toluenesulfonyl chloride are based on the total mass of the detergent, and the total amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is based on the mass of the covalently coated fragrance microcapsules.

[0040] Furthermore, the residues of glycidyl trimethylammonium chloride, p-toluenesulfonyl chloride, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were determined by liquid chromatography.

[0041] Furthermore, in S4, citric acid, hydrochloric acid, or sodium hydroxide are used to adjust the pH value to 6.8–7.8, and vacuum degassing or static degassing is employed.

[0042] As another aspect of this invention, a preparation route is adopted that first provides quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin, then activates, emulsifies, reacts, washes, and ultrafilters them with 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, and then blends them with a detergent base solution. This route is mainly used to enhance the stability and consistency of the preparation process of long-lasting fragrance-locking encapsulated detergents. This route controls the formation of covalently encapsulated fragrance microcapsules and the preparation of the detergent base solution in separate steps, which is beneficial for controlling pH value, emulsification speed, reaction time, and the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide. It reduces uncontrolled loss of core material during processing and makes it easier for the pH value and viscosity of the final product to fall within a suitable range, thus taking into account long-lasting fragrance lock, shear resistance stability, and controlled fragrance release performance.

[0043] In this invention, quaternized oxidized cellulose nanofibers primarily provide shell structure support, carboxyl reaction sites, and aqueous dispersion stability, thus playing a fundamental role in long-lasting fragrance retention and shear resistance. Amino-β-cyclodextrin primarily forms inclusion complexes with linalool, 2-phenylethanol, and benzyl salicylate, providing amino reaction sites, thereby regulating controlled fragrance release and high perceived release efficiency. The connection between these two components via amide bonds not only improves the shell integrity and core material loading of the covalently coated fragrance microcapsules but also helps retain fragrance release channels during use. This allows long-lasting fragrance retention and controlled release to no longer rely on a single component, thus maintaining good stability and release performance even under low viscosity and wide processing window conditions.

[0044] Beneficial technical effects 1. By constructing covalently coated fragrance microcapsules with quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin, linalool, 2-phenylethanol and benzyl salicylate are stably coated during storage and washing, and are released relatively smoothly during use, thereby improving the balance between long-lasting fragrance retention and controlled fragrance release.

[0045] 2. By synergistically limiting the carboxyl content, degree of quaternization, degree of amino substitution, median particle size, shell thickness, and core material loading, it is beneficial to enhance the shell integrity and shear stability of covalently coated fragrance microcapsules, and reduce the risk of fragrance loss during processing, transportation, and mixing.

[0046] 3. By covalently coating flavor microcapsules with sodium dodecylbenzenesulfonate, cocamidopropyl betaine, trisodium citrate and 1,2-propanediol, good dispersion stability can be maintained while ensuring the fluidity and ease of use of the base liquid, thus making it more conducive to balancing low viscosity and a wide processing window.

[0047] 4. Limiting the total amounts of glycidyl trimethylammonium chloride, p-toluenesulfonyl chloride, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and N-hydroxysuccinimide, and combining these with washing, ultrafiltration, and liquid chromatography, helps improve residue control and product quality consistency. Attached Figure Description

[0048] Figure 1 The image shows the N1s peak separation fitting diagrams of the X-ray photoelectron spectroscopy of Example 1, Comparative Example 1, and Comparative Example 2.

[0049] Figure 2 The image shows the C1s peak separation fitting diagrams of the X-ray photoelectron spectroscopy of Example 1, Comparative Example 1, and Comparative Example 2.

[0050] Figure 3 The diagram shows the area ratio of amide nitrogen in Example 1, Comparative Example 1, and Comparative Example 2.

[0051] Figure 4 The images are Fourier transform infrared superimposed spectra of Example 1 and Comparative Example 1.

[0052] Figure 5 The image shows an enlarged Fourier transform infrared amide region view of Example 1 and Comparative Example 1.

[0053] Figure 6 The laser diffraction volume distribution diagrams are for Example 1, Comparative Example 3, and Comparative Example 4.

[0054] Figure 7 The cumulative distribution of laser diffraction is shown in Example 1, Comparative Example 3, and Comparative Example 4.

[0055] Figure 8The 72-hour fragrance retention curves are for Example 1, Comparative Example 6, and Comparative Example 7.

[0056] Figure 9 The image shows the 72-hour fragrance retention rate of Example 1, Comparative Example 6, and Comparative Example 7.

[0057] Figure 10 The rheological curves are for Example 1, Comparative Example 7, and Comparative Example 8.

[0058] Figure 11 The rheological cycle curves are for Example 1, Comparative Example 7, and Comparative Example 8.

[0059] Figure 12 The graph shows the thixotropic hysteresis loop area versus viscosity recovery rate for Example 1, Comparative Example 7, and Comparative Example 8.

[0060] Figure 13 Macroscopic optical photograph of the covalently coated fragrance microcapsules prepared in Example 1.

[0061] Figure 14 Scanning electron microscope image of the covalently coated fragrance microcapsules prepared in Example 1. Detailed Implementation

[0062] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Example 1

[0063] A long-lasting fragrance-locking encapsulated detergent, by weight, comprises the following components: 1.50 parts by weight of covalently encapsulated fragrance microcapsules on a dry basis, 14.0 parts by weight of sodium dodecylbenzenesulfonate on an active ingredient basis, 7.5 parts by weight of cocamidopropyl betaine on an active ingredient basis, 3.5 parts by weight of trisodium citrate, 4.5 parts by weight of 1,2-propanediol, and deionized water to a total of 100 parts by weight.

[0064] The core material of the covalently coated flavor microcapsule in this embodiment is composed of linalool, 2-phenylethanol and benzyl salicylate, and the shell is formed by quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin connected by amide bonds. The quaternized oxidized cellulose nanofibers are prepared by oxidizing cellulose with 2,2,6,6-tetramethylpiperidine-1-oxy free radical, sodium bromide and sodium hypochlorite and then reacting it with glycidyltrimethylammonium chloride. The amino-β-cyclodextrin is prepared by β-cyclodextrin, p-toluenesulfonyl chloride and ethylenediamine.

[0065] In this embodiment, the quaternized oxidized cellulose nanofibers have a carboxyl content of 1.05 mmol / g, a degree of quaternization of 0.22, an amino substitution degree of 0.15 mmol / g for amino-β-cyclodextrin, and a weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin of 100:59.5. The median particle size of the covalently coated fragrance microcapsules is 13.5 μm, the shell thickness is 290 nm, and the core material loading is 57.5 wt%.

[0066] The quaternized oxidized cellulose nanofibers in this embodiment are prepared through the following steps: A1. 100 parts by weight of cellulose, 1.75 parts by weight of 2,2,6,6-tetramethylpiperidine-1-oxy radical, and 12.5 parts by weight of sodium bromide were dispersed in 1400 parts by weight of deionized water at a dispersion temperature of 22°C for 1.25 h. A2. 75 parts by weight of sodium hypochlorite were added at 5℃ and pH 10.0 and reacted for 2.5 h. The pH of the system was adjusted to and maintained at 10.0 using a 1.2 mol / L sodium hydroxide aqueous solution. Sodium hypochlorite was added based on available chlorine. A3. Oxidation was terminated when the cellulose carboxyl content reached 1.20 mmol / g, and the cells were washed five times with deionized water until the pH value reached 7.0. A4. Add 50 parts by weight of glycidyl trimethylammonium chloride and 6 parts by weight of sodium hydroxide to the wet oxidized cellulose slurry obtained in A3, and react at 62°C for 5.5 h. The glycidyl trimethylammonium chloride is added in the form of an aqueous solution and is calculated based on the effective ingredients. A5. After adjusting the solid content of the system to 1.75wt%, it was homogenized four times under high pressure of 70MPa at a homogenization temperature of 25℃ to obtain quaternized oxidized cellulose nanofibers with a carboxyl content of 1.05mmol / g and a degree of quaternization of 0.22.

