Fragrant clothing synthetic leather modified by using plant active ingredients
By using microfiber non-woven fabrics and antibacterial core-shell microcapsule structures in synthetic leather, combined with nano-silica stabilizers, the decomposition and binding force of plant active ingredients in synthetic leather is solved, and the continuous antibacterial and aromatic effects are achieved, and water-resistant and ultraviolet radiation resistance is resistant.
Patent Information
- Application Number
- CN202510447246.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-10
- Publication Date
- 2025-07-18
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
During the high-temperature treatment process, the active ingredients of the plant are easily decomposed or volatile, and the interface binding force is insufficient, resulting in the antibacterial and antioxidant effects not lasting, and the active ingredients are easily degraded under light and high humidity environments, making it difficult to achieve controllable sustained release.
The microfiber non-woven substrate and antibacterial core-shell microcapsule structure are used to form a three-dimensional porous structure through a needle or hydrospinning process. Combining nanosilica stabilizer and plant essential oils, a coating layer is prepared to achieve sustained release antibacterial and aromatic effects.
Synthetic leather has continuous antibacterial properties, is resistant to water washing and UV radiation, has a high initial antibacterial rate, and remains a high antibacterial rate after water washing and UV aging, and has a long-lasting plant aroma.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of synthetic leather, and particularly relates to a scented clothing synthetic leather modified with plant active ingredients. Background Art
[0002] At present, leather products are mainly divided into two categories: natural leather and synthetic leather. Since natural leather products cannot be washed, it is easy to cause the residue of sweat and dirt, which leads to the large reproduction of microorganisms. This not only easily damages and corrodes the leather, but also seriously threatens human health. At the same time, the resources of natural leather are limited and cannot meet the large market demand. Therefore, the development of synthetic leather with excellent performance has gradually become a hot spot in market research and development.
[0003] Synthetic leather refers to a non-woven fabric as the base material. After a series of processing procedures, its structure and performance are similar to those of natural leather, and it has certain air permeability and moisture permeability. Among synthetic leather products, polyurethane synthetic leather has excellent performance and is widely loved by people. With the deepening of the consumption upgrade trend, modern consumers have put forward multi-functional composite requirements for leather products. Among them, the dual-effect leather with both hygienic protection and sensory pleasure is highly favored by the market.
[0004] Plant active ingredients are derived from natural plants, non-toxic and harmless. Polyphenols, flavonoids, saponins, etc. in plant active ingredients have the ability to destroy the cell membrane of bacteria and inhibit the reproduction of microorganisms. Compared with traditional organic antibacterial agents, plant active ingredients are not easy to produce drug resistance and have no toxic side effects. The volatile components in plant essential oils or extracts can be embedded in the microporous structure of synthetic leather and released through friction or temperature changes, enabling the synthetic leather to emit a delicate and natural fragrance. The fragrance-enhancing components often have both antioxidant or antibacterial functions. For example, rosemary extract can not only emit a herbaceous fragrance but also delay the aging of synthetic leather; citrus essential oils inhibit the growth of mold while releasing fragrance.
[0005] Since the manufacturing process of synthetic leather often involves high-temperature treatment, and most plant active ingredients are easily decomposed or volatilized, resulting in the loss of activity; and the interfacial binding force between the synthetic leather substrate and plant active ingredients is insufficient. After washing or ultraviolet irradiation, component migration or precipitation may occur. The antibacterial and antioxidant effects of polyphenols, alkaloids, etc. in plant active ingredients need to be maintained for a long time, but it is difficult to achieve controlled release in the existing technology; and environmental conditions such as light and high humidity are likely to cause the degradation of active ingredients. Summary of the Invention
[0006] Aiming at the deficiencies of the existing technology, the present invention provides a scented clothing synthetic leather modified with plant active ingredients, which has good continuous antibacterial performance, good water wash resistance and ultraviolet irradiation resistance, and has a lasting plant fragrance.
