Fire-retardant and anti-permeation three-proofing bandage and manufacturing process thereof

Abstract

The three-proofing bandage comprises a PAN (Polyacrylonitrile) pre-oxidized cloth layer, and a nano composite layer grows on the surface of the PAN pre-oxidized cloth layer through atomic layer deposition on the fiber surface; the PAN pre-oxidized cloth layer micropore array is drilled through laser, the aperture of the micropore array has gradient, and the micropore array is divided into outer layer holes, transition layer holes and inner layer holes; the modified acrylic acid glue layer is coated on the inner surface of the PAN pre-oxidized cloth layer; the medicine-carrying electrostatic spinning PAN layer is adhered to the surface of the modified acrylic acid glue layer; the chitosan porous membrane is arranged on the surface of the drug-loaded electrostatic spinning PAN layer. The PAN pre-oxidized cloth layer serves as the bandage body and has the fire-resistant and flame-retardant characteristics, meanwhile, the nano-composite layer is deposited on the surface of the PAN pre-oxidized cloth layer, the chemical corrosion resistance is further improved, and the anti-permeation effect is good; moreover, the laser gradient micropore processing has stronger rapid perspiration and bacteria blocking effects, and the overall medical effect is stronger than that of a common three-proofing bandage.

Description

Technical Field

[0001] The present invention belongs to the technical field of three-proof bandages, and in particular relates to a fire-resistant and penetration-proof three-proof bandage and a manufacturing process thereof. Background Art

[0002] Bandage technology, as a medical care product, has continuously advanced over time. In particular, in modern warfare, military bandages, as crucial medical equipment, have seen significant improvements in their protective performance and functionality. Military bandages must not only meet basic requirements for hemostasis and bandaging but also possess multiple protective features, such as waterproofing, dustproofing, and antibacterial properties, to ensure wounds remain clean and heal in harsh environments. These demands have driven the development and application of high-tech bandage products, such as triple-proof bandages.

[0003] Currently, these bandages lack effective wound care in industrial, military, or extreme environments, such as chemical spills and fire rescue. They only offer the bandage's inherent three-protective properties, but their fire retardancy and chemical penetration resistance are poor, making them ineffective in emergency and daily wound care situations. Therefore, further improvements are needed. Summary of the Invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a fire-resistant and anti-penetration triple-proof bandage to avoid the trouble that the conventional three-proof bandages have weak effects in fire retardation and anti-penetration.

[0005] In order to solve the above technical problems, the present invention discloses a fire-resistant and anti-permeation triple-proof bandage, comprising: PAN pre-oxidized cloth layer, the surface of the PAN pre-oxidized cloth layer grows a nanocomposite layer on the fiber surface by atomic layer deposition; The micro-hole array is made by laser drilling in the PAN pre-oxidized fabric layer. The micro-hole array has a gradient aperture and is divided into outer layer holes, transition layer holes, and inner layer holes. A modified acrylic adhesive layer applied to the inner surface of the PAN pre-oxidized fabric layer; a drug-loaded electrospun PAN layer adhered to the surface of a modified acrylic adhesive layer; and A chitosan porous membrane is arranged on the surface of the drug-loaded electrospun PAN layer.

[0006] According to one embodiment of the present invention, the nanocomposite layer is formed by atomic layer deposition of Al2O3 layer and TiO2 layer, and the overall thickness is 30±2 nm.

[0007] According to one embodiment of the present invention, the pore size of the outer layer decreases from 20 μm to 10 μm; the pore size of the transition layer decreases from 10 μm to 7 μm; the pore size of the inner layer decreases from 7 μm to 2 μm, and the pore depths of the three are consistent.

[0008] The present invention also discloses a manufacturing process of a fireproof and anti-permeation three-proof bandage, including: Step a. Pretreatment of the PAN pre-oxidized cloth layer: Provide the PAN pre-oxidized cloth, perform plasma cleaning using O2 plasma with a power of 100W for 5 minutes to remove surface organic substances and increase the -OH active sites; then treat it in a vacuum oven at 80°C for 2 hours to remove excess moisture; Step b. Atomic layer deposition of the nano-composite layer: Grow the nano-composite layer on the fiber surface of the dried PAN pre-oxidized cloth through the atomic layer deposition process. The reaction precursors of Al2O3 are trimethylaluminum and water, with 50 cycles, and the reaction precursors of TiO2 are isopropyl titanate and water, with 20 cycles. The reaction chamber temperature is 80°C.

[0009] Step c. Laser gradient micro-hole processing: Take out the PAN pre-oxidized cloth and place it in an ultraviolet picosecond laser device for laser gradient micro-hole processing to form a micro-hole array; Step d. Coating of the modified acrylic glue layer: Input the PAN pre-oxidized cloth into a coater and coat the modified acrylic glue layer using a gravure roll. The gravure roll has 180 lines / inch and a glue loading of 4.5 g / m², and then perform hot pressing and gluing; Step e. Molding of the chitosan porous membrane: Provide drug-loaded electrospun PAN, form a membrane through the phase separation method, cast a film on the surface of the drug-loaded electrospun PAN using a chitosan acetic acid aqueous solution in combination with a pore-forming agent. The film layer thickness is 100μm, then immerse it in a NaOH coagulation bath with pH = 13 for 15 minutes, take it out and perform supercritical CO2 drying to obtain the drug-loaded electrospun PAN with a chitosan porous membrane; Step f. Adhesion of the drug-loaded electrospun PAN layer: Adhere the drug-loaded electrospun PAN layer to the modified acrylic glue layer for cold pressing and lamination; The pressure is 0.1 MPa and it lasts for 1 minute; Step g. Terminal sterilization: Perform sterilization by electron beam irradiation and then package.

