Temperature-regulating antibacterial microcapsule material as well as preparation method and application thereof

Abstract

The invention discloses a temperature-adjusting antibacterial microcapsule material and a preparation method and application thereof.The preparation method comprises the steps that S1, paraffin and a microcapsule wall material precursor are mixed, heated and stirred, and an oil phase solution is formed; s2, dispersing an emulsifier in a water-phase solvent, heating and stirring to form a water-phase solution; s3, uniformly mixing the oil-phase solution with the water-phase solution, and performing ultrasonic emulsification to obtain a homogeneous oil-in-water emulsion; s4, dropwise adding alkali liquor into the oil-in-water emulsion, initiating hydrolysis and condensation polymerization of the microcapsule wall material precursor, and performing suction filtration, water washing and drying on the obtained product to obtain microcapsule powder; and S5, adding the microcapsule powder into a metal salt solution, carrying out a reaction under heating and stirring conditions, and carrying out suction filtration, water washing and drying on the obtained product to obtain the temperature-adjusting antibacterial microcapsule material. The polysiloxane coated paraffin phase change energy storage microcapsule is prepared by a sol-gel method, and hydroxyl on a wall material is complexed with metal ions, so that the thermal conductivity of the microcapsule is improved, and meanwhile, the antibacterial effect is also enhanced.

Description

Technical Field

[0001] The invention relates to the field of polymer material modification, in particular to a method for preparing a temperature-regulating antibacterial microcapsule material and application of the microcapsule material to a temperature-regulating antibacterial polyamide fiber. Background Art

[0002] Polyamide fiber (nylon) is the earliest synthetic fiber to achieve industrial production and is currently the second largest synthetic fiber in the world. Due to the particularity of its molecular structure, polyamide (PA) has excellent wear resistance, hygroscopicity, dyeability, fatigue resistance, elasticity and good mechanical properties, and is used in large quantities in clothing and household textiles. However, under certain environmental conditions, polyamide fiber products are prone to breeding bacteria, which leads to fiber aging, discoloration, and mildew. At the same time, with the improvement of living standards, people have also put forward higher requirements for the comfort of clothing products. Therefore, the preparation of polyamide fabrics with thermostatic and antibacterial properties is of great market value.

[0003] Phase change thermostatic material is a material that can absorb, store and release heat through a phase transition process within a specific temperature range. It has good stability and can be recycled. It is widely used in energy, construction, military and other fields. The ideal phase change energy storage material should have a large latent heat and high thermal conductivity so that it can absorb and release a large amount of energy during the phase change process. At the same time, its phase change temperature should be able to meet the needs of actual application scenarios, and the melting temperature should be the same as the minimum supercooling to ensure a stable phase change process. In addition, the ideal phase change energy storage material should also have the advantages of stable chemical bonds, safety and greenness. Among the phase change thermostatic materials, paraffin has high latent heat of phase change, stable phase change process, good thermal cycle, and the phase change temperature is close to the human body temperature, which makes it have unmatched advantages over other phase change materials. It has become one of the key research objects of phase change energy storage materials for textiles.

[0004] Paraffin phase change energy storage composite materials have problems such as low thermal conductivity, high volatility, flammability and large volume change during phase change. The main research direction is to prevent paraffin leakage, improve the thermal conductivity of composite materials, and reduce preparation costs. CN117431039A uses paraffin as a phase change component and uses perlite to encapsulate the paraffin, so that the paraffin does not leak after the phase change; CN115926752A uses graphene as the capsule wall to achieve the dual effects of preventing leakage and improving thermal conductivity;

[0005] CN116836452A uses silicone foam as a packaging material to encapsulate paraffin. The phase-change energy storage silicone foam composite material has good sealing performance, no paraffin leakage during use, and good thermal conductivity; CN117165269A improves the thermal conductivity of energy storage materials by adding nanoparticles such as nano silicon carbide, nano silicon dioxide, nano γ-alumina, and nano titanium dioxide to paraffin; CN113789158A uses waste plastics as raw materials to prepare porous carbon for encapsulating paraffin, thereby realizing the recycling of waste plastics and reducing the cost of preparing energy storage materials.

