WO2024066669A1 - Carbon nanofiber-based breathable hazmat suit fabric, and preparation method therefor - Google Patents

Carbon nanofiber-based breathable hazmat suit fabric, and preparation method therefor Download PDF

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Publication number
WO2024066669A1
WO2024066669A1 PCT/CN2023/107139 CN2023107139W WO2024066669A1 WO 2024066669 A1 WO2024066669 A1 WO 2024066669A1 CN 2023107139 W CN2023107139 W CN 2023107139W WO 2024066669 A1 WO2024066669 A1 WO 2024066669A1
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Prior art keywords
carbon nanofiber
layer
adhesive
nanofiber membrane
fabric
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PCT/CN2023/107139
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French (fr)
Chinese (zh)
Inventor
葛建龙
周安琪
张天昊
刘其霞
季涛
单浩如
傅秋霞
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南通大学
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Publication of WO2024066669A1 publication Critical patent/WO2024066669A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B32B37/1292—Application of adhesive selectively, e.g. in stripes, in patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/162—Cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/164—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B32B7/14—Interconnection of layers using interposed adhesives or interposed materials with bonding properties applied in spaced arrangements, e.g. in stripes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing

Definitions

  • the present application belongs to the technical field of anti-virus clothing fabrics, and in particular, relates to a carbon nanofiber-based breathable anti-virus clothing fabric and a preparation method thereof.
  • Carbon nanofiber-based materials have good air permeability and are relatively light. They have important application value in some occasions where the concentration of toxic and harmful chemical pollutants is low and the amount of human movement is large. Carbon nanofiber-based materials use the barrier and adsorption effects of clothing fabrics on biochemical reagent liquids, aerosols, and vapors to achieve a protective effect. The heat and moisture generated by the human body inside the clothing can be dissipated through the fabric, thereby improving the thermal and moisture comfort of wearing protective clothing. Carbon nanofiber-based breathable anti-virus clothing fabrics are usually made of a composite of multiple functional layers, and the core functional layer is the functional layer.
  • carbon nanofiber-based breathable anti-virus clothing fabrics mainly use activated carbon particles or carbon-doped polymer fibers to prepare the functional layer.
  • the existing breathable chemical protective fabric technology still has some bottleneck problems: (1) The functional layer of activated carbon particles is easy to fall off and agglomerate, which causes the uniformity of the functional layer structure to change, thereby affecting the protective stability of the composite fabric; (2) Doping activated carbon into fibers to form carbon-doped fibers can significantly improve the structural stability of the functional layer, but since a considerable portion of the activated carbon doped into the polymer is embedded in the fiber, it is difficult to fully exert the adsorption performance of the activated carbon, thereby affecting the further improvement of the adsorption performance of the functional layer.
  • Carbon nanofiber membrane is obtained by carbonizing polymer nanofiber membrane.
  • Carbon nanofiber membrane has small pore size, high porosity, The advantages of high specific surface area make it have broad application prospects in the field of toxic and harmful chemical gas or aerosol adsorption.
  • due to the poor mechanical properties of carbon nanofiber membranes and easy delamination there is currently no effective technology to realize the composite of carbon nanofiber membranes and traditional fabrics, and related composite fabrics are rarely reported. Therefore, the development of carbon nanofiber-based breathable anti-virus clothing fabrics is of great significance to further improve the application performance of nanofiber-based anti-virus clothing fabrics and enrich their application fields.
  • the present application provides a carbon nanofiber-based breathable anti-virus clothing fabric with good protective effect and stable structure and a preparation method thereof.
  • the technical solution of the present application is: a carbon nanofiber-based breathable anti-virus clothing fabric, the fabric including a base layer, a functional layer and a protective layer, the functional layer is a carbon nanofiber membrane, and also includes a plurality of dispersed bonding points, the bonding points are adhesives embedded in the carbon nanofiber membrane and attached to the upper and lower surfaces of the carbon nanofiber membrane at the same position, the adhesive attached to the lower surface of the carbon nanofiber membrane is the lower bonding layer, the lower bonding layer is bonded to the base layer, the adhesive attached to the upper surface of the carbon nanofiber membrane is the upper bonding layer, the upper bonding layer is bonded to the protective layer.
  • the base layer and the protective layer are woven fabrics
  • the base layer is made of one of nylon and polyester
  • the protective layer is made of one of nylon and aramid.
  • the bonding points are distributed in a strip-shaped dispersion, the vertical strip spacing is 0.5-2 cm, and the bonding point spacing within the vertical strip is 0.5-1 cm.
  • the fabric further includes a base layer, a functional layer and a lower adhesive layer forming a lower cavity, and a protective layer, a functional layer and an upper adhesive layer forming an upper cavity.
  • the adhesive is one of an oily epoxy resin adhesive, an oily phenolic resin adhesive, and a polymethylsiloxane adhesive.
  • the method for preparing the carbon nanofiber membrane comprises the following steps: step 1, using a mixture of polyacrylonitrile and thermosetting phenolic resin in a mass ratio of 3:2 as a spinning polymer system, hydrophobic silica nanoparticles as a doping material, and N,N-dimethylformamide as a spinning solvent, to prepare a precursor nanofiber membrane by continuous electrospinning; step 2, first treating the precursor nanofiber membrane at 150°C in a blast oven for 0.5h, and then heating it to 240°C for 2h; step 3, carbonizing the heat-treated precursor nanofiber membrane at 650-950°C for 2h under the protection of high-purity N2 .
  • the preparation method of the above-mentioned carbon nanofiber-based breathable anti-virus clothing fabric includes the following steps: Step 1 is bonding point coating, preparing a carbon nanofiber membrane and coating an adhesive on its upper surface to form bonding points, the adhesive is embedded in the carbon nanofiber membrane and attached to the lower surface of the carbon nanofiber membrane to form a lower bonding layer and the upper surface to form an upper bonding layer; Step 2 is bonding of each layer, after cleaning and drying the base layer and the protective layer, the base layer is bonded to the lower bonding layer, and the protective layer is bonded to the upper bonding layer to obtain a composite fabric; Step 3, the composite fabric obtained in Step 2 is cured.
  • the curing treatment is a heating treatment with a treatment temperature of 100-150° C. and a treatment time of 10-35 min.
  • the anti-toxic clothing fabric of the present application is an overall interlayer composite structure.
  • the fabric structure is stable and does not lose carbon and has good air permeability and protective effect.
  • the preparation method is simple and easy and has strong integration of multiple technologies.
  • the fabric performance can be flexibly adjusted according to actual application requirements.
  • Carbon nanofiber membrane is used as the functional layer of the anti-toxic clothing fabric. Compared with activated carbon particles, micron-sized activated carbon fibers and polymer nanofibers, carbon nanofiber membrane not only has the characteristics of high specific surface area, chemical corrosion resistance and heat resistance, but also has the characteristics of small pore size, high porosity and good pore connectivity of nanofiber materials. It can effectively improve the anti-toxic clothing fabric's resistance to toxic gas permeability and its adsorption and interception performance of toxic aerosols (vapors).
  • the use of oily adhesive to embed the carbon nanofiber membrane is beneficial to improving the mechanical properties of the carbon nanofiber membrane and enhancing the internal adhesion of the carbon nanofiber membrane, making it less likely to delaminate.
  • the adhesive is also attached to the upper and lower surfaces of the carbon nanofiber membrane, respectively bonding the base layer and the protective layer, thereby achieving bonding reinforcement between the base layer, the functional layer, and the protective layer, forming an overall interlayer composite structure.
  • Dispersed bonding points are used to form cavities between the layers, which ensures the effective adsorption area of the carbon nanofiber membrane in the fabric while ensuring the air permeability and moisture permeability of the anti-virus clothing fabric. It also helps to cushion the impact of the carbon nanofiber membrane when the fabric is deformed under force.
  • FIG1 is a schematic structural diagram of a carbon nanofiber-based breathable anti-virus clothing fabric according to Example 1;
  • FIG2( a ) is a physical picture of the carbon nanofiber membrane of Example 1;
  • FIG2( b ) is a SEM image of the carbon nanofiber membrane of Example 1;
  • FIG3( a ) is a cross-sectional view of the carbon nanofiber-based breathable anti-virus clothing fabric of Example 1, taken vertically on a horizontal plane;
  • FIG3( b ) is a schematic diagram of the bonding point structure of the carbon nanofiber-based breathable anti-virus clothing fabric of Example 1;
  • FIG4( a ) is a graph showing the permeability of the adhesives of Example 1 and Comparative Example 4 on the upper surface of the carbon nanofiber membrane;
  • FIG4( b ) is a graph showing the permeability of the adhesives of Example 1 and Comparative Example 4 on the lower surface of the carbon nanofiber membrane;
  • 1-base layer 2-functional layer, 3-protective layer, 4-adhesive point, 5-lower adhesive layer, 6-upper adhesive layer, 7-lower cavity, 8-upper cavity.