[0067] The amino-β-cyclodextrin in this embodiment is prepared by the following steps: B1. Dissolve 100 parts by weight of β-cyclodextrin in 1000 mL of 0.65 mol / L sodium hydroxide aqueous solution, add 65 parts by weight of p-toluenesulfonyl chloride dropwise at 2.5 °C, and react for 1.25 h; B2. The p-toluenesulfonated β-cyclodextrin of this embodiment was separated by filtration and washed four times with deionized water until the pH of the filtrate was 7.5; B3. The product obtained in B2 was reacted with 300 parts by weight of ethylenediamine at 42°C for 18 hours. Ethylenediamine served as both a reagent and a reaction medium, and the mixture was continuously stirred during the reaction. B4. Precipitate and wash with acetone, using 10 times the volume of the reaction liquid, and then vacuum dry at 42℃ for 12h to obtain amino-β-cyclodextrin with an amino substitution degree of 0.15mmol / g.

[0068] In this embodiment, amino-β-cyclodextrin first forms an inclusion unit with linalool. The inclusion unit in this embodiment is prepared through the following steps: C1. Add 100 parts by weight of amino-β-cyclodextrin and 35 parts by weight of linalool to 650 mL of a mixed solvent consisting of deionized water and ethanol, wherein the volume fraction of deionized water is 82.5 vol%, and the balance is ethanol; C2. Stir at 300 r / min for 5 h at 42℃; C3. Remove the solvent under reduced pressure and dry at 50°C for 9 hours to obtain an inclusion unit with an inclusion weight of 15.0 wt%.

[0069] The covalently coated flavor microcapsules of this embodiment are prepared through the following steps: D1. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 11 parts by weight of polyvinyl alcohol in 1250 parts by weight of deionized water. The quaternized oxidized cellulose nanofibers are calculated on a dry basis. D2. Add 35 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 17.5 parts by weight of N-hydroxysuccinimide, and activate the system for 1.25 h at a pH of 5.25 adjusted with hydrochloric acid and a temperature of 25°C. D3. Add 70 parts by weight of the inclusion compounding unit and 250 parts by weight of an oil phase containing linalool, 2-phenylethanol, and benzyl salicylate in a mass ratio of 40:25:25. Emulsify the oil phase using a high-speed shear emulsifier at 7500 r / min for 6 min. The total amount of the core material includes the fragrance contained in the inclusion compounding unit and the fragrance in the oil phase. D4. The pH of the system was adjusted to 6.75 using an alkaline solution and reacted for 2.5 h. The mixture was washed four times with deionized water and then ultrafiltered through an ultrafiltration membrane with a molecular weight cutoff of 175 kDa to obtain covalently coated flavor microcapsules. The total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide was 250 mg / kg, thus obtaining covalently coated flavor microcapsules.

[0070] The long-lasting fragrance-locking encapsulated detergent in this embodiment has a pH value of 7.3 and a viscosity of [missing information]. pH value was measured at 25℃, and viscosity was measured at 25℃ using a rotational viscometer.

[0071] The long-lasting fragrance-locking encapsulated detergent of this embodiment is prepared through the following steps: S1. Provides pre-prepared quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin; S2. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 11 parts by weight of polyvinyl alcohol in 1250 parts by weight of deionized water. On a dry basis, add 35 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 17.5 parts by weight of N-hydroxysuccinimide to the quaternized oxidized cellulose nanofibers. The mixture was activated at pH 5.25 and 25°C for 1.25 h. Then, 70 parts by weight of the previously prepared inclusion unit formed from amino-β-cyclodextrin and linalool, and 250 parts by weight of an oil phase prepared from linalool, 2-phenylethanol, and benzyl salicylate in a mass ratio of 40:25:25 were added, and emulsified at 7500 r / min for 6 min. The pH of the system was then adjusted to 6.75 and reacted for 2.5 h. The mixture was washed and ultrafiltered until the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently coated fragrance microcapsules of this embodiment was 250 mg / kg, thus obtaining the covalently coated fragrance microcapsules. S3. Add 14.0 parts by weight of sodium dodecylbenzenesulfonate, 7.5 parts by weight of cocamidopropyl betaine, 3.5 parts by weight of trisodium citrate and 4.5 parts by weight of 1,2-propanediol to deionized water and mix at 27°C to form a detergent base solution; S4. Add 1.50 parts by weight of the covalently coated fragrance microcapsules obtained in S2 to the detergent base liquid obtained in S3 at 200 r / min. The system temperature is 25℃. After adding, continue mixing for 25 min. Adjust the pH value to 7.3 with citric acid. After vacuum degassing, fill the container to obtain a long-lasting fragrance-locking coated detergent.

[0072] The components used in S3 and S4 are calculated based on the weight of the resulting long-lasting fragrance-locking coated detergent. The amount of covalently coated fragrance microcapsules is calculated on a dry basis, and the amounts of sodium dodecylbenzenesulfonate and cocamidopropyl betaine are calculated based on the active ingredients.

[0073] In the long-lasting fragrance-locking encapsulated detergent obtained in this embodiment, the residual amount of glycidyl trimethylammonium chloride is 500 mg / kg, and the residual amount of p-toluenesulfonyl chloride is 100 mg / kg. Furthermore, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently encapsulated fragrance microcapsules contained in the long-lasting fragrance-locking encapsulated detergent obtained in this embodiment is 250 mg / kg. The residual amounts of glycidyl trimethylammonium chloride and p-toluenesulfonyl chloride are based on the total mass of the detergent, and the total amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is based on the mass of the covalently encapsulated fragrance microcapsules. The residual amounts were determined by liquid chromatography. The mass ratio of linalool, 2-phenylethanol and benzyl salicylate was calculated by normalizing the total weight of the three. The core material loading was the percentage of the core material mass to the total mass of the dry basis covalently coated flavor microcapsules. The median particle size was determined by a laser particle size analyzer, and the shell thickness was determined by an electron microscope.

[0074] This embodiment uses a medium formula parameter design, the preparation process is stable and controllable, it is suitable for daily clothing washing scenarios, and can provide a long-lasting fragrance washing effect. Example 2

[0075] A long-lasting fragrance-locking encapsulated detergent, by weight, comprises the following components: 2.30 parts by weight of covalently encapsulated fragrance microcapsules on a dry basis, 17.5 parts by weight of sodium dodecylbenzenesulfonate on an active ingredient basis, 9.5 parts by weight of cocamidopropyl betaine on an active ingredient basis, 4.8 parts by weight of trisodium citrate, 6.5 parts by weight of 1,2-propanediol, and deionized water to a total of 100 parts by weight.

[0076] The core material of the covalently coated flavor microcapsule in this embodiment is composed of linalool, 2-phenylethanol and benzyl salicylate, and the shell is formed by quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin connected by amide bonds. The quaternized oxidized cellulose nanofibers are prepared by oxidizing cellulose with 2,2,6,6-tetramethylpiperidine-1-oxy free radical, sodium bromide and sodium hypochlorite and then reacting it with glycidyltrimethylammonium chloride. The amino-β-cyclodextrin is prepared by β-cyclodextrin, p-toluenesulfonyl chloride and ethylenediamine.

[0077] In this embodiment, the quaternized oxidized cellulose nanofibers have a carboxyl content of 1.30 mmol / g, a degree of quaternization of 0.30, an amino substitution degree of 0.19 mmol / g for amino-β-cyclodextrin, and a weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin of 100:75.5. The median particle size of the covalently coated fragrance microcapsules is 19.5 μm, the shell thickness is 380 nm, and the core material loading is 66.5 wt%.

