A modification method for improving the heat storage property of down

Abstract

The invention relates to a modification treatment method for improving the heat storage property of down, and belongs to the technical field of feather treatment. The method of the invention uses down as raw material, designs enzyme treatment to provide a surface activation basis for the down, constructs down micropores through ultrasonic activation, enhances the mechanical properties of the down through cross-linking, adopts composite coating materials to improve the thermal insulation performance and partial hydrophobicity, then adds hydrophobic treatment to further improve the durability, and finally adopts gradient curing to lock the structure; special modification components are designed in each step to match reasonable treatment parameters, so that the prepared modified down has excellent use performance, and the method is simple and easy to implement.

Description

Technical Field

[0001] The invention belongs to the technical field of feather processing, and in particular relates to a modification processing method for improving the heat storage property of down. Background Art

[0002] In the cold winter, down jackets are important equipment for people to resist the severe cold. Its thermal insulation performance mainly depends on the down filling it. The unique structure of down can store a large amount of still air, prevent heat loss, and play a good role in heat insulation and warmth. However, with the improvement of people's living standards and the diversification of outdoor warmth needs, the thermal storage performance of traditional down is gradually difficult to fully meet the requirements, which has prompted researchers and related companies to explore the modification of down to improve its thermal storage performance.

[0003] From the perspective of market demand, the rise of outdoor sports has made people more demanding on the performance of warm clothing. In outdoor activities such as skiing, mountaineering, and hiking, people are exposed to cold environments for a long time, and the warmth-keeping ability of ordinary down jackets is slightly insufficient under extreme conditions. At the same time, consumers also expect down jackets for daily wear to provide more lasting and efficient warmth in scenarios such as low-temperature commuting and long-term outdoor activities. The market is in urgent need of down jackets with better heat storage. From the perspective of technical development, existing down filling materials have certain limitations. Although down itself has a good foundation for warmth, it is limited by its natural characteristics. After humidity changes and long-term use, its fluffiness is easy to decrease, which in turn affects the heat storage performance. When a down jacket is wet, the down will clump, the air storage capacity will decrease, the warmth-keeping effect will be greatly reduced, and it will be difficult to fully restore the original fluffiness after drying. In order to overcome these problems, modifying the down has become an inevitable trend in the improvement of down product technology.

[0004] In recent years, the rapid development of materials science has provided technical support for down modification. The existing modification methods mainly include: (1) Physical modification: mechanically treating down to produce microstructural changes such as microcracks, increase specific surface area, improve the adsorption performance of down, etc., which helps to improve heat storage. Plasma treatment can improve its surface properties and enhance the bonding force between fibers without changing the main components of down, making down less likely to clump during long-term use and maintaining good fluffiness, thereby improving heat storage. (2) Chemical modification: chemical reagents are used to react with down fibers for modification. Specific functional groups are introduced on the surface of down fibers to enhance the water repellency of down and reduce the problem of decreased thermal insulation performance due to moisture. (3) Biological modification: biological enzymes are used to treat down. Different biological enzymes can selectively act on specific components on the surface of down fibers to remove impurities and make the down fibers purer. (4) Surface coating modification: Through nano-coating technology, a layer of nano-material with special functions is covered on the surface of down fibers, which can enhance the water repellency of down and reduce the problem of decreased thermal insulation performance caused by moisture. At the same time, it can also improve the strength of down fibers, so that they can better maintain their fluffiness during long-term use, thereby improving heat storage.

[0005] However, the performance of feathers obtained by various treatment methods varies, and there are still common problems such as poor durability and reduced heat storage after long-term use. The modification effect of some modified down is greatly weakened after multiple washings or long-term use. Although various modification methods can improve the heat storage and other properties of down to a certain extent, it is still difficult to achieve a breakthrough and substantial improvement, and it is still difficult to meet the warmth requirements of some low-temperature scenes.

[0006] Therefore, it is necessary to continuously develop and advance the modification and processing technology of down to further improve the heat storage capacity, meet consumers' demand for high-quality warm clothing, and bring warmer, more comfortable and high-performance down jacket products. Summary of the invention

[0007] Aiming at the problems of insufficient heat storage capacity of existing down materials, poor durability after modification, and decreased heat storage capacity after long-term use. The present invention provides a modification treatment method for improving the heat storage capacity of down, which designs enzyme treatment to provide a basis for surface activation, ultrasonic activation to construct micropores, cross-linking to enhance mechanical properties, composite coating to improve thermal insulation, hydrophobic treatment to ensure durability, and gradient solidification to lock the structure. The modified components and treatment parameters are designed in each step to match each other. The prepared modified down has excellent performance and can effectively improve the problems of insufficient heat storage capacity and poor durability of down. The specific technical scheme is as follows:

[0008] A modification method for improving the heat storage property of down comprises the following steps:

[0009] S1, enzyme treatment: ultrasonic enzymolysis of the down with biological enzyme solution to remove grease on the surface of the down, and to etch the surface of the down to improve the surface defects of the down; rinsing, centrifugal dehydration, to obtain etched down;

[0010] The biological enzyme solution contains lipase, papain, subtilisin and keratinase;

[0011] S2, activation: ultrasonically activate the etched down using an activation solution to generate a uniform microporous structure; rinse and centrifuge to obtain activated down;

[0012] The activation solution contains tea saponin and cocamidopropyl betaine, and the solvents are water and ethanol;