[0006] At present, the research on paraffin phase change energy storage composite materials is mainly aimed at preventing core material leakage, developing new core and wall materials and other packaging technology innovations, but less attention is paid to the added value of energy storage microcapsules in actual application scenarios. Summary of the invention

[0007] In view of this, the present invention provides a temperature-regulating antibacterial microcapsule material and a preparation method thereof. Paraffin is used as a core material, and the content of each component in the paraffin is adjusted to control the phase change temperature, so as to meet the temperature regulation in a wide temperature range. Inorganic polymers are used as wall materials, and phase change energy storage microcapsules containing hydroxyl groups in the wall materials are prepared by a sol-gel method. Metal ions are complexed on the microcapsule wall materials to further improve the antibacterial and thermal conductivity of the microcapsules.

[0008] To achieve the above object, the present invention provides the following technical solutions:

[0009] In a first aspect, the present invention discloses a method for preparing a temperature-regulating antibacterial microcapsule material, comprising the following steps:

[0010] S1, mixing paraffin wax and microcapsule wall material precursor, heating and stirring to form an oil phase solution;

[0011] S2, dispersing the emulsifier in the aqueous phase solvent, heating and stirring to form an aqueous phase solution;

[0012] S3, mixing the oil phase solution and the water phase solution evenly, and obtaining a homogeneous oil-in-water emulsion after ultrasonic emulsification;

[0013] S4, adding alkali solution dropwise into the oil-in-water emulsion to initiate hydrolysis and polycondensation reaction of the microcapsule wall material precursor, and filtering, washing and drying the obtained product to obtain microcapsule powder;

[0014] S5, adding the microcapsule powder into the metal salt solution, reacting under heating and stirring conditions, filtering the obtained product, washing with water, and drying to obtain the temperature-regulating antibacterial microcapsule material.

[0015] As a further embodiment of the present invention: the paraffin is at least one of n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, n-docosane, n-tetracosane, and n-hexacosane;

[0016] As a further solution of the present invention: the microcapsule wall material precursor is at least one of tetramethyl silicate, tetraethyl silicate, and tetra-n-butyl silicate;

[0017] As a further embodiment of the present invention: the emulsifier is at least one of hexadecyltrimethylammonium bromide and sodium dodecylsulfonate;

[0018] As a further embodiment of the present invention: the aqueous phase solvent is a mixture of water and ethanol in a ratio of (60-70) to (40-30) by weight;

[0019] As a further solution of the present invention: the alkali solution is at least one of ammonia water and formamide;

[0020] As a further solution of the present invention: the metal salt solution is Ag + , Cu 2+ 、Zn 2+ At least one of the aqueous solutions, the concentration of the metal salt solution is 1 to 4 mol / L;

[0021] As a further solution of the present invention: paraffin wax and microcapsule wall material precursor are mixed in a mass ratio of 1: (0.8-1.2), and heated and stirred, specifically: heated to 40-60° C., stirred at 400-600 r / min for at least 0.5 h;

[0022] As a further solution of the present invention: the emulsifier and the aqueous phase solvent are mixed in a mass ratio of (2 to 6): 100, and the heating and stirring are specifically: heating to 40 to 60° C., stirring at 400 to 600 r / min for at least 0.5 h;

[0023] As a further solution of the present invention: the oil phase solution and the water phase solution are mixed according to the mass ratio of (15-45):100, and the ultrasonic emulsification time is 20-40 minutes; the molar ratio of alkali to microcapsule wall material precursor in the alkali solution is (5-10):1;

[0024] Another aspect. The present invention discloses the application of the temperature-regulating antibacterial microcapsule material on the temperature-regulating antibacterial polyamide fiber: in a 40-60°C microcapsule aqueous solution with a mass fraction of 10-20%, a binder with a mass fraction of 3-8% is added, the polyamide fiber is treated by a two-immersion and two-rolling process, the rolling rate is 50-70%, the fiber after immersion and rolling is preheated in a heat setting machine at 80°C for 5 minutes, and then the temperature is adjusted to 120°C and dried for 20 minutes to obtain the temperature-regulating antibacterial polyamide fiber.