[0007] To solve the above technical problems, the technical solutions adopted by the present invention are as follows: The fragrance clothing synthetic leather modified with plant active ingredients includes a substrate, a slurry layer and a finishing layer; The substrate uses ultra-fine fiber non-woven fabric as the substrate skeleton and forms a three-dimensional porous structure through needling or hydroentangling process; The fineness of the ultra-fine fiber non-woven fabric is 0.01 - 0.05 denier; The porosity of the substrate is ≥75%;
[0008] The slurry layer includes antibacterial core-shell microcapsules; The preparation of the antibacterial core-shell microcapsules includes the following steps: preparing an antibacterial composite and in-situ polymerization and curing; The method for preparing the antibacterial composite is to mix a plant active ingredient containing phenolic hydroxyl groups with a ZnCl2 solution, adjust the pH to 5 - 6, react at 30 - 35°C for 30 - 40 min, filter, wash and dry to obtain the antibacterial composite; The mass ratio of the plant active ingredient containing phenolic hydroxyl groups to ZnCl2 is 1:0.4 - 0.5; The plant active ingredient containing phenolic hydroxyl groups is any one of menthol, curcumin and tea polyphenols; The concentration of the ZnCl2 solution is 1 - 1.5 mol / L; The method for in-situ polymerization and curing is to disperse the antibacterial composite in a block prepolymer solution, add azobisisobutyronitrile, react at 55 - 60°C for 40 - 60 min, generate a core-shell structure through interfacial polymerization, and then filter, wash and dry to obtain the antibacterial core-shell microcapsules; The solvent in the block prepolymer solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 3:1 - 1.5; The concentration of the block prepolymer solution is 15 - 25 wt%; The mass ratio of the antibacterial composite, block prepolymer and azobisisobutyronitrile is 10:80 - 120:0.6 - 1;
[0009] The preparation method of the block prepolymer is to dissolve initiator ethyl 2-bromoisobutyrate, catalyst copper chloride, complexing agent pentamethyldiethylenetriamine and methyl methacrylate in ethanol, react at 95 - 105°C for 2 - 2.5 h under a nitrogen atmosphere, then add N-isopropylacrylamide after the reaction, react at 35 - 40°C for 20 - 30 h under a nitrogen atmosphere, precipitate the obtained polymerization product in diethyl ether, wash the collected precipitate 3 - 4 times, and then evacuate at 25 - 30°C for 10 - 14 h to obtain the block prepolymer; The mass ratio of methyl methacrylate, ethyl 2-bromoisobutyrate, copper chloride, pentamethyldiethylenetriamine, N-isopropylacrylamide, and ethanol is 100:1-2:0.3-0.6:0.5-1:25-30:150-200; The preparation method of the slurry layer is as follows: blend the antibacterial core-shell microcapsules with polyurethane, immerse the substrate therein, and then use a roller to extrude to fully impregnate the inside of the microfiber leather base fabric. After scraping off the impregnating liquid on the surface, it is coagulated, washed with water, and dried to obtain the slurry layer; The mass ratio of the polyurethane to the antibacterial core-shell microcapsules is 100:2-5; The mass ratio of the polymerization product to diethyl ether is 1:10-20.
[0010] The preparation method of the finishing layer is as follows: using nano-silica as a stabilizer, homogenize the plant essential oil under high pressure of 100-120 MPa for 20-30 min to form an emulsion. Mix the emulsion with polyurethane and photoinitiator TPO, spray it onto the surface of the slurry layer, and form a microcapsule-embedded finishing layer through ultraviolet irradiation; The particle size of the nano-silica is 20-50 nm; The mass ratio of the nano-silica, plant essential oil, polyurethane, and photoinitiator TPO is 3:10-20:65-75:2-3; The plant essential oil is composed of lavender essential oil, jasmine essential oil, and tea essential oil, and the mass ratio of lavender essential oil, jasmine essential oil, and tea essential oil is 2:0.8-1.2:0.8-1.2; The wavelength of the ultraviolet irradiation is 365 nm or 395 nm, and the energy is 500-1000 mJ / cm 2 .
[0011] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) For the fragrance-type clothing synthetic leather modified with plant active ingredients in the present invention, the slurry layer slowly releases antibacterial factors through the antibacterial core-shell microcapsules, enabling the synthetic leather to have continuous antibacterial performance. During the preparation process of the antibacterial core-shell microcapsules, plant phenolic hydroxyl components (such as tea polyphenols) are used to complex with zinc ions to form a metal-phenolic acid coordination network. The zinc ions damage the integrity of the bacterial cell membrane, and the phenolic hydroxyl groups induce the release of reactive oxygen species. The synergistic effect makes the antibacterial rate greater than 95%; The shell of the antibacterial core-shell microcapsules is polymerized from block prepolymers. N-isopropylacrylamide is grafted in the block prepolymers, making the prepolymers have temperature responsiveness. The response temperature is about 32 °C, which can trigger the swelling-shrinking of the shell of the antibacterial core-shell microcapsules according to body temperature and regulate the release rate of the antibacterial agent. The hard segment of methyl methacrylate provides mechanical protection for the shell.