[0013] S3, cross-linking and strengthening: Use treatment liquid to oscillate the activated down to build a cross-linking structure, improve mechanical strength and washing resistance; filter and dehydrate, solidify, and obtain reinforced down;

[0014] The treatment liquid contains 2.5wt% to 3.0wt% of 3-aminopropyltriethoxysilane (APTES), 1.5wt% to 2.0wt% of polyethyleneimine (PEI), 0.5wt% to 0.8wt% of genipin, 0.1wt% to 0.2wt% of vitamin E, and the remaining solvent is a phosphate buffer solution with a pH value of 6.0 to 6.5;

[0015] S4, coating: spraying the coating liquid on the surface of the reinforced down, and drying with air blast to obtain coated down;

[0016] The coating liquid includes the following raw materials in parts by weight: 100 to 120 parts of deionized water, 20 to 30 parts of ethanol, 5 to 8 parts of bamboo charcoal powder, 4 to 6 parts of silica aerogel, 2 to 4 parts of polypropyl silsesquioxane, 2 to 4 parts of polyurethane, 0.1 to 0.15 parts of silane coupling agent, 0.1 to 0.3 parts of cocamidopropyl betaine and 0.1 to 0.3 parts of 2,6-di-tert-butyl-p-cresol;

[0017] S5, hydrophobic treatment: using a hydrophobic agent to perform surface hydrophobic treatment on the coated down by spraying, and air drying to obtain hydrophobic down;

[0018] S6, gradient curing: hot air treatment at 80℃~85℃ for 40min~60min to promote cross-linking, UV curing for 5min~10min to complete down modification.

[0019] In S1 of the above method, the mass ratio of the components of the biological enzyme solution is water: lipase: papain: subtilisin: keratin = (100-120): (0.1-0.15): (0.005-0.01): (0.001-0.003): (0.0005-0.001), and the pH value is 7.0-8.0; the bath ratio of down and biological enzyme solution is 1kg / 50L-1kg / 60L.

[0020] In S1 of the above method, the ultrasonic power is 30W-50W, the ultrasonic frequency is 20kHz-25kHz; the enzymatic hydrolysis temperature is 40℃-50℃, and the enzymatic hydrolysis time is 80min-100min; and the rinsing is performed 3-4 times with deionized water at 80℃-85℃.

[0021] In S2 of the above method, the mass ratio of the components of the activation solution is water: ethanol: tea saponin: cocamidopropyl betaine = (100-120): (20-30): (0.3-0.5): (0.3-0.5); the bath ratio of the etched down and the activation solution is 1kg / 70L-1kg / 80L.

[0022] In S2 of the above method, the frequency of ultrasound is 70kHz to 80kHz, and the power density is 1.8W / cm 2 ~2.0W / cm 2 ; The activation temperature is 30℃~35℃, and the activation time is 40min~60min; rinsing is carried out 3 to 4 times with deionized water at 80℃~85℃.

[0023] In S3 of the above method, the bath ratio of activated down and treatment liquid is 1kg / 25L~1kg / 30L; the amplitude of oscillation is 12mm~18mm, and the frequency of oscillation is 100 times / min~120 times / min; the temperature of oscillation treatment is 50℃~55℃, and the time of oscillation treatment is 120min~150min; curing is hot air curing at 80℃~85℃ for 30min~50min to form a Si-O-Si and amide bond cross-linking network.

[0024] In S4 of the above method, the bamboo charcoal powder is a nano-scale powder; the silica aerogel is a nano-scale powder; the silane coupling agent is KH-570; the mass ratio of the spray is, reinforced down: coating liquid = 1: (1.5-2); the blast drying temperature is 50°C-60°C, and the blast drying time is 1h-2h.

[0025] In S5 of the above method, the hydrophobic agent includes the following raw materials in parts by weight: 50 to 55 parts of methyltrimethoxysilane, 20 to 25 parts of ethanol, 25 to 30 parts of deionized water, and 0.1 to 0.3 parts of acetic acid (to promote hydrolysis and condensation reaction).

[0026] In S5 of the above method, the spray mass ratio is, coated down: hydrophobic agent = 1: (1 to 1.5); the blast drying temperature is 50° C. to 60° C., and the blast drying time is 1 h to 2 h.

[0027] In S6 of the above method, the parameters of UV curing are: wavelength 254nm, intensity 80mW / cm 2 .

[0028] The present invention provides a modification method for improving the heat storage property of down, and the beneficial effects are as follows:

[0029] 1. Enzyme treatment can effectively remove grease from the surface of down, etch the surface of down, and significantly increase the degree of surface defects of down. The enzyme dosage and treatment parameter design will not lead to excessive etching, which will significantly reduce the strength of down. During the enzymatic hydrolysis process, lipase specifically targets the grease components on the surface of down, and decomposes the grease into glycerol and fatty acids through enzymatic reaction, thereby achieving the purpose of removing grease, making the down cleaner, and reducing the adverse effects of grease on the performance of down. Papain, subtilisin and keratinase act on the protein structure on the surface of down. Under the synergy of ultrasound, the cavitation effect generated by ultrasound can enhance the contact and reaction efficiency between the enzyme and the surface of down, so that these enzymes can etch the surface of down more effectively and increase the specific surface area of ​​down. Controlling reasonable treatment parameters will not lead to excessive etching. Reasonable increase in specific surface area means that down can be better combined with various reagents and materials in subsequent treatments, laying the foundation for improving the adsorption performance and heat storage performance of down.