  • the fabrics used in the following examples are polyester woven fabric, commercially available polyester taffeta fabric, with a grammage of 80 g/m 2 ; nylon woven fabric, commercially available 340T twill nylon, with a grammage of 146 g/m 2 ; aramid woven fabric, commercially available 200D plain aramid cloth, with a grammage of 60 g/m 2 ; polymethylsiloxane adhesive purchased from Dow Chemical Company, oily phenolic resin adhesive purchased from Shenzhen Yoshida Chemical Co., Ltd., and oily epoxy resin adhesive purchased from Ningbo Mingsheng Adhesive Co., Ltd.
  • the carbon nanofiber membrane is an electrospun carbon nanofiber membrane.
  • the carbon sources used to prepare the carbon nanofiber membrane are polyacrylonitrile (molecular weight of 90,000, purchased from Jiangsu Kunshan Hongyu Plastic Co., Ltd.) and thermosetting phenolic resin (purchased from Henan Hengyuan New Materials).
  • Silica nanoparticles and N,N-dimethylformamide are purchased from Shanghai McLean Biochemical Technology Co., Ltd.
  • the electrospinning process uses a 5-nozzle (spacing 5cm) reciprocating electrospinning machine, and the receiving substrate uses a 70cm wide polypropylene non-woven fabric.
  • the electrospinning voltage is 25kV, the spinning distance is 20cm, the temperature is 25°C, and the humidity is 50%; the pre-oxidation of the nanofiber membrane is carried out in a hot air oven, and the carbonization of the nanofiber membrane is carried out in a vacuum tube furnace.
  • the moisture permeability test of the anti-virus clothing fabrics of the embodiments and comparative examples in this application refers to GB/T 12704.2 "Test method for moisture permeability of textile fabrics Part 2: Evaporation method", and the anti-virus performance test of the anti-virus clothing fabrics refers to Appendix B of GJB 3253-1998 "Specifications for flame-retardant camouflage anti-virus clothing” for the "liquid-gas” anti-virus time test method for the inner layer material of the anti-virus clothing; the peel strength of the anti-virus clothing fabrics refers to "FZ/T 60011-2016 Composite fabric peeling strength test method".
  • a carbon nanofiber-based breathable anti-virus clothing fabric includes a base layer 1, a functional layer 2 and a protective layer 3.
  • the functional layer 2 is a carbon nanofiber membrane and also includes a plurality of dispersed bonding points 4.
  • the structure is shown in FIG1 .
  • the bonding points 4 are adhesives embedded in the carbon nanofiber membrane and attached to the upper and lower surfaces of the carbon nanofiber membrane at the same position.
  • the structure of the bonding points 4 is shown in the enlarged view circled in FIG1 .
  • the preparation of the above-mentioned carbon nanofiber membrane includes the following steps: step 1, taking a polyacrylonitrile/thermosetting phenolic resin mixture with a mass ratio of 3:2 as a spinning polymer system, taking hydrophobic silica nanoparticles (particle size 7-40nm) as a doping material, and using N,N-dimethylformamide as a spinning solvent to prepare a spinning solution, wherein the mass of the polymer in the spinning solution is 3.6g, accounting for 12wt% of the total content, and the mass of the silica nanoparticles is 0.54g, accounting for 15% of the mass of the spinning polymer, and 30.54g of the spinning solution is added to an electrospinning machine for spinning to prepare precursor nanofibers; step 2, first treating the precursor nanofibers at 150°C in a blast oven for 0.5h, and then heating to 240°C for 2h; step 3, the heat-treated precursor nanofibers are placed in a high-purity N 2 was carbonized at 850 ° C
  • FIG2(a) is a real picture of the carbon nanofiber membrane
  • FIG2(b) is a SEM image of the carbon nanofiber membrane.
  • the carbon nanofiber membrane not only has the characteristics of high specific surface area, chemical corrosion resistance and heat resistance, but also has the characteristics of small pore size, high porosity and good pore connectivity of nanofiber materials. It can effectively improve the anti-toxic gas permeability resistance of the anti-toxic clothing fabric and the adsorption and interception performance of toxic aerosols (vapors).
  • the preparation of the carbon nanofiber-based breathable anti-virus clothing fabric includes the following steps: Step 1 is bonding point coating, in which the obtained carbon nanofiber membrane is evenly coated with adhesive on its upper surface, the adhesive is embedded in the carbon nanofiber membrane and attached to the upper and lower surfaces of the carbon nanofiber membrane, the adhesive is an oily epoxy resin adhesive, the amount of adhesive used is about 9.72 mg/ cm2 , the vertical strip spacing of the bonding point is 2 cm, and the spacing of the bonding points in the vertical strip is 0.5 cm; Step 2 is bonding of each layer, taking nylon woven fabric and aramid woven fabric, boiling and cleaning, and then fully drying in a blast oven, the nylon woven fabric is the base layer, and the aramid woven fabric is the protective layer composite Fixed on the surface of the carbon nanofiber membrane; Step three is a curing treatment, and the bonding points in the composite fabric obtained in Step two are heated and cured, the heating temperature is 100°C, the time is 35 minutes, and the carbon nanofiber-based breathable anti-virus clothing fabric is
  • Figure 3 (a) is a cross-sectional view of the carbon nanofiber-based breathable anti-virus clothing fabric of this embodiment vertically on the horizontal plane;
  • Figure 3 (b) is a schematic diagram of the bonding point structure of the carbon nanofiber-based breathable anti-virus clothing fabric of this embodiment.
  • the adhesive is attached to the lower surface of the carbon nanofiber membrane as the lower bonding layer 5, and the lower bonding layer 5 is bonded to the base layer 1.
  • the adhesive is attached to the upper surface of the carbon nanofiber membrane as the upper bonding layer 6, and the upper bonding layer 6 is bonded to the protective layer 3.
  • the base layer 1, the functional layer 2 and the lower bonding layer 5 surround the lower cavity 7, and the protective layer 3, the functional layer 2 and the upper bonding layer 6 surround the upper cavity 8; in Figure 3 (b), multiple dispersed bonding points are distributed in a strip-shaped dispersed manner.
  • the carbon nanofiber-based breathable anti-virus clothing fabric obtained in Example 1 has a moisture permeability of about 1685 g/(m 2 ⁇ 24 h), an effective protection time against mustard gas simulant (pentyl sulfide) of more than 48 h, and a peel strength of about 1.18 kN/m.
  • step 3 is to carbonize the heat-treated precursor nanofiber at 650°C for 2h under the protection of high-purity N2 to obtain the carbon nanofiber membrane.
  • the vertical strip spacing of the bonding point is 1cm
  • the bonding point spacing in the vertical strip is 1cm
  • the adhesive is an oily phenolic resin adhesive
  • the amount of adhesive is about 11.3mg/ cm2 ;
  • the base layer is polyester woven fabric, and the protective layer is aramid woven fabric; step 3, during the heating and curing treatment, the heating temperature is 125°C and the time is 20min.
  • the carbon nanofiber-based breathable anti-virus clothing fabric obtained in this embodiment has a moisture permeability of about 1420 g/(m 2 ⁇ 24 h), an effective protection time against mustard gas simulant (pentyl sulfide) of more than 48 h, and a peel strength of about 1.244 kN/m.
  • step 3 is to carbonize the heat-treated precursor nanofiber at 950°C for 2h under the protection of high-purity N2 to obtain carbon nanofiber.
  • the vertical strip spacing of the bonding point is 0.5cm
  • the bonding point spacing in the vertical strip is 1cm
  • the adhesive is polymethylsiloxane adhesive
  • the amount of adhesive is about 12.9mg/ cm2 ;
  • the base layer is polyester woven fabric, and the protective layer is nylon woven fabric; step 3, heat curing treatment, the heating temperature is 150°C, and the time is 10min.
  • the carbon nanofiber-based breathable anti-virus clothing fabric obtained in this embodiment has a moisture permeability of about 1850 g/(m 2 ⁇ 24 h), an effective protection time against mustard gas simulant (pentyl sulfide) of more than 48 h, and a peel strength of about 1.4 kN/m.
  • Example 2 The same as Example 1, except that the carbon nanofiber membrane is not included.
  • the anti-toxicity of the fabric was tested, and the results showed that ordinary fabrics had no protective effect against mustard gas simulant (pentyl sulfide).
  • Example 2 The same as Example 1, the difference is that the distribution spacing of the bonding points is different, the vertical strip spacing of the bonding points is 0.1 cm, and the spacing between the bonding points in the vertical strip is 0.1 cm.
  • the moisture permeability of the carbon nanofiber-based breathable anti-virus clothing fabric is 130g/(m 2 ⁇ 24h)
  • the effective protection time against mustard gas simulant (pentyl sulfide) is more than 48h
  • the peel strength is 2.24kN/m.
