A composite fabric for heat-retaining clothing and a preparation process thereof

Abstract

The present application relates to a kind of composite fabric for heat retention clothing and its preparation process, belong to textile fabric technical field.The composite fabric is made of graphene modified polyester fiber, cotton fiber and wool is blended according to specific mass ratio;Wherein, graphene modified polyester fiber is made by hydrothermal method in nanoscale composite graphene and medical stone, then by melt spinning, it has the high thermal conductivity of graphene and the high far infrared emissivity of medical stone.The fabric is made by blending weaving, and is treated by finishing liquid, the formula of the finishing liquid is as follows, by weight percentage, water-based polyurethane dispersion 8~12%, nano silver colloid 1~1.5%, nano boron nitride 0.5~1%, hydrophilic amino silicone oil 1.5~2.5%, tea polyphenol extract 0.3~0.5%, the rest is deionized water.The composite fabric of the present application realizes the synergistic thermal management of internal heating and external temperature locking, and has the comprehensive performance of good warm-keeping performance, high comfort and high antibacterial rate.

Description

Technical Field

[0001] This invention belongs to the field of textile fabric technology, and relates to a composite fabric for heat-generating and warm clothing and its preparation process. Background Technology

[0002] The field of thermal clothing focuses on developing functional garments that provide long-lasting, efficient warmth while ensuring comfort. As people's living standards improve and their needs for outdoor activities and demanding work environments increase, the performance requirements for thermal clothing are becoming increasingly stringent.

[0003] Traditional thermal insulation fabrics, such as wool and down, primarily rely on the physical properties of the materials to achieve their warmth-retaining function. However, they suffer from limitations such as limited insulation performance, large size and weight, and a lack of active heating capabilities. With technological advancements, new types of heat-generating thermal insulation fabrics are constantly emerging, among which heat-generating fabrics based on the principle of electrothermal conversion have attracted considerable attention. These fabrics typically integrate conductive materials into the fibers or on the fabric surface. Powered by an external power source, these conductive materials heat up, thus achieving active heating and warmth. However, they also present challenges such as complex manufacturing processes and safety concerns regarding electrothermal fabrics.

[0004] Therefore, there is an urgent need to develop a composite fabric for heat-generating and heat-insulating clothing and its preparation process. Summary of the Invention

[0005] The purpose of this invention is to provide a composite fabric for heat-generating and heat-insulating clothing and its preparation process, which has the characteristics of good heat-generating and heat-insulating effects.

[0006] The objective of this invention can be achieved through the following technical solutions: A composite fabric for heat-generating and thermal insulation clothing, said composite fabric is made of a blend of graphene-modified polyester fiber, cotton fiber, and wool. The preparation method of graphene-modified polyester fiber is as follows: S1-1: The pretreated nano-maifan stone is added to the graphene oxide aqueous dispersion and ultrasonically dispersed for 2-4 h. Then it is transferred to a reaction vessel and treated at 180-220℃ for 6-8 h. After filtration, washing and drying, the composite powder is obtained. S1-2: The composite powder is ball-milled with polyethylene glycol-400 and polyethylene terephthalate chips for 10-30 min at a speed of 150-250 rpm. Then, the mixture is melt-blended and granulated at 200-240℃ using a twin-screw extruder to obtain the functional masterbatch. S1-3: The functional masterbatch is mixed with polyethylene terephthalate chips and vacuum dried at 120~140℃ for 4~8 h to obtain a blend. S1-4: The blend is fed into a screw extrusion spinning machine, melted at 265~285℃, extruded through a spinneret, and cooled in air to form nascent fibers; S1-5: The nascent fiber is subjected to primary stretching at 75~95℃, followed by secondary stretching at 120~140℃, with a total stretching ratio of 3~5. Finally, it is relaxed and heat-set at 130~150℃ to obtain the graphene-modified polyester fiber.

[0007] As a preferred embodiment of the present invention, the pretreatment step of nano-maifan stone in S1-1 is to purify it by acid washing and then modify it with γ-aminopropyltriethoxysilane.