[0030] 2. Activation can promote the formation of uniform microporous structure of down, improve the fluffiness, air permeability and adsorption capacity of subsequent treatment liquid. During the ultrasonic activation process, reasonable ultrasonic parameter vibration acts on the down and activation liquid system. On the one hand, tea saponin and cocamidopropyl betaine in the activation liquid act as surfactants, reducing the surface tension between the down and the activation liquid, so that the down can be more fully in contact with the activation liquid; on the other hand, the mechanical vibration of ultrasound causes the internal structure of the down fiber to change, resulting in a uniform microporous structure. Ethanol as a solvent not only helps tea saponin and cocamidopropyl betaine and other ingredients to be evenly dispersed, but also penetrates into the interior of the down fiber to assist in the formation of a microporous structure, thereby improving the fluffiness and air permeability of the down, and enhancing the ability of the down to store still air, thereby improving the warmth performance, and is also conducive to the adsorption and reaction of the subsequent treatment liquid.

[0031] 3. The cross-linking enhancement step successfully constructs a cross-linking structure, greatly improving the mechanical strength and washing resistance of the down, and ensuring stable performance during long-term use. During the oscillation process, the ethoxy groups in 3-aminopropyltriethoxysilane (APTES) are hydrolyzed under certain conditions to generate silanol groups, which can condense with each other to form Si-O-Si bonds, and react with groups such as hydroxyl groups on the surface of the down to connect the down fibers. Polyethyleneimine (PEI) contains a large number of amino groups, and genipin contains multiple active groups, which can react with each other to form cross-linked structures such as amide bonds. Vitamin E plays an antioxidant role to prevent performance degradation due to oxidation during the treatment process. Through these cross-linking reactions, a stable network structure is formed between the down fibers, which greatly improves the mechanical strength of the down. During multiple washings and long-term use, the structure is not easily destroyed, and can maintain good fluffiness and heat storage performance.

[0032] 4. Coating treatment can significantly improve the heat storage, thermal insulation and comprehensive performance of down, giving down some new characteristics. Bamboo charcoal powder is a nano-scale powder with rich pore structure and certain adsorption performance. It can absorb heat in the environment and store it. At the same time, it has a certain far-infrared radiation function to promote heat accumulation. Silica aerogel is also a nano-scale powder. It is a highly efficient thermal insulation material with extremely low thermal conductivity. It can effectively prevent heat loss and greatly improve the thermal insulation performance of down. Polypropylsilsesquioxane, polyurethane and other substances form a continuous coating layer on the surface of down, which enhances the bonding force between down fibers and improves the surface performance and overall stability of down. Silane coupling agent KH-570 can better combine inorganic materials such as bamboo charcoal powder and silica aerogel with organic materials such as polypropyl silsesquioxane and polyurethane. Cocamidopropyl betaine, as a surfactant, helps to evenly disperse the ingredients. 2,6-di-tert-butyl-p-cresol has an antioxidant effect and protects the performance of the coating material. These ingredients work together to significantly improve the heat storage and overall performance of down.

[0033] 5. Hydrophobic treatment can form a hydrophobic layer on the surface of down, effectively reduce moisture adsorption, prevent down from agglomerating due to moisture, and maintain good thermal insulation performance. Methyltrimethoxysilane undergoes hydrolysis and condensation reaction under the catalysis of acetic acid, and its methoxyl group is hydrolyzed to generate silanol groups. The silanol groups condense with each other to form a siloxane network structure with hydrophobic properties and adhere to the surface of down. Ethanol and deionized water are used as solvents to make methyltrimethoxysilane evenly dispersed and fully contact with down. This hydrophobic layer can prevent direct contact between water and down. When the down encounters a humid environment, water cannot penetrate into the inside of the down, thereby avoiding the agglomeration of the down due to moisture, ensuring the ability of the down to store still air, and maintaining good thermal insulation performance.

[0034] 6. Gradient curing In order to further promote the cross-linking reaction, the modification effect of the down is more stable, the structure is more solid, and the comprehensive performance and durability of the down are significantly improved. Hot air treatment can provide sufficient energy for the cross-linking reaction, promote the further reaction of the cross-linking bonds of 3-aminopropyltriethoxysilane (APTES), polyethyleneimine (PEI) and other cross-linking bonds that have not been completely reacted in the previous steps, and make the cross-linking network more perfect. In UV curing, ultraviolet rays can excite some photosensitive groups and trigger some free radical reactions, further promoting the cross-linking reaction, making the internal structure of the down more stable, thereby improving the comprehensive performance and durability of the down, and ensuring that the modification effect will not be easily weakened during long-term use.

[0035] In summary, the method of the present invention uses down as raw material, designs enzyme treatment to provide a surface activation basis for the down, ultrasonic activation constructs down micropores, cross-links the mechanical properties of the down, uses composite coating materials to improve thermal insulation and partial hydrophobicity, and then adds hydrophobic treatment to further improve durability, and finally uses gradient curing to lock the structure; each step designs a special modified component that is coordinated with reasonable processing parameters, and the prepared modified down has excellent performance, the method is simple and easy, and has good practical value. DETAILED DESCRIPTION

[0036] The present invention is further described below in conjunction with specific implementation cases, but the present invention is not limited to these embodiments.

