Phase change temperature control materials and their use in fibers, fabrics, and fillings.

Abstract

This invention belongs to the technical field of phase-change temperature control materials. Conventional phase-change materials have problems such as low thermal conductivity, poor water resistance and stability, and performance degradation during long-term use in textile applications. [Solution] The present invention provides a phase-change microcapsule, manufactured by a method including surface modification of inorganic nanoparticles, preparation of a shell material solution and a core material solution, wherein the shell material is a cross-linked polyvinylpyrrolidone / 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl copolymer composite material doped with inorganic nanoparticles, and the manufacturing method includes these steps. This provides a phase-change temperature control material with excellent thermal conductivity and water-wash resistance, which can be applied as a pre-spinning additive, a filling material, or a coating on the surface of woven fabrics, and is useful for work clothes, cold-weather gear, etc.

Description

Technical Field

[0001] The present invention belongs to the technical field of phase change temperature regulating materials, and more specifically, relates to the use of phase change temperature regulating materials and their fibers, fabrics, and waddings for filling.

Background Art

[0002] With the continuous development of modern science and technology and the increasing demands for people's quality of life and the performance of various fiber products, according to statistics, the market scale of high-performance fibers in China reached 45 billion Chinese yuan in 2023, and the global market scale of high-performance fibers reached 131.917 billion Chinese yuan. Furthermore, it is predicted that the global market scale of high-performance fibers will reach 238.983 billion Chinese yuan in 2029.

[0003] Fibers with temperature-regulating functions are an important field of high-performance fibers, and the consumer demand for fiber products capable of realizing temperature-regulating functions is increasing.

[0004] Generally, the following problems exist in commercially available fibers with temperature-regulating functions.

[0005] (1) The limited temperature regulation range Since the phase change temperature of general phase change materials is relatively fixed and limited to a narrow range, it is difficult to meet the requirements of complex and highly variable actual environmental temperatures.

[0006] For example, a certain phase change material suitable for indoor heat preservation in winter has its phase change temperature set at 20 - 22°C. However, when the indoor temperature fluctuates beyond this range, the temperature regulation effect significantly decreases, and it cannot function effectively in a high-temperature environment in summer (e.g., above 30°C) or in a severely cold winter (e.g., below 0°C).

[0007] (2) The low thermal conductivity Many phase-change materials have low thermal conductivity and slow heat transfer rates within the material, which means that the process of heat absorption or release does not occur quickly enough, affecting the immediacy and effectiveness of temperature control.

[0008] In actual use, even if the ambient temperature has already changed significantly, the phase change material may not have yet completed heat exchange, resulting in a significant delay in temperature regulation.

[0009] (3) Problems related to stability After multiple phase change cycles, stability issues such as phase separation and leakage may occur, resulting in a decrease in temperature control performance.

[0010] For example, certain phase-change materials are prone to phase separation during long-term use due to density differences between different phase states and compatibility issues between the material and the support. As a result, the phase-change material, which is originally uniformly dispersed, may no longer be able to perform its temperature-regulating function properly.

[0011] Conventional technologies have proposed methods to improve the thermal conductivity of phase-change materials by compounding them with highly thermally conductive materials such as graphene and carbon nanotubes. Attempts have also been made to improve stability to a certain extent by optimizing the formulation and support method of the phase-change material. Furthermore, as a novel temperature-regulating material, materials that achieve temperature regulation by changing their molecular structure or physical state in response to changes in ambient temperature have also been proposed.

[0012] However, despite some progress in the technologies described above, the following challenges still exist for temperature-regulating materials in the textile field: it is difficult to improve thermal conductivity while simultaneously achieving performance in areas such as phase change latent heat and stability; the temperature control range is not sufficiently wide, and the sensitivity to temperature changes is low, making it unsuitable for applications requiring high-precision temperature control; and furthermore, the wash resistance is poor, with the temperature control function significantly degrading after multiple washes. [Overview of the Initiative] [Problems that the invention aims to solve]

[0013] In order to solve the problems that exist in the prior art, the present invention provides a phase-change temperature control material and its use in fibers, fabrics, and fillings, and aims to achieve the following inventive objectives.