[0025] As a further solution of the present invention: the adhesive is water-soluble polyurethane.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The polysiloxane (wall material)-coated paraffin (core material) phase change energy storage microcapsules were prepared by the "sol-gel method". Paraffin has high latent heat of phase change, stable phase change process, good thermal cycling, and phase change temperature is close to human body temperature, which has advantages for body sensory adjustment. Inorganic polymers have higher thermal conductivity than organic materials. The prepared phase change microcapsules can respond to external temperature changes more quickly, which is beneficial to improving the thermal conductivity and flame retardant properties of the material. At the same time, the polyhydroxyl groups on the wall material can provide sites for complexing metal ions. The complexing of metal ions by the microcapsule wall material can not only improve the thermal conductivity of the material, but also enhance the antibacterial effect of the material.

[0028] (2) Thermostatic and antibacterial polyamide fibers were prepared by loading thermostatic and antibacterial microcapsules onto the surface of PA6 fibers through a sizing process. The fibers prepared by this method have good thermostatic and antibacterial properties. After washing 30 times, they still have good thermostatic and antibacterial effects. At the same time, the production process is simple and suitable for large-scale production. DETAILED DESCRIPTION

[0029] For ease of understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0031] The specific information of the raw materials used in the following examples and comparative examples is shown in Table 1 below.

[0032] Table 1

[0033]

[0034]

[0035] It is to be understood that the above raw materials and reagents are only examples of some specific embodiments of the present invention, so that the technical solution of the present invention is clearer, and it does not mean that the present invention can only use the above reagents, and the specific scope in the claims shall prevail. In addition, the "parts" described in the examples and comparative examples, unless otherwise specified, refer to parts by weight.

[0036] Any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0037] Example 1

[0038] (1) Preparation of temperature-regulating antibacterial microcapsules

[0039] S1. paraffin (n-octadecane) and tetraethyl silicate were mixed in a mass ratio of 1:1, heated to 50° C., and stirred at 500 r / min for 0.5 h to form an oil phase solution;

[0040] S2, hexadecyltrimethylammonium bromide and an aqueous phase solvent (m water: m ethanol = 65:35) were mixed in a mass ratio of 4:100, heated to 50° C., and stirred at 500 r / min for 0.5 h to form an aqueous phase solution;

[0041] S3, mixing the oil phase solution and the water phase solution in a mass ratio of 30:100, stirring at a rate of 10000 r / min, ultrasonic emulsification for 30 min, and homogenizing to form an oil-in-water emulsion;

[0042] S4, adding ammonia water and tetraethyl silicate dropwise to the water-in-oil emulsion in a molar ratio of 7:1 to initiate hydrolysis and polycondensation of tetraethyl silicate, the reaction temperature is 50° C., the stirring rate is 500 r / min, and after reacting for 20 hours, the microcapsule powder is filtered, washed with water, and dried;

[0043] S5. Add the microcapsule powder into 4 mol / L Ag2SO4 aqueous solution, heat to 50°C, and stir at 200 r / min for 4 h. After the reaction is completed, filter, wash with water, and dry to obtain temperature-regulating antibacterial microcapsules.

[0044] (2) Preparation of temperature-regulating antibacterial polyamide fibers

[0045] S6. Add 5% PU-530 as an adhesive to a 20% microcapsule aqueous solution at 50°C, and use a two-immersion and two-rolling process to treat the PA6 fiber with a rolling rate of 70%. The fiber after immersion and rolling is preheated in a heat setting machine at 80°C for 5 minutes, and then the temperature is adjusted to 120°C and dried for 20 minutes to obtain a temperature-regulating antibacterial microcapsule polyamide fiber.

[0046] Example 2

[0047] (1) Preparation of temperature-regulating antibacterial microcapsules:

[0048] S1, paraffin wax (m 正十四烷 :m 正二十六烷 =2:3) and tetramethyl silicate in a mass ratio of 1:0.8, heated to 50°C, and stirred at 500r / min for 0.5h to form an oil phase solution;

[0049] S2, sodium dodecyl sulfate and aqueous solvent (m 水 :m 乙醇 =60:40) in a mass ratio of 2:100, heated to 50°C, and stirred at 500r / min for 0.5h to form an aqueous solution;

[0050] S3, mixing the oil phase solution and the water phase solution in a mass ratio of 15:100, stirring at a rate of 10000 r / min, ultrasonic emulsification for 30 min, and homogenizing to form an oil-in-water emulsion;

[0051] S4, adding formamide and tetramethyl silicate dropwise into the oil-in-water emulsion at a molar ratio of 10:1 to initiate hydrolysis and polycondensation of tetramethyl silicate, the reaction temperature is 50° C., the stirring rate is 500 r / min, and after reacting for 20 hours, the microcapsule powder is filtered, washed with water, and dried;

[0052] S5. Add the microcapsule powder into 1 mol / L Ag2SO4 aqueous solution, heat to 50°C, and stir at 200r / min for 4h. After the reaction is completed, filter, wash with water, and dry to obtain temperature-regulating antibacterial microcapsules.

