Microcapsule material, microcapsule using microcapsule material and preparation method of microcapsule

Abstract

The invention discloses a microcapsule material, a microcapsule using the microcapsule material and a preparation method of the microcapsule, and relates to the technical field of daily chemical products. The microcapsule material comprises an addition polymer formed by a ring-opening reaction of epoxy resin and bio-based polyamine, poly (beta-amino ester) formed by a Michael addition reaction of acrylate and phenyl polyamine, and at least one cationic polymer containing quaternary ammonium groups. The microcapsule material shows certain biodegradability, the biodegradation rate of the microcapsule material exceeds 20% within 28 days, and the applied microcapsule can effectively meet the friction fragrance release performance requirement required by essence wrapping, so that after the obtained essence-encapsulated microcapsule is stored in a lotion at 45 DEG C for 28 days, the fragrance release performance of the microcapsule material is not influenced by the friction fragrance release performance, and the fragrance release performance of the microcapsule material is not influenced by the friction fragrance release performance. The excellent friction aroma releasing capability and the adhesion capability on the fabric can still be maintained, and the excellent thermal stability is shown.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of daily chemical products, in particular to a microcapsule material, a microcapsule and a preparation method thereof. BACKGROUND

[0002] Fragrance is an important ingredient that adds specific aroma to products and enhances sensory experience, with a wide range of applications, covering daily chemicals, food, beverages, cosmetics and other industries. However, the high volatility and relatively low stability of fragrance make it prone to deterioration during storage, transportation and use, resulting in changes in fragrance and flavor, and thus reducing the utilization rate of fragrance. In order to solve these problems, microcapsule technology is widely used in the packaging of fragrance. By wrapping fragrance in tiny capsules, microcapsule technology can effectively protect fragrance from environmental factors such as temperature, humidity, light and oxygen, reducing volatile loss and oxidative deterioration. This packaging method not only helps maintain the original aroma and flavor of fragrance, but also prolongs its service life and significantly improves its application value.

[0003] Microcapsule technology encapsulates active substances through a "core-shell" structure, in which the core material is surrounded by a polymer shell, which can be lipophilic, hydrophobic or hydrophilic compounds, etc. The release rate of the core material and its diffusion through the capsule wall can be controlled by adjusting the composition of the wall material and / or the cross-linking degree of the wall material, while the cross-linking degree of the wall material directly affects the strength and properties of the microcapsule wall. The wall materials commonly used to encapsulate fragrance or similar active substances include melamine formaldehyde, urea-formaldehyde or polyurea, etc. (Perignon, C. et al., Journal of Microencapsulation 2015, 32(1), 1-15). These materials are widely used due to their high mechanical strength, good impermeability, low cost and appropriate brittleness, which allows them to break under frictional pressure and release fragrance, providing a long-lasting and pleasant olfactory experience. However, these wall materials are usually non-biodegradable and involve harmful substances such as formaldehyde and isocyanate, which can pose a threat to the environment and the health of workers and users. In recent years, with the improvement of people's living standards and the enhancement of health awareness, consumers have increasingly strong demand for alternative fragrance microcapsules. Therefore, it is of great significance to develop new fragrance microcapsules with good stability, good olfactory performance and biodegradability.

[0004] Patent CN118201703A discloses a core-shell microcapsule composition with certain biodegradability. The microcapsule shell is mainly composed of a polymer obtained by the addition reaction of an epoxide and a polyamine. This polymer is an alternative microcapsule that does not involve formaldehyde or isocyanate. Analysis according to OECD 301F standards shows that the polymer can achieve a degradation rate of up to 60% within 45 days, exhibiting good biodegradability. However, this patent does not investigate the stability of microcapsules constructed from this polymer in detergent solutions. CN119386789A discloses a strategy of combining epoxy-polyamine polymers with polyamides, which greatly improves their stability in detergents. However, the polyamide significantly weakens or even eliminates their biodegradability.