[0014] To improve the stability of phase change materials, enable more precise temperature control, and impart multiple functions to textile products, such as temperature control, perspiration, and moisture absorption / conduction, thereby adapting them to the needs of multiple fields.

[0015] To improve the thermal conductivity, mechanical strength, and compatibility with fibrous substrates of phase-change temperature control materials, and to ensure water resistance. [Means for solving the problem]

[0016] To solve the above problems, the present invention employs the following technical means.

[0017] One object of the present invention is to provide a phase change temperature control material, and a method for manufacturing the phase change temperature control material includes the following steps.

[0018] S1: Surface modification of inorganic nanoparticles Inorganic nanoparticles are added to anhydrous ethanol and ultrasonically dispersed for 5-10 minutes. A silane coupling agent is then added and mixed uniformly, followed by a reaction for 6-8 hours. After that, centrifugation, washing, and drying are performed to obtain modified inorganic nanoparticles.

[0019] Preferably, the inorganic nanoparticles are one or more of graphene, titanium dioxide, boron nitride, and carbon nanotubes.

[0020] More preferably, the particle size of the inorganic nanoparticles is 4 to 10 nm.

[0021] Preferably, the silane coupling agent is KH570 (γ-Methacryloxypropyltrimethoxysilane), and its addition amount is 13-20% based on the mass of the inorganic nanoparticles.

[0022] S2: Preparation of the shell material solution N-vinylpyrrolidone, 2-acrylate-2-[[(butylamino)-carbonyl]oxy]ethyl, and modified inorganic nanoparticles are added into absolute ethanol. After stirring for 20-30 minutes, an initiator and a crosslinking agent are added and stirred for another 5-10 minutes. By setting the stirring speed at 200-300 r / min, a shell material solution is obtained.

[0023] Preferably, the mass ratio of the N-vinylpyrrolidone, 2-acrylate-2-[[(butylamino)-carbonyl]oxy]ethyl, modified inorganic nanoparticles, and absolute ethanol is 10-14:4-6:1.2-1.6:70-80.

[0024] Preferably, the initiator is azobisisobutyronitrile, and its addition amount is 1.3-1.8% based on the mass of the N-vinylpyrrolidone.

[0025] Preferably, the crosslinking agent is N,N-methylenebisacrylamide, and its addition amount is 2-3% based on the mass of the N-vinylpyrrolidone.

[0026] S3: Preparation of the core material solution A phase change material and an emulsifier are added into deionized water. Using a constant temperature magnetic stirrer, under the condition of 40-50 °C and at a stirring speed of 800-1000 r / min, stir for 20-30 minutes to obtain a core material solution.

[0027] Preferably, the phase change material is one or more of n-octadecane, paraffin, palmitic acid and its esters, fatty acids and their esters, pentaerythritol, and trimethylolethane.

[0028] Preferably, the emulsifier is one or more of the following: sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, Span 80 (sorbitan monooleate), and Tween 80 (polysorbate 80).

[0029] Preferably, the mass ratio of the phase change material, emulsifier, and deionized water is 20-26:4-7:60-70.

[0030] S4: Manufacturing of phase-change temperature control materials By stirring the core material solution at a stirring speed of 600-700 r / min while adding the shell material solution to the core material solution, then raising the temperature to 65-75°C and reacting under a nitrogen atmosphere for 6-7 hours, a phase-change microcapsule suspension is obtained in which the phase-change material serves as the core material and the shell material is a cross-linked polyvinylpyrrolidone / 2-(butylamino)-carbonyl]oxy]ethyl copolymer composite material doped with inorganic nanoparticles.

[0031] The resulting suspension is filtered under reduced pressure, washed with an ethanol solution, dried, and then pulverized to obtain a phase change temperature control material.

[0032] Preferably, the volume ratio of the core material solution to the shell material solution is 1 to 1.1:1.3 to 1.7.

[0033] Preferably, the drying temperature is 60-80°C and the drying time is 12-24 hours.