[0012] (2)The fragrance-type clothing synthetic leather modified with plant active ingredients of the present invention uses nano-silica in the finishing layer to stabilize the essential oil emulsion (particle size ≈ 200 - 500 nm) through the Pickering effect. The nano-silica adsorbs at the oil-water interface, and its surface hydroxyl groups are negatively charged. Through steric hindrance and electrostatic repulsion, it stabilizes the nano-emulsion formed by high-pressure homogenization of plant essential oils. Its high specific surface area can effectively encapsulate plant essential oil particles and prevent aggregation.
[0013] Silica adsorbs on the surface of plant essential oil droplets to form a core-shell structure. In the cured finishing layer, the polyurethane network structure and the silica-plant essential oil core-shell structure form a gradient release, realizing the slow-release function of plant fragrance.
[0014] (3)The fragrance-type clothing synthetic leather modified with plant active ingredients of the present invention has good continuous antibacterial performance, good water washing resistance and ultraviolet irradiation resistance. Among them, the initial antibacterial rate against Staphylococcus aureus is 99.3 - 99.6%, the antibacterial rate against Escherichia coli is 98.8 - 99.0%, and the antibacterial rate against Klebsiella pneumoniae is 95.6 - 96.2%; after washing 20 times, the antibacterial rate against Staphylococcus aureus is 86.8 - 87.5%, the antibacterial rate against Escherichia coli is 85.6 - 86.2%, and the antibacterial rate against Klebsiella pneumoniae is 86.4 - 86.7%; after ultraviolet accelerated aging, the antibacterial rate against Staphylococcus aureus is 85.2 - 86.6%, the antibacterial rate against Escherichia coli is 83.5 - 84.7%, and the antibacterial rate against Klebsiella pneumoniae is 80.4 - 81.9%.
[0015] (4)The fragrance-type clothing synthetic leather modified with plant active ingredients of the present invention has a long-lasting plant fragrance. The initial plant fragrance level is 4, and the plant fragrance level is 3 after washing 20 times. Specific Embodiments
[0016] In order to have a clearer understanding of the technical features, objectives and effects of the present invention, the specific embodiments of the present invention are now described.
[0017] Example 1 The preparation of the fragrance-type clothing synthetic leather modified with plant active ingredients includes the following steps: preparing antibacterial core-shell microcapsules, preparing a slurry layer, and preparing a finishing layer; (1)Preparing antibacterial core-shell microcapsules A. Preparing an antibacterial composite Mix menthol with a 1 mol / L ZnCl2 solution, adjust the pH to 5, react at 30 °C for 40 min, filter, wash, and dry to obtain the antibacterial composite; The mass ratio of the phenolic hydroxyl group-containing plant active ingredient to ZnCl2 is 1:0.4.
[0018] B. In-situ polymerization and curing Disperse the antibacterial composite in the block prepolymer solution, add azobisisobutyronitrile, and react at 55 °C for 60 min. A core-shell structure is formed through interfacial polymerization, and then the antibacterial core-shell microcapsules are obtained through filtration, washing, and drying. The solvent in the block prepolymer solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 3:1. The concentration of the block prepolymer solution is 15 wt%. The mass ratio of the antibacterial composite, block prepolymer, and azobisisobutyronitrile is 10:80:0.6. The preparation method of the block prepolymer is as follows: Dissolve ethyl 2-bromoisobutyrate as the initiator, copper chloride as the catalyst, pentamethyldiethylenetriamine as the complexing agent, and methyl methacrylate in ethanol, react at 95 °C for 2.5 h under a nitrogen atmosphere. After the reaction is completed, add N-isopropylacrylamide and react at 35 °C for 30 h under a nitrogen atmosphere. Precipitate the obtained polymerization product in diethyl ether, wash the collected precipitate 4 times, and then vacuum at 25 °C for 14 h to obtain the block prepolymer. The mass ratio of methyl methacrylate, ethyl 2-bromoisobutyrate, copper chloride, pentamethyldiethylenetriamine, N-isopropylacrylamide, and ethanol is 100:1:0.3:0.5:25:150. The mass ratio of the polymerization product to diethyl ether is 1:10.