[0005] Patents CN113853250 A and US2024 / 0033702A1 disclose a method for obtaining poly(β-amino ester) (an addition polymer of acrylate and amine) by polymerizing it at the oil-water interface using the Michael addition reaction between amines and acrylates, and then forming microcapsules. These microcapsules encapsulate active substances, and the polymer shell possesses high biodegradability. Analysis according to the OECD 301F method shows that the polymer can degrade by more than 90% within 28 days. Patent CN116472303A discloses a composite wall material of polyacrylate (PAC) and poly(β-amino ester) (PAC / PBAE) formed by pre-forming a PBAE prepolymer and then undergoing free radical polymerization. This wall material not only has better encapsulation properties but also exhibits certain biodegradability. In addition, patent CN116322628 A and PCT patent WO 2023 / 137224 A2 also describe a method for hybridizing poly(β-amino ester) with poly(β-thioester), and the resulting microcapsules also exhibit excellent performance in terms of storage stability and biodegradability of the polymer shell. CN119350632A discloses a polysiloxane and poly(β-amino ester) composite microcapsule, which shows improved stability at room temperature.

[0006] It can be seen that some progress has been made in the preparation of biodegradable microcapsules using poly(β-amino esters). However, existing technologies still have some shortcomings: First, the performance of fragrance microcapsules prepared based on poly(β-amino esters) in terms of frictional fragrance release is generally unsatisfactory (generally scoring less than 3 out of 5 points on a sensory evaluation scale, while non-biodegradable microcapsules constructed using materials such as melamine-formaldehyde, urea-formaldehyde, or polyurea generally score above 4 points); second, some techniques, such as hybridizing poly(β-amino esters) with poly(β-thioesters), may produce unpleasant odors due to the use of excessive thiols. Furthermore, the stability problem of poly(β-amino ester) microcapsules in systems containing surfactants, such as laundry detergent, has not yet been effectively solved.

[0007] The fragrance microcapsules constructed from the aforementioned addition polymers of epoxy resins and polyamines or poly(β-amino esters) do not involve toxic formaldehyde and isocyanates and possess a certain degree of biodegradability. While these are beneficial to the environment and health, their stability and frictional fragrance release performance still lag significantly behind microcapsules constructed from traditional materials such as melamine-formaldehyde, urea-formaldehyde, or polyurea, thus limiting their applications. Therefore, there is a need to use eco-friendly materials to provide new microcapsules without compromising their performance, particularly in terms of stability in challenging media such as consumer detergents, while also exhibiting good olfactory properties. Summary of the Invention

[0008] The present invention aims to provide a novel fragrance microcapsule with good stability and olfactory properties. The microcapsule material possesses certain biodegradability. This microcapsule material comprises an addition polymer of epoxy resin and bio-based polyamine, a poly(β-amino ester) formed from acrylate and phenyl polyamine, and at least one cationic polymer with polyquaternary ammonium groups. This microcapsule is easy to synthesize and exhibits the required stability in challenging base materials such as aqueous phases and fabric detergents. The microcapsule material construction process does not involve formaldehyde or isocyanates and possesses certain biodegradability, making it a high-performance and environmentally friendly novel microcapsule. This microcapsule can effectively encapsulate active substances (such as fragrances, essential oils, or other oils), and the shell easily ruptures under frictional pressure to release the contents. Furthermore, when this microcapsule is applied to liquid detergents, the contents remain stable during storage or throughout the shelf life.

[0009] The objective of this invention is achieved through the following technical solutions.

[0010] A novel fragrance microcapsule material with good stability and good olfactory properties is provided, which is prepared based on a novel addition polymer and a cationic polymer. The microcapsule material comprises an addition polymer of epoxy resin and bio-based polyamine, a poly(β-amino ester) formed by acrylate and phenyl polyamine, and at least one cationic polymer containing a quaternary ammonium group.

[0011] The addition polymer of the epoxy resin and the bio-based polyamine is formed by a ring-opening reaction between the epoxy group of the epoxy resin and the amine functional group. The epoxy resin is a compound having at least two epoxy functional groups; the bio-based polyamine is selected from polymers formed from amino acid monomers or amino acids having two primary amines.