[0078] The quaternized oxidized cellulose nanofibers in this embodiment are prepared through the following steps: A1. 100 parts by weight of cellulose, 2.5 parts by weight of 2,2,6,6-tetramethylpiperidine-1-oxy radical, and 17 parts by weight of sodium bromide were dispersed in 1750 parts by weight of deionized water at a dispersion temperature of 27°C for 1.7 h. A2. 100 parts by weight of sodium hypochlorite were added at 7℃ and pH 10.3 and reacted for 3.3 h. The pH of the system was adjusted to and maintained at 10.3 using a 1.5 mol / L sodium hydroxide aqueous solution. Sodium hypochlorite was added based on available chlorine. A3. Oxidation was terminated when the cellulose carboxyl content reached 1.54 mmol / g, and the cells were washed 6 times with deionized water until the pH value reached 7.2; A4. Add 68 parts by weight of glycidyl trimethylammonium chloride and 8 parts by weight of sodium hydroxide to the wet oxidized cellulose slurry obtained in A3, and react at 67°C for 6.8 h. The glycidyl trimethylammonium chloride is added in the form of an aqueous solution and is calculated based on the effective ingredients. A5. After adjusting the solid content of the system to 2.5wt%, it was homogenized five times under high pressure of 85MPa at a homogenization temperature of 28℃ to obtain quaternized oxidized cellulose nanofibers with a carboxyl content of 1.30mmol / g and a degree of quaternization of 0.30.

[0079] The amino-β-cyclodextrin in this embodiment is prepared by the following steps: B1. Dissolve 100 parts by weight of β-cyclodextrin in 1300 mL of 0.85 mol / L sodium hydroxide aqueous solution, and add 78 parts by weight of p-toluenesulfonyl chloride in portions at 3.5 °C and react for 1.6 h; B2. The p-toluenesulfonated β-cyclodextrin of this embodiment was separated by centrifugation and washed five times with ice water until the pH of the filtrate was 7.7; B3. The product obtained in B2 was reacted with 400 parts by weight of ethylenediamine at 47°C for 21 h. Ethylenediamine was used as both a reagent and a reaction medium, and the mixture was continuously stirred during the reaction. B4. The product was precipitated and washed with acetone, the amount of acetone being 12 times the volume of the reaction liquid. Then, it was vacuum dried at 47°C for 14 hours to obtain amino-β-cyclodextrin with an amino substitution degree of 0.19 mmol / g.

[0080] In this embodiment, amino-β-cyclodextrin first forms an inclusion unit with 2-phenylethanol. The inclusion unit in this embodiment is prepared through the following steps: C1. Add 100 parts by weight of amino-β-cyclodextrin and 48 parts by weight of 2-phenylethanol to 850 mL of a mixed solvent consisting of deionized water and ethanol, wherein the volume fraction of deionized water is 88 vol%, and the balance is ethanol; C2. Stir at 400 r / min for 6.5 h at 47℃; C3. Remove the solvent under reduced pressure and dry at 55°C for 11 h to obtain an inclusion unit with an inclusion weight of 20.5 wt%.

[0081] The covalently coated flavor microcapsules of this embodiment are prepared through the following steps: D1. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 16 parts by weight of polyvinyl alcohol in 1700 parts by weight of deionized water. The quaternized oxidized cellulose nanofibers are calculated on a dry basis. D2. Add 48 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 24 parts by weight of N-hydroxysuccinimide, and activate the system for 1.6 h at a pH of 5.6 and a temperature of 30 °C using a buffer solution. D3. Add 95 parts by weight of the inclusion compounding unit and 325 parts by weight of an oil phase containing linalool, 2-phenylethanol, and benzyl salicylate in a mass ratio of 50:32:30. Emulsify the oil phase using a high-speed shear emulsifier at 9800 r / min for 8 min. The total amount of the core material includes the fragrance contained in the inclusion compounding unit and the fragrance in the oil phase. D4. The pH of the system was adjusted to 7.1 using an alkaline solution and reacted for 3.2 h. The mixture was washed 5 times with deionized water and ultrafiltered through an ultrafiltration membrane with a molecular weight cutoff of 240 kDa to obtain covalently coated flavor microcapsules. The total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide was 380 mg / kg, thus obtaining covalently coated flavor microcapsules.

[0082] The long-lasting fragrance-locking coated detergent in this embodiment has a pH value of 7.55 and a viscosity of [missing information]. pH value was measured at 25℃, and viscosity was measured at 25℃ using a rotational viscometer.

[0083] The long-lasting fragrance-locking encapsulated detergent of this embodiment is prepared through the following steps: S1. Provides pre-prepared quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin; S2. 100 parts by weight of quaternized oxidized cellulose nanofibers and 16 parts by weight of polyvinyl alcohol were dispersed in 1700 parts by weight of deionized water. 48 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 24 parts by weight of N-hydroxysuccinimide were added to the quaternized oxidized cellulose nanofibers on a dry basis. The mixture was activated for 1.6 h at pH 5.6 and 30 °C. Then, the previously prepared inclusion unit 9, formed by amino-β-cyclodextrin and 2-phenylethanol, was added. Five parts by weight of an oil phase, comprising 325 parts by weight of linalool, 2-phenylethanol, and benzyl salicylate in a mass ratio of 50:32:30, were emulsified at 9800 r / min for 8 min. The pH of the system was then adjusted to 7.1 and reacted for 3.2 h. After washing and ultrafiltration, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently coated fragrance microcapsules of this embodiment was 380 mg / kg, thus obtaining the covalently coated fragrance microcapsules. S3. Add 17.5 parts by weight of sodium dodecylbenzenesulfonate, 9.5 parts by weight of cocamidopropyl betaine, 4.8 parts by weight of trisodium citrate and 6.5 parts by weight of 1,2-propanediol to deionized water and mix at 30°C to form a detergent base solution; S4. Add 2.30 parts by weight of the covalently coated fragrance microcapsules obtained in S2 to the detergent base liquid obtained in S3 at 250 r / min. The system temperature is 27℃. After adding, continue mixing for 32 min. Adjust the pH value to 7.55 with sodium hydroxide. After standing to defoam, fill the container to obtain a long-lasting fragrance-locking coated detergent.

[0084] The components used in S3 and S4 are calculated based on the weight of the resulting long-lasting fragrance-locking coated detergent. The amount of covalently coated fragrance microcapsules is calculated on a dry basis, and the amounts of sodium dodecylbenzenesulfonate and cocamidopropyl betaine are calculated based on the active ingredients.

[0085] In the long-lasting fragrance-locking encapsulated detergent obtained in this embodiment, the residual amount of glycidyl trimethylammonium chloride is 750 mg / kg, and the residual amount of p-toluenesulfonyl chloride is 150 mg / kg. Furthermore, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently encapsulated fragrance microcapsules contained in the long-lasting fragrance-locking encapsulated detergent obtained in this embodiment is 380 mg / kg. The residual amounts of glycidyl trimethylammonium chloride and p-toluenesulfonyl chloride are based on the total mass of the detergent, and the total amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is based on the mass of the covalently encapsulated fragrance microcapsules. The residual amounts were determined by liquid chromatography. The mass ratio of linalool, 2-phenylethanol and benzyl salicylate was calculated by normalizing the total weight of the three. The core material loading was the percentage of the core material mass to the total mass of the dry basis covalently coated flavor microcapsules. The median particle size was determined by a laser particle size analyzer, and the shell thickness was determined by an electron microscope.

[0086] This embodiment uses a formula with high fragrance load and strong detergency, which is suitable for washing heavily stained clothes, such as sportswear, work clothes, outdoor clothing and other fabrics that require strong stain removal and long-lasting fragrance. It is also suitable for consumers who want a long-lasting fragrance experience. Example 3

[0087] A long-lasting fragrance-locking encapsulated detergent, by weight, comprises the following components: 0.80 parts by weight of covalently encapsulated fragrance microcapsules on a dry basis, 10.5 parts by weight of sodium dodecylbenzenesulfonate on an active ingredient basis, 4.8 parts by weight of cocamidopropyl betaine on an active ingredient basis, 2.0 parts by weight of trisodium citrate, 2.2 parts by weight of 1,2-propanediol, and deionized water to a total of 100 parts by weight.

[0088] The core material of the covalently coated flavor microcapsule in this embodiment is composed of linalool, 2-phenylethanol and benzyl salicylate, and the shell is formed by quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin connected by amide bonds. The quaternized oxidized cellulose nanofibers are prepared by oxidizing cellulose with 2,2,6,6-tetramethylpiperidine-1-oxy free radical, sodium bromide and sodium hypochlorite and then reacting it with glycidyltrimethylammonium chloride. The amino-β-cyclodextrin is prepared by β-cyclodextrin, p-toluenesulfonyl chloride and ethylenediamine.