  • Example 2 The same as Example 1, the difference is that the distribution spacing of the bonding points is different, the vertical strip spacing of the bonding points is 2.5 cm, and the spacing between the bonding points in the vertical strip is 1 cm.
  • the moisture permeability of the carbon nanofiber-based breathable anti-virus clothing fabric is 2380g/(m 2 ⁇ 24h)
  • the effective protection time against mustard gas simulant (pentyl sulfide) is more than 48h
  • the peel strength is 0.26kN/m.
  • Example 2 The same as Example 1, except that the adhesive is a water-based epoxy resin adhesive.
  • FIG. 4(a) is a penetration diagram of the adhesive of Example 1 and Comparative Example 4 on the upper surface of the carbon nanofiber membrane
  • Figure 4(b) is a penetration diagram of the adhesive of Example 1 and Comparative Example 4 on the lower surface of the carbon nanofiber membrane. It can be seen from Figure 4(b) that since the water-based epoxy resin adhesive did not penetrate the carbon nanofiber membrane, the base layer and the protective layer can only be bonded to the surface of the carbon nanofiber membrane.
  • the carbon fiber nanomembrane is easy to delaminate
  • the carbon nanofiber-based breathable anti-virus clothing fabric is easy to be peeled off and has poor stability; while the oil-based epoxy resin adhesive can penetrate the carbon nanofiber membrane, solving the problem of easy delamination of the carbon membrane, and making the carbon nanofiber-based breathable anti-virus clothing fabric have better stability.
  • the carbon nanofiber-based anti-virus clothing fabric of Examples 1-3 has a good protective effect, ensures the effective adsorption area of the carbon nanofiber film in the fabric, and ensures the air permeability and moisture permeability of the carbon nanofiber-based breathable anti-virus clothing fabric, and also has good structural stability. From Example 1, compared with Comparative Example 2 and Comparative Example 3, it can be seen that the bonding point spacing has an effect on the anti-toxicity, moisture permeability, and stability of the carbon nanofiber-based breathable anti-virus clothing fabric.
  • Example 1 compared with Comparative Example 4, the adhesive used in this application can penetrate and embed the carbon nanofiber film, thereby bonding the upper and lower fabric woven fabrics, while improving the mechanical properties of the carbon nanofiber film, so that the carbon nanofiber-based breathable anti-virus clothing fabric has good structural stability.

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

A carbon nanofiber-based breathable hazmat suit fabric and a preparation method therefor, which relate to the technical field of hazmat suit fabrics. The fabric comprises a substrate layer, a functional layer and a protective layer. The functional layer is made of a carbon nanofiber membrane and further comprises multiple scattered adhesive points. The adhesive points are formed by an adhesive embedded in the carbon nanofiber membrane and are attached to the upper surface and the lower surface of the carbon nanofiber membrane at the same position. The adhesive attached to the lower surface of the carbon nanofiber membrane forms a lower adhesive layer. The lower adhesive layer is bonded with the substrate layer. The adhesive attached to the upper surface of the carbon nanofiber membrane forms an upper adhesive layer. The upper adhesive layer is bonded with the protective layer. The preparation method for the fabric comprises: coating the adhesive patches; bonding the layers; and carrying out curing treatment. The prepared carbon nanofiber-based breathable hazmat suit fabric has a stable structure, good air permeation performance and protection effects.

Description

一种碳纳米纤维基透气式防毒服面料及其制备方法Carbon nanofiber-based breathable anti-virus clothing fabric and preparation method thereof
相关申请Related Applications
本申请要求于2022年9月30日提交中国专利局、申请号为2022112095276、申请名称为“一种碳纳米纤维基透气式防毒服面料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed with the China Patent Office on September 30, 2022, with application number 2022112095276 and application name “A carbon nanofiber-based breathable anti-virus clothing fabric and its preparation method”, the entire contents of which are incorporated by reference in this application.
技术领域Technical Field
本申请属于防毒服面料技术领域，尤其涉及一种碳纳米纤维基透气式防毒服面料及其制备方法。The present application belongs to the technical field of anti-virus clothing fabrics, and in particular, relates to a carbon nanofiber-based breathable anti-virus clothing fabric and a preparation method thereof.
背景技术Background technique
碳纳米纤维基具有较好的透气性且较为轻便，在一些有毒有害化学污染物浓度较低且人员运动量较大的场合具有重要应用价值。碳纳米纤维基是利用服装面料对生化试剂液体、气溶胶、蒸汽的阻隔和吸附作用来达到防护效果，服装内部人体产生的热量和湿气可以透过面料散发出来，从而改善防护服的穿着热湿舒适性。碳纳米纤维基透气式防毒服面料通常由多个功能层复合制成，其核心功能层为功能层。目前，碳纳米纤维基透气式防毒服面料主要采用活性炭颗粒或掺炭高聚物纤维来制备功能层。然而，现有透气式化学防护面料技术仍存在一些瓶颈问题：(1)活性碳颗粒功能层容易脱落、团聚导致功能层结构的均匀性发生变化，从而影响复合面料的防护稳定性；(2)将活性炭掺杂到纤维中形成掺炭纤维可以显著改善功能层的结构稳定性，但由于掺杂到聚合物中的活性炭有相当一部分被包埋到了纤维内部，导致活性炭的吸附性能难以充分发挥，从而影响到功能层的吸附性能的进一步提升。Carbon nanofiber-based materials have good air permeability and are relatively light. They have important application value in some occasions where the concentration of toxic and harmful chemical pollutants is low and the amount of human movement is large. Carbon nanofiber-based materials use the barrier and adsorption effects of clothing fabrics on biochemical reagent liquids, aerosols, and vapors to achieve a protective effect. The heat and moisture generated by the human body inside the clothing can be dissipated through the fabric, thereby improving the thermal and moisture comfort of wearing protective clothing. Carbon nanofiber-based breathable anti-virus clothing fabrics are usually made of a composite of multiple functional layers, and the core functional layer is the functional layer. At present, carbon nanofiber-based breathable anti-virus clothing fabrics mainly use activated carbon particles or carbon-doped polymer fibers to prepare the functional layer. However, the existing breathable chemical protective fabric technology still has some bottleneck problems: (1) The functional layer of activated carbon particles is easy to fall off and agglomerate, which causes the uniformity of the functional layer structure to change, thereby affecting the protective stability of the composite fabric; (2) Doping activated carbon into fibers to form carbon-doped fibers can significantly improve the structural stability of the functional layer, but since a considerable portion of the activated carbon doped into the polymer is embedded in the fiber, it is difficult to fully exert the adsorption performance of the activated carbon, thereby affecting the further improvement of the adsorption performance of the functional layer.
国外专利US11172175、US7582578B2、DE102004024075B4，国内专利CN107584824A、CN201110146047.5所公开的技术均采用活性炭纤维织物作为功能层，在一定程度上解决了活性炭颗粒存在的问题。然而，由于上述技术采用的活性炭纤维是将传统的微米级聚合物纤维进行碳化、活化后所得，活性炭纤维的直径仍处于微米级，由此构成的织物纤维间的孔隙尺寸较大，导致其耐毒气渗透性较差，因此需要采用较厚的功能层。国外专利US2010/0319113A1公开了一种新型化学防护织物，该技术将掺杂有不同颗粒的静电纺聚合物纳米纤维膜作为阻隔层与其他织物进行复合，所得静电纺纤维膜中纤维的直径较小，由此带来的小孔径特性可以有效减缓毒气的渗透速率增加面料的吸附效率。然而，由于该技术采用的是聚合物纳米纤维，所得纳米纤维膜的比表面积较低，因而其对有毒有害化学气体或气溶胶的吸附性能有限，此外聚合物纳米纤维的耐候性和化学稳定性也难以保障，从而最终会影响到防护面料性能。The technologies disclosed in foreign patents US11172175, US7582578B2, DE102004024075B4, and domestic patents CN107584824A and CN201110146047.5 all use activated carbon fiber fabrics as functional layers, which solve the problems of activated carbon particles to a certain extent. However, since the activated carbon fibers used in the above-mentioned technologies are obtained by carbonizing and activating traditional micron-level polymer fibers, the diameter of the activated carbon fibers is still at the micron level, and the pore size between the fibers of the fabric thus formed is relatively large, resulting in poor resistance to toxic gas permeability, so a thicker functional layer is required. Foreign patent US2010/0319113A1 discloses a new type of chemical protective fabric, which uses an electrospun polymer nanofiber membrane doped with different particles as a barrier layer to be compounded with other fabrics. The diameter of the fibers in the resulting electrospun fiber membrane is relatively small, and the resulting small pore size characteristics can effectively slow down the penetration rate of toxic gases and increase the adsorption efficiency of the fabric. However, since this technology uses polymer nanofibers, the resulting nanofiber membrane has a low specific surface area, and therefore its adsorption performance for toxic and harmful chemical gases or aerosols is limited. In addition, the weather resistance and chemical stability of polymer nanofibers are difficult to guarantee, which will ultimately affect the performance of protective fabrics.