[0012] The poly(β-amino ester) is formed by a Michael addition reaction between an acrylate functional group and an amine; the acrylate is a compound containing at least two acrylate functional groups, and the phenyl polyamine is a compound containing at least one phenyl and a primary amine or two secondary amine functional groups.

[0013] The epoxy resin and bio-based polyamine addition polymer, as well as the poly(β-amino ester) polymer, are all formed through interfacial polymerization.

[0014] The epoxy resin is selected from at least one of diepoxy functional group compounds, triepoxy functional group compounds, and tetraepoxy functional group compounds.

[0015] In some specific embodiments, the epoxy resin is selected from at least one of P-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, resorcinol diglycidyl ether, and 2,2-bis-(4-glycyloxyphenyl)propane.

[0016] The preferred acrylate structural formula is X-(-O(C=O)-CH=CH2)n or X-(-O(C=O)-C(CH3)=CH2)n, where n ≥ 2, and X is a molecule connecting n acrylate structural units.

[0017] More preferably, the acrylate is selected from at least one of polyacrylates such as diacrylate, triacrylate, tetraacrylate, pentaacrylate, and hexaacrylate.

[0018] In some specific embodiments, the acrylate is selected from at least one of tetraethylene glycol diacrylate, polyethoxylated trimethylolpropane triacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, waterborne aliphatic polyurethane acrylate, and diurea dimethacrylate isomer mixture (UDMA).

[0019] The phenyl polyamine is selected from at least one of phenyl-containing primary amines, bis-primary amines and tri-primary amines, bis-secondary amines, and polyamines containing secondary and primary amines.

[0020] The bio-based polyamine is selected from one of histidine, tryptophan, lysine, arginine, cysteine, polylysine, and polyarginine.

[0021] The cationic polymer is selected from quaternary ammonium salt-substituted chitosan; the cationic polymer is covalently linked to the outer surface of the microcapsule shell by a curing agent; the mass ratio of cationic polymer to curing agent is 5:(2.5-1.5), preferably 5:2.

[0022] The curing agent is selected from aqueous glycidyl ethers such as 1,4-butanediol diglycidyl ether, 1,2-bis(ethylene oxide-2-ylmethoxy)ethane, and glycerol tri(1,2-epoxy)propyl ether.

[0023] The surface of the microcapsule material is coated with a cationic polymer, which helps the capsules deposit on surfaces such as fabrics, hair, and skin.

[0024] The microcapsule materials described above, by weight percentage of the raw materials used in preparation, contain 10-38% epoxy resin, 18-64% acrylate, 5-23% bio-based polyamine, 6-20% phenyl polyamine, and 8-12% cationic polymer.

[0025] The present invention also provides a microcapsule comprising a core material and a wall material formed therefrom, wherein the core material is encapsulated within the wall material.

[0026] Preferably, the mass ratio of the core material to the wall material is (1.4-5.6):1.

[0027] Preferably, the core material is a hydrophobic material; more preferably, the hydrophobic material comprises essential oils, deodorants, or combinations thereof.