[0008] As a preferred embodiment of the present invention, the mass ratio of nano-maifanite and graphene oxide in S1-1 is (1~2):10.

[0009] As a preferred embodiment of the present invention, the amount of polyethylene glycol-400 added in S1-2 is 10-20% of the mass of the composite powder.

[0010] As a preferred embodiment of the present invention, the mass ratio of the composite powder to the polyethylene terephthalate chips in S1-2 is (1~1.5):10.

[0011] As a preferred embodiment of the present invention, the functional masterbatch and polyethylene terephthalate chips in S1-3 are mixed at a mass ratio of 1:(15~25).

[0012] As a preferred embodiment of the present invention, the mass ratio of the graphene-modified polyester fiber, cotton fiber and wool is (30~40):(20~30):(5~10).

[0013] A process for preparing a composite fabric for heat-generating and thermally insulating clothing, the specific steps of which are as follows: The graphene-modified polyester fiber, cotton fiber and wool are blended to form yarn, and the yarn is woven into a greige fabric by a loom. The greige fabric is immersed in a finishing solution at 40~50℃ for 10~20 min, and the immersed fabric is pre-dried at 80~90℃ for 3~5 min, then dried at 130~140℃, and then washed and shaped to obtain the composite fabric.

[0014] As a preferred embodiment of the present invention, the finishing liquid is formulated as follows: by weight percentage, 8-12% aqueous polyurethane dispersion, 1-1.5% nano silver colloid, 0.5-1% nano boron nitride, 1.5-2.5% hydrophilic amino silicone oil, 0.3-0.5% tea polyphenol extract, and the balance being deionized water.

[0015] As a preferred embodiment of the present invention, after impregnation, the sample is rolled to a liquid content of 55-65%.

[0016] The graphene-modified polyester fiber prepared in this invention utilizes a hydrothermal method to construct a composite structure of graphene and maifan stone at the nanoscale, which is then uniformly dispersed within a polyester matrix. Nano-maifan stone is a highly efficient far-infrared radiation material; when excited by human body temperature, it continuously radiates far-infrared rays of 4-14 μm. This wavelength is easily absorbed by the human body and converted into heat energy, producing a perceived warming effect. Graphene forms a highly thermally conductive network framework, enabling rapid and uniform transfer of human body heat to the maifan stone particles throughout the fiber, further improving the heating efficiency and response speed of maifan stone and avoiding the shortcomings of slow thermal response and uneven heating of traditional far-infrared materials. The two-dimensional structure of graphene has high thermal conductivity; when a localized area of ​​the human body overheats, it can rapidly diffuse heat to a larger area of ​​the fabric, preventing heat accumulation; when the environment cools, it can evenly distribute human body heat, reducing cold spots. Furthermore, the far-infrared rays emitted by maifan stone have a wavelength similar to the vibrational frequency of human cell molecules, which, through molecular resonance, helps promote local blood circulation.

[0017] 30-40% graphene-modified fibers serve as the core function, providing a highly efficient far-infrared radiation source and a rapid heat conduction network, laying the foundation for the fabric's active heating performance. Simultaneously, the 5-10% wool's naturally crimped, fluffy structure constructs a highly efficient static air insulation layer within the fabric, synergizing with active heating to significantly improve overall warmth retention and avoid the heat loss issues that can occur with relying solely on functional fibers. 20-30% cotton fibers quickly absorb perspiration, preventing a cold, damp feeling on the skin; they also ensure that absorbed moisture is promptly evaporated or conducted to the graphene fiber areas, whose heating effect effectively counteracts the coldness caused by evaporation. Furthermore, the addition of cotton and wool greatly improves the feel of pure synthetic fabrics, giving them a soft, skin-friendly natural touch and better drape. The small amount of wool also enhances the fabric's elasticity and pilling resistance, achieving an optimal balance between performance and cost.