[0037] Embodiment 1: A modification method for improving the heat storage property of down, comprising the following steps:

[0038] S1, enzyme treatment: the bath ratio of down to biological enzyme solution is 1kg / 55L, and the biological enzyme solution is used to perform ultrasonic enzymolysis on the down, the ultrasonic power is 40W, the ultrasonic frequency is 22kHz, the enzymolysis temperature is 45℃, and the enzymolysis time is 90min, so as to remove the grease on the surface of the down and etch the surface of the down to improve the surface defects of the down; the down is rinsed with 82℃ deionized water for 3 times, and centrifuged for dehydration to obtain the etched down;

[0039] The mass ratio of the components of the biological enzyme solution is water: lipase: papain: subtilisin: keratinase = 110: 0.12: 0.008: 0.002: 0.0008, and the pH value is 7.5;

[0040] S2, Activation: The bath ratio of etched down and activation solution is 1kg / 75L, and the etched down is ultrasonically activated with the activation solution. The frequency of the ultrasound is 75kHz and the power density is 1.9W / cm 2 ; The activation temperature is 32°C, the activation time is 50 minutes, and a uniform microporous structure is generated; the down is rinsed three times with deionized water at 82°C, and centrifuged for dehydration to obtain activated down;

[0041] The mass ratio of the components of the activation solution is water: ethanol: tea saponin: cocamidopropyl betaine = 110:25:0.4:0.4;

[0042] S3, cross-linking reinforcement: the activated down was subjected to oscillation treatment with the treatment liquid at a bath ratio of 1kg / 28L, the amplitude of the oscillation was 15mm, the frequency of the oscillation was 110 times / min; the temperature of the oscillation treatment was 52°C, the oscillation treatment time was 130min, a cross-linking structure was constructed, the mechanical strength and washing resistance were improved; the down was filtered and dehydrated, and the down was cured with hot air at 83°C for 40min to form a Si-O-Si and amide bond cross-linking network to obtain reinforced down;

[0043] The treatment solution contains 2.8 wt% 3-aminopropyltriethoxysilane (APTES), 1.8 wt% polyethyleneimine (PEI), 0.65 wt% genipin, 0.15 wt% vitamin E, and the remaining solvent is a phosphate buffer solution with a pH value of 6.3;

[0044] S4, coating: the coating liquid is sprayed on the surface of the reinforced down in a mass ratio of reinforced down: coating liquid = 1:1.8, and then dried with forced air at 55°C for 1.5h to obtain coated down;

[0045] The coating liquid includes the following raw materials in parts by mass: 110 parts of deionized water, 25 parts of ethanol, 6.5 parts of bamboo charcoal powder, 5 parts of silica aerogel, 3 parts of polypropyl silsesquioxane, 3 parts of polyurethane, 0.12 parts of silane coupling agent KH-570, 0.2 parts of cocamidopropyl betaine and 0.2 parts of 2,6-di-tert-butyl-p-cresol; the bamboo charcoal powder is a nano-scale powder; the silica aerogel is a nano-scale powder;

[0046] S5, hydrophobic treatment: spray the coated down with the hydrophobic agent at a spray mass ratio of 1:1.3, and dry with forced air at 55°C for 1.5h to obtain hydrophobic down;

[0047] The hydrophobic agent includes the following raw materials in parts by weight: 52 parts of methyltrimethoxysilane, 23 parts of ethanol, 28 parts of deionized water and 0.2 parts of acetic acid (to promote hydrolysis and condensation reaction).

[0048] S6, gradient curing: 82℃ hot air treatment for 50min to promote crosslinking, wavelength 254nm, intensity 80mW / cm 2 UV curing for 8 minutes under the conditions completed the down modification.

[0049] Embodiment 2: A modification method for improving the heat storage property of down, comprising the following steps:

[0050] S1, enzyme treatment: the bath ratio of down to biological enzyme solution is 1kg / 50L, and the biological enzyme solution is used to perform ultrasonic enzymolysis on the down, the ultrasonic power is 30W, the ultrasonic frequency is 20kHz, the enzymolysis temperature is 40℃, and the enzymolysis time is 80min, so as to remove the grease on the surface of the down and etch the surface of the down to improve the surface defects of the down; the down is rinsed with 80℃ deionized water for 3 times, and centrifuged for dehydration to obtain the etched down;

[0051] The mass ratio of the components of the biological enzyme solution is water: lipase: papain: subtilisin: keratinase = 100: 0.1: 0.005: 0.001: 0.0005, and the pH value is 7.0;

[0052] S2, activation: the bath ratio of etched down and activation solution is 1kg / 70L, and the etched down is ultrasonically activated with the activation solution. The frequency of the ultrasound is 70kHz and the power density is 1.8W / cm 2 ; The activation temperature is 30°C, the activation time is 40 minutes, and a uniform microporous structure is generated; the down is rinsed three times with deionized water at 80°C, and centrifuged for dehydration to obtain activated down;

[0053] The mass ratio of the components of the activation solution is water: ethanol: tea saponin: cocamidopropyl betaine = 100:20:0.3:0.3;

[0054] S3, cross-linking reinforcement: the activated down was subjected to oscillation treatment with the treatment liquid at a bath ratio of 1kg / 25L, the amplitude of the oscillation was 12mm, the frequency of the oscillation was 100 times / min; the oscillation temperature was 50°C, the oscillation time was 120min, a cross-linking structure was constructed, the mechanical strength and washing resistance were improved; the down was filtered and dehydrated, and hot air cured at 80°C for 30min to form a Si-O-Si and amide bond cross-linking network to obtain reinforced down;