[0028] The essential oils mentioned are selected from vanillin, phenethyl alcohol, citral, methyl dihydrojasmonate, linalool, ionone, methylhexylcinnamaldehyde, geraniol acetate, vanillin, coumarin, peach aldehyde, coconut aldehyde, musk, propyldecyl lactone, ethyl vanillin, linalool, citronellol, benzyl alcohol, carvone, benzaldehyde, benzyl acetate, cymene, dihydrocoumarin, ethoxyethyl acetate, linalool, terpineol, lavender oil, acetophenone, allyl hexanoate, 3,7-dimethyl-2,6-octadienyl hexadecanoate, ethyl furanone, anisyl acetate, benzyl benzoate, dihydrocoumarin, cyclohexyl acetate, 2-(benzoyl)octanol, 3,7-dimethyl-2,6-octadienyl oxo(phenyl)acetic acid, α-methyl-4-(1-methylethyl)phenylpropanal, (E)-3,7-dimethyl-2-phenylpropanal, etc. ,6-Octadienol, l-p-Menthene-4-ol, 4-(p-hydroxyphenyl)-2-butanone, grapefruit aldehyde, trans-2-heptenal, linalool oxide, trans-2-hexenal, cis-3-hexenyl carbamate, cis-3-hexenyl acetate, rose ether, (3-methyl-4-phenylethoxybutane-1-yl)benzene, eugenol, isoeugenol methyl ether, isopropyl methylthiazole, p-hydroxybenzyl acetone, cis-3-hexenol, lauric acid, menthol, methyl anthranilate, 2-methyl butyl acetate, 2-methyl butyrate, nerol, isopreneol, 3-hydroxy-4-methyl-5-ethyl-2(5H)-furanone, methyl sorbate, 2-ethyl-3,5-dimethylpyrazine, 2-acetyl-2-thiazoline, methylthiopropionaldehyde, furfuryl mercaptan, δ-decyl lactone, 1 4-Cyclohexanediethyl dicarboxylate, ethyl 3-methyl-3-phenylglycidyl ester, 3-hydroxy-4,5-dimethyl-2(5H)furanone, ethyl 2-trans-4-cis-decadienoate, trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexenyl)-1-butanone, maltol, (6R)-perhydro-3,6-dimethylbenzo[B]furan-2-one, α-methyl-4-(1-methylethyl)phenylpropanal, 6-pentyl-2H-tetrahydropyran-2-one, damasconone, 1-methyl-4-(1-methylethyl)-1- At least one of the following: 4-cyclohexadiene, hexyl 2-hydroxybenzoate, isobornyl acetate, 3-phenyl-2-propenol, α-ionone, 1,1-dimethoxy-2,2,5-trimethyl-4-hexane, vetiverol, 2-methyl-3-furanthiol, isobutyrate terpene ester, 3-isobutyl-2-methoxypyrazine, ethyl 2-methoxy-4-methylphenyl carbonate, rose oil, dipropylene glycol, 8-methoxycedrine, 5-methylfurfural, 8-methoxy-1-menthol, 6,5,2-methylheptenone, cedrenol, and 1-methylthiohexanol.

[0029] The method for preparing the above microcapsules includes the following steps: (1) Dissolve the emulsifier in water to prepare an aqueous phase W; (2) Mix the core material, acrylate and epoxy resin to form an oil phase O; (3) Disperse the oil phase O obtained in step (2) in the aqueous phase W to form an oil-in-water emulsion O / W; (4) Add bio-based polyamine to the oil-in-water emulsion O / W obtained in step (3) and carry out the first polymerization reaction at 30℃-60℃; (5) A second polymerization reaction was carried out at 60°C-90°C by adding phenyl polyamine to the emulsion obtained in step (4); (6) Add cationic polymer and curing agent, mix, and cure at 40℃-80℃ to obtain the microcapsule dispersion; (7) After cooling to room temperature, collect the microcapsules to obtain microcapsules.

[0030] Preferably, the mass ratio of the emulsifier to water is 1:(15-50), and the emulsifier is selected from at least one of gum arabic, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), methylcellulose or polyacrylamide; more preferably, it is polyvinyl alcohol (PVA), with a degree of alcoholysis preferably of 88% and an average molecular weight preferably of 74800 g / mol.

[0031] Compared with existing technologies, the present invention has the following advantages: This invention provides a novel microcapsule material suitable for encapsulating various hydrophobic / lipophilic oily core materials. The microcapsule material comprises an addition polymer of epoxy resin and bio-based polyamines, a poly(β-amino ester) formed from acrylates and phenyl polyamines, and at least one cationic polymer. The microcapsules prepared by this invention have a moderate size (20 μm < Dv50 < 45 μm), effectively meeting the requirements for frictional fragrance release performance in fragrance encapsulation. The microcapsules prepared by this invention significantly improve encapsulation performance, allowing the fragrance-encapsulated microcapsules to maintain excellent frictional fragrance release ability and adhesion to fabrics after 28 days of storage in washing liquid at 45°C, exhibiting excellent thermal stability. Furthermore, the microcapsule construction process does not involve toxic substances such as formaldehyde and isocyanates; simultaneously, the microcapsule shell also exhibits a certain degree of biodegradability, with a biodegradation rate exceeding 20% ​​within 28 days. In summary, the microcapsule material of this invention and the microcapsules applied thereto possess advantages in functionality, environmental friendliness, and safety of use.