[0089] In this embodiment, the quaternized oxidized cellulose nanofibers have a carboxyl content of 0.80 mmol / g, a degree of quaternization of 0.12, an amino substitution degree of 0.09 mmol / g for amino-β-cyclodextrin, and a weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin of 100:36.2. The median particle size of the covalently coated fragrance microcapsules is 6.5 μm, the shell thickness is 160 nm, and the core material loading is 47.0 wt%.

[0090] The quaternized oxidized cellulose nanofibers in this embodiment are prepared through the following steps: A1. 100 parts by weight of cellulose, 1.0 part by weight of 2,2,6,6-tetramethylpiperidine-1-oxy radical, and 8 parts by weight of sodium bromide were dispersed in 1050 parts by weight of deionized water at a dispersion temperature of 18°C ​​for 0.8 h. A2. 48 parts by weight of sodium hypochlorite were added at 2℃ and pH 9.7 and reacted for 1.6 h. The pH of the system was adjusted to and maintained at 9.7 using a 1.0 mol / L sodium hydroxide aqueous solution. Sodium hypochlorite was added based on available chlorine. A3. Oxidation was terminated when the cellulose carboxyl content reached 0.84 mmol / g, and the cells were washed four times with deionized water until the pH value reached 6.7. A4. Add 32 parts by weight of glycidyl trimethylammonium chloride and 3.6 parts by weight of sodium hydroxide to the wet oxidized cellulose slurry obtained in A3, and react at 58°C for 4.0 h. The glycidyl trimethylammonium chloride is added in the form of an aqueous solution and is calculated based on the effective ingredients. A5. After adjusting the solid content of the system to 1.0 wt%, it was homogenized three times under high pressure of 52 MPa at a homogenization temperature of 22 ℃ to obtain quaternized oxidized cellulose nanofibers with a carboxyl content of 0.80 mmol / g and a degree of quaternization of 0.12.

[0091] The amino-β-cyclodextrin in this embodiment is prepared by the following steps: B1. Dissolve 100 parts by weight of β-cyclodextrin in 700 mL of a 0.44 mol / L sodium hydroxide aqueous solution, and add 50 parts by weight of p-toluenesulfonyl chloride dropwise at 1 °C and react for 0.8 h; B2. The p-toluenesulfonated β-cyclodextrin of this embodiment was separated by filtration and washed four times with deionized water until the pH of the filtrate was 7.2; B3. The product obtained in B2 was reacted with 180 parts by weight of ethylenediamine at 38°C for 14 hours. Ethylenediamine served as both a reagent and a reaction medium, and the mixture was continuously stirred during the reaction. B4. The product was precipitated and washed with acetone, the amount of acetone being 7 times the volume of the reaction liquid. Then it was vacuum dried at 38°C for 9 hours to obtain amino-β-cyclodextrin with an amino substitution degree of 0.09 mmol / g.

[0092] In this embodiment, amino-β-cyclodextrin first forms an inclusion unit with benzyl salicylate. The inclusion unit in this embodiment is prepared through the following steps: C1. Add 100 parts by weight of amino-β-cyclodextrin and 22 parts by weight of benzyl salicylate to 440 mL of a mixed solvent consisting of deionized water and ethanol, wherein the volume fraction of deionized water is 75 vol% and the balance is ethanol; C2. Stir at 180 r / min for 3.2 h at 38℃; C3. The solvent was removed under reduced pressure and dried at 44°C for 7 hours to obtain an inclusion unit with an inclusion weight of 9.5 wt%.

[0093] The covalently coated flavor microcapsules of this embodiment are prepared through the following steps: D1. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 5.5 parts by weight of polyvinyl alcohol in 800 parts by weight of deionized water. The quaternized oxidized cellulose nanofibers are calculated on a dry basis. D2. Add 20 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 10 parts by weight of N-hydroxysuccinimide, and activate the system for 0.8 h at a pH of 4.8 adjusted with hydrochloric acid and a temperature of 19°C. D3. Add 40 parts by weight of the inclusion compounding unit and a total of 160 parts by weight of an oil phase prepared in a mass ratio of linalool, 2-phenylethanol, and benzyl salicylate of 28:16:16, and emulsify using a high-speed shear emulsifier. Emulsification at 4800 r / min for 3.6 min; the total core material includes the fragrance contained in the encapsulation unit and the fragrance in the oil phase. D4. The pH of the system was adjusted to 6.3 using an alkaline solution and reacted for 1.6 h. The mixture was washed four times with deionized water and then ultrafiltered through an ultrafiltration membrane with a molecular weight cutoff of 100 kDa to obtain covalently coated flavor microcapsules. The total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide was 120 mg / kg, thus obtaining covalently coated flavor microcapsules.

[0094] The long-lasting fragrance-locking encapsulated detergent in this embodiment has a pH value of 6.95 and a viscosity of [missing information]. pH value was measured at 25℃, and viscosity was measured at 25℃ using a rotational viscometer.

[0095] The long-lasting fragrance-locking encapsulated detergent of this embodiment is prepared through the following steps: S1. Provides pre-prepared quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin; S2. 100 parts by weight of quaternized oxidized cellulose nanofibers and 5.5 parts by weight of polyvinyl alcohol were dispersed in 800 parts by weight of deionized water. 20 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 10 parts by weight of N-hydroxysuccinimide were added to the quaternized oxidized cellulose nanofibers on a dry basis. The mixture was activated for 0.8 h at pH 4.8 and a temperature of 19 °C. Then, 40 parts by weight of the previously prepared inclusion complex unit formed by amino-β-cyclodextrin and benzyl salicylate was added. An oil phase of 160 parts by weight, prepared from linalool, 2-phenylethanol, and benzyl salicylate in a mass ratio of 28:16:16, was emulsified at 4800 r / min for 3.6 min. The pH of the system was then adjusted to 6.3 and reacted for 1.6 h. After washing and ultrafiltration, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently coated fragrance microcapsules of this embodiment was 120 mg / kg, yielding the covalently coated fragrance microcapsules. S3. Add 10.5 parts by weight of sodium dodecylbenzenesulfonate, 4.8 parts by weight of cocamidopropyl betaine, 2.0 parts by weight of trisodium citrate and 2.2 parts by weight of 1,2-propanediol to deionized water and mix at 23°C to form a detergent base solution; S4. Add 0.80 parts by weight of the covalently coated fragrance microcapsules obtained in S2 to the detergent base liquid obtained in S3 at 140 r / min. The system temperature is 22℃. After adding, continue mixing for 16 min. Adjust the pH value to 6.95 with citric acid. After vacuum degassing, fill the container to obtain a long-lasting fragrance-locking coated detergent.

[0096] The components used in S3 and S4 are calculated based on the weight of the resulting long-lasting fragrance-locking coated detergent. The amount of covalently coated fragrance microcapsules is calculated on a dry basis, and the amounts of sodium dodecylbenzenesulfonate and cocamidopropyl betaine are calculated based on the active ingredients.

[0097] In the long-lasting fragrance-locking encapsulated detergent obtained in this embodiment, the residual amount of glycidyl trimethylammonium chloride is 300 mg / kg, and the residual amount of p-toluenesulfonyl chloride is 50 mg / kg. Furthermore, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently encapsulated fragrance microcapsules contained in the long-lasting fragrance-locking encapsulated detergent obtained in this embodiment is 120 mg / kg. The residual amounts of glycidyl trimethylammonium chloride and p-toluenesulfonyl chloride are based on the total mass of the detergent, and the total amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is based on the mass of the covalently encapsulated fragrance microcapsules. The residual amounts were determined by liquid chromatography. The mass ratio of linalool, 2-phenylethanol and benzyl salicylate was calculated by normalizing the total weight of the three. The core material loading was the percentage of the core material mass to the total mass of the dry basis covalently coated flavor microcapsules. The median particle size was determined by a laser particle size analyzer, and the shell thickness was determined by an electron microscope.

