High-adsorption modified essence microcapsule, preparation method thereof and application of high-adsorption modified essence microcapsule in daily chemical washing
By preparing highly adsorption modified flavor microcapsules, the thermal stability and mechanical strength of flavor microcapsules are improved by using weak cationic polyurethane resin and stabilizer, the thermal stability and mechanical strength of flavor microcapsules are solved, and the problems of poor thermal stability and insufficient mechanical strength of traditional flavor microcapsules are achieved, and good results are achieved The aroma adsorption and sustained release effect and reduces the amount of formaldehyde residue, which is suitable for daily chemical washing.
Patent Information
- Application Number
- CN202411222041.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-02
- Publication Date
- 2024-12-06
AI Technical Summary
Traditional fragrance microcapsules have poor thermal stability, insufficient mechanical strength, and are prone to rupture, resulting in poor fragrance durability. Many products with good fragrance retention performance contain formaldehyde, which is harmful to the human body and the environment.
Using raw materials such as oily flavors, emulsifiers, prepolymers, modifiers, stabilizers and formaldehyde capture agents, high adsorption modified flavor microcapsules are prepared through emulsification and reaction steps, and weak cationic polyurethane resin is used as a modifier to combine fat Alcohol polyoxyethylene ether and polysaccharide polymers act as stabilizers to form microcapsules with good thermal stability and mechanical strength.
It significantly improves the thermal stability and mechanical strength of the fragrance micro capsules, reduces the amount of formaldehyde residue, enhances the adsorption and sustained release of the fragrance, extends the fragrance retention time, and maintains stability in the detergent, making it difficult to delaminate , the product quality is stable and can be stored for a long time.
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Figure CN119075853A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of essence microcapsules, and in particular relates to a high-absorption modified essence microcapsule and a preparation method thereof and application in daily chemical washing. Background Art
[0002] Fragrances are widely used in various fields such as textiles, daily chemicals, wall coverings, leather odor masking, and food and tobacco. Traditional flavors are characterized by high volatility and short action time, and are easily affected by light, oxygen, temperature, acid and alkali, resulting in serious loss of fragrance. Fragrance microcapsules are mainly made of natural or synthetic polymer materials as shell materials to coat the fragrances, which can effectively isolate the external environment, improve the stability and sustained release of the fragrance, and achieve a long-lasting fragrance effect. At present, the fragrance microcapsules sold on the market have poor thermal stability and insufficient mechanical strength. The shell material is easily affected by the external environment and breaks, resulting in poor fragrance persistence. Most of the fragrance microcapsules with good fragrance retention performance contain formaldehyde, which is harmful to the human body and the environment. Therefore, it is of great significance to develop a fragrance microcapsule with excellent thermal stability and mechanical strength, good fragrance retention performance and no formaldehyde. Summary of the invention
[0003] The present invention provides a highly adsorbable modified essence microcapsule and a preparation method thereof and application in daily chemical washing. The microcapsule has extremely low residual formaldehyde content, good adsorption performance on fabrics, stable product emulsion without stratification, stable properties, stable dispersion in detergent matrix, stable product quality, and long-term storage. The microcapsule has good thermal stability and mechanical strength, and good sealing and fragrance retention performance.
[0004] The technical solution of the present invention is to provide a high-absorption modified flavor microcapsule, comprising the following raw materials in parts by weight: 20 to 35 parts of oily flavor, 1.5 to 4 parts of emulsifier, 3 to 5 parts of prepolymer, 5 to 10 parts of modifier, 5 to 10 parts of stabilizer, 1.5 to 3 parts of pH adjuster, 2 to 5 parts of formaldehyde scavenger and 36 to 58 parts of water; wherein the modifier is a weak cationic polyurethane resin copolymer.
[0005] In some embodiments, the oily flavor includes, but is not limited to, one or more of perfume flavor, floral flavor, fruity flavor, and herbal flavor.
[0006] In some embodiments, the emulsifier is one or more of styrene-maleic anhydride copolymer sodium salt, sodium dodecylbenzene sulfonate, ethylene-maleic anhydride copolymer, and acyl glycinate.