[0032] Mechanism Explanation: This invention successfully constructs a novel microcapsule material based on novel addition polymers and cationic polymers by synergistically integrating an addition polymer of epoxy resin and bio-based polyamine, a poly(β-amino ester) formed by acrylate and phenyl polyamine, and a cationic polymer coated on the shell surface. Microcapsules using this material exhibit significantly improved thermal stability and triboelectric aroma release performance. Firstly, an interfacial polymerization technique was used to construct a first addition polymer of epoxy resin and bio-based polyamine, and a second addition polymer of acrylate and phenyl polyamine. The composite configuration of these two polymers not only significantly enhances the sealing and encapsulation ability of the wall material on the core material but also optimizes the brittleness of the wall material. Secondly, the cationic polymer is coated on the shell surface using covalent bonding technology, giving it better stability in washing liquids. These two improvements work together to ultimately endow the microcapsules with excellent storage / thermal stability and efficient triboelectric aroma release performance. Thirdly, the use of bio-based polyamine and acrylate gives the microcapsule shell a certain degree of biodegradability. Attached Figure Description

[0033] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 An optical microscopic image of the fragrance-encapsulated microcapsules provided in Embodiment 1 of the present invention.

[0035] Figure 2 An optical microscopic image of the fragrance-encapsulated microcapsules provided in Embodiment 9 of the present invention.

[0036] Figure 3 This is an optical microscopic image of the fragrance-encapsulated microcapsules provided in Embodiment 11 of the present invention.

[0037] Figure 4 This is an optical microscopic image of the fragrance-encapsulated microcapsules provided in Comparative Example 4 of the present invention. Detailed Implementation

[0038] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. It should be noted that the described embodiments are only a part of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of the present invention.

[0039] Table 1 lists the compound categories, names, and abbreviations of the raw materials used in the examples / comparative examples below.

[0040] Table 1. Comparison of Compound Names and Abbreviations The composition of the essential oils used in the following examples and comparative examples is shown in Table 2.

[0041] Table 2. Composition of essential oils The following examples or comparative methods for preparing microcapsules encapsulating fragrances are as follows: (1) Dissolve the emulsifier in water to prepare an aqueous phase W; (2) Epoxy resin and acrylate are dispersed in essential oil to obtain oil phase O; (3) The oil phase O obtained in step (2) is gradually added to the aqueous phase W prepared in step (1), and the oil phase is dispersed in the aqueous phase by mechanical stirring to form an oil-in-water emulsion O / W; (4) Add bio-based polyamine to the oil-in-water emulsion O / W obtained in step (3) and carry out the first polymerization reaction at 45±5℃; (5) A second polymerization reaction was carried out at 75±5°C by adding phenyl polyamine to the emulsion obtained in step (4); (6) Add cationic polymer CQAS-40 and curing agent BDDE, and cure at 60±5℃ to obtain microcapsule dispersion; (7) After cooling to room temperature, discharge the material, collect the microcapsules, and obtain microcapsules containing the fragrance.

[0042] Following the method described above, microcapsules containing fragrances as described in Examples 1-14 were prepared. In Examples 1-14, the amount of emulsifier PVA was 2.4 g, dissolved in 40 g of water to prepare aqueous phase W; the amount of fragrance oil was 20 g; the amount of cationic polymer was 0.5 g; the amount of curing agent was 0.2 g; and the ingredients of epoxy resin compound, amino acid, phenyl polyamine, and acrylate are shown in Table 3.