[0055] The treatment solution contains 2.5 wt% 3-aminopropyltriethoxysilane (APTES), 1.5 wt% polyethyleneimine (PEI), 0.5 wt% genipin, 0.1 wt% vitamin E, and the remaining solvent is a phosphate buffer solution with a pH value of 6.0;

[0056] S4, coating: spray the coating liquid on the surface of the reinforced down in a mass ratio of reinforced down: coating liquid = 1:1.5, and dry with air at 50°C for 1h to obtain coated down;

[0057] The coating liquid includes the following raw materials in parts by mass: 100 parts of deionized water, 20 parts of ethanol, 5 parts of bamboo charcoal powder, 4 parts of silica aerogel, 2 parts of polypropyl silsesquioxane, 2 parts of polyurethane, 0.1 parts of silane coupling agent KH-570, 0.1 parts of cocamidopropyl betaine and 0.1 parts of 2,6-di-tert-butyl-p-cresol; the bamboo charcoal powder is a nano-scale powder; the silica aerogel is a nano-scale powder;

[0058] S5, hydrophobic treatment: spray the coated down with the hydrophobic agent in a spraying mass ratio of coated down to hydrophobic agent = 1:1, and dry with forced air at 50° C. for 1 h to obtain hydrophobic down;

[0059] The hydrophobic agent includes the following raw materials in parts by weight: 50 parts of methyltrimethoxysilane, 20 parts of ethanol, 25 parts of deionized water and 0.1 parts of acetic acid (to promote hydrolysis and condensation reaction).

[0060] S6, gradient curing: 80℃ hot air treatment for 40min to promote crosslinking, at a wavelength of 254nm and an intensity of 80mW / cm 2 UV curing for 5 minutes under the conditions to complete the down modification.

[0061] Embodiment 3: A modification method for improving the heat storage property of down, comprising the following steps:

[0062] S1, enzyme treatment: the bath ratio of down to biological enzyme solution is 1kg / 60L, and the biological enzyme solution is used to perform ultrasonic enzymolysis on the down, the ultrasonic power is 50W, the ultrasonic frequency is 25kHz, the enzymolysis temperature is 50℃, and the enzymolysis time is 100min, so as to remove the grease on the surface of the down, etch the surface of the down, and improve the surface defects of the down; rinse with 85℃ deionized water for 4 times, centrifuge and dehydrate to obtain etched down;

[0063] The mass ratio of the components of the biological enzyme solution is water: lipase: papain: subtilisin: keratinase = 120: 0.15: 0.01: 0.003: 0.001, and the pH value is 8.0;

[0064] S2, activation: the bath ratio of etched down and activation solution is 1kg / 80L, and the etched down is ultrasonically activated with the activation solution, the frequency of the ultrasound is 80kHz, and the power density is 2.0W / cm 2 ; The activation temperature is 35°C, the activation time is 60 minutes, and a uniform microporous structure is generated; the down is rinsed 4 times with deionized water at 85°C, and centrifuged to obtain activated down;

[0065] The mass ratio of the components of the activation solution is water: ethanol: tea saponin: cocamidopropyl betaine = 120:30:0.5:0.5;

[0066] S3, cross-linking reinforcement: the activated down was subjected to oscillation treatment with the treatment liquid at a bath ratio of 1kg / 30L, the amplitude of the oscillation was 18mm, the frequency of the oscillation was 120 times / min; the oscillation temperature was 55°C, the oscillation time was 150min, a cross-linking structure was constructed, the mechanical strength and washing resistance were improved; the down was filtered and dehydrated, and the down was cured with hot air at 85°C for 50min to form a Si-O-Si and amide bond cross-linking network to obtain reinforced down;

[0067] The treatment solution contains 3.0 wt% 3-aminopropyltriethoxysilane (APTES), 2.0 wt% polyethyleneimine (PEI), 0.8 wt% genipin, 0.2 wt% vitamin E, and the remaining solvent is a phosphate buffer solution with a pH value of 6.5;

[0068] S4, coating: spray the coating liquid on the surface of the reinforced down in a mass ratio of reinforced down: coating liquid = 1:2, and dry with forced air at 60°C for 2h to obtain coated down;

[0069] The coating liquid includes the following raw materials in parts by mass: 120 parts of deionized water, 30 parts of ethanol, 8 parts of bamboo charcoal powder, 6 parts of silica aerogel, 4 parts of polypropyl silsesquioxane, 4 parts of polyurethane, 0.15 parts of silane coupling agent KH-570, 0.3 parts of cocamidopropyl betaine and 0.3 parts of 2,6-di-tert-butyl-p-cresol; the bamboo charcoal powder is a nano-scale powder; the silica aerogel is a nano-scale powder;

[0070] S5, hydrophobic treatment: spray the coated down with the hydrophobic agent at a spray mass ratio of 1:1.5, and dry with forced air at 60°C for 2h to obtain hydrophobic down;

[0071] The hydrophobic agent includes the following raw materials in parts by weight: 55 parts of methyltrimethoxysilane, 25 parts of ethanol, 30 parts of deionized water and 0.3 parts of acetic acid (to promote hydrolysis and condensation reaction).

[0072] S6, gradient curing: 85℃ hot air treatment for 60min to promote crosslinking, wavelength 254nm, intensity 80mW / cm 2 UV curing for 10 minutes under the conditions completed the down modification.