[0019] (2) Prepare the slurry layer The base material uses ultra-fine fiber non-woven fabric with a fineness of 0.01 denier as the base material skeleton, and a three-dimensional porous structure is formed through a needling process. The porosity of the base material is ≥75%. Blend the antibacterial core-shell microcapsules with polyurethane, immerse the base material in it, and then use a roller to squeeze to fully impregnate the inside of the ultra-fine leather base fabric. After scraping off the impregnating liquid on the surface, obtain the slurry layer through coagulation, water washing, and drying. The mass ratio of the polyurethane and the antibacterial core-shell microcapsules is 100:2.
[0020] (3) Prepare the finishing layer Using nano-silica as a stabilizer, homogenize plant essential oil at 100 MPa for 30 min to form an emulsion. Mix the emulsion with polyurethane and photoinitiator TPO, spray it onto the surface of the slurry layer, and form a microcapsule-embedded finishing layer through ultraviolet irradiation. The particle size of the nano-silica is 20 nm. The mass ratio of the nano-silica, plant essential oil, polyurethane, and photoinitiator TPO is 3:10:65:2. The plant essential oil is composed of lavender essential oil, jasmine essential oil, and tea essential oil, and the mass ratio of lavender essential oil, jasmine essential oil, and tea essential oil is 2:0.8:0.8; The wavelength of the ultraviolet irradiation is 365 nm, and the energy is 500 mJ / cm 2 .
[0021] Example 2 The preparation of the fragrance-type clothing synthetic leather modified with plant active ingredients includes the following steps: preparing antibacterial core-shell microcapsules, preparing a slurry layer, and preparing a finishing layer; (1) Preparation of antibacterial core-shell microcapsules A. Preparation of antibacterial complex Mix curcumin with a 1.2 mol / L ZnCl2 solution, adjust the pH to 5.5, react at 32 °C for 35 min, filter, wash, and dry to obtain the antibacterial complex; The mass ratio of the phenolic hydroxyl group-containing plant active ingredient to ZnCl2 is 1:0.45.
[0022] B. In-situ polymerization and curing Disperse the antibacterial complex in the block prepolymer solution, add azobisisobutyronitrile, react at 58 °C for 50 min, generate a core-shell structure through interfacial polymerization, and then filter, wash, and dry to obtain the antibacterial core-shell microcapsules; The solvent in the block prepolymer solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 3:1.2; The concentration of the block prepolymer solution is 20 wt%; The mass ratio of the antibacterial complex, block prepolymer, and azobisisobutyronitrile is 10:100:0.8; The preparation method of the block prepolymer is to dissolve the initiator ethyl 2-bromoisobutyrate, catalyst copper chloride, complexing agent pentamethyldiethylenetriamine, and methyl methacrylate in ethanol, react at 100 °C for 2.2 h under a nitrogen atmosphere, then add N-isopropylacrylamide after the reaction is completed, react at 38 °C for 25 h under a nitrogen atmosphere, precipitate the obtained polymerization product in diethyl ether, wash the collected precipitate 3 times, and then vacuum at 28 °C for 12 h to obtain the block prepolymer; The mass ratio of methyl methacrylate, ethyl 2-bromoisobutyrate, copper chloride, pentamethyldiethylenetriamine, N-isopropylacrylamide, and ethanol is 100:1.5:0.4:0.8:28:180; The mass ratio of the polymerization product to diethyl ether is 1:15.
[0023] (2) Preparation of the slurry layer The base material uses an ultra-fine fiber non-woven fabric with a fineness of 0.02 denier as the base material skeleton, and a three-dimensional porous structure is formed through a hydrospinning process. The porosity of the base material is ≥75%; The antibacterial core-shell microcapsules are blended with polyurethane. The base material is immersed therein, and then roller extrusion is used to fully impregnate the inside of the ultra-fine leather base fabric. After scraping off the impregnating liquid on the surface, it is coagulated, washed with water, and dried to obtain a slurry layer; The mass ratio of the polyurethane to the antibacterial core-shell microcapsules is 100:3.