[0018] The aqueous polyurethane dispersion in the finishing solution forms a continuous, soft film on the fiber surface, firmly adhering other functional components and imparting a certain degree of abrasion resistance and anti-pilling properties to the fabric, without affecting its breathability. Nano-boron nitride, a low-infrared emissivity material, works synergistically with maifan stone. The maifan stone within the fabric radiates far-infrared rays for active heating, while the surface-finished nano-boron nitride reflects heat lost through radiant radiation back into the fabric, thus locking in heat. This, combined with the internal heating function of the fibers, forms a synergistic system of internal heating and external heat retention, significantly improving overall warmth retention efficiency and reducing heat loss. Hydrophilic amino silicone oil, acting as a softener and hydrophilic modifier, gives the fabric a smooth, soft feel and enhances its moisture-wicking properties, improving wearing comfort. Nano-silver colloids provide the fabric with excellent antibacterial effects. Tea polyphenol extract, as a natural antibacterial synergist, when combined with nano-silver, broadens the antibacterial spectrum and delays silver ion resistance. At the same time, as an antioxidant and stabilizer, it prevents the unsaturated groups in nano-silver and fibers from oxidizing and discoloring, thus improving the color durability of the fabric. In addition, it also helps to stabilize and disperse nano-silver and form weak bonds with fibers, thereby improving the washability of the finishing effect.

[0019] The beneficial effects of this invention are: This invention constructs a nanocomposite structure of graphene and maifan stone using a hydrothermal method and uniformly disperses it in polyester fibers, achieving a synergistic effect of active heating and efficient heat distribution. Maifan stone, when stimulated by body temperature, continuously radiates far-infrared rays that are easily absorbed by the human body, generating a direct warming sensation. The highly thermally conductive three-dimensional network constructed by graphene not only rapidly transfers heat to each maifan stone particle, improving its heating response speed, but also prevents localized overheating or overcooling. After blending graphene-modified fibers with cotton and wool in a specific ratio, the instantaneous moisture absorption and wicking capacity of cotton is further integrated with the long-lasting static air layer insulation effect of wool, forming a dynamic comfort system of moisture absorption, heat generation, and heat preservation, significantly improving the overall warmth retention rate. Finally, after finishing treatment, a multifunctional protective layer is constructed on the fiber surface: nano-boron nitride and the internal heating element together form a three-dimensional warmth preservation system of internal heating and external heat retention; nano-silver and tea polyphenols provide long-lasting broad-spectrum antibacterial properties; and hydrophilic amino silicone oil gives the fabric a soft and smooth touch and excellent hydrophilicity. Detailed Implementation

[0020] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0021] It should be noted that, unless otherwise specified, the present invention does not specifically limit the source of the raw materials used in the following embodiments. Commercially available products or products prepared by conventional preparation methods that are well known to those skilled in the art can be used. Experimental methods that do not specify specific conditions are all conventional methods and conventional conditions well known in the art.

[0022] The pretreatment steps for nano-maifan stone are as follows: place nano-maifan stone powder in a 2 M hydrochloric acid solution, stir at 65℃ for 2 h, and obtain powder A by centrifugation, washing and drying; γ-aminopropyltriethoxysilane, ethanol and deionized water were mixed in a mass ratio of 1:49:1, the pH was adjusted to 4.5, and the mixture was stirred at room temperature for 30 min to obtain solution B. Powder A was dispersed in anhydrous ethanol, and solution B was added dropwise while stirring. The mixture was refluxed at 70°C for 4 h, and the pretreated nano-maifan stone was obtained by centrifugation, washing and drying. Example 1