[0073] In the above embodiments: goose down is selected as the raw material of down. The enzyme activity of lipase is 100,000 U / g, which is sourced from Jiangsu Baifeng Biotechnology Co., Ltd. The enzyme activity of papain is 100,000 U / g, which is sourced from Shandong Xinghongsheng Biotechnology Co., Ltd. The enzyme activity of subtilisin is 40,000 U / g, which is sourced from Shaanxi Yunhe Biotechnology Co., Ltd. The enzyme activity of keratinase is 200,000 U / g, which is sourced from Weifang Ruichen Biotechnology Co., Ltd. Tea saponin is sourced from Shaanxi Haibo Biotechnology Co., Ltd., with a purity of 90%. Cocoamidopropyl betaine is sourced from Guangzhou Zhengjia Chemical Co., Ltd., model CAB-35. 3-Aminopropyl triethoxysilane (APTES) is KH-550, which is sourced from Dongguan Kangjin New Materials Technology Co., Ltd. Polyethyleneimine (PEI) is sourced from Shanghai Aoji Chemical Co., Ltd., model 8365. Genipin is sourced from Shanxi Qixin Biotechnology Co., Ltd., with a purity of 98%. Vitamin E is sourced from Shaanxi Linzhou Biotechnology Co., Ltd. Silica aerogel is sourced from Lingshou County Jinyuan Mining Processing Plant, nanometer level. Polypropylsilsesquioxane comes from Shanghai Ke New Material Technology Co., Ltd. Polyurethane comes from Yantai Caihua Polyurethane Technology Co., Ltd., brand shp105, density 20g / cm 3 Silane coupling agent KH-570 was sourced from Dongguan Shanyi Plastic Chemical Co., Ltd. 2,6-di-tert-butyl-p-cresol was sourced from Jinan Jinbang Environmental Protection Technology Co., Ltd., model 264T501. Methyltrimethoxysilane was sourced from Jinan Yunuo Chemical Co., Ltd.

[0074] Comparative Example 1

[0075] The S1 enzyme treatment step was omitted; other parameters and methods were the same as in Example 1.

[0076] Comparative Example 2

[0077] The S2 activation step was omitted; other parameters and methods were the same as in Example 1.

[0078] Comparative Example 3

[0079] In S2, tea saponin and cocamidopropyl betaine are not added to the activation solution (tea saponin and cocamidopropyl betaine are replaced by water); other parameters and methods are the same as in Example 1.

[0080] Comparative Example 4

[0081] The S3 cross-linking enhancement step was omitted; other parameters and methods were the same as in Example 1.

[0082] Comparative Example 5

[0083] In S3, no polyethyleneimine is added to the treatment solution; other parameters and methods are the same as in Example 1.

[0084] Comparative Example 6

[0085] In S3, genipin and vitamin E are not added to the treatment solution; other parameters and methods are the same as in Example 1.

[0086] Comparative Example 7

[0087] The S4 coating step was omitted; other parameters and methods were the same as in Example 1.

[0088] Comparative Example 8

[0089] In S4, no polypropyl silsesquioxane is added to the coating solution (polypropyl silsesquioxane is replaced by deionized water); other parameters and methods are the same as in Example 1.

[0090] Comparative Example 9

[0091] In S4, neither polypropyl silsesquioxane nor polyurethane is added to the coating solution (polypropyl silsesquioxane and polyurethane are replaced by deionized water); other parameters and methods are the same as in Example 1.

[0092] Comparative Example 10

[0093] In S6, UV curing is not performed; other parameters and methods are the same as in Example 1.

[0094] The modified down products prepared in the above-mentioned embodiments and comparative examples were subjected to usage tests.

[0095] 1. Fluffiness test:

[0096] According to GB / T 10288 "Test Methods for Down and Feather", a fluff meter was used for measurement. 50g of sample was randomly selected from the modified down of each embodiment and comparative example and placed in the sample container of the fluff meter to ensure that the down was evenly distributed. The container containing the sample was placed on the fluff meter and a 2.5g / cm 2 The pressure was maintained for 2 minutes to simulate the slight compression in actual use. After 2 minutes, the pressure was released to allow the down to naturally recover its fluffy state. After 10 minutes, the sample height value displayed on the fluff meter was read and recorded. Each sample was measured 3 times and the average value was taken as the fluffiness of the sample. The test results are shown in Table 1 below.

[0097] 2. Thermal storage performance test:

[0098] Use a test sample bag with a size of 15cm×15cm, fill it with the modified down of each embodiment and comparative example, and the filling amount is 100g, to ensure uniform filling. Install the sample bag tightly on the test cavity of the thermal protection performance tester to ensure that the joints are well sealed to prevent heat loss from affecting the test results. Set the ambient temperature to -20℃ and the heat flux to 100W / ㎡, start the test equipment, and make it run stably; record the temperature on the other side of the sample after 30 minutes. The test results are shown in Table 1 below.

[0099] 3. Durability test:

[0100] Place the sample bag filled with modified down in a washing machine that meets the standards. According to the AATCC 61-2013 standard, add 5g of standard detergent per liter of water, the bath ratio is 1:30 (1kg / 30L), set the washing program to the normal washing mode, and the washing time is 30 minutes. After washing, take out the sample bag, gently squeeze to remove excess water, and then put it in a 60℃ oven to dry for 2 hours. Repeat the washing and drying steps for a total of 20 times, and then test the fluffiness and heat storage performance after washing according to the above-mentioned fluffiness test and heat storage performance test methods, compare the data before and after washing, and calculate the fluffiness retention rate and heat storage performance retention rate; where the heat storage performance retention rate % = temperature difference after washing 20 times / initial temperature difference × 100%. The test results are shown in Table 1 below.