[0034] Explanation of the effects and benefits of the invention To improve the problem of phase change materials being prone to leakage or leaching, it is known that the phase change material can be coated with a polymer material to form a microcapsule structure. However, conventional polymer shell materials have low thermal conductivity, insufficient mechanical strength, and weak bonding ability with fibers. Therefore, when used in the textile field, prolonged washing can cause the microcapsules to detach or break, leading to a decrease in the temperature regulation performance of the fibers.

[0035] Therefore, in this invention, a cross-linked polyvinylpyrrolidone / 2-2-[[(butylamino)-carbonyl]oxy]ethyl copolymer composite material doped with inorganic nanoparticles is used as the shell material.

[0036] Adding inorganic nanoparticles to the shell material can improve its thermal conductivity. However, when inorganic nanoparticles are added directly to the shell material, the bond between the two is merely physical, resulting in a weak bond and making the inorganic nanoparticles prone to falling off.

[0037] Therefore, in this invention, inorganic nanoparticles are first modified using KH570 (γ-Methacryloxypropyltrimethoxysilane) and a carbon-carbon double bond is introduced to their surface to obtain modified inorganic nanoparticles. These modified inorganic nanoparticles participate in the radical polymerization reaction of the shell material and are doped into the shell material in the form of covalent bonds, thereby improving the thermal conductivity stability and reusability of the microcapsules.

[0038] A phase-change temperature control material using cross-linked polyvinylpyrrolidone as the shell material can form a dense protective coating layer on the core material, and because cross-linked polyvinylpyrrolidone has excellent compatibility with the substrate and good hygroscopic properties, it can improve the moisture absorption and perspiration performance of fibers, fabrics, stuffings, or coatings to a certain extent.

[0039] However, because cross-linked polyvinylpyrrolidone has a highly rigid pyrrole ring, the shell material has high rigidity and stability but poor flexibility, making it prone to brittle fracture. In addition, doping with inorganic nanoparticles also leads to a decrease in the flexibility of the shell material. When added to fibers, although the effect on fiber strength is not significant, prolonged washing may damage the shell material and cause the phase change material to leach out.

[0040] Therefore, in this invention, by copolymerizing 2-(butylamino)-carbonyl]oxyethyl 2-acrylate having a flexible block, the destruction of the phase change temperature control material by water washing is suppressed or avoided, and the water washability is improved.

[0041] A second object of the present invention is to provide a use for a phase-change temperature control material in fibers, fabrics, and stuffing materials, which includes adding it to a fiber substrate in the form of pre-spinning addition, using it in the manufacture of stuffing material for stuffing materials, or preparing it as a coating liquid and forming a coating film on the surface of a fabric by methods such as hot rolling or spray coating.

[0042] Preferably, the fiber substrate includes, but is not limited to, polyester, nylon, acrylic, polypropylene, polyurethane, lyocell fiber, and a type of viscose fiber.

[0043] Preferably, the fabric includes, but is not limited to, a nonwoven fabric, a nylon-polyurethane blend fabric, or a polyester-polyurethane blend fabric. [Effects of the Invention]

[0044] By employing the technical means described above, the present invention achieves the following technical effects.

[0045] 1. The phase-change temperature control material produced by the present invention has good compatibility and dispersibility, and has potential use in a wide range of fields such as work clothes, fire-resistant clothing, cold weather gear, bedding, sportswear, shoes and hats.

[0046] 2. The phase change temperature control material manufactured according to the present invention has excellent thermal conductivity, and its thermal conductivity is 1.36 to 1.54 W / (m·K).

[0047] 3. The phase-change temperature-regulating material produced by the present invention has good compatibility with various fiber substrates. When introduced into the fiber substrate by pre-spinning addition, the resulting fibers and fabrics possess moisture absorption and sweat-wicking functions, as well as excellent temperature regulation performance. In particular, it exhibits excellent temperature response even when rapidly transitioning from a room temperature environment of approximately 25°C to an environment below 0°C, mitigating temperature changes and improving the perceived comfort of the human body.