碳纳米纤维膜是将聚合物纳米纤维膜经碳化所得，碳纳米纤维膜具有小孔径、高孔隙率、 高比表面积等优点，使其在有毒有害化学气体或气溶胶吸附领域有着广阔的应用前景，但由于碳纳米纤维膜力学性能较差且易分层，目前尚无有效技术实现碳纳米纤维膜与传统织物进行复合，相关复合面料也鲜有报道。因此开发碳纳米纤维基透气式防毒服面料对于进一步提升纳米纤维基防毒服面料的应用性能且丰富其应用领域具有重要意义。Carbon nanofiber membrane is obtained by carbonizing polymer nanofiber membrane. Carbon nanofiber membrane has small pore size, high porosity, The advantages of high specific surface area make it have broad application prospects in the field of toxic and harmful chemical gas or aerosol adsorption. However, due to the poor mechanical properties of carbon nanofiber membranes and easy delamination, there is currently no effective technology to realize the composite of carbon nanofiber membranes and traditional fabrics, and related composite fabrics are rarely reported. Therefore, the development of carbon nanofiber-based breathable anti-virus clothing fabrics is of great significance to further improve the application performance of nanofiber-based anti-virus clothing fabrics and enrich their application fields.
发明内容Summary of the invention
为解决上述现有技术中防毒服面料功能结构不稳定、防护性能不佳，同时改善碳纳米纤维膜用于吸附功能层时力学性能较差且易分层的技术问题，本申请提供一种防护效果好、结构稳定的碳纳米纤维基透气式防毒服面料及其制备方法。In order to solve the technical problems that the functional structure of anti-virus clothing fabrics in the above-mentioned prior art is unstable and the protective performance is poor, and at the same time improve the poor mechanical properties and easy delamination of the carbon nanofiber membrane when used for the adsorption functional layer, the present application provides a carbon nanofiber-based breathable anti-virus clothing fabric with good protective effect and stable structure and a preparation method thereof.
为达到上述目的，本申请的技术方案：一种碳纳米纤维基透气式防毒服面料，面料包括基底层、功能层和保护层，所述功能层为碳纳米纤维膜，还包括多个的分散粘合点，所述粘合点为粘合剂嵌入碳纳米纤维膜并在同一位置附着在碳纳米纤维膜的上表面和下表面，粘合剂附着在碳纳米纤维膜的下表面为下粘合层，下粘合层与基底层粘合，粘合剂附着在碳纳米纤维膜的上表面为上粘合层，上粘合层与保护层粘合。To achieve the above-mentioned purpose, the technical solution of the present application is: a carbon nanofiber-based breathable anti-virus clothing fabric, the fabric including a base layer, a functional layer and a protective layer, the functional layer is a carbon nanofiber membrane, and also includes a plurality of dispersed bonding points, the bonding points are adhesives embedded in the carbon nanofiber membrane and attached to the upper and lower surfaces of the carbon nanofiber membrane at the same position, the adhesive attached to the lower surface of the carbon nanofiber membrane is the lower bonding layer, the lower bonding layer is bonded to the base layer, the adhesive attached to the upper surface of the carbon nanofiber membrane is the upper bonding layer, the upper bonding layer is bonded to the protective layer.
在一实施例中，所述基底层和保护层为机织物，基底层的材质为锦纶、涤纶中的一种，保护层的材质为锦纶、芳纶中的一种。In one embodiment, the base layer and the protective layer are woven fabrics, the base layer is made of one of nylon and polyester, and the protective layer is made of one of nylon and aramid.
在一实施例中，所述粘合点的分布为条形分散式，条形分散式的竖条间距为0.5-2cm，竖条内粘合点间距为0.5-1cm。In one embodiment, the bonding points are distributed in a strip-shaped dispersion, the vertical strip spacing is 0.5-2 cm, and the bonding point spacing within the vertical strip is 0.5-1 cm.
在一实施例中，面料还包括基底层、功能层与下粘合层围成下空腔，保护层、功能层与上粘合层围成上空腔。In one embodiment, the fabric further includes a base layer, a functional layer and a lower adhesive layer forming a lower cavity, and a protective layer, a functional layer and an upper adhesive layer forming an upper cavity.
在一实施例中，粘合剂为油性环氧树脂粘合剂、油性酚醛树脂粘合剂、聚甲基硅氧烷粘合剂中的一种。In one embodiment, the adhesive is one of an oily epoxy resin adhesive, an oily phenolic resin adhesive, and a polymethylsiloxane adhesive.
在一实施例中，所述碳纳米纤维膜的制备方法，包括如下步骤：步骤1，以质量比为3：2的聚丙烯腈和热固性酚醛树脂混合物为纺丝聚合物体系，以疏水性二氧化硅纳米颗粒为掺杂物质，以N,N-二甲基甲酰胺为纺丝溶剂，通过连续静电纺丝制备前驱体纳米纤维膜；步骤2，将前驱体纳米纤维膜在鼓风烘箱中先以150℃处理0.5h，随后升温至240℃处理2h；步骤3，将热处理后的前驱体纳米纤维膜在高纯N2保护下以650-950℃进行碳化处理2h。In one embodiment, the method for preparing the carbon nanofiber membrane comprises the following steps: step 1, using a mixture of polyacrylonitrile and thermosetting phenolic resin in a mass ratio of 3:2 as a spinning polymer system, hydrophobic silica nanoparticles as a doping material, and N,N-dimethylformamide as a spinning solvent, to prepare a precursor nanofiber membrane by continuous electrospinning; step 2, first treating the precursor nanofiber membrane at 150°C in a blast oven for 0.5h, and then heating it to 240°C for 2h; step 3, carbonizing the heat-treated precursor nanofiber membrane at 650-950°C for 2h under the protection of high-purity N2 .
上述碳纳米纤维基透气式防毒服面料的制备方法，包括以下步骤：步骤一为粘合点涂布，制备碳纳米纤维膜并在其上表面涂布粘合剂形成粘合点，粘合剂嵌入碳纳米纤维膜及附在碳纳米纤维膜的下表面形成下粘合层和上表面形成上粘合层；步骤二为各层粘合，对基底层和保护层进行清洗干燥后，将基底层与下粘合层粘合，以及保护层与上粘合层粘合得到复合面料；步骤三，将步骤二所得复合面料进行固化处理。 The preparation method of the above-mentioned carbon nanofiber-based breathable anti-virus clothing fabric includes the following steps: Step 1 is bonding point coating, preparing a carbon nanofiber membrane and coating an adhesive on its upper surface to form bonding points, the adhesive is embedded in the carbon nanofiber membrane and attached to the lower surface of the carbon nanofiber membrane to form a lower bonding layer and the upper surface to form an upper bonding layer; Step 2 is bonding of each layer, after cleaning and drying the base layer and the protective layer, the base layer is bonded to the lower bonding layer, and the protective layer is bonded to the upper bonding layer to obtain a composite fabric; Step 3, the composite fabric obtained in Step 2 is cured.
在一实施例中，所述固化处理为加热处理，处理温度为100-150℃，时间为10-35min。In one embodiment, the curing treatment is a heating treatment with a treatment temperature of 100-150° C. and a treatment time of 10-35 min.
有益效果Beneficial Effects
(1)本申请防毒服面料为整体层间复合结构，面料结构稳定不掉炭且具有良好的透气性能和防护效果，制备方法简单易行且多元技术结合性强，面料性能可以根据实际应用需求进行灵活调整。(1) The anti-toxic clothing fabric of the present application is an overall interlayer composite structure. The fabric structure is stable and does not lose carbon and has good air permeability and protective effect. The preparation method is simple and easy and has strong integration of multiple technologies. The fabric performance can be flexibly adjusted according to actual application requirements.
(2)采用碳纳米纤维膜作为防毒服面料的功能层，相比于活性炭颗粒、微米级活性炭纤维以及聚合物纳米纤维，碳纳米纤维膜不仅具有高比表面积、耐化学腐蚀、耐热的特性还具有纳米纤维材料的孔径小、孔隙率高、孔道连通性好等特点，由此可以有效提升防毒服面料的耐有毒气体渗透性和对有毒气溶胶(蒸汽)的吸附拦截性能。(2) Carbon nanofiber membrane is used as the functional layer of the anti-toxic clothing fabric. Compared with activated carbon particles, micron-sized activated carbon fibers and polymer nanofibers, carbon nanofiber membrane not only has the characteristics of high specific surface area, chemical corrosion resistance and heat resistance, but also has the characteristics of small pore size, high porosity and good pore connectivity of nanofiber materials. It can effectively improve the anti-toxic clothing fabric's resistance to toxic gas permeability and its adsorption and interception performance of toxic aerosols (vapors).