[0043] Table 3. Ingredients of Microcapsules Encapsulating Fragrances in Examples 1-14 Comparative Examples 1-4 The preparation methods of the microcapsules in Comparative Examples 1-4 were the same as those in Example 1, and the ingredients of epoxy resin, phenyl polyamine, amino acid, acrylate and acrylamide were as shown in Table 4. Specifically, compared with Example 1, in Comparative Example 1, acrylate and phenyl polyamine were not added to prevent the formation of addition polymers of acrylate and phenyl polyamine in the wall material; in Comparative Example 2, epoxy resin and amino acid were not added to prevent the formation of addition polymers of epoxy resin and biobased polyamine in the wall material; in Comparative Example 3, acrylate was replaced with acrylamide to form polyamide materials in the wall material; in Comparative Example 4, after adding the cationic polymer, the curing agent was not added and the curing operation was not carried out.

[0044] Table 4 Ingredient list for preparing microcapsules in Comparative Examples 1-4 Note: In Comparative Example 4, the curing agent was not added and the curing operation was not carried out.

[0045] The particle sizes of the microcapsules in the above examples and comparative examples were measured.

[0046] Test method: The particle size was measured using a Malvern Mastersizer 2000s particle size analyzer. 15 g of the samples of Examples 1-14 and Comparative Examples 1-4 were taken respectively and dispersed in 30 g of deionized water, and stirred evenly to form a suspension. The suspension was dropped into the degassed circulating water connected to the scattering cell for measurement. Dv (50) corresponded to the median of the distribution and was used as a measure of the volume average size of the microcapsules; according to the experience of those skilled in the art, when 20 μm < Dv50 < 50 μm, the microcapsule size was more suitable for the friction fragrance release function. The specific measurement results are shown in Table 5 below.

[0047] Table 5 Dv50 test results of microcapsules in Examples 1-14 and Comparative Examples 1-4 The optical microscopic image of the microcapsule encapsulating fragrance in Example 1 is as Figure 1 shown; the optical microscopic image of the microcapsule encapsulating fragrance in Example 9 is as Figure 2 shown; the optical microscopic image of the microcapsule encapsulating fragrance in Example 11 is as Figure 3 shown; the optical microscopic image of the microcapsule encapsulating fragrance in Comparative Example 4 is as Figure 4 shown.

[0048] As can be seen from Table 5, the microcapsules prepared by the present invention are within the range of 20 μm < Dv50 < 45 μm, indicating that this method is suitable for the preparation of fragrance microcapsules, especially suitable for the preparation of microcapsules with friction fragrance release performance.

[0049] The following performance tests were performed on the microcapsules of the above embodiments and comparative examples.

[0050] 1) Microcapsule frictional aroma release performance test Test Method: Take 5g of the microcapsule samples from Examples 1-14 and Comparative Examples 1-4 respectively, disperse them in 45g of deionized water, and stir until a uniform suspension is formed. Take 4g of the suspension and add it to 96g of laundry detergent base material (fragrance-only), and stir until there is no agglomeration to obtain a series of laundry detergent samples containing microcapsules. Take 10g of the laundry detergent sample and dissolve it in 2L of water. Add a towel (30cm×30cm square towel) to the solution, soak for 15 minutes, hand-wash 10 times, wring dry, rinse twice with 2L of water, and air dry naturally (for more than 6 hours). Evaluate the fragrance of the towel before and after rubbing.

[0051] The fragrance intensity was evaluated by four professional fragrance tasters, and the score ranged from 0 to 5 points. The scoring criteria are shown in Table 6 below.

[0052] Table 6. Fragrance Evaluation Criteria The fragrance release performance of microcapsules was evaluated by comparing the fragrance intensity of towels before and after rubbing. The specific evaluation results are shown in Table 7 below.

[0053] Table 7 Evaluation results of the frictional aroma release performance of the microcapsules obtained in Examples 1-14 and Comparative Examples 1-4 As shown in Table 7, the microcapsules prepared in the embodiments of the present invention exhibit excellent rubbing fragrance release performance, with fragrance scores above 3 points after rubbing with a washed towel. Comparing the results of Examples 8, 12, and 14, it was found that reducing the wall material thickness weakened the rubbing fragrance release performance. Comparing the results of Examples 1 and 7, it is indicated that the rubbing fragrance release performance tends to stabilize after the wall material thickness reaches a certain level. From the results of Comparative Examples 1 and 2, it can be seen that the lack of epoxy resin and bio-based polyamine addition polymers or poly(β-amino esters) affects the brittleness of the wall material, thus reducing the rubbing fragrance release performance of the obtained microcapsules. This indicates that the function of the microcapsule wall material requires the combined action of these two materials; reducing either one will affect the overall brittleness of the wall material, thereby affecting the rubbing fragrance release performance of the microcapsules. Comparative Example 3 shows that replacing acrylate with acrylamide does not affect its rubbing fragrance release performance, while Comparative Example 4 shows that the cationic polymer, even without curing, does not affect the rubbing fragrance release performance.