[0053] (2) Preparation of temperature-regulating antibacterial polyamide fibers

[0054] S6. In a 5% microcapsule aqueous solution at 50°C, using 5% PU-530 as an adhesive, the PA6 fiber was treated by a two-immersion and two-rolling process with a rolling rate of 50%. The fiber after immersion and rolling was preheated in a heat setting machine at 80°C for 5 minutes, and then the temperature was adjusted to 120°C and dried for 20 minutes to obtain a temperature-regulating antibacterial microcapsule polyamide fiber.

[0055] Example 3

[0056] (1) Preparation of temperature-regulating antibacterial microcapsules

[0057] S1, paraffin wax (m 正十六烷 :m 正二十烷 =1:1) and tetra-n-butyl silicate in a mass ratio of 1:1.2, heated to 50°C, and stirred at 500r / min for 0.5h to form an oil phase solution;

[0058] S2, hexadecyltrimethylammonium bromide and aqueous solvent (m 水 :m 乙醇 =70:30) in a mass ratio of 6:100, heated to 50°C, and stirred at 500r / min for 0.5h to form an aqueous solution;

[0059] S3, mixing the oil phase solution and the water phase solution in a mass ratio of 45:100, stirring at a rate of 10000 r / min, ultrasonic emulsification for 30 min, and homogenizing to form an oil-in-water emulsion;

[0060] S4, adding ammonia water and tetrabutyl silicate dropwise to the water-in-oil emulsion at a molar ratio of 5:1 to initiate hydrolysis and polycondensation of tetrabutyl silicate, the reaction temperature is 50° C., the stirring rate is 500 r / min, and after reacting for 20 hours, the microcapsule powder is filtered, washed with water, and dried;

[0061] S5. Add the microcapsule powder into a 4 mol / L CuSO4 aqueous solution, heat to 50°C, and stir at 200 r / min for 4 hours. After the reaction is completed, filter, wash with water, and dry to obtain temperature-regulating antibacterial microcapsules.

[0062] (2) Preparation of temperature-regulating antibacterial polyamide fibers

[0063] S6. In a 20% microcapsule aqueous solution at 50°C, PU-530 with a mass fraction of 5% was used as an adhesive, and the PA6 fiber was treated by a two-immersion and two-rolling process with a rolling rate of 67%. The fiber after immersion and rolling was preheated in a heat setting machine at 80°C for 5 minutes, and then the temperature was adjusted to 120°C and dried for 20 minutes to obtain a temperature-regulating antibacterial microcapsule polyamide fiber.

[0064] Example 4

[0065] (1) Preparation of temperature-regulating antibacterial microcapsules

[0066] S1. paraffin (n-hexacosane) and tetra-n-butyl silicate were mixed in a mass ratio of 1:1, heated to 50° C., and stirred at 500 r / min for 0.5 h to form an oil phase solution;

[0067] S2, hexadecyltrimethylammonium bromide and aqueous solvent (m 水 :m 乙醇 =70:30) in a mass ratio of 3:100, heated to 50°C, and stirred at 500r / min for 0.5h to form an aqueous solution;

[0068] S3, mixing the oil phase solution and the water phase solution in a mass ratio of 30:100, stirring at a rate of 10000 r / min, ultrasonic emulsification for 30 min, and homogenizing to form an oil-in-water emulsion;

[0069] S4, adding ammonia water and tetrabutyl silicate dropwise to the water-in-oil emulsion in a molar ratio of 8:1 to initiate hydrolysis and polycondensation of tetrabutyl silicate, the reaction temperature is 50° C., the stirring rate is 500 r / min, and after reacting for 20 hours, the microcapsule powder is filtered, washed with water, and dried;

[0070] S5. Add the microcapsule powder into a 4 mol / L ZnSO4 aqueous solution, heat to 50°C, and stir at 200 r / min for 4 hours. After the reaction is completed, filter, wash with water, and dry to obtain temperature-regulating antibacterial microcapsules.