(3)采用油性粘合剂嵌入碳纳米纤维膜，有利于改善碳纳米纤维膜的力学性能，提高碳纳米纤维膜内部的粘合力，使不易分层，同时，在膜的同一位置，粘合剂也附在碳纳米纤维膜的上表面和下表面，分别粘合基底层和保护层，实现了基底层、功能层、保护层之间的粘接加固，形成整体层间复合结构。(3) The use of oily adhesive to embed the carbon nanofiber membrane is beneficial to improving the mechanical properties of the carbon nanofiber membrane and enhancing the internal adhesion of the carbon nanofiber membrane, making it less likely to delaminate. At the same time, at the same position of the membrane, the adhesive is also attached to the upper and lower surfaces of the carbon nanofiber membrane, respectively bonding the base layer and the protective layer, thereby achieving bonding reinforcement between the base layer, the functional layer, and the protective layer, forming an overall interlayer composite structure.
(4)采用分散式的粘结点并在各层间形成空腔，确保面料内碳纳米纤维膜的有效吸附面积的同时，保障防毒服面料的透气透湿性，也有助于缓冲面料受力发生形变时对碳纳米纤维膜的冲击。(4) Dispersed bonding points are used to form cavities between the layers, which ensures the effective adsorption area of the carbon nanofiber membrane in the fabric while ensuring the air permeability and moisture permeability of the anti-virus clothing fabric. It also helps to cushion the impact of the carbon nanofiber membrane when the fabric is deformed under force.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是实施例1的碳纳米纤维基透气式防毒服面料的结构示意图；FIG1 is a schematic structural diagram of a carbon nanofiber-based breathable anti-virus clothing fabric according to Example 1;
图2(a)是实施例1的碳纳米纤维膜的实物图；FIG2( a ) is a physical picture of the carbon nanofiber membrane of Example 1;
图2(b)是实施例1的碳纳米纤维膜的SEM图；FIG2( b ) is a SEM image of the carbon nanofiber membrane of Example 1;
图3(a)是实施例1的碳纳米纤维基透气式防毒服面料的垂于水平面的剖视图；FIG3( a ) is a cross-sectional view of the carbon nanofiber-based breathable anti-virus clothing fabric of Example 1, taken vertically on a horizontal plane;
图3(b)是实施例1的碳纳米纤维基透气式防毒服面料的粘合点结构示意图；FIG3( b ) is a schematic diagram of the bonding point structure of the carbon nanofiber-based breathable anti-virus clothing fabric of Example 1;
图4(a)是实施例1及对比例4的粘合剂分别在碳纳米纤维膜上表面的渗透性能图；FIG4( a ) is a graph showing the permeability of the adhesives of Example 1 and Comparative Example 4 on the upper surface of the carbon nanofiber membrane;
图4(b)是实施例1及对比例4的粘合剂分别在碳纳米纤维膜下表面的渗透性能图；FIG4( b ) is a graph showing the permeability of the adhesives of Example 1 and Comparative Example 4 on the lower surface of the carbon nanofiber membrane;
其中，1-基底层、2-功能层、3-保护层、4-粘合点、5-下粘合层、6-上粘合层、7-下空腔、8-上空腔。Among them, 1-base layer, 2-functional layer, 3-protective layer, 4-adhesive point, 5-lower adhesive layer, 6-upper adhesive layer, 7-lower cavity, 8-upper cavity.
具体实施方式Detailed ways
以下实施例中所采用的面料为涤纶机织物，市售涤塔夫面料，克重为80g/m2；锦纶机织物，市售340T斜纹尼龙，克重为146g/m2；芳纶机织物，市售200D平纹芳纶布，克重为60g/m2；聚甲基硅氧烷粘合剂购置于陶氏化学公司(Dow Chemical Company)，油性酚醛树脂粘合剂购置于深圳市吉田化工有限公司，油性环氧树脂粘合剂购置于宁波铭盛胶黏剂有限公司。 The fabrics used in the following examples are polyester woven fabric, commercially available polyester taffeta fabric, with a grammage of 80 g/m 2 ; nylon woven fabric, commercially available 340T twill nylon, with a grammage of 146 g/m 2 ; aramid woven fabric, commercially available 200D plain aramid cloth, with a grammage of 60 g/m 2 ; polymethylsiloxane adhesive purchased from Dow Chemical Company, oily phenolic resin adhesive purchased from Shenzhen Yoshida Chemical Co., Ltd., and oily epoxy resin adhesive purchased from Ningbo Mingsheng Adhesive Co., Ltd.
碳纳米纤维膜为静电纺碳纳米纤维膜，制备碳纳米纤维膜所采用的碳源为聚丙烯腈(分子量为9万，购买于江苏昆山鸿昱塑胶有限公司)和热固性酚醛树脂(购买于河南恒源新材料)，二氧化硅纳米颗粒、N,N-二甲基甲酰胺均购置于上海麦克林生化科技有限公司。静电纺丝过程采用5喷头(间距5cm)往复式静电纺机，接收基材选用幅宽为70cm聚丙烯无纺布。静电纺丝电压为25kV，纺丝距离为20cm，温度为25℃，湿度为50％；纳米纤维膜的预氧化采用热风烘箱进行，纳米纤维膜的碳化处理采用真空管式炉。The carbon nanofiber membrane is an electrospun carbon nanofiber membrane. The carbon sources used to prepare the carbon nanofiber membrane are polyacrylonitrile (molecular weight of 90,000, purchased from Jiangsu Kunshan Hongyu Plastic Co., Ltd.) and thermosetting phenolic resin (purchased from Henan Hengyuan New Materials). Silica nanoparticles and N,N-dimethylformamide are purchased from Shanghai McLean Biochemical Technology Co., Ltd. The electrospinning process uses a 5-nozzle (spacing 5cm) reciprocating electrospinning machine, and the receiving substrate uses a 70cm wide polypropylene non-woven fabric. The electrospinning voltage is 25kV, the spinning distance is 20cm, the temperature is 25℃, and the humidity is 50%; the pre-oxidation of the nanofiber membrane is carried out in a hot air oven, and the carbonization of the nanofiber membrane is carried out in a vacuum tube furnace.
本申请对实施例及对比例的防毒服面料的透湿性能测试，参考GB/T 12704.2《纺织品织物透湿性试验方法第2部分：蒸发法》，防毒服面料的防毒性能测试参照GJB 3253-1998《阻燃伪装防毒服规范》附录B对防毒服内层材料的“液-气”防毒时间试验方法；对防毒服面料的剥离强度参考《FZ/T 60011-2016复合织物剥离强力试验方法》。The moisture permeability test of the anti-virus clothing fabrics of the embodiments and comparative examples in this application refers to GB/T 12704.2 "Test method for moisture permeability of textile fabrics Part 2: Evaporation method", and the anti-virus performance test of the anti-virus clothing fabrics refers to Appendix B of GJB 3253-1998 "Specifications for flame-retardant camouflage anti-virus clothing" for the "liquid-gas" anti-virus time test method for the inner layer material of the anti-virus clothing; the peel strength of the anti-virus clothing fabrics refers to "FZ/T 60011-2016 Composite fabric peeling strength test method".
实施例1Example 1
碳纳米纤维基透气式防毒服面料，面料包括基底层1、功能层2和保护层3，功能层2为碳纳米纤维膜，还包括多个分散的粘合点4，结构如图1所示，所述粘合点4为粘合剂嵌入碳纳米纤维膜并在同一位置附着在碳纳米纤维膜的上表面和下表面，粘合点4的结构如图1用圆线圈出的放大图所示。A carbon nanofiber-based breathable anti-virus clothing fabric includes a base layer 1, a functional layer 2 and a protective layer 3. The functional layer 2 is a carbon nanofiber membrane and also includes a plurality of dispersed bonding points 4. The structure is shown in FIG1 . The bonding points 4 are adhesives embedded in the carbon nanofiber membrane and attached to the upper and lower surfaces of the carbon nanofiber membrane at the same position. The structure of the bonding points 4 is shown in the enlarged view circled in FIG1 .