[0054] 2) Stability testing of microcapsules If microcapsules are mixed into consumer products, such as laundry detergent, and the product's function remains unchanged after a period of storage, and the microcapsules still have good fragrance release properties, then the microcapsules are considered to have good stability.

[0055] Test Method: The laundry detergent samples with microcapsules obtained above were placed at 45℃ for 28 days. 10g of each laundry detergent sample was dissolved in 2L of water. A 30cm x 30cm square towel was added to the solution, soaked for 15 minutes, hand-washed 10 times, wrung out, rinsed twice with 2L of water, and air-dried for more than 6 hours. The fragrance of the towel before and after rubbing was evaluated. The stability of the microcapsules was evaluated by comparing the fragrance intensity of the towel before and after rubbing. The specific evaluation results are shown in Table 8 below. Table 8 Evaluation Results of Friction Fragrance Release Performance of Microcapsules Obtained in Examples 1-14 and Comparative Examples 1-4 As shown in Table 8, the microcapsules of the embodiments using the technical solution of the present invention exhibited a fragrance release score of over 2.0 after being placed at 45°C for 28 days, with some (Examples 1, 2, 6, 7, 9, 11, and 13) reaching 3.0, demonstrating excellent thermal stability. Comparing Example 1 and Comparative Examples 1 and 2 in Tables 7 and 8, it was found that the lack of addition polymers of epoxy resin and bio-based polyamines or poly(β-amino esters) not only affected the frictional fragrance release performance of the microcapsules but also significantly impacted their stability in the laundry detergent. Comparing the test results of Example 1 and Comparative Example 3, it was found that replacing acrylate with acrylamide did not affect its frictional fragrance release performance and also showed good stability in the laundry detergent; while Comparative Example 4 showed that the lack of curing of the cationic polymer had a significant negative impact on its stability in the laundry detergent.

[0056] 3) Biodegradability test of microcapsule polymer shell A batch of microcapsules prepared according to Example 1 and Comparative Example 3 were provided. The microcapsule shells were opened by grinding, emptied, and washed to remove essential oils and organic solubles. The biodegradability of the obtained microcapsule shells was then tested according to OECD Method 301F (OECD Guidelines for Testing of Chemicals: Ready Biodegradability). The test results are shown in Table 9 below. After 28 days of incubation, the biodegradation percentage of the microcapsule shells obtained in Example 1 exceeded 20%, while the biodegradation percentage of the microcapsule shells obtained in Comparative Example 3 was 3%. This indicates that incorporating a portion of polyamide into the microcapsule shells leads to a significant decrease in their biodegradability. The poly(β-amino ester) formed by phenyl polyamine and acrylate exhibits superior biodegradability compared to the polyamide-amine material formed by phenyl polyamine and difunctional acrylamide.

[0057] Table 9. Biodegradability test results of the microcapsule shells obtained in Example 1 and Comparative Example 3. The above description only illustrates some specific embodiments of the present invention, but the scope of protection of the present invention is by no means limited thereto. Any person skilled in the art can easily conceive of various equivalent improvements or alternatives within the technical framework disclosed in this invention, and these improvements or alternatives should undoubtedly be included within the scope of protection of this invention. Therefore, the scope of protection of this invention should be strictly determined according to the scope defined in the appended claims.