[0007] In some embodiments, the prepolymer is a melamine-formaldehyde prepolymer; the formaldehyde scavenger is one or more of urea, ethylene urea, and polyvinyl alcohol.
[0008] In some embodiments, the stabilizer is one or more of fatty alcohol polyoxyethylene ether and / or polysaccharide polymer; the pH adjuster is one or more of acetic acid, citric acid and sodium hydroxide.
[0009] The present invention also relates to a method for preparing the microcapsules, which is characterized by comprising the following steps: S1, emulsifier dispersed in water, and then add the oily flavor and mix to obtain an O / W type emulsion; S2. After the emulsification is completed, the speed is reduced, the prepolymer is added for reaction, the temperature is increased for insulation, and then the modifier is added to continue the reaction, and finally the formaldehyde scavenger is added to continue the reaction; After the reaction of S3 and S2 is completed, the temperature is lowered, a pH adjuster is added, and then a stabilizer is added and dispersed evenly to obtain a highly adsorbed modified flavor microcapsule emulsion.
[0010] In some embodiments, the emulsifier in S1 is dispersed in water to prepare a 3-5% mixed solution; the mass ratio of the oily essence to the emulsifier mixed solution is 1:2-4. During emulsification, a high shear dispersing emulsifier is used at 60°C and a speed of 1000-3000 rpm for 5-20 minutes.
[0011] In some embodiments, after the emulsification in S2 is completed, the rotation speed is reduced to 800-1500 rpm, the prepolymer is added to react for 10-30 minutes, the temperature is raised to 75-85°C, and then the modifier is added after keeping warm for 1-3 hours to react for 1-2 hours, and finally the formaldehyde scavenger is added to react for 1-1.5 hours. In some embodiments, the temperature in S3 is lowered to below 40° C., a pH adjuster is added to adjust the pH of the system to 5-7, and a stabilizer is added and dispersed and stirred for 10-20 minutes.
[0012] The invention also relates to the application of the microcapsule in the field of daily chemical washing.
[0013] The present invention has the following beneficial effects: When preparing the microcapsules of the present invention, the oil-soluble flavor and the anionic emulsifier solution are firstly mixed uniformly, sheared to a uniform emulsion state, the emulsion is adjusted to be acidic, the prepolymer is slowly added, and after mixing uniformly, heated and stirred for curing, a modifier is added during the reaction for cross-linking reaction, and then a formaldehyde scavenger is added, and finally a stabilizer is added to finally obtain the flavor microcapsule emulsion.
[0014] The present invention adopts weak cationic polyurethane resin copolymer as a modifier. With the addition of the modifier, some weak cationic groups can be formed on the surface of the microcapsule. The obtained fragrance microcapsules can be combined with detergents such as laundry detergent, softener, and fragrance beads. After washing, the microcapsules with weak cationic groups can be more adsorbed and deposited on the surface of fabrics such as clothes and towels, and can slowly release fragrance or break and release fragrance after being squeezed, thereby prolonging the fragrance retention effect of the fragrance and increasing the fragrance retention performance of the detergent. With fatty alcohol polyoxyethylene ether and / or polysaccharide polymer as stabilizers, the hydrophilic and lipophilic groups on the molecular chain of fatty alcohol polyoxyethylene ether can form micelles in the solution, and the polysaccharide polymer can increase the viscosity of the emulsion and be adsorbed on the surface of the particles to prevent the particles from aggregating, thereby playing a role in stabilizing the suspension, and can improve the stability of the product emulsion, have stable properties and no stratification, can be evenly dispersed in the detergent matrix, and have stable product quality and can be stored for a long time. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1 This is a 3000x SEM photo of the flavor microcapsule prepared in Example 4; Figure 2 is the TGA thermogravimetric curve of the flavor microcapsule prepared in Example 4; Figure 3 This is a SEM photograph of fabric washed with the fragrance microcapsules prepared in Example 4 after adding detergent. DETAILED DESCRIPTION
[0016] The present invention is described in detail below in conjunction with specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and a specific operation process, but the protection scope of the present invention is not limited to the following embodiments.