[0048] 4. By preparing the phase-change temperature control material manufactured according to the present invention as a coating liquid and applying it to the surface of a woven fabric by methods such as hot rolling or spray coating, and then drying it, a coating film can be formed on the surface of the woven fabric. This allows for precise temperature control while minimizing the impact on the texture and mechanical properties of the fabric, making it suitable for summer cooling fabrics, blankets, and other textile products.

[0049] 5. By adding phase-change temperature-regulating materials to fibers, fabrics, and fillings, the thermal insulation performance can be improved. For example, when phase-change temperature-regulating materials are added to fillings, the heat retention rate can reach over 80% (measured according to GB / T 35762-2017). [Brief explanation of the drawing]

[0050] [Figure 1] This figure shows the temperature control state when cotton with filling cotton (initial temperature 10°C) prepared according to Example 1 and commercially available general cotton (initial temperature 10°C) are placed in a 40°C environment. [Figure 2] This figure shows the temperature control state when cotton with filling cotton (initial temperature 40°C) prepared according to Example 1 and commercially available general cotton (initial temperature 40°C) are placed in a 10°C environment. [Modes for carrying out the invention]

[0051] The present invention will be further described below based on specific examples. Example 1 A phase-change temperature control material and its use in fibers, fabrics, and fillings, wherein the manufacture of the phase-change temperature control material includes the following steps.

[0052] S1: Surface modification of inorganic nanoparticles Inorganic nanoparticles were added to anhydrous ethanol, ultrasonically dispersed for 8 minutes, a silane coupling agent was added and mixed uniformly, and the mixture was allowed to react for 7 hours. After that, centrifugation, washing, and drying were performed to obtain modified inorganic nanoparticles.

[0053] The inorganic nanoparticles are graphene, and their particle size is 7 nm.

[0054] The silane coupling agent is KH570 (γ-Methacryloxypropyltrimethoxysilane), and the amount added is 15% of the mass of the inorganic nanoparticles.

[0055] S2: Preparation of shell material solution N-vinylpyrrolidone, 2-(butylamino)-carbonyl]oxyethyl 2-acrylate, and modified inorganic nanoparticles were added to anhydrous ethanol and stirred for 25 minutes. After stirring for 25 minutes, an initiator and a crosslinking agent were added and the mixture was stirred for a further 7 minutes at a stirring speed of 250 r / min to obtain a shell material solution.

[0056] The mass ratio of N-vinylpyrrolidone, 2-(butylamino)-carbonyl]oxyethyl 2-acrylate, modified inorganic nanoparticles, and anhydrous ethanol is 12:5:1.5:75.

[0057] The initiator is azobisisobutyronitrile, and its amount added is 1.5% relative to the mass of N-vinylpyrrolidone.

[0058] The crosslinking agent is N,N-methylenebisacrylamide, and its amount added is 2.5% relative to the mass of N-vinylpyrrolidone.

[0059] S3: Preparation of core material solution The phase change material and emulsifier were added to deionized water, and the mixture was stirred for 25 minutes at a constant temperature magnetic stirrer at 45°C with a stirring speed of 900 r / min to obtain the core material solution.

[0060] The phase change material is palmitic acid, and the emulsifier is sodium dodecylbenzenesulfonate.

[0061] The mass ratio of the phase change material, emulsifier, and deionized water is 24:6:65.

[0062] S4: Manufacturing of phase-change temperature control materials While stirring the core material solution at a stirring speed of 650 r / min, the shell material solution was added to the core material solution, and then the temperature was raised to 70°C. The reaction was carried out for 6.5 hours under nitrogen protection conditions to obtain a phase-change microcapsule suspension in which the phase-change material served as the core material and the shell material was a cross-linked polyvinylpyrrolidone / 2-(butylamino)-carbonyl]oxy]ethyl copolymer composite material doped with inorganic nanoparticles.

[0063] The resulting suspension was filtered by suction, washed with a 70% ethanol solution, dried, and ground to 1 μm to obtain a phase change temperature control material.