上述碳纳米纤维膜的制备，包括如下步骤：步骤1，取质量比为3：2的聚丙烯腈/热固性酚醛树脂混合物为纺丝聚合物体系，以疏水性二氧化硅纳米颗粒(粒径7-40nm)为掺杂物质，以N,N-二甲基甲酰胺为纺丝溶剂配置纺丝液，其中纺丝液中聚合物的质量为3.6g，占总含量为12wt％，二氧化硅纳米颗粒的质量为0.54g，占纺丝聚合物质量的15％，将30.54g的纺丝液加入静电纺丝机中进行纺丝制备前驱体纳米纤维；步骤2，将前驱体纳米纤维在鼓风烘箱中先以150℃处理0.5h，随后升温至240℃处理2h；步骤3，将热处理后的前驱体纳米纤维在高纯N2保护下以850℃进行碳化处理2h，得到碳纳米纤维膜，如图2(a)所示为碳纳米纤维膜实物图，如图2(b)所示为碳纳米纤维膜的SEM图像，碳纳米纤维膜不仅具有高比表面积、耐化学腐蚀、耐热的特性还具有纳米纤维材料的孔径小、孔隙率高、孔道连通性好等特点，由此可以有效提升防毒服面料的耐有毒气体渗透性和对有毒气溶胶(蒸汽)的吸附拦截性能。The preparation of the above-mentioned carbon nanofiber membrane includes the following steps: step 1, taking a polyacrylonitrile/thermosetting phenolic resin mixture with a mass ratio of 3:2 as a spinning polymer system, taking hydrophobic silica nanoparticles (particle size 7-40nm) as a doping material, and using N,N-dimethylformamide as a spinning solvent to prepare a spinning solution, wherein the mass of the polymer in the spinning solution is 3.6g, accounting for 12wt% of the total content, and the mass of the silica nanoparticles is 0.54g, accounting for 15% of the mass of the spinning polymer, and 30.54g of the spinning solution is added to an electrospinning machine for spinning to prepare precursor nanofibers; step 2, first treating the precursor nanofibers at 150°C in a blast oven for 0.5h, and then heating to 240°C for 2h; step 3, the heat-treated precursor nanofibers are placed in a high-purity N 2 was carbonized at 850 ° C for 2 h under the protection of a carbon fiber film to obtain a carbon nanofiber membrane. FIG2(a) is a real picture of the carbon nanofiber membrane, and FIG2(b) is a SEM image of the carbon nanofiber membrane. The carbon nanofiber membrane not only has the characteristics of high specific surface area, chemical corrosion resistance and heat resistance, but also has the characteristics of small pore size, high porosity and good pore connectivity of nanofiber materials. It can effectively improve the anti-toxic gas permeability resistance of the anti-toxic clothing fabric and the adsorption and interception performance of toxic aerosols (vapors).
上述碳纳米纤维基透气式防毒服面料的制备，包括如下步骤：步骤一为粘合点涂布，将所得碳纳米纤维膜在其上表面均匀涂布粘合剂，粘合剂嵌入碳纳米纤维膜及附在碳纳米纤维膜的上表面和下表面，粘合剂为油性环氧树脂粘合剂，用胶量约为9.72mg/cm2，粘合点的竖条间距为2cm，竖条内粘合点间距为0.5cm；步骤二为各层粘合，取锦纶机织物和芳纶机织物进行沸煮清洗后，在鼓风烘箱中充分干燥，锦纶机织物为基底层，芳纶机织物为保护层复合 固定在碳纳米纤维膜表面；步骤三为固化处理，对步骤二所得复合面料中的粘合点进行加热固化处理，加热温度为100℃，时间为35min，待粘合点完全固化后得到碳纳米纤维基透气式防毒服面料。图3(a)为本实施例碳纳米纤维基透气式防毒服面料垂于水平面的剖视图；图3(b)为本实施例碳纳米纤维基透气式防毒服面料的粘合点结构示意图，在图3(a)中，粘合剂附在碳纳米纤维膜的下表面为下粘合层5，下粘合层5与基底层1粘合，粘合剂附在碳纳米纤维膜的上表面为上粘合层6，上粘合层6与保护层3粘合，基底层1、功能层2与下粘合层5围成下空腔7，保护层3、功能层2与上粘合层6围成上空腔8；在图3(b)中，多个分散的粘合点为条形分散式分布。The preparation of the carbon nanofiber-based breathable anti-virus clothing fabric includes the following steps: Step 1 is bonding point coating, in which the obtained carbon nanofiber membrane is evenly coated with adhesive on its upper surface, the adhesive is embedded in the carbon nanofiber membrane and attached to the upper and lower surfaces of the carbon nanofiber membrane, the adhesive is an oily epoxy resin adhesive, the amount of adhesive used is about 9.72 mg/ cm2 , the vertical strip spacing of the bonding point is 2 cm, and the spacing of the bonding points in the vertical strip is 0.5 cm; Step 2 is bonding of each layer, taking nylon woven fabric and aramid woven fabric, boiling and cleaning, and then fully drying in a blast oven, the nylon woven fabric is the base layer, and the aramid woven fabric is the protective layer composite Fixed on the surface of the carbon nanofiber membrane; Step three is a curing treatment, and the bonding points in the composite fabric obtained in Step two are heated and cured, the heating temperature is 100°C, the time is 35 minutes, and the carbon nanofiber-based breathable anti-virus clothing fabric is obtained after the bonding points are completely cured. Figure 3 (a) is a cross-sectional view of the carbon nanofiber-based breathable anti-virus clothing fabric of this embodiment vertically on the horizontal plane; Figure 3 (b) is a schematic diagram of the bonding point structure of the carbon nanofiber-based breathable anti-virus clothing fabric of this embodiment. In Figure 3 (a), the adhesive is attached to the lower surface of the carbon nanofiber membrane as the lower bonding layer 5, and the lower bonding layer 5 is bonded to the base layer 1. The adhesive is attached to the upper surface of the carbon nanofiber membrane as the upper bonding layer 6, and the upper bonding layer 6 is bonded to the protective layer 3. The base layer 1, the functional layer 2 and the lower bonding layer 5 surround the lower cavity 7, and the protective layer 3, the functional layer 2 and the upper bonding layer 6 surround the upper cavity 8; in Figure 3 (b), multiple dispersed bonding points are distributed in a strip-shaped dispersed manner.
经测试，实施例1所得碳纳米纤维基透气式防毒服面料的透湿量约为1685g/(m2·24h)，对芥子气模拟剂(戊硫醚)的有效防护时间达48h以上，剥离强度约为1.18kN/m。According to the test, the carbon nanofiber-based breathable anti-virus clothing fabric obtained in Example 1 has a moisture permeability of about 1685 g/(m 2 ·24 h), an effective protection time against mustard gas simulant (pentyl sulfide) of more than 48 h, and a peel strength of about 1.18 kN/m.
实施例2Example 2
与实施例1相同，区别在于：Same as Example 1, except that:
在碳纳米纤维膜的制备中，步骤3将热处理后的前驱体纳米纤维在高纯N2保护下以650℃进行碳化处理2h，得到碳纳米纤维膜。在碳纳米纤维基透气式防毒服面料的制备中，步骤一，粘合点的竖条间距为1cm，竖条内粘合点间距为1cm，粘合剂为油性酚醛树脂粘合剂，用胶量约为11.3mg/cm2；步骤二，基底层为涤纶机织物，保护层为芳纶机织物；步骤三，加热固化处理时，加热温度为125℃，时间为20min。In the preparation of the carbon nanofiber membrane, step 3 is to carbonize the heat-treated precursor nanofiber at 650°C for 2h under the protection of high-purity N2 to obtain the carbon nanofiber membrane. In the preparation of the carbon nanofiber-based breathable anti-virus clothing fabric, step 1, the vertical strip spacing of the bonding point is 1cm, the bonding point spacing in the vertical strip is 1cm, the adhesive is an oily phenolic resin adhesive, and the amount of adhesive is about 11.3mg/ cm2 ; step 2, the base layer is polyester woven fabric, and the protective layer is aramid woven fabric; step 3, during the heating and curing treatment, the heating temperature is 125°C and the time is 20min.
经测试，本实施例所得碳纳米纤维基透气式防毒服面料的透湿量约为1420g/(m2·24h)左，对芥子气模拟剂(戊硫醚)的有效防护时间达48h以上，剥离强度约为1.244kN/m。According to the test, the carbon nanofiber-based breathable anti-virus clothing fabric obtained in this embodiment has a moisture permeability of about 1420 g/(m 2 ·24 h), an effective protection time against mustard gas simulant (pentyl sulfide) of more than 48 h, and a peel strength of about 1.244 kN/m.
实施例3Example 3
与实施例1相同，区别在于：Same as Example 1, except that:
在碳纳米纤维膜的制备中，步骤3将热处理后的前驱体纳米纤维在高纯N2保护下以950℃进行碳化处理2h，得到碳纳米纤维。在碳纳米纤维基透气式防毒服面料的制备中，步骤一，粘合点的竖条间距为0.5cm，竖条内粘合点间距为1cm，粘合剂为聚甲基硅氧烷粘合剂，用胶量约为12.9mg/cm2；步骤二，基底层为涤纶机织物，保护层为锦纶机织物；步骤三，加热固化处理，加热温度为150℃，时间为10min。In the preparation of carbon nanofiber membrane, step 3 is to carbonize the heat-treated precursor nanofiber at 950°C for 2h under the protection of high-purity N2 to obtain carbon nanofiber. In the preparation of carbon nanofiber-based breathable anti-virus clothing fabric, step 1, the vertical strip spacing of the bonding point is 0.5cm, the bonding point spacing in the vertical strip is 1cm, the adhesive is polymethylsiloxane adhesive, and the amount of adhesive is about 12.9mg/ cm2 ; step 2, the base layer is polyester woven fabric, and the protective layer is nylon woven fabric; step 3, heat curing treatment, the heating temperature is 150°C, and the time is 10min.