[0017] Example 1 A high-absorption modified flavor microcapsule for daily chemical washing comprises the following raw materials: 80 g of oily flavor, 180 g of emulsifier dispersion (5%), 30 g of modifier, 15 g of prepolymer, 8 g of formaldehyde scavenger, 20 g of suspension stabilizer, and 40 g of pH regulator.
[0018] The oily essence is Chanel essence.
[0019] The emulsifier dispersion is a styrene-maleic anhydride copolymer aqueous solution.
[0020] The prepolymer is a melamine-formaldehyde prepolymer.
[0021] The formaldehyde scavenger is urea.
[0022] The modifier is weak cationic polyurethane resin copolymer ARRISTAN CPU. The suspension stabilizer is fatty alcohol polyoxyethylene ether.
[0023] The pH adjuster is a 20% citric acid aqueous solution.
[0024] The fragrance microcapsules for long-lasting fragrance of detergents are prepared by the following steps: 80g of Chanel fragrance is added to 180g of styrene-maleic anhydride copolymer aqueous solution, and a high shear dispersing emulsifier is used for emulsification at a speed of 1500rpm for 10min to obtain a stable O / W type emulsion. After the emulsification is completed, 15g of prepolymer is added for reaction for 30min, the temperature is raised to 75°C and kept warm for 0.5h, and then the temperature is continued to rise to 85°C and kept warm for 2h, and a modifier is added to continue to keep warm for 1h, 8g of urea is added, and the reaction is continued for 1h, and then the temperature is lowered to 40°C, 40g of 20% citric acid aqueous solution is added to adjust the pH value of the emulsion to 5.5, and finally 15g of suspension stabilizer is added and stirred and dispersed for 20min to obtain a high-absorption modified fragrance microcapsule emulsion for daily chemical washing.
[0025] Example 2 A high-absorption modified flavor microcapsule for daily chemical washing comprises the following raw materials: 80 g of oily flavor, 180 g of emulsifier dispersion (4%), 25 g of modifier, 20 g of prepolymer, 8 g of formaldehyde scavenger, 18 g of suspension stabilizer, and 40 g of pH regulator.
[0026] The oily essence is rose essence.
[0027] The emulsifier dispersion is a styrene-maleic anhydride copolymer aqueous solution.
[0028] The prepolymer is a melamine-formaldehyde prepolymer.
[0029] The formaldehyde scavenger is cyclohexyl urea.
[0030] The modifier is weak cationic polyurethane resin copolymer ARRISTAN CPU.
[0031] The suspension stabilizer is a polysaccharide polymer.
[0032] The pH adjuster is 20% acetic acid solution.
[0033] The fragrance microcapsules for long-lasting fragrance of detergents are prepared by the following steps: 80g of rose essence is added to 180g of emulsifier dispersion, and emulsified at 2000rpm for 10min using a high shear dispersing emulsifier to obtain a stable O / W type emulsion. After the emulsification is completed, 20g of prepolymer is added to react for 30min, the temperature is raised to 75℃ and kept for 0.5h, and then the temperature is further raised to 85℃ and kept for 2h, 25g of modifier is added and kept for 1h, and then 8g of cyclohexyl urea is added and the reaction is continued for 1h, and then the temperature is lowered to 40℃, 40g of acetic acid solution is added to adjust the pH value of the emulsion to 5.5, and finally 18g of suspension stabilizer is added and stirred and dispersed for 20min to obtain a high-absorption modified fragrance microcapsule emulsion for daily chemical washing.
[0034] Example 3 A high-absorption modified flavor microcapsule for daily chemical washing comprises the following raw materials: 90 g of oily flavor, 180 g of emulsifier dispersion (5%), 20 g of modifier, 18 g of prepolymer, 9 g of formaldehyde scavenger, 20 g of suspension stabilizer, and 40 g of pH regulator.
[0035] The oily essence is peach essence.
[0036] The emulsifier dispersion is an aqueous solution of sodium dodecylbenzenesulfonate.
[0037] The prepolymer is a melamine-formaldehyde prepolymer.
[0038] The formaldehyde scavenger is polyvinyl alcohol.
[0039] The modifier is weak cationic polyurethane resin copolymer ARRISTAN CPU.