[0064] The volume ratio of the core material solution to the shell material solution is 1.05:1.55.

[0065] The drying temperature is 70°C, and the drying time is 20 hours.

[0066] Example 2 A phase-change temperature control material and its use in fibers, fabrics, and fillings, wherein the manufacture of the phase-change temperature control material includes the following steps.

[0067] S1: Surface modification of inorganic nanoparticles Inorganic nanoparticles were added to anhydrous ethanol, ultrasonically dispersed for 5 minutes, a silane coupling agent was added and mixed uniformly, and the mixture was allowed to react for 6 hours. After that, centrifugation, washing, and drying were performed to obtain modified inorganic nanoparticles.

[0068] The inorganic nanoparticles are titanium dioxide, and their particle size is 4 nm.

[0069] The silane coupling agent is KH570 (γ-Methacryloxypropyltrimethoxysilane), and the amount added is 13% of the mass of the inorganic nanoparticles.

[0070] S2: Preparation of shell material solution N-vinylpyrrolidone, 2-(butylamino)-carbonyl]oxyethyl 2-acrylate, and modified inorganic nanoparticles were added to anhydrous ethanol and stirred for 20 minutes. After stirring for 20 minutes, an initiator and a crosslinking agent were added and the mixture was stirred for a further 5 minutes at a stirring speed of 200 r / min to obtain a shell material solution.

[0071] The mass ratio of N-vinylpyrrolidone, 2-(butylamino)-carbonyl]oxyethyl 2-acrylate, modified inorganic nanoparticles, and anhydrous ethanol is 10:4:1.2:70.

[0072] The initiator is azobisisobutyronitrile, and the amount added is 1.3% relative to the mass of N-vinylpyrrolidone.

[0073] The crosslinking agent is N,N-methylenebisacrylamide, and its amount added is 2% relative to the mass of N-vinylpyrrolidone.

[0074] S3: Preparation of core material solution The phase change material and emulsifier were added to deionized water, and the mixture was stirred for 20 minutes at a constant temperature magnetic stirrer at 40°C with a stirring speed of 800 r / min to obtain the core material solution.

[0075] The phase change material is paraffin, and the emulsifier is Tween 80.

[0076] The mass ratio of the phase change material, emulsifier, and deionized water is 20:4:60.

[0077] S4: Manufacturing of phase-change temperature control materials While stirring the core material solution at a stirring speed of 600 r / min, the shell material solution was added to the core material solution, and then the temperature was raised to 65°C. The reaction was carried out for 6 hours under nitrogen protection to obtain a phase-change microcapsule suspension in which the phase-change material served as the core material and the cross-linked polyvinylpyrrolidone / 2-acrylate-2-[[(butylamino)-carbonyl]oxy]ethyl copolymer composite material doped with inorganic nanoparticles served as the shell material.

[0078] The resulting suspension was filtered by suction, washed with a 70% ethanol solution, dried, and ground to 1 μm to obtain a phase change temperature control material.

[0079] The volume ratio of the core material solution to the shell material solution is 1:1.3.

[0080] The drying temperature is 80°C, and the drying time is 12 hours.

[0081] Example 3 A phase-change temperature control material and its use in fibers, fabrics, and fillings, wherein the manufacture of the phase-change temperature control material includes the following steps.

[0082] S1: Surface modification of inorganic nanoparticles Inorganic nanoparticles were added to anhydrous ethanol, ultrasonically dispersed for 10 minutes, a silane coupling agent was added and mixed uniformly, and the mixture was allowed to react for 8 hours. After that, centrifugation, washing, and drying were performed to obtain modified inorganic nanoparticles.

[0083] The inorganic nanoparticles are boron nitride, and their particle size is 10 nm.

[0084] The silane coupling agent is KH570 (γ-Methacryloxypropyltrimethoxysilane), and the amount added is 20% of the mass of the inorganic nanoparticles.