经测试，本实施例所得碳纳米纤维基透气式防毒服面料的透湿量为1850g/(m2·24h)左右，对芥子气模拟剂(戊硫醚)的有效防护时间达48h以上，剥离强度约为1.4kN/m。According to the test, the carbon nanofiber-based breathable anti-virus clothing fabric obtained in this embodiment has a moisture permeability of about 1850 g/(m 2 ·24 h), an effective protection time against mustard gas simulant (pentyl sulfide) of more than 48 h, and a peel strength of about 1.4 kN/m.
对比例1Comparative Example 1
与实施例1相同，区别在于不含碳纳米纤维膜。经测试，对不含碳纳米纤维膜功能层的面 料的防毒性进行测试，结果表明普通面料对芥子气模拟剂(戊硫醚)无防护效果。The same as Example 1, except that the carbon nanofiber membrane is not included. The anti-toxicity of the fabric was tested, and the results showed that ordinary fabrics had no protective effect against mustard gas simulant (pentyl sulfide).
对比例2Comparative Example 2
与实施例1相同，区别在于粘合点的分布间距不同，粘合点的竖条间距0.1cm，竖条内粘合点间距为0.1cm。The same as Example 1, the difference is that the distribution spacing of the bonding points is different, the vertical strip spacing of the bonding points is 0.1 cm, and the spacing between the bonding points in the vertical strip is 0.1 cm.
经测试，制得碳纳米纤维基透气式防毒服面料的透湿量为130g/(m2·24h)，对芥子气模拟剂(戊硫醚)的有效防护时间达48h以上，剥离强度为2.24kN/m。According to the test, the moisture permeability of the carbon nanofiber-based breathable anti-virus clothing fabric is 130g/(m 2 ·24h), the effective protection time against mustard gas simulant (pentyl sulfide) is more than 48h, and the peel strength is 2.24kN/m.
对比例3Comparative Example 3
与实施例1相同，区别在于粘合点的分布间距不同，粘合点的竖条间距2.5cm，竖条内粘合点间距为1cm。The same as Example 1, the difference is that the distribution spacing of the bonding points is different, the vertical strip spacing of the bonding points is 2.5 cm, and the spacing between the bonding points in the vertical strip is 1 cm.
经测试，制得碳纳米纤维基透气式防毒服面料的透湿量为2380g/(m2·24h)，对芥子气模拟剂(戊硫醚)的有效防护时间达48h以上，剥离强度为0.26kN/m。According to the test, the moisture permeability of the carbon nanofiber-based breathable anti-virus clothing fabric is 2380g/(m 2 ·24h), the effective protection time against mustard gas simulant (pentyl sulfide) is more than 48h, and the peel strength is 0.26kN/m.
对比例4Comparative Example 4
与实施例1相同，区别在于粘合剂为水性环氧树脂粘合剂。The same as Example 1, except that the adhesive is a water-based epoxy resin adhesive.
对水性环氧树脂粘合剂和油性环氧树脂粘合剂与碳纳米纤维膜的渗透嵌入效果进行对比，水性环氧树脂粘合剂标记为1号，油性环氧树脂粘合剂标记2号，结果如图4(a)和图4(b)所示，图4(a)为实施例1和对比例4的粘合剂在碳纳米纤维膜上表面的渗透图，图4(b)为实施例1和对比例4的粘合剂在碳纳米纤维膜下表面的渗透图。从图4(b)可以看出由于水性环氧树脂粘合剂未渗透碳纳米纤维膜，基底层与保护层仅能与碳纳米纤维膜表面粘合，由于碳纤维纳米膜易分层，使该碳纳米纤维基透气式防毒服面料易被剥离，稳定性差；而油性环氧树脂粘合剂可以渗透碳纳米纤维膜，解决了碳膜易分层的问题，使该碳纳米纤维基透气式防毒服面料具有较好的稳定性。The penetration and embedding effects of water-based epoxy resin adhesive and oil-based epoxy resin adhesive on carbon nanofiber membrane were compared. The water-based epoxy resin adhesive was marked as No. 1 and the oil-based epoxy resin adhesive was marked as No. 2. The results are shown in Figures 4(a) and 4(b). Figure 4(a) is a penetration diagram of the adhesive of Example 1 and Comparative Example 4 on the upper surface of the carbon nanofiber membrane, and Figure 4(b) is a penetration diagram of the adhesive of Example 1 and Comparative Example 4 on the lower surface of the carbon nanofiber membrane. It can be seen from Figure 4(b) that since the water-based epoxy resin adhesive did not penetrate the carbon nanofiber membrane, the base layer and the protective layer can only be bonded to the surface of the carbon nanofiber membrane. Since the carbon fiber nanomembrane is easy to delaminate, the carbon nanofiber-based breathable anti-virus clothing fabric is easy to be peeled off and has poor stability; while the oil-based epoxy resin adhesive can penetrate the carbon nanofiber membrane, solving the problem of easy delamination of the carbon membrane, and making the carbon nanofiber-based breathable anti-virus clothing fabric have better stability.
实施例1-3的碳纳米纤维基防毒服面料具有良好的防护效果，确保面料内碳纳米纤维膜的有效吸附面积的同时，保障碳纳米纤维基透气式防毒服面料的透气透湿性，还具有良好的结构稳定性。从实施例1与对比例2、对比例3对比，可以看出粘合点间距对碳纳米纤维基透气式防毒服面料防毒性、透湿性、稳定性的影响，过小的粘合点竖条间距和竖条内粘合点间距使碳纳米纤维基防毒服面料透湿性变差，过大的粘合点的竖条间距和竖条内粘合点间距使碳纳米纤维基防毒服面料的稳定性变差。从实施例1与对比例1对比，可以看出碳纳米纤维膜对碳纳米纤维基透气式防毒服面料防毒性能的作用。从实施例1与对比例4对比，本申请采用的粘合剂能够渗透嵌入碳纳米纤维膜，从而粘合上下面料机织物，同时改善碳纳米纤维膜的力学性能，使碳纳米纤维基透气式防毒服面料结构稳定性好。 The carbon nanofiber-based anti-virus clothing fabric of Examples 1-3 has a good protective effect, ensures the effective adsorption area of the carbon nanofiber film in the fabric, and ensures the air permeability and moisture permeability of the carbon nanofiber-based breathable anti-virus clothing fabric, and also has good structural stability. From Example 1, compared with Comparative Example 2 and Comparative Example 3, it can be seen that the bonding point spacing has an effect on the anti-toxicity, moisture permeability, and stability of the carbon nanofiber-based breathable anti-virus clothing fabric. The vertical bar spacing of the bonding point that is too small and the bonding point spacing in the vertical bar make the carbon nanofiber-based anti-virus clothing fabric moisture permeability worse, and the vertical bar spacing of the bonding point that is too large and the bonding point spacing in the vertical bar make the stability of the carbon nanofiber-based anti-virus clothing fabric worse. From Example 1, compared with Comparative Example 1, it can be seen that the carbon nanofiber film has an effect on the anti-toxic performance of the carbon nanofiber-based breathable anti-virus clothing fabric. From Example 1, compared with Comparative Example 4, the adhesive used in this application can penetrate and embed the carbon nanofiber film, thereby bonding the upper and lower fabric woven fabrics, while improving the mechanical properties of the carbon nanofiber film, so that the carbon nanofiber-based breathable anti-virus clothing fabric has good structural stability.

Claims (8)

  1. 一种碳纳米纤维基透气式防毒服面料，面料包括基底层(1)、功能层(2)和保护层(3)，其中，所述功能层(2)为碳纳米纤维膜，还包括多个分散的粘合点(4)，所述粘合点(4)为粘合剂嵌入碳纳米纤维膜并在同一位置附着在碳纳米纤维膜的上表面和下表面，粘合剂附着在碳纳米纤维膜的下表面为下粘合层(5)，下粘合层(5)与基底层(1)粘合，粘合剂附着在碳纳米纤维膜的上表面为上粘合层(6)，上粘合层(6)与保护层(3)粘合。A carbon nanofiber-based breathable anti-virus clothing fabric, the fabric comprising a base layer (1), a functional layer (2) and a protective layer (3), wherein the functional layer (2) is a carbon nanofiber membrane, and further comprising a plurality of dispersed bonding points (4), wherein the bonding points (4) are adhesives embedded in the carbon nanofiber membrane and attached to the upper surface and the lower surface of the carbon nanofiber membrane at the same position, wherein the adhesive is attached to the lower surface of the carbon nanofiber membrane as a lower bonding layer (5), the lower bonding layer (5) is bonded to the base layer (1), and the adhesive is attached to the upper surface of the carbon nanofiber membrane as an upper bonding layer (6), the upper bonding layer (6) is bonded to the protective layer (3).