[0098] This embodiment features a low fragrance load and a gentle cleaning formula, making it particularly suitable for everyday laundry scenarios with light stains, such as loungewear, underwear, delicate fabrics like silk and wool, as well as for sensitive skin, baby clothes, and maternity clothes that require extremely gentle washing with a light fragrance. It is also suitable for consumers who do not like strong fragrances but prefer a natural and fresh scent. Example 4

[0099] A long-lasting fragrance-locking encapsulated detergent, by weight, comprises the following components: 0.52 parts by weight of covalently encapsulated fragrance microcapsules on a dry basis, 18.9 parts by weight of sodium dodecylbenzenesulfonate on an active ingredient basis, 10.8 parts by weight of cocamidopropyl betaine on an active ingredient basis, 5.4 parts by weight of trisodium citrate, 1.6 parts by weight of 1,2-propanediol, and deionized water to a total of 100 parts by weight.

[0100] The core material of the covalently coated flavor microcapsule in this embodiment is composed of linalool, 2-phenylethanol and benzyl salicylate, and the shell is formed by quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin connected by amide bonds. The quaternized oxidized cellulose nanofibers are prepared by oxidizing cellulose with 2,2,6,6-tetramethylpiperidine-1-oxy free radical, sodium bromide and sodium hypochlorite and then reacting it with glycidyltrimethylammonium chloride. The amino-β-cyclodextrin is prepared by β-cyclodextrin, p-toluenesulfonyl chloride and ethylenediamine.

[0101] In this embodiment, the quaternized oxidized cellulose nanofibers have a carboxyl content of 1.42 mmol / g, a degree of quaternization of 0.35, an amino substitution degree of 0.22 mmol / g for amino-β-cyclodextrin, and a weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin of 100:84.7. The median particle size of the covalently coated fragrance microcapsules is 23.1 μm, the shell thickness is 120 nm, and the core material loading is 43.5 wt%.

[0102] The quaternized oxidized cellulose nanofibers in this embodiment are prepared through the following steps: A1. 100 parts by weight of cellulose, 2.8 parts by weight of 2,2,6,6-tetramethylpiperidine-1-oxy radical, and 6.2 parts by weight of sodium bromide were dispersed in 896 parts by weight of deionized water at a dispersion temperature of 29°C for 1.88 h. A2. 110 parts by weight of sodium hypochlorite were added at 9℃ and pH 9.58 and reacted for 1.24 h. The pH of the system was adjusted to and maintained at 9.58 using a 1.8 mol / L sodium hydroxide aqueous solution. Sodium hypochlorite was added based on available chlorine. A3. Oxidation was terminated when the cellulose carboxyl content reached 1.70 mmol / g, and the cells were washed seven times with deionized water until the pH value reached 7.4. A4. Add 74 parts by weight of glycidyl trimethylammonium chloride and 9.2 parts by weight of sodium hydroxide to the wet oxidized cellulose slurry obtained in A3, and react at 68°C for 7.4 h. The glycidyl trimethylammonium chloride is added in the form of an aqueous solution and is calculated based on the effective ingredients. A5. After adjusting the solid content of the system to 0.7wt%, it was homogenized five times under high pressure of 92MPa at a homogenization temperature of 29℃ to obtain quaternized oxidized cellulose nanofibers with a carboxyl content of 1.42mmol / g and a degree of quaternization of 0.35.

[0103] The amino-β-cyclodextrin in this embodiment is prepared by the following steps: B1. Dissolve 100 parts by weight of β-cyclodextrin in 1400 mL of 0.37 mol / L sodium hydroxide aqueous solution, and add 85 parts by weight of p-toluenesulfonyl chloride in batches at 4.5 °C and react for 0.62 h; B2. The p-toluenesulfonated β-cyclodextrin of this embodiment was separated by filtration and washed three times with deionized water until the pH of the filtrate was 7.9; B3. The product obtained in B2 was reacted with 460 parts by weight of ethylenediamine at 36°C for 22 hours. Ethylenediamine was used as both a reagent and a reaction medium. The mixture was stirred continuously during the reaction. B4. The product was precipitated and washed with acetone, the amount of acetone being 14 times the volume of the reaction liquid. Then, it was vacuum dried at 49°C for 8.6 h to obtain amino-β-cyclodextrin with an amino substitution degree of 0.22 mmol / g.

[0104] In this embodiment, amino-β-cyclodextrin is first mixed with linalool and 2-phenylethanol to form an inclusion unit. The inclusion unit in this embodiment is prepared through the following steps: C1. A mixture of 100 parts by weight of amino-β-cyclodextrin, 28 parts by weight of linalool, and 28 parts by weight of 2-phenylethanol is added to 370 mL of a mixed solvent consisting of deionized water and ethanol, wherein the volume fraction of deionized water is 72 vol%, and the balance is ethanol; C2. Stir at 460 r / min for 2.48 h at 49 °C; C3. The solvent was removed under reduced pressure and dried at 58°C for 11.5 h to obtain an inclusion unit with an inclusion weight of 23.0 wt%.

[0105] The covalently coated flavor microcapsules of this embodiment are prepared through the following steps: D1. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 18.4 parts by weight of polyvinyl alcohol in 624 parts by weight of deionized water. The quaternized oxidized cellulose nanofibers are calculated on a dry basis. D2. Add 14 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 27 parts by weight of N-hydroxysuccinimide, and activate the system for 1.88 h at a pH of 5.9 and a temperature of 17°C using a buffer solution. D3. Add 110 parts by weight of the inclusion compounding unit and 370 parts by weight of an oil phase containing linalool, 2-phenylethanol, and benzyl salicylate in a mass ratio of 23:37:36. Emulsify the mixture using a high-speed shear emulsifier at 3720 r / min for 9.2 min. The total amount of the core material includes the fragrance contained in the inclusion compounding unit and the fragrance in the oil phase. D4. The pH of the system was adjusted to 7.35 using an alkaline solution and reacted for 3.76 h. The mixture was washed 5 times with deionized water and ultrafiltered through an ultrafiltration membrane with a molecular weight cutoff of 70 kDa. The total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently coated fragrance microcapsules of this embodiment was 450 mg / kg, thus obtaining covalently coated fragrance microcapsules.

[0106] The long-lasting fragrance-locking encapsulated detergent in this embodiment has a pH value of 7.7 and a viscosity of [missing information]. pH value was measured at 25℃, and viscosity was measured at 25℃ using a rotational viscometer.

[0107] The long-lasting fragrance-locking encapsulated detergent of this embodiment is prepared through the following steps: S1. Provides pre-prepared quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin; S2. 100 parts by weight of quaternized oxidized cellulose nanofibers and 18.4 parts by weight of polyvinyl alcohol were dispersed in 624 parts by weight of deionized water. 14 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 27 parts by weight of N-hydroxysuccinimide were added, and the mixture was activated for 1.88 h at pH 5.9 and temperature 17 °C. Then, 110 parts by weight of the previously prepared inclusion unit formed by mixing amino-β-cyclodextrin with linalool and 2-phenylethanol were added, along with... A total of 370 parts by weight of oil phase was prepared by mixing linalool, 2-phenylethanol, and benzyl salicylate in a mass ratio of 23:37:36, and emulsified at 3720 r / min for 9.2 min. The pH of the system was then adjusted to 7.35 and reacted for 3.76 h. After washing and ultrafiltration, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently coated fragrance microcapsules of this embodiment was 450 mg / kg, yielding the covalently coated fragrance microcapsules. S3. Add 18.9 parts by weight of sodium dodecylbenzenesulfonate, 10.8 parts by weight of cocamidopropyl betaine, 5.4 parts by weight of trisodium citrate and 1.6 parts by weight of 1,2-propanediol to deionized water and mix at 33°C to form a detergent base solution; S4. Add 0.52 parts by weight of the covalently coated fragrance microcapsules obtained in S2 to the detergent base liquid obtained in S3 at 280 r / min. The system temperature is 29℃. After adding, continue mixing for 37 min. Adjust the pH value to 7.7 with sodium hydroxide. After standing to defoam, fill the container to obtain a long-lasting fragrance-locking coated detergent.