[0040] The suspension stabilizer is fatty alcohol polyoxyethylene ether.
[0041] The pH adjuster is 20% acetic acid solution.
[0042] The fragrance microcapsules for long-lasting fragrance of detergents are prepared by the following steps: 90g of peach essence is added to 180g of emulsifier dispersion, and a high shear dispersing emulsifier is used for emulsification at a speed of 2500rpm for 8min to obtain a stable O / W type emulsion. After the emulsification is completed, 18g of prepolymer is added for reaction for 30min, the temperature is raised to 75℃ and kept for 0.5h, and then the temperature is further raised to 85℃ and kept for 2h, 20g of modifier is added and kept for 1h, and then 9g of polyvinyl alcohol is added and the reaction is continued for 1h, and then the temperature is lowered to 40℃, 40g of acetic acid solution is added to adjust the pH value of the emulsion to 5.5, and finally 20g of suspension stabilizer is added and stirred and dispersed for 20min to obtain a high-absorption modified fragrance microcapsule emulsion for daily chemical washing.
[0043] Example 4 A high-absorption modified flavor microcapsule for daily chemical washing comprises the following raw materials: 80 g of oily flavor, 160 g of emulsifier dispersion (5%), 30 g of modifier, 16 g of prepolymer, 8 g of formaldehyde scavenger, 20 g of suspension stabilizer, and 40 g of pH regulator.
[0044] The oily essence is lemon essence.
[0045] The emulsifier dispersion is a styrene-maleic anhydride copolymer aqueous solution.
[0046] The prepolymer is a melamine-formaldehyde prepolymer.
[0047] The formaldehyde scavenger is urea.
[0048] The modifier is a weak cationic polyurethane resin copolymer.
[0049] The suspension stabilizer is fatty alcohol polyoxyethylene ether.
[0050] The pH adjuster is 20% citric acid solution.
[0051] The fragrance microcapsules for long-lasting fragrance of detergents are prepared by the following steps: 80g of lemon essence is added to 160g of emulsifier dispersion, and emulsified at 2000rpm for 10min using a high shear dispersing emulsifier to obtain a stable O / W type emulsion. After the emulsification is completed, 16g of prepolymer is added to react for 30min, the temperature is raised to 75℃ and kept warm for 0.5h, and then the temperature is continued to rise to 85℃ and kept warm for 2h, 30g of modifier is added and kept warm for 1h, and then 8g of urea is added and the reaction is continued for 1h, and then the temperature is lowered to 40℃, 40g of citric acid solution is added to adjust the pH value of the emulsion to 5.5, and finally 20g of suspension stabilizer is added and stirred and dispersed for 20min to obtain a high-absorption modified fragrance microcapsule emulsion for daily chemical washing.
[0052] Comparative Example 1 Based on Example 4, the only difference is that the modifier is a cationic acrylamide copolymer. The rest is the same as Example 4. Comparative Example 2 Based on Example 4, the difference is that no modifier is added, and the rest is the same as Example 4.
[0053] Take 0.3 g of each of the fragrance microcapsules prepared in Examples 1, 2, 3, 4, and Comparative Examples 1 and 2, add them to 100 g of laundry detergent matrix and mix them evenly, take 10 g of the fragranced laundry detergent and add it to an 8L washing machine, wash it normally for 45 minutes, dehydrate it, take it out and dry it; Then, 0.3g of each pure essence of different fragrances in the above case was added to 100g of laundry detergent base, and 10g of fragranced laundry detergent was added to an 8L washing machine. After washing normally for 45 minutes, it was dehydrated and taken out to dry. 10 g of normal non-perfumed laundry detergent was added to an 8L washing machine, and washed normally for 45 minutes, then dehydrated, taken out and air-dried as a blank control. The above-mentioned laundry was dried and compared, and the fragrance was evaluated, as shown in Table 1.
[0054] Table 1 Comparison of detergent fragrance test
[0055] Note: The aroma degree is divided into four levels: +, ++, +++, ++++. + means no fragrance, ++ means a faint fragrance, +++ means a light fragrance, and ++++ means a strong fragrance.