[0085] S2: Preparation of shell material solution N-vinylpyrrolidone, 2-(butylamino)-carbonyl]oxyethyl 2-acrylate, and modified inorganic nanoparticles were added to anhydrous ethanol and stirred for 30 minutes. After stirring for 30 minutes, an initiator and a crosslinking agent were added and the mixture was stirred for another 10 minutes at a stirring speed of 300 r / min to obtain a shell material solution.

[0086] The mass ratio of N-vinylpyrrolidone, 2-(butylamino)-carbonyl]oxyethyl 2-acrylate, modified inorganic nanoparticles, and anhydrous ethanol is 14:6:1.6:80.

[0087] The initiator is azobisisobutyronitrile, and its amount added is 1.8% relative to the mass of N-vinylpyrrolidone.

[0088] The crosslinking agent is N,N-methylenebisacrylamide, and its amount added is 3% of the mass of N-vinylpyrrolidone.

[0089] S3: Preparation of core material solution The phase change material and emulsifier were added to deionized water, and the mixture was stirred for 30 minutes at a constant temperature magnetic stirrer at a stirring speed of 1000 r / min at 50°C to obtain the core material solution.

[0090] The phase change material is n-octadecane, and the emulsifier is sodium dodecyl sulfate.

[0091] The mass ratio of the phase change material, emulsifier, and deionized water is 26:7:70.

[0092] S4: Manufacturing of phase-change temperature control materials While stirring the core material solution at a stirring speed of 700 r / min, the shell material solution was added to the core material solution, and then the temperature was raised to 75°C. The reaction was carried out for 7 hours under nitrogen protection to obtain a phase-change microcapsule suspension in which the phase-change material served as the core material and the cross-linked polyvinylpyrrolidone / 2-acrylate-2-[[(butylamino)-carbonyl]oxy]ethyl copolymer composite material doped with inorganic nanoparticles served as the shell material.

[0093] The resulting suspension was filtered by suction, washed with a 70% ethanol solution, dried, and ground to 1 μm to obtain a phase change temperature control material.

[0094] The volume ratio of the core material solution to the shell material solution is 1.1:1.7.

[0095] The drying temperature is 60°C, and the drying time is 24 hours.

[0096] Comparative Example 1 Comparative Example 1 was created by selecting a representative example (Example 1), removing 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate from S2, and keeping all other aspects the same as Example 1.

[0097] Comparative Example 2 Comparative Example 2 was created by selecting a representative example (Example 1), removing step S1, directly adding unmodified inorganic nanoparticles in step S2, and keeping all other steps the same as in Example 1.

[0098] Comparative Example 3 Comparative Example 3 was created by selecting a representative example (Example 1), removing the modified inorganic nanoparticles in S2, and keeping everything else the same as Example 1.

[0099] The thermal conductivity of the phase-change temperature control materials obtained in Examples 1-3 and Comparative Examples 1-3 was measured. The specific data is shown in Table 1.

[0100] Table 1 JPEG0007883809000002.jpg19170

[0101] Table 1 shows that the phase-change temperature control materials obtained in Examples 1-3 have high thermal conductivity, while Comparative Example 3 has low thermal conductivity. This indicates that the addition of inorganic nanoparticles significantly improves the thermal conductivity. The reason why the thermal conductivity of Comparative Example 2 is lower than that of Example 1 is that the inorganic nanoparticles in Comparative Example 2 were unmodified and had low dispersibility in the shell material, resulting in lower thermal conductivity compared to Example 1.

[0102] Next, Examples 1-3 and Comparative Examples 1-3 were added to the lyocell fiber spinning solution in a pre-spinning form, and temperature-regulating fibers were produced by wet spinning. Fabric was then made from these temperature-regulating fibers. Furthermore, the mechanical properties of the fibers, the enthalpy value of the fabric, and the sweat-wicking effect were measured. The details are shown in Table 2.