[0024] (3)Prepare the finishing layer Using nano-silica as a stabilizer, plant essential oil is emulsified by high-pressure homogenization at 110 MPa for 25 minutes to form an emulsion. The emulsion is mixed with polyurethane and photoinitiator TPO, and sprayed onto the surface of the slurry layer. After ultraviolet irradiation, a microcapsule-embedded finishing layer is formed; The particle size of the nano-silica is 30 nm; The mass ratio of the nano-silica, plant essential oil, polyurethane, and photoinitiator TPO is 3:15:70:2.5; The plant essential oil is composed of lavender essential oil, jasmine essential oil, and tea essential oil, and the mass ratio of lavender essential oil, jasmine essential oil, and tea essential oil is 2:1:1; The wavelength of the ultraviolet irradiation is 365 nm, and the energy is 800 mJ / cm 2 。
[0025] Example 3 The preparation of a fragrance-type clothing synthetic leather modified with plant active ingredients includes the following steps: preparing antibacterial core-shell microcapsules, preparing a slurry layer, and preparing a finishing layer; (1)Prepare antibacterial core-shell microcapsules A. Prepare an antibacterial complex Tea polyphenols are mixed with a 1.5 mol / L ZnCl2 solution, the pH is adjusted to 6, and the reaction is carried out at 35 °C for 30 minutes. After filtration, washing, and drying, an antibacterial complex is obtained; The mass ratio of the phenolic hydroxyl group-containing plant active ingredient to ZnCl2 is 1:0.5.
[0026] B. In-situ polymerization and curing The antibacterial complex is dispersed in a block prepolymer solution, azobisisobutyronitrile is added, and the reaction is carried out at 60 °C for 40 minutes. A core-shell structure is formed through interfacial polymerization, and then after filtration, washing, and drying, antibacterial core-shell microcapsules are obtained; The solvent in the block prepolymer solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 3:1.5; The concentration of the block prepolymer solution is 25 wt%; The mass ratio of the antibacterial composite, block prepolymer, and azobisisobutyronitrile is 10:120:1; The preparation method of the block prepolymer is as follows: Ethyl 2-bromoisobutyrate as the initiator, copper chloride as the catalyst, pentamethyldiethylenetriamine as the complexing agent, and methyl methacrylate are dissolved in ethanol. The reaction is carried out for 2 h at 105 °C under a nitrogen atmosphere. After the reaction is completed, N-isopropylacrylamide is added, and the reaction is carried out for 20 h at 40 °C under a nitrogen atmosphere. The obtained polymerization product is precipitated in diethyl ether, the collected precipitate is washed 3 times, and then vacuumized at 30 °C for 10 h to obtain the block prepolymer; The mass ratio of methyl methacrylate, ethyl 2-bromoisobutyrate, copper chloride, pentamethyldiethylenetriamine, N-isopropylacrylamide, and ethanol is 100:2:0.6:1:30:200; The mass ratio of the polymerization product to diethyl ether is 1:20.
[0027] (2) Preparation of the slurry layer The base material uses ultra-fine fiber non-woven fabric with a fineness of 0.05 denier as the base material skeleton, and a three-dimensional porous structure is formed through a hydrospinning process. The porosity of the base material is ≥75%; The antibacterial core-shell microcapsules are blended with polyurethane, and the base material is immersed therein. Then, it is extruded with a roller to fully impregnate the inside of the ultra-fine leather base fabric. After scraping off the impregnating liquid on the surface, it is coagulated, washed with water, and dried to obtain the slurry layer; The mass ratio of the polyurethane to the antibacterial core-shell microcapsules is 100:5.
[0028] (3) Preparation of the finishing layer Using nano-silica as a stabilizer, plant essential oil is emulsified by high-pressure homogenization at 120 MPa for 20 min to form an emulsion. The emulsion is mixed with polyurethane and photoinitiator TPO, and sprayed onto the surface of the slurry layer. After ultraviolet irradiation, a microcapsule-embedded finishing layer is formed; The particle size of the nano-silica is 50 nm; The mass ratio of the nano-silica, plant essential oil, polyurethane, and photoinitiator TPO is 3:20:75:3; The plant essential oil is composed of lavender essential oil, jasmine essential oil, and tea essential oil. The mass ratio of lavender essential oil, jasmine essential oil, and tea essential oil is 2:1.2:1.2; The wavelength of the ultraviolet irradiation is 395 nm, and the energy is 1000 mJ / cm 2 .