[0071] (2) Preparation of temperature-regulating antibacterial polyamide fibers

[0072] S6. In a 10% microcapsule aqueous solution at 50°C, using 5% PU-530 as an adhesive, the PA6 fiber was treated by a two-immersion and two-rolling process with a rolling rate of 55%. The fiber after immersion and rolling was preheated in a heat setting machine at 80°C for 5 minutes, and then the temperature was adjusted to 120°C and dried for 20 minutes to obtain a temperature-regulating antibacterial microcapsule polyamide fiber.

[0073] Example 5

[0074] (1) Preparation of temperature-regulating antibacterial microcapsules

[0075] S1. Paraffin (n-tetradecane) and tetraethyl silicate were mixed in a mass ratio of 1:1.2, heated to 50° C., and stirred at 500 r / min for 0.5 h to form an oil phase solution;

[0076] S2, sodium dodecyl sulfate and aqueous solvent (m 水 :m 乙醇 =70:30) in a mass ratio of 5:100, heated to 50°C, and stirred at 500r / min for 0.5h to form an aqueous solution;

[0077] S3, mixing the oil phase solution and the water phase solution in a mass ratio of 40:100, stirring at a rate of 10000 r / min, ultrasonic emulsification for 30 min, and homogenizing to form an oil-in-water emulsion;

[0078] S4, adding formamide and tetraethyl silicate dropwise to the oil-in-water emulsion at a molar ratio of 5:1 to initiate hydrolysis and polycondensation of tetraethyl silicate, the reaction temperature is 50° C., the stirring rate is 500 r / min, and after reacting for 20 hours, the microcapsule powder is filtered, washed with water, and dried;

[0079] S5. Add the microcapsule powder into a 4 mol / L CuSO4 aqueous solution, heat to 50°C, and stir at 200 r / min for 4 hours. After the reaction is completed, filter, wash with water, and dry to obtain temperature-regulating antibacterial microcapsules.

[0080] (2) Preparation of temperature-regulating antibacterial polyamide fibers

[0081] S6. In a 15% microcapsule aqueous solution at 50°C, using 5% PU-530 as an adhesive, the PA6 fiber was treated by a two-immersion and two-rolling process, with a rolling rate of 63%. The fiber after immersion and rolling was preheated in a heat setting machine at 80°C for 5 minutes, and then the temperature was adjusted to 120°C and dried for 20 minutes to obtain a temperature-regulating antibacterial microcapsule polyamide fiber.

[0082] Comparative Example 1

[0083] Except that paraffin (n-octadecane) and tetraethyl silicate are mixed in a mass ratio of 1:0.6 in step S1, the rest is the same as in Example 1.

[0084] Comparative Example 2

[0085] Except that paraffin (n-octadecane) and tetraethyl silicate are mixed in a mass ratio of 1:1.4 in step S1, the rest is the same as in Example 1.

[0086] Comparative Example 3

[0087] In addition to step S2, the m of the aqueous solvent 水 :m 乙醇 Except for the ratio of 20:80, the rest is consistent with Example 1.

[0088] Comparative Example 4

[0089] In addition to step S2, the m of the aqueous solvent 水 :m 乙醇 Except for the ratio of 90:10, the rest are consistent with Example 1.

[0090] Comparative Example 5

[0091] In addition to step S3, m 油相溶液 :m 水相溶液 =10:100, the rest are consistent with Example 1.

[0092] Comparative Example 6

[0093] In addition to step S3, m 油相溶液 :m 水相溶液 =50:100, the rest are consistent with Example 1.

[0094] Comparative Example 7

[0095] Except that in step S4, the molar ratio of ammonia water to tetraethyl silicate is 4:1, the rest is consistent with Example 1.

[0096] Comparative Example 8

[0097] Except that in step S4, the molar ratio of ammonia water to tetraethyl silicate is 12:1, the rest is consistent with Example 1.

[0098] Comparative Example 9

[0099] Except that in step S5, the concentration of the Ag2SO4 aqueous solution is 0.5 mol / L, the rest is consistent with Example 1.