[0023] A composite fabric for heat-generating and thermal insulation clothing, said composite fabric is made of a blend of graphene-modified polyester fiber, cotton fiber, and wool. The preparation method of graphene-modified polyester fiber is as follows: S1-1: The pretreated nano-maifan stone was added to the graphene oxide aqueous dispersion. The mass ratio of nano-maifan stone to graphene oxide was 1.5:10. The dispersion was ultrasonically dispersed for 3 h, and then transferred to a reaction vessel and treated at 200℃ for 7 h. After filtration, washing and drying, the composite powder was obtained. S1-2: The composite powder, polyethylene glycol-400, and polyethylene terephthalate chips were ball-milled and mixed for 20 minutes. The amount of polyethylene glycol-400 added was 15% of the mass of the composite powder, and the mass ratio of the composite powder to the polyethylene terephthalate chips was 1.2:10. The ball milling speed was 200 rpm. Then, the mixture was melt-blended and granulated at 220℃ using a twin-screw extruder to obtain the functional masterbatch. S1-3: The functional masterbatch and polyethylene terephthalate chips are mixed at a mass ratio of 1:20 and vacuum dried at 130°C for 6 h to obtain a blend. S1-4: The blend is fed into a screw extrusion spinning machine, melted at 275°C, extruded through a spinneret, and cooled in air to form nascent fibers; S1-5: The nascent fiber is subjected to primary stretching at 85°C, followed by secondary stretching at 130°C, with a total stretching ratio of 4. Finally, it is relaxed and heat-set at 140°C to obtain the graphene-modified polyester fiber.

[0024] A process for preparing a composite fabric for heat-generating and thermally insulating clothing, the specific steps of which are as follows: The graphene-modified polyester fiber, cotton fiber, and wool are blended in a mass ratio of 35:25:7 to form yarn. The yarn is woven into a greige fabric using a loom. The greige fabric is immersed in a finishing solution at 45°C for 15 minutes, removed, and rolled to a liquid retention rate of 60%. The rolled fabric is pre-dried at 85°C for 4 minutes, then dried at 135°C, and finally washed and shaped to obtain the composite fabric.

[0025] The finishing solution has the following formulation by weight percentage: 10% aqueous polyurethane dispersion, 1.2% nano silver colloid, 0.8% nano boron nitride, 2% hydrophilic amino silicone oil, 0.4% tea polyphenol extract, and the balance being deionized water. Example 2

[0026] A composite fabric for heat-generating and thermal insulation clothing, said composite fabric is made of a blend of graphene-modified polyester fiber, cotton fiber, and wool. The preparation method of graphene-modified polyester fiber is as follows: S1-1: The pretreated nano-maifan stone was added to the graphene oxide aqueous dispersion at a mass ratio of 1:10. The dispersion was ultrasonically dispersed for 2 h, then transferred to a reaction vessel and treated at 180℃ for 6 h. After filtration, washing and drying, the composite powder was obtained. S1-2: The composite powder, polyethylene glycol-400, and polyethylene terephthalate chips were ball-milled and mixed for 10 min. The amount of polyethylene glycol-400 added was 10% of the mass of the composite powder, and the mass ratio of the composite powder to the polyethylene terephthalate chips was 1:10. The ball milling speed was 150 rpm. Then, the mixture was melt-blended and granulated at 200℃ using a twin-screw extruder to obtain the functional masterbatch. S1-3: The functional masterbatch and polyethylene terephthalate chips are mixed at a mass ratio of 1:15 and vacuum dried at 120°C for 4 h to obtain the blend. S1-4: The blend is fed into a screw extrusion spinning machine, melted at 265°C, extruded through a spinneret, and cooled in air to form nascent fibers; S1-5: The nascent fiber is subjected to primary stretching at 75°C, followed by secondary stretching at 120°C, with a total stretching ratio of 3. Finally, it is relaxed and heat-set at 130°C to obtain the graphene-modified polyester fiber.

[0027] A process for preparing a composite fabric for heat-generating and thermally insulating clothing, the specific steps of which are as follows: The graphene-modified polyester fiber, cotton fiber, and wool are blended in a mass ratio of 30:20:5 to form yarn. The yarn is woven into a greige fabric using a loom. The greige fabric is immersed in a finishing solution at 40°C for 20 minutes. After removal, it is rolled to a liquid retention rate of 55%. The rolled fabric is pre-dried at 80°C for 5 minutes, then dried at 130°C, and finally washed and shaped to obtain the composite fabric.