[0103] Table 2 JPEG0007883809000003.jpg90170

[0104] Table 2 shows that the phase-change temperature-regulating materials obtained in Examples 1-3 had better compatibility with the fiber substrate, resulting in better mechanical properties of the resulting fibers and excellent thermal conductivity and sweat-wicking functions. In Comparative Example 1, 2-2-[[(butylamino)-carbonyl]oxy]ethyl acrylic acid was not added, and the breaking strength of the fibers decreased due to a reduction in the flexible block. In Comparative Example 2, the bonding between inorganic nanoparticles and the shell material remained merely physical bonding and lacked chemical bonding strength, making them prone to falling off during the fiber manufacturing process and becoming "foreign matter," resulting in a significant decrease in the mechanical properties of the fibers. In Comparative Example 3, since inorganic nanoparticles were not added, the enthalpy value of the fibers was low and the sweat-wicking effect was insufficient.

[0105] Note: The permeate surface wetting time, permeate surface water absorption rate, and unidirectional transfer index were measured according to "GB / T 21655.2-2019".

[0106] Next, Examples 1-3 and Comparative Examples 1-3 were added to the filling material, and their heat retention effects were measured. The specific results are shown in Table 3.

[0107] Table 3 JPEG0007883809000004.jpg35170

[0108] Table 3 shows that the phase-change temperature control materials obtained in Examples 1-3 have good compatibility with the filling cotton and also have good water-wash resistance. The phase-change temperature control material obtained in Comparative Example 1 did not have 2-2-[[(butylamino)-carbonyl]oxy]ethyl acrylic acid added, and the reduction in the flexible block caused a decrease in the heat retention performance of the filling cotton with water washing. This is because the reduction in the flexible block makes the shell material of the phase-change temperature control material more susceptible to damage, and the damage to the shell material during the water washing process causes a decrease in the heat retention performance of the filling cotton. The phase-change temperature control material obtained in Comparative Example 2 has uneven dispersion of inorganic nanoparticles in the shell material and is prone to falling off, resulting in relatively poor water-wash resistance. In Comparative Example 3, since inorganic nanoparticles were not added, the overall heat retention effect was low, but the water-wash resistance of the heat retention performance was good.

[0109] The temperature control state of cotton with the filling material prepared in Example 1 added, and commercially available general temperature-regulating cotton, under varying temperatures was measured and plotted as curves. Here, the cotton with the filling material prepared in Example 1 was used as the test sample, and the commercially available general temperature-regulating cotton was used as the control sample. Specifically, this is shown in Figures 1 and 2.

[0110] Figures 1 and 2 show that when the ambient temperature changes rapidly, the cotton with the filling material prepared in Example 1 exhibits less strict temperature regulation, and thus more precise temperature regulation.

[0111] Next, the phase change temperature control materials obtained in Examples 1-3 and Comparative Example 1 were added to deionized water and uniformly stirred to prepare a coating solution (solid content 40%). This was spray-applied to the surface of a fabric, the fabric composition being 85% nylon and 15% polyurethane, and the application rate was 50 g / m². 2 Furthermore, a coating film was formed on the surface of the fabric by drying it at 120-150°C for 3-5 minutes. The enthalpy value and contact coolness of the coated fabric were measured. The specifics are shown in Table 4.

[0112] Table 4 JPEG0007883809000005.jpg51170

[0113] Table 4 shows that the coating solutions prepared from the phase-change temperature control materials obtained in Examples 1-3 exhibit good bonding with the fabric, good water-wash resistance, and a small decrease in enthalpy value after 20 washes. In contrast, the coated fabrics made from the phase-change temperature control materials obtained in Comparative Examples 1 and 2 showed a significant decrease in enthalpy value after 20 washes. This indicates that the phase-change temperature control material obtained in Comparative Example 1 is easily damaged, and the inorganic nanoparticles in the phase-change temperature control material obtained in Comparative Example 2 tend to fall off, thus demonstrating poor water-wash resistance.

[0114] Unless otherwise specified, all ratios in this invention are mass ratios, and all percentages are mass percentages. Furthermore, all raw materials are commercially available.