[0029] Example 4 The preparation of a fragrance-type clothing synthetic leather modified with plant active ingredients includes the following steps: preparation of antibacterial core-shell microcapsules, preparation of a slurry layer, and preparation of a finishing layer; (1) Preparation of antibacterial core-shell microcapsules A. Preparation of antibacterial composite Mix curcumin with 1.2 mol / L ZnCl2 solution, adjust the pH to 5.5, react at 32 °C for 35 min, filter, wash, and dry to obtain the antibacterial composite; The mass ratio of the phenolic hydroxyl group-containing plant active ingredient to ZnCl2 is 1:0.45.
[0030] B. In-situ polymerization and curing Disperse the antibacterial composite in the methyl methacrylate prepolymer solution, add azobisisobutyronitrile, react at 58 °C for 50 min, generate a core-shell structure through interfacial polymerization, and then filter, wash, and dry to obtain antibacterial core-shell microcapsules; The solvent in the methyl methacrylate prepolymer solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 3:1.2; The concentration of the methyl methacrylate prepolymer solution is 20 wt%; The mass ratio of the antibacterial composite, methyl methacrylate prepolymer, and azobisisobutyronitrile is 10:100:0.8; The number-average molecular weight of the methyl methacrylate prepolymer is 1000.
[0031] (2) Preparation of the slurry layer The substrate uses ultrafine fiber non-woven fabric with a fineness of 0.02 denier as the substrate skeleton, forms a three-dimensional porous structure through hydroentangling process, and the porosity of the substrate is ≥75%; Blend the antibacterial core-shell microcapsules with polyurethane, immerse the substrate in it, then use a roller to squeeze to fully impregnate the inside of the superfine leather base fabric, scrape off the impregnating liquid on the surface, and obtain the slurry layer after solidification, washing, and drying; The mass ratio of the polyurethane to the antibacterial core-shell microcapsules is 100:3.
[0032] (3) Preparation of the finishing layer Using nano-silica as a stabilizer, emulsify the plant essential oil at 110 MPa high-pressure homogenization for 25 min to form an emulsion, mix the emulsion with polyurethane and photoinitiator TPO, spray it onto the surface of the slurry layer, and form a microcapsule-embedded finishing layer through ultraviolet irradiation; The particle size of the nano-silica is 30 nm; The mass ratio of the nano-silica, plant essential oil, polyurethane, and photoinitiator TPO is 3:15:70:2.5; The plant essential oil is composed of a mixture of lavender essential oil, jasmine essential oil, and tea essential oil, and the mass ratio of lavender essential oil, jasmine essential oil, and tea essential oil is 2:1:1; The wavelength of the ultraviolet irradiation is 365 nm, and the energy is 800 mJ / cm 2 .
[0033] Example 5 Preparation of a fragrance-modified synthetic leather for clothing using plant active ingredients includes the following steps: preparing antibacterial core-shell microcapsules, preparing a slurry layer, and preparing a finishing layer; (1) Preparation of antibacterial core-shell microcapsules A. Preparation of an antibacterial complex Mix curcumin with a 1.2 mol / L ZnCl2 solution, adjust the pH to 5.5, react at 32 °C for 35 min, filter, wash, and dry to obtain the antibacterial complex; The mass ratio of the phenolic hydroxyl group-containing plant active ingredient to ZnCl2 is 1:0.45.
[0034] B. In-situ polymerization and curing Disperse the antibacterial complex in a block prepolymer solution, add azobisisobutyronitrile, react at 58 °C for 50 min, generate a core-shell structure through interfacial polymerization, and then filter, wash, and dry to obtain the antibacterial core-shell microcapsules; The solvent in the block prepolymer solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 3:1.2; The concentration of the block prepolymer solution is 20 wt%; The mass ratio of the antibacterial complex, block prepolymer, and azobisisobutyronitrile is 10:100:0.8; The preparation method of the block prepolymer is to dissolve the initiator ethyl 2-bromoisobutyrate, catalyst copper chloride, complexing agent pentamethyldiethylenetriamine, and methyl methacrylate in ethanol, react at 100 °C for 2.2 h under a nitrogen atmosphere, then add N-isopropylacrylamide after the reaction is completed, react at 38 °C for 25 h under a nitrogen atmosphere, precipitate the obtained polymerization product in diethyl ether, wash the collected precipitate 3 times, and then vacuum at 28 °C for 12 h to obtain the block prepolymer; The mass ratio of methyl methacrylate, ethyl 2-bromoisobutyrate, copper chloride, pentamethyldiethylenetriamine, N-isopropylacrylamide, and ethanol is 100:1.5:0.4:0.8:28:180; The mass ratio of the polymerization product to diethyl ether is 1:15.