[0056] As can be seen from Table 1, the highly adsorbable modified fragrance microcapsule emulsion of the present invention can greatly improve the adsorption performance of microcapsules on fabrics and increase the fragrance retention time of fabrics. The application of microcapsule technology can change the state of the fragrance, slowly release the fragrance or release the fragrance after being squeezed and broken, thereby increasing the fragrance retention effect of the detergent.
[0057] Take 200g of the highly adsorbed modified flavor microcapsule emulsion prepared in Example 4 above and divide it into 2 portions of 100g. Also take 2 portions of 100g each of the commercially available melamine system flavor microcapsules. Place one portion of the modified flavor microcapsule emulsion and the commercially available product in a laboratory fume hood, and the other portion in a 50°C constant temperature oven. Observe the state of the emulsion at different time intervals and record the stability of the flavor microcapsule emulsion, as shown in Table 2.
[0058] Table 2 Comparison of stability of flavor microcapsule emulsion
[0059] From the comparison results in the above table, it can be seen that the high-adhesion modified flavor microcapsule emulsion prepared in the present invention has good storage stability at room temperature and 40-50°C environment, which solves the problems of poor stability and easy stratification of flavor microcapsule products on the market.
[0060] The above embodiments describe the preferred implementation of the present invention, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.
Claims
1. A highly adsorbable modified flavor microcapsule, characterized in that: The invention comprises the following raw materials in parts by weight: 20-35 parts of oily essence, 1.5-4 parts of emulsifier, 3-5 parts of prepolymer, 5-10 parts of modifier, 5-10 parts of stabilizer, 1.5-3 parts of pH adjuster, 2-5 parts of formaldehyde scavenger and 36-58 parts of water; wherein the modifier is a weak cationic polyurethane resin copolymer.
2. The microcapsule according to claim 1, characterized in that: The oily flavor includes, but is not limited to, one or more of perfume flavor, floral flavor, fruity flavor, and herbal flavor.
3. The microcapsule according to claim 1, characterized in that: The emulsifier is one or more of styrene-maleic anhydride copolymer sodium salt, sodium dodecylbenzene sulfonate, ethylene-maleic anhydride copolymer, and acyl glycine salt.
4. The microcapsule according to claim 1, characterized in that: The prepolymer is melamine-formaldehyde prepolymer; the formaldehyde scavenger is one or more of urea, cyclohexane urea and polyvinyl alcohol.
5. The microcapsule according to claim 1, characterized in that: The stabilizer is one or more of fatty alcohol polyoxyethylene ether and / or polysaccharide polymer; the pH adjuster is one or more of acetic acid, citric acid, sodium hydroxide and ammonium chloride.
6. The method for preparing microcapsules according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1, emulsifier dispersed in water, and then add the oily flavor and mix to obtain an O / W type emulsion; S2. After the emulsification is completed, the speed is reduced, the prepolymer is added for reaction, the temperature is increased for insulation, and then the modifier is added to continue the reaction, and finally the formaldehyde scavenger is added to continue the reaction; After the reaction of S3 and S2 is completed, the temperature is lowered, a pH adjuster is added, and then a stabilizer is added and dispersed evenly to obtain a highly adsorbed modified flavor microcapsule emulsion.
7. The preparation method according to claim 6, characterized in that: The emulsifier in S1 is dispersed in water to prepare a 3-5% mixed liquid; the mass ratio of the oily flavor to the emulsifier mixed liquid is 1:2-4.
8. The preparation method according to claim 6, characterized in that: After the emulsification in S2 is completed, the rotation speed is reduced to 800-1500rpm, the prepolymer is added to react for 10-30min, the temperature is raised to 75-85°C, and then the modifier is added and reacted for 1-2h after being kept warm for 1-3h, and finally the formaldehyde scavenger is added to react for 1-1.5h.
9. The preparation method according to claim 6, characterized in that: The temperature in S3 is lowered to below 40°C, a pH adjuster is added to adjust the pH of the system to 5-7, and a stabilizer is added to disperse and stir for 10-20 minutes.
10. Use of the microcapsule according to any one of claims 1 to 5 or the microcapsule obtained by the preparation method according to any one of claims 6 to 9 in the field of daily chemical cleaning.