Claims

1. A microcapsule material, characterized in that, The invention comprises an addition polymer formed by the ring-opening reaction of epoxy resin and bio-based polyamine, a poly(β-amino ester) formed by the Michael addition reaction of acrylate and phenyl polyamine, and at least one cationic polymer containing a quaternary ammonium group. The epoxy resin is a compound having at least two epoxy functional groups, and the bio-based polyamine is selected from amino acid monomers or polymers formed from amino acids having two primary amines. The acrylate is a compound containing at least two acrylate functional groups, and the phenyl polyamine is a compound containing at least one phenyl and a primary amine functional group, or a compound containing at least one phenyl and two secondary amine functional groups.

2. The microcapsule material according to claim 1, characterized in that, The epoxy resin is selected from at least one of diepoxy functional group compounds, triepoxy functional group compounds, and tetraepoxy functional group compounds.

3. The microcapsule material according to claim 2, characterized in that, The epoxy resin is selected from at least one of P-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline, N,N,N',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, resorcinol diglycidyl ether, and 2,2-bis-(4-glycoxyphenyl)propane.

4. The microcapsule material according to claim 1, characterized in that, The acrylate structure is X-(-O(C=O)-CH=CH2)n or X-(-O(C=O)-C(CH3)=CH2)n, where n ≥ 2, and X is a molecule connecting n acrylate structural units.

5. The microcapsule material according to claim 1, characterized in that, The acrylate is selected from at least one of tetraethylene glycol diacrylate, polyethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, waterborne aliphatic polyurethane acrylate, and a mixture of diurea dimethacrylate isomers.

6. The microcapsule material according to claim 1, characterized in that, The phenyl polyamine is selected from at least one of phenyl-containing primary amines, bis-primary amines and tri-primary amines, bis-secondary amines, and polyamines containing secondary and primary amines.

7. The microcapsule material according to claim 1, characterized in that, The bio-based polyamine is selected from one of histidine, tryptophan, lysine, arginine, cysteine, polylysine, or polyarginine.

8. The microcapsule material according to claim 1, characterized in that, The cationic polymer is selected from quaternary ammonium salt-substituted chitosan and is covalently linked to the outer surface of the microcapsule material by a curing agent.

9. The microcapsule material according to claim 8, characterized in that, The curing agent is selected from at least one of 1,4-butanediol diglycidyl ether, 1,2-bis(ethylene oxide-2-ylmethoxy)ethane, and glycerol tri(1,2-epoxy)propyl ether.

10. The microcapsule material according to claim 9, characterized in that, The mass ratio of the cationic polymer to the curing agent is 5:(2.5-1.5).

11. The microcapsule material according to any one of claims 1-10, characterized in that, Based on the mass percentage of the raw materials used in preparation, the content of epoxy resin is 10-38%, the content of acrylate is 18-64%, the content of bio-based polyamine is 5-23%, the content of phenyl polyamine is 6-20%, and the content of cationic polymer is 8-12%.

12. A microcapsule, characterized in that, It includes a core material and a wall material formed from the microcapsule material according to any one of claims 1-10, wherein the core material is encapsulated within the wall material.

13. The microcapsule according to claim 12, characterized in that, The core material is a fragrance oil, a deodorant, or a combination thereof.

14. A method for preparing microcapsules as described in claim 12 or 13, comprising the following steps: (1) Dissolve the emulsifier in water to prepare an aqueous phase W; (2) Mix the core material, acrylate and epoxy resin to form an oil phase O; (3) Disperse the oil phase O obtained in step (2) in the aqueous phase W to form an oil-in-water emulsion O / W; (4) Add bio-based polyamine to the oil-in-water emulsion O / W obtained in step (3) and carry out the first polymerization reaction at 30℃-60℃; (5) A second polymerization reaction was carried out at 60°C-90°C by adding phenyl polyamine to the emulsion obtained in step (4); (6) Add cationic polymer and curing agent, mix and cure at 40℃-80℃ to obtain the dispersion of the microcapsules; (7) After cooling to room temperature, collect the microcapsules to obtain microcapsules.

15. The preparation method according to claim 14, characterized in that, In step (1), the mass ratio of emulsifier to water is 1:(15-50); the emulsifier is selected from at least one of gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, and polyacrylamide.

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