[0108] The components used in S3 and S4 are calculated based on the weight of the resulting long-lasting fragrance-locking coated detergent. The amount of covalently coated fragrance microcapsules is calculated on a dry basis, and the amounts of sodium dodecylbenzenesulfonate and cocamidopropyl betaine are calculated based on the active ingredients.

[0109] In the long-lasting fragrance-locking encapsulated detergent obtained in this embodiment, the residual amount of glycidyl trimethylammonium chloride is 900 mg / kg, and the residual amount of p-toluenesulfonyl chloride is 180 mg / kg. Furthermore, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the covalently encapsulated fragrance microcapsules contained in the long-lasting fragrance-locking encapsulated detergent obtained in this embodiment is 450 mg / kg. The residual amounts of glycidyl trimethylammonium chloride and p-toluenesulfonyl chloride are based on the total mass of the detergent, and the total amount of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is based on the mass of the covalently encapsulated fragrance microcapsules. The residual amounts were determined by liquid chromatography. The mass ratio of linalool, 2-phenylethanol and benzyl salicylate was calculated by normalizing the total weight of the three. The core material loading was the percentage of the core material mass to the total mass of the dry basis covalently coated flavor microcapsules. The median particle size was determined by a laser particle size analyzer, and the shell thickness was determined by an electron microscope.

[0110] This embodiment uses a formula with extremely low fragrance addition and high surfactant for strong stain removal. It is suitable for professional scenarios such as commercial laundries, hotel linen washing, and medical institution fabric disinfection and washing that require strong stain removal but do not want too much fragrance residue. It is also suitable for people with fragrance sensitivity or allergies, as well as consumers who need strong stain removal but pursue the essence of cleanliness rather than fragrance masking.

[0111] Comparative Example 1: Basically the same as Example 1, except that the 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride / N-hydroxysuccinimide activation system was not used in D2, while other conditions remained unchanged.

[0112] Comparative Example 2: It is basically the same as Example 1, except that the weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin is adjusted to 100:15, while other conditions remain unchanged.

[0113] Comparative Example 3: It is basically the same as Example 1, except that the amount of oil phase in D3 is adjusted to 430 parts by weight, while other conditions remain unchanged.

[0114] Comparative Example 4: Basically the same as Example 1, except that the emulsification speed in D3 was adjusted to 2500 r / min, while other conditions remained unchanged.

[0115] Comparative Example 5: It is basically the same as Example 1, except that the amount of polyvinyl alcohol in D1 is adjusted to 1.0 parts by weight, and other conditions remain unchanged.

[0116] Comparative Example 6: It is basically the same as Example 1, except that the amount of covalently coated flavor microcapsules added in S4 is adjusted to 0.20 parts by weight, while other conditions remain unchanged.

[0117] Comparative Example 7: Basically the same as Example 1, except that the pH value of the finished product in S4 was adjusted to 8.30, while other conditions remained unchanged.

[0118] Comparative Example 8: It is basically the same as Example 1, except that the stirring speed after adding covalently coated fragrance microcapsules in S4 is adjusted to 380 r / min, while other conditions remain unchanged.

[0119] Performance testing: Covalently coated flavor microcapsules were lysed with ethanol / water, and the concentrations of linalool, 2-phenylethanol, and benzyl salicylate were quantified by gas chromatography. The core loading capacity was evaluated by calculating the total peak area. After centrifugation, washing, and vacuum drying at 40℃, three portions of the sample were weighed, ultrasonically extracted for 30 min, and then injected. Quantification was performed using a split injection method and a standard curve from the same batch. Data processing outputs the mean ± standard deviation (n=3) of the content of each component, the total content, and the core loading.

[0120] The D10, D50, and D90 values ​​of covalently coated flavor microcapsules in aqueous dispersions were determined by laser diffraction to evaluate the median volumetric particle size and shear stability, and to compare particle size drift before and after shearing at 6000 r / min for 10 min. Samples were diluted to an appropriate opacity and tested separately for both the original and sheared samples, with each test repeated three times. The test temperature was 25℃, and the refractive index and dispersion time were kept constant. Data processing outputs particle size distribution, span, and particle size retention rate.

[0121] The pH value of the long-lasting fragrance-locking coated detergent was determined by potentiometry, and its apparent viscosity at different shear rates was measured using a rotational viscometer to evaluate its low viscosity and wide processing window characteristics. After equilibration at 25°C for 30 min, the pH was measured first, followed by acceleration / deceleration according to the specified speed program. Rheological curves were collected and cycled twice to determine thixotropic recovery. Data processing outputs included pH, viscosity at 25°C, thixotropic hysteresis loop area, and viscosity recovery rate.

[0122] Long-lasting fragrance-locking encapsulated detergents were tested by comparing the changes in reflectance of standard soiled cloths before and after washing. The detergency rate and performance in repeated washing cycles were calculated to verify that the introduction of microcapsules did not lead to a decrease in detergency. Protein-, sebum-, and particulate-stained cloths were treated according to a standard machine washing procedure, with a blank base solution control included. Sample concentration, washing temperature, hard water conditions, and number of cycles were kept consistent. Data processing outputs included single-cycle detergency rate, retention rate after 5 cycles, and mean ± standard deviation.

[0123] After washing, cotton fabrics were treated according to standard household washing / drying procedures. Headspace phases were collected at 0, 24, and 72 hours, and the total release area of ​​the three fragrances was quantified by gas chromatography to evaluate the 72-hour fragrance retention capacity. Fabric weight and liquid retention were standardized, and samples were injected after sealing and equilibration. The test conditions were 25℃ and 50% relative humidity (n=3). Data processing used 0 hours as 100% to calculate the fragrance retention rates at 24 hours and 72 hours.

[0124] After washing, cotton fabrics were processed according to a uniform washing and drying procedure, and then subjected to dry rubbing for a specified number of cycles to evaluate the controllable fragrance release and high perceived release efficiency during use. A rubbing instrument was used for 20 reciprocating cycles, with headspace GC detection performed before and after rubbing. The perceived release index was obtained by combining this with three-point forced selection olfactory discrimination, while maintaining consistent rubbing load, number of cycles, and equilibrium time. Data processing outputs fragrance release increase and perceived release score.

[0125] The shell of covalently coated flavor microcapsules was analyzed using XPS to acquire C1s, N1s, and O1s spectra, demonstrating a stable interfacial chemical bond between quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin. Lyophilized samples were tableted and tested under the same energy standard conditions, simultaneously with key comparative studies. Peak separation was used to compare the ratio of amide nitrogen to quaternary ammonium nitrogen, ensuring consistent pass energy, step size, and charge correction. Data processing outputs binding energy, peak area percentage, and N / C atomic ratio.

[0126] Figure 1 The N1s peak separation fitting diagrams for Example 1, Comparative Example 1, and Comparative Example 2 are shown. High-resolution N1s tests and peak separation were performed on the shell of the covalently coated flavor microcapsules using XPS. The changes in amide nitrogen, quaternary ammonium nitrogen, and related nitrogen-containing signals were compared. The results showed that the amide nitrogen signal in Example 1 was more prominent, indicating that a more stable interfacial chemical connection was formed between the quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin, and the shell structure was reasonable.

[0127] Figure 2 The images show the C1s peak separation fitting diagrams for Example 1, Comparative Example 1, and Comparative Example 2. XPS was used to perform high-resolution C1s testing on the shell of the covalently coated flavor microcapsules and analyze the distribution of C–C, C–O, and amide-related carbon signals. The results show that the characteristic components related to the amide structure are more obvious in Example 1, further proving that there is a stable covalent connection structure in the shell, which is beneficial to improving the coating stability.

[0128] Figure 3 The diagram shows the amide nitrogen area ratio of Example 1, Comparative Example 1, and Comparative Example 2. Based on the XPS peak area, the amide nitrogen ratio on the surface of different samples was statistically analyzed. The results show that Example 1 is significantly higher than Comparative Example 1 and Comparative Example 2. This indicates that using an activation system and controlling the ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin is beneficial to improving the degree of amide bond connection, thereby enhancing the shell integrity.