[0101] Table 1 Test results

[0102]

[0103] It can be seen from the above results that the modified down of Examples 1 to 3 has good fluffiness and hydrophobicity, can improve the warmth retention effect, and improve the washability, and maintain the warmth retention effect for a long time.

[0104] In comparative example 1 (S1 enzyme treatment step omitted), no enzyme treatment was performed, and the grease and impurities on the surface of the down were not removed, which would hinder the effective combination of other components with the down fibers in the subsequent treatment steps; the penetration of the activation liquid was blocked, and a good microporous structure could not be formed, and the storage capacity of static air was reduced. At the same time, without etching, the surface of the down was still smooth, with a small specific surface area, and insufficient surface defects affected the subsequent cross-linking and coating effects, making it difficult to effectively prevent heat loss, and the heat storage performance was reduced. Due to the presence of surface impurities, the structure formed in the subsequent treatment process was not stable enough and was easily washed off, resulting in the destruction of the down structure after washing treatment and poor durability.

[0105] In Comparative Example 2 (activation step S2 omitted), no activation treatment was performed, and no uniform microporous structure was generated on the surface of the down fiber. These microporous structures are essential for storing still air, which is a good thermal insulation medium. The lack of microporous structures leads to a decrease in the thermal insulation performance of down. The lack of an activation step reduces the number of sites available for bonding on the surface of the down fiber during subsequent treatment, making the structure after treatment less strong. During multiple washings, the structure is easily damaged and has poor durability.

[0106] In comparative example 3 (in S2, tea saponin and cocamidopropyl betaine are not added to the activation solution), tea saponin and cocamidopropyl betaine, as surfactants with different mechanisms, can reduce the surface tension between the down and the solvent, make the down evenly dispersed in the activation solution, and promote the activation reaction. The lack of tea saponin (natural nonionic surfactant) leads to reduced solution permeability; the lack of cocamidopropyl betaine (zwitterionic surfactant) causes uneven fiber dispersion, and some down cannot be fully activated, and a good thermal insulation structure cannot be formed. Due to the uneven dispersion of down, the activation treatment effect is inconsistent. In the subsequent treatment process, the binding force between the down and other components in different parts is different. During multiple washings, the parts with weak binding force are easy to fall off, resulting in unstable structure, poor durability and unevenness.

[0107] In comparative example 4 (S3 cross-linking and strengthening step omitted), the cross-linking structure was not constructed, and the relative positions of the down fibers were prone to change. When affected by external factors, the displacement of the fibers would cause the space for storing still air to be destroyed, affecting the thermal insulation effect. Without the protection of the cross-linking network, the down fibers were easily damaged and broken by mechanical forces during multiple washings, resulting in structural destruction and poor durability.

[0108] In comparative example 5 (in S3, polyethyleneimine is not added to the treatment solution), polyethyleneimine has multiple amino groups and can undergo cross-linking reactions with other components to form a stable three-dimensional network structure. Without polyethyleneimine, the cross-linking network is not perfect, the structural stability is poor, and it is easy to deform when subjected to heat flow shock, affecting the thermal insulation effect. The imperfect cross-linking network is easy to be damaged and broken during multiple washings, and the durability is poor.

[0109] In Comparative Example 6 (in S3, no genipin and vitamin E are added to the treatment liquid), genipin can undergo a cross-linking reaction with down fibers and other components, has flexibility, and enhances the stability of the structure. Vitamin E has an antioxidant effect and can prevent the cross-linked structure from being oxidized and destroyed during use. The lack of genipin (natural cross-linking agent) leads to insufficient cross-linking of collagen; the lack of VE (antioxidant) accelerates oxidative degradation. Without these two components, the cross-linked structure is not stable enough and is easily oxidized, affecting the thermal insulation performance. Insufficient cross-linking and easy oxidation make the structure more easily destroyed during multiple washings and have poor durability.

[0110] Comparative Example 7 (omit S4 coating step), without coating layer, cannot further enhance the thermal insulation performance of down. Bamboo charcoal powder, silica aerogel and other components in the coating liquid have good thermal insulation performance, and the lack of coating layer makes it impossible to fully utilize the thermal insulation effect of these components. Without the protection of the coating layer, the down is directly exposed to the external environment and is easily eroded by moisture, dust, etc. During multiple washing processes, the structure is more easily damaged and the durability is poor.

[0111] In comparative example 8 (in S4, polypropyl silsesquioxane is not added to the coating liquid), polypropyl silsesquioxane has good heat insulation and structural reinforcement effects. The absence of siloxane as a flexible crosslinking agent causes the polyurethane rigid coating to be brittle and cracked, and the interface bonding strength is insufficient. The absence of siloxane reduces the heat insulation performance and structural stability of the coating layer, and heat is more easily transferred under the action of heat flow. The structural stability is affected, and the coating layer is easy to fall off during multiple washings, resulting in a low retention rate of heat storage performance.