[0035] (2) Preparation of the slurry layer The substrate uses ultrafine fiber non-woven fabric with a fineness of 0.02 denier as the substrate skeleton, forms a three-dimensional porous structure through a hydrospinning process, and the porosity of the substrate is ≥75%; Blend the antibacterial core-shell microcapsules with polyurethane, immerse the substrate in it, then use a roller to extrude to fully impregnate the inside of the ultra-fine leather base fabric, scrape off the impregnating liquid on the surface, and obtain the slurry layer after coagulation, water washing, and drying; The mass ratio of the polyurethane to the antibacterial core-shell microcapsules is 100:3.
[0036] (3) Preparation of the coating layer Emulsify the plant essential oil under high pressure homogenization at 110 MPa for 25 min to form an emulsion. Mix the emulsion with polyurethane and photoinitiator TPO, and spray it onto the surface of the slurry layer. After ultraviolet irradiation, a microcapsule-embedded coating layer is formed; The mass ratio of the plant essential oil, polyurethane, and photoinitiator TPO is 15:70:2.5; The plant essential oil is composed of a mixture of lavender essential oil, jasmine essential oil, and tea essential oil. The mass ratio of lavender essential oil, jasmine essential oil, and tea essential oil is 2:1:1; The wavelength of the ultraviolet irradiation is 365 nm, and the energy is 800 mJ / cm 2 .
[0037] Test Example 1 For the synthetic leather prepared in Examples 1-4, detect the initial antibacterial rate, the antibacterial rate after 20 times of washing, and the antibacterial rate after ultraviolet accelerated aging. The ultraviolet lamp used for ultraviolet accelerated aging is a UVA-340 lamp tube, the irradiance is 0.76 W / m², the temperature is 60 °C, and the time is 200 h. The test results are shown in Table 1.
[0038] Table 1 Antibacterial properties of synthetic leather
[0039] As can be seen from Table 1, the initial antibacterial rate of the synthetic leather prepared in Examples 1-3 reaches more than 95%. After 20 times of washing, the antibacterial rate still reaches more than 85%. After ultraviolet accelerated aging, the antibacterial rate reaches more than 80%. This shows that the synthetic leather of the present invention has persistent antibacterial properties; in Example 4, a methyl methacrylate prepolymer is used to replace the block prepolymer. Although the initial antibacterial rate of the prepared synthetic leather is relatively high, the antibacterial performance after 20 times of washing and after ultraviolet accelerated aging shows a significant decline. This shows that the antibacterial core-shell microcapsules prepared by the present invention using a specific block prepolymer can achieve slow release, have a strong structure, are resistant to washing, and can effectively resist ultraviolet radiation.
[0040] Test Example 2 For the synthetic leather prepared in Examples 1-3 and Example 5, conduct a test on the persistence of the plant fragrance. The test results are evaluated according to a 5-level system. The grading standard is as follows: Level 5: Obvious plant fragrance, perceivable at a distance of 30 cm; Level 4: Medium-strength plant fragrance, perceivable at a distance of 15 cm; Level 3: Weak smell, perceivable when close; Level 2: Very faint smell, perceivable under high temperature or friction; Level 1: Almost no fragrance, unable to be detected by sensory means. The test results are shown in Table 2.
[0041] Table 2 Fragrance persistence performance of synthetic leather
[0042] As can be seen from Table 2, the initial plant fragrance of the synthetic leather prepared in Examples 1-3 is Grade 4, and the plant fragrance can still reach Grade 3 after 20 times of washing, and the plant fragrance can be released persistently; in Example 5, nano-silica was omitted in the preparation of the finishing layer, and the initial plant fragrance was relatively strong, but the plant fragrance was only Grade 2 after 20 times of washing, and the plant fragrance could not be maintained persistently; it shows that the nano-silica added in the preparation process of the finishing layer can reduce the release rate of the plant fragrance and increase the persistence of the plant fragrance.