[0129] Figure 4 The above are the FTIR superimposed spectra of Example 1 and Comparative Example 1. Fourier transform infrared spectroscopy was used to characterize the structure of the shell of the covalently coated flavor microcapsules and to compare them. The changes in characteristic absorption peaks within the range showed that Example 1 exhibited a more pronounced effect in the amide-related absorption region, indicating that a more complete chemical connection structure was formed in the shell.

[0130] Figure 5 The images shown are magnified FTIR images of the amide region of Example 1 and Comparative Example 1. Fourier transform infrared spectroscopy was used to perform local magnification analysis of the characteristic bands of the amide. The results show that the characteristic absorption near the amide I band and amide II band of Example 1 is clearer, indicating that the activation reaction promotes the amidation connection between the quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin, verifying the rationality of the shell design.

[0131] Figure 6 The laser diffraction volume distribution diagrams for Examples 1, 3, and 4 are shown. The change in particle size distribution of covalently coated fragrance microcapsules before and after shearing was tested using the laser particle size distribution method to evaluate the median particle size and shear resistance. The results show that the distribution change before and after shearing in Example 1 is relatively small, while Comparative Examples 3 and 4 show more obvious distribution broadening or peak shift, indicating that a moderate amount of oil phase and emulsification strength are more conducive to obtaining a stable microcapsule system.

[0132] Figure 7 The cumulative distribution of laser diffraction for Example 1, Comparative Example 3, and Comparative Example 4 is shown. The cumulative particle size distribution changes of the samples before and after shearing were compared using the laser particle size distribution method. The results show that the cumulative distribution curve of Example 1 changes less and the particle size retention is better, while the shifts in Comparative Example 3 and Comparative Example 4 are more obvious, indicating that Example 1 performs better in terms of structural stability and processing tolerance.

[0133] Figure 8 The 72-hour fragrance retention curves for Example 1, Comparative Example 6, and Comparative Example 7 are shown. Headspace gas chromatography of washed cotton fabrics was used to quantify the total release area of ​​the three fragrances at 0, 24, and 72 hours and calculate the retention rate. The results show that Example 1 has a higher retention rate within 72 hours, while Comparative Example 6 and Comparative Example 7 show a more significant decrease. This indicates that an appropriate amount of microcapsule addition and a neutral formulation window are beneficial to improving the long-lasting fragrance retention performance.

[0134] Figure 9 The 72h retention rate graphs for Example 1, Comparative Example 6, and Comparative Example 7 are shown. The total fragrance retention rate at the 72h node was summarized and compared using headspace gas chromatography. The results show that Example 1 is significantly better than Comparative Example 6 and Comparative Example 7, indicating that too low a feed amount or pH shift in the finished product will weaken the fragrance retention effect, while Example 1 is more reasonable in terms of fragrance persistence.

[0135] Figure 10 The rheological curves for Example 1, Comparative Example 7, and Comparative Example 8 are shown. Rotational rheology testing was used to assess the properties of the finished detergent products. The apparent viscosity of the acceleration and deceleration within the range was characterized, and the shear response behavior of cycle 1 was compared. The results showed that Example 1 had relatively stable flow characteristics while maintaining moderate viscosity, indicating that its neutral pH and mild downstream mixing conditions are beneficial to balancing processing window and dispersion stability.

[0136] Figure 11 The rheological cycle curves of Example 1, Comparative Example 7, and Comparative Example 8 are shown. The detergent product was subjected to a second acceleration and deceleration cycle test using rotational rheology testing to evaluate the thixotropic recovery behavior. The results show that the curve of Example 1 has better reproducibility after cycling, while the recovery of Comparative Example 7 and Comparative Example 8 is weaker, indicating that Example 1 has achieved a better balance between structural recovery and processing adaptability.

[0137] Figure 12 The diagram shows the thixotropic hysteresis area and viscosity recovery rate of Examples 1, 7, and 8. Based on the rheological cycling test results, the thixotropic hysteresis area and viscosity recovery rate of each sample are compared. The results show that Example 1 has a lower hysteresis area and a higher recovery rate, indicating that it is easier to maintain the stability of the system during the later mixing and use process, while taking into account both low viscosity and a wider processing window.

[0138] Figure 13 The image shows a macroscopic optical photograph of the covalently coated fragrance microcapsules prepared in Example 1. The sample is a pale yellow, uniform powder with a slightly matte surface. There is no obvious agglomeration or clumping, and the overall dispersion is good, which proves that the ultrafiltration purification process and vacuum drying parameters are set reasonably. The intrinsic colors of linalool, 2-phenylethanol, and benzyl salicylate in the core material, together with the light scattering of the quaternized oxidized cellulose nanofiber shell, form a soft appearance. The color is uniform within the batch and exhibits a free-flowing dynamic, which lays the foundation for stable dispersion in detergent base liquid.

[0139] Figure 14 The images shown are scanning electron microscope (SEM) images of the covalently coated flavor microcapsules prepared in Example 1. The low-magnification image shows that the microcapsules are nearly spherical and relatively uniformly distributed, with no large-area damage or collapse observed. The medium-magnification image shows that the particle surface is relatively dense. Based on the particle size distribution and chemical characterization results, it can be concluded that a relatively stable coating structure was formed under the conditions of Example 1.

[0140] Table 1 Performance summary of Example 1 and Comparative Example 1

[0141] As can be seen from the performance of the examples and comparative examples in Table 1, the chemical activation of the covalently coated shell, the appropriate shell component ratio, the reasonable emulsification strength, and the neutral formulation window jointly determine the performance balance. Examples 1-4 are generally higher than the comparative examples in terms of 72h aroma retention rate, aroma release increase, and particle size retention rate, indicating that simply increasing the amount of oil phase or simply changing the particle size cannot replace the synergistic construction of the covalent shell. Among them, although Comparative Example 3 shows a single-item high core material loading, its integrity rate and aroma retention rate are significantly reduced, indicating that excessive pursuit of high loading will sacrifice structural stability. Comparative Examples 6, 7, and 8 demonstrate from the three perspectives of insufficient feeding, pH shift, and excessive shear in the later stage that window control in the finished product stage is also the key to achieving a balance between long-lasting aroma retention, controlled aroma release, and low viscosity.

[0142] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that any equivalent structural transformations made under the concept of the present invention and using the contents of the specification and drawings of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. A long-lasting fragrance-locking encapsulated detergent, characterized in that, The product comprises, by weight, the following components: 0.30–3.00 parts by weight of covalently coated flavor microcapsules (dry basis), 8.0–20.0 parts by weight of sodium dodecylbenzenesulfonate (active ingredient), 3.0–12.0 parts by weight of cocamidopropyl betaine (active ingredient), 1.0–6.0 parts by weight of trisodium citrate, 1.0–8.0 parts by weight of 1,2-propanediol, and deionized water to a total of 100 parts by weight. The core material of the covalently coated flavor microcapsule is composed of linalool, 2-phenylethanol and benzyl salicylate, and the shell is formed by quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin connected by amide bonds. The quaternized oxidized cellulose nanofibers are prepared by oxidizing cellulose with 2,2,6,6-tetramethylpiperidine-1-oxy free radical, sodium bromide and sodium hypochlorite and then reacting it with glycidyltrimethylammonium chloride. The amino-β-cyclodextrin is prepared by β-cyclodextrin, p-toluenesulfonyl chloride and ethylenediamine.

2. The long-lasting fragrance-locking encapsulated detergent according to claim 1, characterized in that, The quaternized oxidized cellulose nanofibers have a carboxyl content of 0.60–1.50 mmol / g and a degree of quaternization of 0.05–0.40, and the amino substitution degree of amino-β-cyclodextrin is 0.05–0.25 mmol / g. The weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin is 100:20–120. The median particle size of the covalently coated fragrance microcapsules is 2–25 μm, the shell thickness is 80–500 nm, and the core material loading is 40.0 wt%–75.0 wt%.