[0028] The finishing solution has the following formulation by weight percentage: 8% aqueous polyurethane dispersion, 1% nano silver colloid, 0.5% nano boron nitride, 1.5% hydrophilic amino silicone oil, 0.3% tea polyphenol extract, and the balance being deionized water. Example 3

[0029] A composite fabric for heat-generating and thermal insulation clothing, said composite fabric is made of a blend of graphene-modified polyester fiber, cotton fiber, and wool. The preparation method of graphene-modified polyester fiber is as follows: S1-1: The pretreated material was added to the graphene oxide aqueous dispersion. The mass ratio of nano-maifanite to graphene oxide was 2:10. The mixture was ultrasonically dispersed for 4 h, then transferred to a reaction vessel and treated at 220℃ for 8 h. After filtration, washing and drying, the composite powder was obtained. S1-2: The composite powder, polyethylene glycol-400, and polyethylene terephthalate chips were ball-milled for 30 minutes. The amount of polyethylene glycol-400 added was 20% of the mass of the composite powder, and the mass ratio of the composite powder to the polyethylene terephthalate chips was 1.5:10. The ball milling speed was 250 rpm. Then, the mixture was melt-blended and granulated at 240°C using a twin-screw extruder to obtain the functional masterbatch. S1-3: The functional masterbatch and polyethylene terephthalate chips are mixed at a mass ratio of 1:25 and vacuum dried at 140°C for 8 h to obtain a blend. S1-4: The blend is fed into a screw extrusion spinning machine, melted at 285°C, extruded through a spinneret, and cooled in air to form nascent fibers; S1-5: The nascent fiber is subjected to primary stretching at 95°C, followed by secondary stretching at 140°C, with a total stretching ratio of 5. Finally, it is relaxed and heat-set at 150°C to obtain the graphene-modified polyester fiber.

[0030] A process for preparing a composite fabric for heat-generating and thermally insulating clothing, the specific steps of which are as follows: The graphene-modified polyester fiber, cotton fiber, and wool are blended in a mass ratio of 40:30:10 to form yarn. The yarn is woven into a greige fabric using a loom. The greige fabric is immersed in a finishing solution at 50°C for 10 minutes. After removal, it is rolled to a liquid retention rate of 65%. The rolled fabric is pre-dried at 90°C for 3 minutes, then dried at 140°C, and finally washed and shaped to obtain the composite fabric.

[0031] The finishing solution has the following formulation by weight percentage: 12% aqueous polyurethane dispersion, 1.5% nano silver colloid, 1% nano boron nitride, 2.5% hydrophilic amino silicone oil, 0.5% tea polyphenol extract, and the balance being deionized water.

[0032] Comparative Example 1 The difference between this comparative example and Example 1 is that unmodified polyester fiber is used instead of graphene-modified polyester fiber; otherwise, they are the same as in Example 1.

[0033] Comparative Example 2 The difference between this comparative example and Example 1 is that graphene oxide is not added; otherwise, they are the same as in Example 1.

[0034] Comparative Example 3 The difference between this comparative example and Example 1 is that no nano-maifan stone was added; otherwise, they are the same as in Example 1.

[0035] Comparative Example 4 The difference between this comparative example and Example 1 is that no pretreatment of the nano-maifan stone is performed; otherwise, they are the same as in Example 1.

[0036] Comparative Example 5 The difference between this comparative example and Example 1 is that no nano boron nitride is added to the finishing solution; otherwise, they are the same as in Example 1.

[0037] Comparative Example 6 The difference between this comparative example and Example 1 is that no tea polyphenol extract was added to the finishing solution; otherwise, they are the same as in Example 1.

[0038] Comparative Example 7 The difference between this comparative example and Example 1 is that no nano-silver colloid is added to the finishing solution; otherwise, they are the same as in Example 1.

[0039] Performance testing The thermal insulation performance of the composite fabric prepared according to the test examples was determined according to GB / T11048-2008 standard; the far-infrared radiation temperature rise of the composite fabric prepared according to the test examples was determined according to GB / T 30127-2013 standard; and the antibacterial performance of the composite fabric prepared according to the test examples was determined according to GB / T20944.3-2008 standard. The specific experimental results are summarized in the table below.