[0043] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. A fragrance-impregnated synthetic leather for clothing modified with plant active ingredients, characterized in that, The synthetic leather comprises a base material, a slurry layer and a finishing layer; The slurry layer comprises antibacterial core-shell microcapsules; The preparation of the antibacterial core-shell microcapsules comprises the following steps: preparing an antibacterial composite and in-situ polymerization and curing; The method of in-situ polymerization and curing is to disperse the antibacterial composite in a block prepolymer solution, add azobisisobutyronitrile, react at 55-60 °C for 40-60 min, generate a core-shell structure through interfacial polymerization, and then obtain the antibacterial core-shell microcapsules through filtration, washing and drying; The preparation method of the block prepolymer is to dissolve the initiator ethyl 2-bromoisobutyrate, the catalyst copper chloride, the complexing agent pentamethyldiethylenetriamine and methyl methacrylate in ethanol, react at 95-105 °C for 2-2.5 h under a nitrogen atmosphere, add N-isopropylacrylamide after the reaction is completed, react at 35-40 °C for 20-30 h under a nitrogen atmosphere, precipitate the obtained polymerization product in ether, wash the collected precipitate 3-4 times, and then vacuumize at 25-30 °C for 10-14 h to obtain the block prepolymer.
2. The fragrance-type clothing synthetic leather modified with plant active ingredients according to claim 1, characterized in that In the step of in-situ polymerization and curing, The solvent in the block prepolymer solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 3:1-1.5; The concentration of the block prepolymer solution is 15-25 wt%; The mass ratio of the antibacterial composite, the block prepolymer and azobisisobutyronitrile is 10:80-120:0.6-1.
3. The fragrance-type clothing synthetic leather modified with plant active ingredients according to claim 1, characterized in that, In the preparation step of the block prepolymer, the mass ratio of methyl methacrylate, ethyl 2-bromoisobutyrate, copper chloride, pentamethyldiethylenetriamine, N-isopropylacrylamide and ethanol is 100:1-2:0.3-0.6:0.5-1:25-30:150-200.
4. The scented clothing synthetic leather modified with plant active ingredients according to claim 1, characterized in that, The method for preparing the antibacterial composite is to mix a plant active ingredient containing a phenolic hydroxyl group with a ZnCl2 solution, adjust the pH to 5-6, react at 30-35 °C for 30-40 min, and obtain the antibacterial composite through filtration, washing and drying.
5. The fragrance-impregnated garment synthetic leather modified with plant active ingredients according to claim 4, characterized in that, In the step of preparing the antibacterial composite, The mass ratio of the plant active ingredient containing a phenolic hydroxyl group to ZnCl2 is 1:0.4-0.5; The plant active ingredient containing a phenolic hydroxyl group is any one of menthol, curcumin and tea polyphenols; The concentration of the ZnCl2 solution is 1-1.5 mol / L.
6. The fragrance-type clothing synthetic leather modified with plant active ingredients according to claim 1, wherein, The preparation method of the slurry layer is to blend the antibacterial core-shell microcapsules with polyurethane, immerse the base material therein, then use a roller to extrude so that the inside of the microfiber leather base fabric is fully impregnated, scrape off the impregnating liquid on the surface, and obtain the slurry layer through coagulation, water washing and drying; The mass ratio of the polyurethane to the antibacterial core-shell microcapsules is 100:2-5.
7. The fragrance-type clothing synthetic leather modified with plant active ingredients according to claim 1, characterized in that, The base material uses ultra-fine fiber non-woven fabric as the base material skeleton and forms a three-dimensional porous structure through needling or hydroentangling process.
8. The scented clothing synthetic leather modified with plant active ingredients according to claim 1, characterized in that, The preparation method of the finishing layer is to use nano-silica as a stabilizer, emulsify plant essential oil at 100-120 MPa by high-pressure homogenization for 20-30 min to form an emulsion, mix the emulsion with polyurethane and photoinitiator TPO, spray it onto the surface of the slurry layer, and form a microcapsule-embedded finishing layer through ultraviolet irradiation.
9. The scented garment synthetic leather modified with plant active ingredients according to claim 8, characterized in that, In the preparation steps of the finishing layer, the mass ratio of nano-silica, plant essential oil, polyurethane and photoinitiator TPO is 3: 10-20: 65-75: 2-3.
10. The fragrant clothing synthetic leather modified with plant active ingredients according to claim 1, characterized in that, In the preparation steps of the finishing layer, The plant essential oil is composed of lavender essential oil, jasmine essential oil and tea essential oil, and the mass ratio of lavender essential oil, jasmine essential oil and tea essential oil is 2: 0.8-1.2: 0.8-1.2; The particle size of the nano-silica is 20-50 nm; The wavelength of the ultraviolet irradiation is 365 nm or 395 nm, and the energy is 500 - 1000 mJ / cm 2 .