[0100] Comparative Example 10

[0101] Except that in step S5, the concentration of the Ag2SO4 aqueous solution is 5 mol / L, the rest is consistent with Example 1.

[0102] Comparative Example 11

[0103] Except that in step S6, the mass fraction of the microcapsule aqueous solution is 5%, the rest is consistent with Example 1.

[0104] Comparative Example 12

[0105] Except that in step S6, the mass fraction of the microcapsule aqueous solution is 25%, the rest is consistent with Example 1.

[0106] Performance Testing:

[0107] The test standard for microcapsule surface morphology refers to: JY / T 0584-2020; the test standard for microcapsule particle size distribution refers to: GB / T19077-2016; the test standard for microcapsule DSC refers to: GB / T 19466.1-2004; the test standard for fiber antibacterial performance refers to GB / T 20944.3-2008. The characterization results of temperature-regulating and antibacterial microcapsules are shown in Table 2, and the antibacterial effect of polyamide fibers loaded with temperature-regulating and antibacterial microcapsules is shown in Table 3.

[0108] Table 2

[0109]

[0110] Table 3

[0111]

[0112]

[0113] According to the test results in Table 1-2, the thermoregulating antibacterial microcapsules prepared in Examples 1 to 5 of the present invention have complete coating and uniform particle size of about 1 μm; thermoregulating microcapsules in the temperature range of 6 to 56°C can be prepared by controlling the core material composition, the phase change enthalpy is 131 to 167 J / g, the microcapsule coverage rate is above 90%, and the mass fraction of the loaded metal can reach 2.2%.

[0114] A comprehensive comparison of Example 1 with Comparative Examples 1 and 2 shows that the ratio of the core material and the wall material needs to be adapted. When the ratio of the core material is too large, the ratio of the microcapsules covering the core material is large, the latent heat of phase change is large, the average particle size of the microcapsules is large, but the prepared microcapsules are unstable and there is a risk of shell rupture; when the ratio of the wall material is too large, the wall material polymer will stick to the surface of the microcapsule, affecting the phase change temperature adjustment effect.

[0115] A comprehensive comparison of Example 1 with Comparative Examples 3 and 4 shows that the ratio of water to ethanol in the aqueous solvent needs to be adapted. Tetraethyl silicate is insoluble in water but soluble in ethanol. If the ethanol content in the aqueous solvent is too low, tetraethyl silicate cannot be enriched from the oil phase solution to the outside, which is not conducive to the later polymerization coating; if the ethanol content in the aqueous solvent is too high, it is not conducive to the emulsification of the solution and cannot be effectively coated to form microcapsules.

[0116] Within a certain range, as the emulsifier content increases, the particle size of the microcapsules becomes smaller, the specific surface area becomes larger, and the amount of complexed metal increases. A comprehensive comparison of Example 1 with Comparative Examples 5 and 6 shows that when the amount of emulsifier is too small, the oil phase in the emulsion cannot be fully emulsified and dispersed, and the enrichment ability for the wall material monomer is also poor, and the prepared microcapsules are easy to agglomerate and have irregular shapes; when the amount of emulsifier is too high, after the emulsifier molecules on the surface of the paraffin droplets reach saturation, the free emulsifier molecules can also enrich part of the wall material precursors, affecting the coverage rate of the wall material to the core material.

[0117] A comprehensive comparison of Example 1 with Comparative Examples 7 and 8 shows that when the amount of alkaline liquid ammonia water is too small, the reaction of tetraethyl silicate is not complete and the coverage rate is low; when the amount of ammonia water is too large, it will trigger a reaction between the microcapsule wall materials, resulting in stickiness, affecting the phase change temperature control effect.

[0118] A comprehensive comparison of Example 1 with Comparative Examples 9 and 10 shows that the concentration of the metal salt solution is too low, and the amount of metal ions complexed on the surface of the microcapsules is insufficient; after reaching saturation, the amount of metal ions complexed on the surface of the microcapsules will not increase significantly even if the concentration of the metal salt solution is further increased.

[0119] A comprehensive comparison of Example 1 with Comparative Examples 11 and 12 shows that the concentration of the microcapsule aqueous solution is too low, the temperature-regulating antibacterial microcapsules loaded on the fiber surface are small, and the antibacterial effect is weak; as the concentration of the microcapsule aqueous solution increases, the content of the temperature-regulating antibacterial microcapsules loaded on the fiber surface gradually increases and reaches saturation, and the antibacterial effect will not be significantly improved at this time.