[0040] As can be seen from the examples and comparative data, the composite fabric of the present invention has good warmth retention and antibacterial properties.

[0041] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention are still within the scope of the present invention.

Claims

1. A composite fabric for heat-generating and thermal clothing, characterized in that, The composite fabric is made of a blend of graphene-modified polyester fiber, cotton fiber, and wool. The preparation method of graphene-modified polyester fiber is as follows: S1-1: The pretreated nano-maifan stone is added to the graphene oxide aqueous dispersion and ultrasonically dispersed for 2-4 h. Then it is transferred to a reaction vessel and treated at 180-220℃ for 6-8 h. After filtration, washing and drying, the composite powder is obtained. S1-2: The composite powder is ball-milled with polyethylene glycol-400 and polyethylene terephthalate chips for 10-30 minutes at a speed of 150-250 rpm. Then, the mixture is melt-blended and granulated at 200-240℃ using a twin-screw extruder to obtain the functional masterbatch. S1-3: The functional masterbatch is mixed with polyethylene terephthalate chips and vacuum dried at 120~140℃ for 4~8 h to obtain a blend. S1-4: The blend is fed into a screw extrusion spinning machine, melted at 265~285℃, extruded through a spinneret, and cooled in air to form nascent fibers; S1-5: The nascent fiber is subjected to primary stretching at 75~95℃, followed by secondary stretching at 120~140℃, with a total stretching ratio of 3~5. Finally, it is relaxed and heat-set at 130~150℃ to obtain the graphene-modified polyester fiber.

2. The composite fabric for heat-generating and thermal clothing according to claim 1, characterized in that, The pretreatment steps for the nano-maifanite in S1-1 are acid washing purification and surface modification with γ-aminopropyltriethoxysilane.

3. The composite fabric for heat-generating and thermal clothing according to claim 1, characterized in that, The mass ratio of nano-maifanite and graphene oxide in S1-1 is (1~2):

10.

4. The composite fabric for heat-generating and thermal clothing according to claim 1, characterized in that, The amount of polyethylene glycol-400 added in S1-2 is 10-20% of the mass of the composite powder.

5. A composite fabric for heat-generating and thermal clothing according to claim 1, characterized in that, The mass ratio of the composite powder to polyethylene terephthalate chips in S1-2 is (1~1.5):

10.

6. The composite fabric for heat-generating and thermal clothing according to claim 1, characterized in that, The functional masterbatch in S1-3 is mixed with polyethylene terephthalate chips at a mass ratio of 1:(15~25).

7. The composite fabric for heat-generating and thermal clothing according to claim 1, characterized in that, The mass ratio of the graphene-modified polyester fiber, cotton fiber and wool is (30~40):(20~30):(5~10).

8. A process for preparing a composite fabric for heat-generating and thermally insulating clothing as described in any one of claims 1 to 7, characterized in that, The specific steps of the preparation process are as follows. The graphene-modified polyester fiber, cotton fiber and wool are blended to form yarn, and the yarn is woven into a greige fabric by a loom. The greige fabric is immersed in a finishing solution at 40~50℃ for 10~20 min, and the immersed fabric is pre-dried at 80~90℃ for 3~5 min, then dried at 130~140℃, and then washed and shaped to obtain the composite fabric.

9. The preparation process of a composite fabric for heat-generating and thermal clothing according to claim 8, characterized in that, The finishing solution has the following formulation by weight percentage: 8-12% aqueous polyurethane dispersion, 1-1.5% nano silver colloid, 0.5-1% nano boron nitride, 1.5-2.5% hydrophilic amino silicone oil, 0.3-0.5% tea polyphenol extract, and the balance being deionized water.

10. The preparation process of a composite fabric for heat-generating and thermal clothing according to claim 8, characterized in that, After impregnation, the product is removed and rolled until the liquid content is 55-65%.

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