  2. 根据权利要求1所述的碳纳米纤维基透气式防毒服面料，其中，所述基底层(1)和保护层(3)为机织物，基底层的材质为锦纶、涤纶中的一种，保护层的材质为锦纶、芳纶中的一种。According to claim 1, the carbon nanofiber-based breathable anti-virus clothing fabric, wherein the base layer (1) and the protective layer (3) are woven fabrics, the base layer is made of one of nylon and polyester, and the protective layer is made of one of nylon and aramid.
  3. 根据权利要求1所述的碳纳米纤维基透气式防毒服面料，其中，所述粘合点(4)的分布为条形分散式，条形分散式的竖条间距为0.5-2cm，竖条内粘合点间距为0.5-1cm。According to claim 1, the carbon nanofiber-based breathable anti-virus clothing fabric is distributed in a strip-shaped dispersion, the vertical strip spacing of the strip-shaped dispersion is 0.5-2 cm, and the bonding point spacing within the vertical strip is 0.5-1 cm.
  4. 根据权利要求1所述的碳纳米纤维基透气式防毒服面料，其中，还包括基底层(1)、功能层(2)与下粘合层(5)围成下空腔(7)，保护层(3)、功能层(2)与上粘合层(6)围成上空腔(8)。The carbon nanofiber-based breathable anti-virus clothing fabric according to claim 1, further comprising a base layer (1), a functional layer (2) and a lower adhesive layer (5) forming a lower cavity (7), and a protective layer (3), a functional layer (2) and an upper adhesive layer (6) forming an upper cavity (8).
  5. 根据权利要求1所述的碳纳米纤维基透气式防毒服面料，其中，粘合剂为油性环氧树脂粘合剂、油性酚醛树脂粘合剂、聚甲基硅氧烷粘合剂中的一种。According to the carbon nanofiber-based breathable anti-virus clothing fabric of claim 1, wherein the adhesive is one of an oily epoxy resin adhesive, an oily phenolic resin adhesive, and a polymethylsiloxane adhesive.
  6. 根据权利要求1所述的碳纳米纤维基透气式防毒服面料，其中，所述碳纳米纤维膜的制备方法，包括如下步骤：步骤1，以质量比为3：2的聚丙烯腈和热固性酚醛树脂混合物为纺丝聚合物体系，以二氧化硅纳米颗粒为掺杂物质，以N,N-二甲基甲酰胺为纺丝溶剂，通过连续静电纺丝制备前驱体纳米纤维膜；步骤2，将前驱体纳米纤维膜在鼓风烘箱中先以150℃处理0.5h，随后升温至240℃处理2h；步骤3，将热处理后的前驱体纳米纤维膜在高纯N2保护下以650-950℃进行碳化处理2h。The carbon nanofiber-based breathable anti-virus clothing fabric according to claim 1, wherein the method for preparing the carbon nanofiber membrane comprises the following steps: step 1, using a mixture of polyacrylonitrile and thermosetting phenolic resin in a mass ratio of 3:2 as a spinning polymer system, using silicon dioxide nanoparticles as a doping material, and using N,N-dimethylformamide as a spinning solvent, to prepare a precursor nanofiber membrane by continuous electrospinning; step 2, first treating the precursor nanofiber membrane at 150°C in a blast oven for 0.5h, and then heating it to 240°C for 2h; step 3, carbonizing the heat-treated precursor nanofiber membrane at 650-950°C for 2h under the protection of high-purity N2 .
  7. 权利要求1所述的碳纳米纤维基透气式防毒服面料的制备方法，其中，包括以下步骤：The method for preparing the carbon nanofiber-based breathable anti-virus clothing fabric according to claim 1, comprising the following steps:
    步骤一，制备碳纳米纤维膜并在其上表面涂布粘合剂形成粘合点，粘合剂嵌入碳纳米纤维膜及附在碳纳米纤维膜的下表面形成下粘合层(5)和上表面形成上粘合层(6)；Step 1, preparing a carbon nanofiber membrane and coating an adhesive on its upper surface to form bonding points, wherein the adhesive is embedded in the carbon nanofiber membrane and attached to the lower surface of the carbon nanofiber membrane to form a lower bonding layer (5) and the upper surface to form an upper bonding layer (6);
    步骤二，对基底层(1)和保护层(3)进行清洗干燥后，将基底层(1)与下粘合层(5)粘合，以及保护层(3)与上粘合层(6)粘合得到复合面料；Step 2: After cleaning and drying the base layer (1) and the protective layer (3), the base layer (1) is bonded to the lower adhesive layer (5), and the protective layer (3) is bonded to the upper adhesive layer (6) to obtain a composite fabric;
    步骤三，将步骤二所得复合面料进行固化处理。 Step three, curing the composite fabric obtained in step two.
  8. 根据权利要求7所述的碳纳米纤维基透气式防毒服面料的制备方法，其中，所述固化处理为加热处理，处理温度为100-150℃，时间为10-35min。 The method for preparing a carbon nanofiber-based breathable anti-virus clothing fabric according to claim 7, wherein the curing treatment is a heating treatment, the treatment temperature is 100-150°C, and the time is 10-35min.
PCT/CN2023/107139 2022-09-30 2023-07-13 Carbon nanofiber-based breathable hazmat suit fabric, and preparation method therefor WO2024066669A1 (en)

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Publication number Priority date Publication date Assignee Title
CN115519859A (en) * 2022-09-30 2022-12-27 南通大学 Carbon nanofiber-based breathable gas-defense garment fabric and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070004301A1 (en) * 2004-07-05 2007-01-04 Peter Heinrich Textile composite material comprising activated carbon fibres and production thereof
JP2008036985A (en) * 2006-08-08 2008-02-21 Kurashiki Seni Kako Kk Laminated sheet excellent in windproof and moisture-permeable waterproof properties, cloth using same, and their production methods
CN111513404A (en) * 2020-04-02 2020-08-11 青岛大学 High-moisture-absorption intelligent heat-dissipation medical protective clothing composite fabric and preparation method thereof
CN215882907U (en) * 2021-07-03 2022-02-22 吴江思尔夫纺织有限公司 Sun-proof fabric
CN114749039A (en) * 2022-05-31 2022-07-15 南通大学 Super-hydrophilic and underwater super-oleophobic carbon nanofiber membrane and preparation method thereof
CN115519859A (en) * 2022-09-30 2022-12-27 南通大学 Carbon nanofiber-based breathable gas-defense garment fabric and preparation method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2642819Y (en) * 2003-06-25 2004-09-22 中国人民解放军总后勤部军需装备研究所士兵***研究中心 Repeatedly wearable protective clothing for anti-SARS with water vapor permeability
CN102632648A (en) * 2012-04-12 2012-08-15 东华大学 High-efficiency waterproof moisture-permeable shell fabric and preparation method thereof
WO2016099147A1 (en) * 2014-12-18 2016-06-23 주식회사 아모그린텍 Waterproof and moisture permeable fabric, and manufacturing method therefor
CN107584824A (en) * 2017-09-11 2018-01-16 赵晓明 A kind of multifunctional ventilating type frog suit fabric and preparation method thereof
EP3806684A1 (en) * 2018-06-15 2021-04-21 Alpinestars Research S.p.A. Method for joining together two protective materials and protective garment comprising an article made using this method
KR102242369B1 (en) * 2020-02-14 2021-04-20 (주)유니크라미 Manufacturing method for fabric enhanced warterproof and breathable function
CN113276524B (en) * 2021-05-27 2022-11-08 华东理工大学 Composite fabric for gas protective clothing and preparation method thereof
CN114318664B (en) * 2021-12-23 2023-11-14 南通大学 Flexible carbon nanofiber membrane with orientation structure and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070004301A1 (en) * 2004-07-05 2007-01-04 Peter Heinrich Textile composite material comprising activated carbon fibres and production thereof
JP2008036985A (en) * 2006-08-08 2008-02-21 Kurashiki Seni Kako Kk Laminated sheet excellent in windproof and moisture-permeable waterproof properties, cloth using same, and their production methods
CN111513404A (en) * 2020-04-02 2020-08-11 青岛大学 High-moisture-absorption intelligent heat-dissipation medical protective clothing composite fabric and preparation method thereof
CN215882907U (en) * 2021-07-03 2022-02-22 吴江思尔夫纺织有限公司 Sun-proof fabric
CN114749039A (en) * 2022-05-31 2022-07-15 南通大学 Super-hydrophilic and underwater super-oleophobic carbon nanofiber membrane and preparation method thereof
CN115519859A (en) * 2022-09-30 2022-12-27 南通大学 Carbon nanofiber-based breathable gas-defense garment fabric and preparation method thereof

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