[0120] Through a comprehensive comparison of Examples 1 to 5 and Comparative Examples 1 to 12, it can be seen that by using 5% by mass PU-530 as an adhesive, the PA6 fiber loaded with microcapsules still has obvious antibacterial properties against Escherichia coli and Staphylococcus aureus after washing 30 times.

[0121] Although this specification is described according to implementation modes, not every implementation mode includes only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

[0122] Therefore, the above description is only a preferred embodiment of the present application and is not intended to limit the scope of implementation of the present application; that is, all equivalent changes made according to the scope of the claims of the present application are within the protection scope of the claims of the present application.

Claims

1. A method for preparing a temperature-regulating antibacterial microcapsule material, characterized in that: The following steps are involved: S1, mixing paraffin wax and microcapsule wall material precursor, heating and stirring to form an oil phase solution; S2, dispersing the emulsifier in the aqueous phase solvent, heating and stirring to form an aqueous phase solution; S3, mixing the oil phase solution and the water phase solution evenly, and obtaining a homogeneous oil-in-water emulsion after ultrasonic emulsification; S4, adding alkali solution dropwise into the oil-in-water emulsion to initiate hydrolysis and polycondensation reaction of the microcapsule wall material precursor, and filtering, washing and drying the obtained product to obtain microcapsule powder; S5, adding the microcapsule powder into the metal salt solution, reacting under heating and stirring conditions, filtering the obtained product, washing with water, and drying to obtain the temperature-regulating antibacterial microcapsule material.

2. The preparation method according to claim 1, characterized in that: The paraffin wax is at least one of n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, n-docosane, n-tetracosane and n-hexacosane; the microcapsule wall material precursor is at least one of tetramethyl silicate, tetraethyl silicate and tetra-n-butyl silicate.

3. The preparation method according to claim 1, characterized in that: The emulsifier is at least one of hexadecyltrimethylammonium bromide and sodium dodecyl sulfate; the aqueous phase solvent is a mixture of water and ethanol in a weight ratio of (60-70): (40-30); the alkali solution is at least one of ammonia water and formamide.

4. The preparation method according to claim 1, characterized in that: The metal salt solution is Ag + , Cu 2+ 、Zn 2+ At least one of the aqueous solutions, the concentration of the metal salt solution is 1 to 4 mol / L.

5. The preparation method according to claim 1, characterized in that: In step S1, paraffin wax and microcapsule wall material precursor are mixed in a mass ratio of 1: (0.8-1.2), and heated and stirred. Specifically, the mixture is heated to 40-60° C. and stirred at 400-600 r / min for at least 0.5 h.

6. The preparation method according to claim 1, characterized in that: In step S2, the emulsifier and the aqueous phase solvent are mixed in a mass ratio of (2 to 6): 100, and heated and stirred. Specifically, the mixture is heated to 40 to 60° C. and stirred at 400 to 600 r / min for at least 0.5 h.

7. The preparation method according to claim 1, characterized in that: In step S3, the oil phase solution and the water phase solution are mixed in a ratio of (15-45) to 100 by weight, and the ultrasonic emulsification time is 20-40 minutes.

8. The preparation method according to claim 1, characterized in that: In step S4, the molar ratio of alkali to microcapsule wall material precursor in the alkali solution is (5-10):

1.

9. An application of a temperature-regulating antibacterial microcapsule material as claimed in claims 1 to 8 on a temperature-regulating antibacterial polyamide fiber, characterized in that: The preparation method of the temperature-regulating antibacterial polyamide fiber is as follows: A 10-20% by mass fraction of a temperature-regulating antibacterial microcapsule aqueous solution at 40-60°C is added with a 3-8% by mass fraction adhesive, and the polyamide fiber is treated by a double-dipping and double-rolling process with a rolling rate of 50-70%. The dipped and rolled fiber is preheated in a heat setting machine at 80°C for 5 minutes, and then the temperature is adjusted to 120°C for drying for 20 minutes to obtain a temperature-regulating antibacterial polyamide fiber.

10. A use according to claim 9, characterized in that The adhesive is water-soluble polyurethane.

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