[0115] Finally, it should be noted that the above description is merely a preferred embodiment of the present invention and does not limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art can modify the technical means described in each of the above embodiments or substitute some of the technical features with equivalent ones. Any modification, equivalent substitution, improvement, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for manufacturing a phase change temperature control material, S1. Surface modification of inorganic nanoparticles: A process to obtain modified inorganic nanoparticles by adding inorganic nanoparticles to anhydrous ethanol, ultrasonically dispersing them for 5 to 10 minutes, adding a silane coupling agent and mixing uniformly, reacting for 6 to 8 hours, followed by centrifugation, washing, and drying. S2. Preparation of shell material solution: Add N-vinylpyrrolidone, 2-2-[[(butylamino)-carbonyl]oxy]ethyl acrylate, and modified inorganic nanoparticles to anhydrous ethanol and stir for 20 to 30 minutes. Then, add the initiator and crosslinking agent and stir for a further 5 to 10 minutes, maintaining a stirring speed of 200 to 300 r / min to obtain the shell material solution. S3. Preparation of core material solution: A process to obtain a core material solution by adding a phase change material and an emulsifier to deionized water and stirring for 20 to 30 minutes at a stirring speed of 800 to 1000 r / min under conditions of 40 to 50°C using a constant temperature magnetic stirrer. S4. Manufacturing of phase change temperature control material: A process to obtain a phase change temperature control material by adding the shell material solution to the core material solution while stirring at a stirring speed of 600 to 700 r / min, then raising the temperature to 65 to 75°C and reacting under nitrogen protection conditions for 6 to 7 hours, thereby obtaining a phase change microcapsule suspension, and then filtration the phase change microcapsule suspension by suction, washing with ethanol solution, drying, and grinding. A method for producing a phase change temperature control material, characterized by including the following:

2. The inorganic nanoparticles in S1 are one or more of graphene, titanium dioxide, boron nitride, and carbon nanotubes. The manufacturing method according to claim 1, wherein the particle size of the inorganic nanoparticles is 4 to 10 nm.

3. The manufacturing method according to claim 1, wherein the silane coupling agent in S1 is KH570, and the amount added is 13 to 20% of the mass of inorganic nanoparticles.

4. The manufacturing method according to claim 1, wherein in S2, the mass ratio of N-vinylpyrrolidone, 2-(butylamino)-carbonyl]oxyethyl 2-acrylate, modified inorganic nanoparticles, and anhydrous ethanol is 10 to 14:4 to 6:1.2 to 1.6:70 to 80.

5. The initiator in S2 is azobisisobutyronitrile, and the amount added is 1.3 to 1.8% relative to the mass of N-vinylpyrrolidone. The manufacturing method according to claim 1, wherein the crosslinking agent is N,N-methylenebisacrylamide, and the amount added is 2 to 3% of the mass of N-vinylpyrrolidone.

6. The manufacturing method according to claim 1, wherein the phase change material in S3 is one or more of n-octadecane, paraffin, palmitic acid and its esters, fatty acids and their esters, pentaerythritol, and trimethylolethane.

7. The manufacturing method according to claim 1, wherein the emulsifier in S3 is one or more of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, Span 80, and Tween 80.

8. The manufacturing method according to claim 1, wherein in S3, the mass ratio of the phase change material, emulsifier, and deionized water is 20 to 26: 4 to 7: 60 to 70.

9. In S4, the volume ratio of the core material solution to the shell material solution is 1 to 1.1:1.3 to 1.

7. The manufacturing method according to claim 1, wherein the drying temperature is 60 to 80°C and the drying time is 12 to 24 hours.

10. The use of phase change temperature control materials in fibers, fabrics, and fillings, The phase change temperature control material is manufactured by the manufacturing method described in any one of claims 1 to 9. The aforementioned uses include adding it to a fiber substrate in the form of pre-spinning addition, using it in the manufacture of filling cotton, and preparing it as a coating solution and forming a coating film on the surface of a fabric by hot rolling or spray application. The aforementioned fiber substrate is a type of polyester, nylon, acrylic, polypropylene, polyurethane, lyocell fiber, and viscose fiber. The use of a phase-change temperature control material in which the aforementioned fabric is a type of nonwoven fabric, nylon-polyurethane fabric, or polyester-polyurethane fabric.

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