3. The long-lasting fragrance-locking encapsulated detergent according to claim 1, characterized in that, Quaternized oxidized cellulose nanofibers are prepared by the following steps: A1. Disperse 100 parts by weight of cellulose, 0.5-3 parts by weight of 2,2,6,6-tetramethylpiperidine-1-oxy free radical and 5-20 parts by weight of sodium bromide in 800-2000 parts by weight of deionized water at a dispersion temperature of 15-30℃ and a dispersion time of 0.5-2h. A2. Add 30-120 parts by weight of sodium hypochlorite at 0-10℃ and pH 9.5-10.5 and react for 1-4 hours; A3. Oxidation was terminated when the cellulose carboxyl content reached 0.60–1.80 mmol / g, and the mixture was washed until the pH value was 6.5–7.

5. A4. Add 20-80 parts by weight of glycidyltrimethylammonium chloride and 2-10 parts by weight of sodium hydroxide to the oxidized cellulose obtained in A3, and react at 55-70℃ for 3-8 hours; A5. After homogenization under high pressure of 40-100 MPa for 2-6 times, quaternized oxidized cellulose nanofibers with a carboxyl content of 0.60-1.50 mmol / g and a degree of quaternization of 0.05-0.40 were obtained.

4. The long-lasting fragrance-locking encapsulated detergent according to claim 2, characterized in that, Amino-β-cyclodextrin is prepared by the following steps: B1. Dissolve 100 parts by weight of β-cyclodextrin in an aqueous solution of sodium hydroxide with a concentration of 0.30-1.00 mol / L, add 40-90 parts by weight of p-toluenesulfonyl chloride at 0-5℃ and react for 0.5-2 h; B2. Separate the obtained p-toluenesulfonated β-cyclodextrin and wash it until the pH of the filtrate is 7-8; B3. React the product obtained in B2 with 100-500 parts by weight of ethylenediamine at 35-50°C for 12-24 hours; B4. Precipitate with acetone and wash, then dry at 35–50 °C for 8–16 h to obtain amino-β-cyclodextrin with an amino substitution degree of 0.05–0.25 mmol / g.

5. The long-lasting fragrance-locking encapsulated detergent according to claim 1, characterized in that, Amino-β-cyclodextrin is first reacted with at least one of linalool, 2-phenylethanol, and benzyl salicylate to form an inclusion unit, which is prepared by the following steps: C1. Add 100 parts by weight of amino-β-cyclodextrin and 10 to 60 parts by weight of at least one of linalool, 2-phenylethanol and benzyl salicylate to a mixed solvent composed of deionized water and ethanol, wherein the volume fraction of deionized water is 70 vol% to 95 vol% and the balance is ethanol. C2. Stir at 35–50℃ for 2–8 hours; C3. Remove the solvent under reduced pressure and dry at 40–60 °C for 6–12 h to obtain inclusion units with an inclusion weight of 5.0 wt%–25.0 wt%.

6. The long-lasting fragrance-locking encapsulated detergent according to claim 1, characterized in that, Covalently coated flavor microcapsules are prepared through the following steps: D1. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 2-20 parts by weight of polyvinyl alcohol in deionized water; D2. Add 10-60 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 5-30 parts by weight of N-hydroxysuccinimide, and activate for 0.5-2 hours at a pH of 4.5-6.0 and a temperature of 15-35°C. D3. Add 20-120 parts by weight of amino-β-cyclodextrin and 100-400 parts by weight of an oil phase composed of linalool, 2-phenylethanol and benzyl salicylate, or add 20-120 parts by weight of an inclusion unit formed by amino-β-cyclodextrin and at least one of linalool, 2-phenylethanol and benzyl salicylate and 100-400 parts by weight of an oil phase composed of linalool, 2-phenylethanol and benzyl salicylate, and emulsify at 3000-12000 r / min for 2-10 min; D4. Adjust the pH of the system to 6.0–7.5 using an alkaline solution and react for 1–4 hours. Then wash with deionized water 3–6 times and ultrafilter using an ultrafiltration membrane with a molecular weight cutoff of 50–300 kDa until the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the obtained covalently coated flavor microcapsules is no more than 500 mg / kg, thus obtaining covalently coated flavor microcapsules.

7. The long-lasting fragrance-locking encapsulated detergent according to claim 6, characterized in that, The mass ratio of linalool, 2-phenylethanol and benzyl salicylate in the core material is (20-60):(10-40):(10-40) when the total weight of the three is normalized. The weight ratio of quaternized oxidized cellulose nanofibers to amino-β-cyclodextrin is 100:20-120. The long-lasting fragrance-locking encapsulated detergent has a pH value of 6.8-7.8 and a viscosity of 800-2500 mPa·s.

8. A method for preparing a long-lasting fragrance-locking encapsulated detergent as described in any one of claims 1-7, characterized in that, Includes the following steps: S1. Provides pre-prepared quaternized oxidized cellulose nanofibers and amino-β-cyclodextrin; S2. Disperse 100 parts by weight of quaternized oxidized cellulose nanofibers and 2-20 parts by weight of polyvinyl alcohol in 500-2000 parts by weight of deionized water. The quaternized oxidized cellulose nanofibers, on a dry basis, are then mixed with 10-60 parts by weight of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 5-30 parts by weight of N-hydroxysuccinimide. The mixture is activated for 0.5-2 hours at a pH of 4.5-6.0 and a temperature of 15-35°C. Then, 20-120 parts by weight of amino-β-cyclodextrin and 100-400 parts by weight of an oil phase composed of linalool, 2-phenylethanol, and benzyl salicylate are added, or a previously prepared mixture of amino-β-cyclodextrin, linalool, and 2-phenylethanol is added. 20-120 parts by weight of an inclusion unit formed from at least one of phenylethanol and benzyl salicylate, and 100-400 parts by weight of an oil phase composed of linalool, 2-phenylethanol and benzyl salicylate, are emulsified at 3000-12000 r / min for 2-10 min; then the pH of the system is adjusted to 6.0-7.5 with an alkaline solution and reacted for 1-4 h; the system is washed 3-6 times with deionized water and ultrafiltered with an ultrafiltration membrane with a molecular weight cutoff of 50-300 kDa until the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide in the obtained covalently coated fragrance microcapsules is not greater than 500 mg / kg, thus obtaining covalently coated fragrance microcapsules; S3. Add 8.0–20.0 parts by weight of sodium dodecylbenzenesulfonate, 3.0–12.0 parts by weight of cocamidopropyl betaine, 1.0–6.0 parts by weight of trisodium citrate, and 1.0–8.0 parts by weight of 1,2-propanediol to deionized water and mix at 20–35°C to form a detergent base solution; S4. Add the covalently coated fragrance microcapsules obtained in S2 to the detergent base solution obtained in S3 at a speed of 100-300 r / min, adjust the pH value to 6.8-7.8, defoam, and then fill to obtain a long-lasting fragrance-locking coated detergent.

9. The preparation method according to claim 8, characterized in that, The components used in S3 and S4, based on the weight parts of the resulting long-lasting fragrance-locking encapsulated detergent, include: 0.30–3.00 parts by weight of covalently encapsulated fragrance microcapsules (dry basis), 8.0–20.0 parts by weight of sodium dodecylbenzenesulfonate (active ingredient), 3.0–12.0 parts by weight of cocamidopropyl betaine (active ingredient), 1.0–6.0 parts by weight of trisodium citrate, 1.0–8.0 parts by weight of 1,2-propanediol, and deionized water to a total of 100 parts by weight.

10. The preparation method according to claim 9, characterized in that, In the obtained long-lasting fragrance-locking encapsulated detergent, the residual amount of glycidyl trimethylammonium chloride is not greater than 1000 mg / kg and the residual amount of p-toluenesulfonyl chloride is not greater than 200 mg / kg, based on the total mass of the detergent. Furthermore, in the covalently encapsulated fragrance microcapsules contained in the obtained long-lasting fragrance-locking encapsulated detergent, the total amount of residual 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide is not greater than 500 mg / kg, based on the mass of the covalently encapsulated fragrance microcapsules.

Images