[0112] In comparative example 9 (in S4, polypropyl silsesquioxane and polyurethane are not added to the coating liquid at the same time), the absence of polypropyl silsesquioxane and polyurethane seriously affects the structure and thermal insulation performance of the coating layer. The two act synergistically in the coating layer to form a stable thermal insulation structure, and the heat loss is accelerated after the absence of polypropyl silsesquioxane and polyurethane. The structure is unstable, and the coating layer is easily damaged during multiple washing processes, and the thermal storage performance retention rate is further reduced.

[0113] In comparative example 10 (UV curing is not performed in S6), UV curing can promote the further progress of the cross-linking reaction and form a denser cross-linking network. UV curing can trigger a free radical reaction to strengthen the Si-O-Si network. Thermal curing alone leads to insufficient cross-linking density and an unstable structure. Under the action of heat flow, it is easy to deform, affecting the thermal insulation effect. Insufficient cross-linking can easily destroy the structure during multiple washings, and the thermal storage performance retention rate is reduced.

Claims

1. A modification method for improving the heat storage of down, characterized in that: The steps include: S1, enzyme treatment: using biological enzyme solution to perform ultrasonic enzymolysis on the down at 40°C to 50°C for 80min to 100min, rinsing, centrifugal dehydration, and obtaining etched down; The mass ratio of the components of the biological enzyme solution is water: lipase: papain: subtilisin: keratin = (100-120): (0.1-0.15): (0.005-0.01): (0.001-0.003): (0.0005-0.001), and the pH value is 7.0-8.0; the bath ratio of down and biological enzyme solution is 1kg / 50L-1kg / 60L; S2, activation: using an activation liquid to ultrasonically activate the etched down at 30°C to 35°C for 40min to 60min to generate a uniform microporous structure; rinsing, centrifugal dehydration, and obtaining activated down; The mass ratio of the components of the activation solution is water: ethanol: tea saponin: cocamidopropyl betaine = (100-120): (20-30): (0.3-0.5): (0.3-0.5); the bath ratio of the etched down and the activation solution is 1kg / 70L-1kg / 80L; S3, cross-linking enhancement: the activated down is subjected to oscillation treatment with a treatment liquid to construct a cross-linking structure; Filter, dehydrate and solidify to obtain reinforced down; The treatment liquid contains 2.5wt% to 3.0wt% of 3-aminopropyltriethoxysilane, 1.5wt% to 2.0wt% of polyethyleneimine, 0.5wt% to 0.8wt% of genipin, 0.1wt% to 0.2wt% of vitamin E, and the remaining solvent is a phosphate buffer solution with a pH value of 6.0 to 6.5; S4, coating: spraying the coating liquid on the surface of the reinforced down in a mass ratio of reinforced down: coating liquid = 1: (1.5-2), and drying with air to obtain coated down; The coating liquid includes the following raw materials in parts by weight: 100 to 120 parts of deionized water, 20 to 30 parts of ethanol, 5 to 8 parts of bamboo charcoal powder, 4 to 6 parts of silica aerogel, 2 to 4 parts of polypropyl silsesquioxane, 2 to 4 parts of polyurethane, 0.1 to 0.15 parts of silane coupling agent, 0.1 to 0.3 parts of cocamidopropyl betaine and 0.1 to 0.3 parts of 2,6-di-tert-butyl-p-cresol; S5, hydrophobic treatment: using a hydrophobic agent to perform surface hydrophobic treatment on the coated down by spraying, and air drying to obtain hydrophobic down; S6, gradient curing: 80℃~85℃ hot air treatment for 40min~60min to promote crosslinking, at a wavelength of 254nm and an intensity of 80mW / cm 2 Under the above conditions, UV curing is performed for 5 to 10 minutes to complete the modification of the down.

2. A modification method for improving the heat storage property of down according to claim 1, characterized in that: In S1, the power of ultrasound is 30W-50W, and the frequency of ultrasound is 20kHz-25kHz; and rinsing is performed 3-4 times with deionized water at 80°C-85°C.

3. A modification method for improving the heat storage property of down according to claim 1, characterized in that: In S2, the frequency of ultrasound is 70kHz to 80kHz, and the power density is 1.8W / cm 2 ~2.0W / cm 2 ; Rinse with 80℃~85℃ deionized water 3 to 4 times.

4. The modification method for improving the heat storage property of down according to claim 1, characterized in that: In S3, the bath ratio of activated down and treatment liquid is 1kg / 25L~1kg / 30L; the amplitude of oscillation is 12mm~18mm, and the frequency of oscillation is 100 times / min~120 times / min; the temperature of oscillation treatment is 50℃~55℃, and the time of oscillation treatment is 120min~150min; and the curing is hot air curing at 80℃~85℃ for 30min~50min.

5. The modification method for improving the heat storage property of down according to claim 1, characterized in that: In S4, the bamboo charcoal powder is a nano-scale powder; the silica aerogel is a nano-scale powder; the silane coupling agent is KH-570; the air drying temperature is 50° C. to 60° C., and the air drying time is 1 h to 2 h.

6. The modification method for improving the heat storage property of down according to claim 1, characterized in that: In S5, the hydrophobic agent includes the following raw materials in parts by weight: 50 to 55 parts of methyltrimethoxysilane, 20 to 25 parts of ethanol, 25 to 30 parts of deionized water, and 0.1 to 0.3 parts of acetic acid.

7. The modification method for improving the heat storage property of down according to claim 1, characterized in that: In S5, the spray mass ratio is, coated down: hydrophobic agent = 1: (1 to 1.5); the air drying temperature is 50°C to 60°C, and the air drying time is 1h to 2h.

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