[0010] According to an embodiment of the present invention, after the above step b, it is necessary to anneal in a nitrogen environment at 150°C for 1 hour to enhance the film layer density.

[0011] According to an embodiment of the present invention, after annealing in the above step b, hexamethyldisilazane vapor is introduced to make the surface contact angle > 100°.

[0012] According to an embodiment of the present invention, in the above step c, the laser energy density of the outer layer holes is 2.5 J / cm², the laser energy density of the transition holes is 1.8 J / cm², and the laser energy density of the inner layer holes is 0.5 J / cm².

[0013] Compared with the prior art, the present invention can achieve the following technical effects: By using PAN pre-oxidized cloth as the bandage body, it has fire-resistant and flame-retardant properties. At the same time, a nano-composite layer is deposited on its surface to further enhance its chemical corrosion resistance and provide good anti-penetration effect. In addition, laser gradient microporous processing has stronger rapid perspiration and bacterial barrier effects. The overall medical effect is stronger than that of ordinary three-proof bandages.

[0014] Of course, any product implementing the present invention does not necessarily need to achieve all of the above-mentioned technical effects at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The drawings described herein are used to provide a further understanding of the present invention and constitute a part of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings: Figure 1 2. It is a cross-sectional schematic diagram of a fire-resistant and anti-permeation triple-proof bandage according to an embodiment of the present invention; Figure 2 is a schematic diagram of a laser micro-hole according to an embodiment of the present invention; Figure 3 It is a manufacturing process flow chart of an embodiment of the present invention; Figure 4 are the key process parameters of atomic layer deposition in Example 1 of the present invention; Figure 5 This is the fire retardant and anti-penetration test table in Example 1 of the present invention; Figure 6 This is a grading chart of the judgment criteria for Examples 1-3 of the present invention. Figure ID

[0016] PAN pre-oxidized cloth layer 10, nanocomposite layer 20, modified acrylic glue layer 30, drug-loaded electrospun PAN layer 40, chitosan porous membrane 50, outer layer pores 61, transition layer pores 62, inner layer pores 63. DETAILED DESCRIPTION

[0017] The following will describe the embodiments of the present invention in detail with reference to the accompanying drawings and examples, so that the implementation process of how the present invention applies technical means to solve technical problems and achieve technical effects can be fully understood and implemented accordingly.

[0018] Please refer to Figure 1 and Figure 2 , Figure 1 2. It is a cross-sectional schematic diagram of a fire-resistant and anti-permeation triple-proof bandage according to an embodiment of the present invention; Figure 2 Schematic diagram of laser micro-hole according to an embodiment of the present invention.

[0019] As shown in the figure, a three-proof bandage with fire resistance and anti-permeation includes: a PAN pre-oxidized fabric layer 10, on the surface of which a nano-composite layer 20 is grown on the fiber surface by atomic layer deposition; a microporous array is formed in the PAN pre-oxidized fabric layer 10 by laser drilling, and the pore diameters of the microporous array have a gradient, which are divided into outer layer pores 61, transition layer pores 62, and inner layer pores 63; a modified acrylic glue layer 30 coated on the inner surface of the PAN pre-oxidized fabric layer 10; a drug-loaded electrospun PAN layer 40 adhered to the surface of the modified acrylic glue layer 30; and a chitosan porous membrane 50 disposed on the surface of the drug-loaded electrospun PAN layer 40.

[0020] In an embodiment of the present invention, the PAN pre-oxidized fabric layer 10 is selected from a polyacrylonitrile-based fiber pre-oxidized fabric as the bandage body, which has fire and flame retardant properties. The Al2O3 / TiO2 nano-composite layer 20 is grown on the surface by atomic layer deposition on the fiber surface, which can improve the chemical corrosion resistance. After testing, it can withstand 98% concentrated sulfuric acid for ≥4h. It plays a high-strength anti-permeation role in special situations such as chemical leakage. Laser drilling is carried out and the pore diameters change in a gradient, aiming to facilitate one-way sweating, that is, only allowing liquid to seep out from the inside to the outside, and enhancing air permeability.

[0021] The modified acrylic glue layer 30 is coated on the inner surface of the PAN pre-oxidized fabric layer 10 and can still maintain good viscosity after encountering water. The drug-loaded electrospun PAN layer 40 and the chitosan porous membrane 50 act as dressings to complete the functions of hemostasis and drug release, strengthening medical protection.

[0022] The nano-composite layer 20 of the present invention deposits an Al2O3 layer and a TiO2 layer by atomic layer deposition, and the overall thickness is 30±2nm.

[0023] Such as Figure 2 , the pore diameter of the outer layer pores 61 decreases from 20μm in a gradient to 10μm; the pore diameter of the transition layer pores 62 decreases from 10μm in a gradient to 7μm; the pore diameter of the inner layer pores 63 decreases from 7μm in a gradient to 2μm, and the pore depths of the three are the same. A gradient change is formed, and the whole has a taper. The pore diameter of the outer layer pores 61 is larger to achieve rapid sweating, the transition pores are for transition to achieve droplet fragmentation, and the innermost inner layer pores have the smallest pore diameter to complete bacteria blocking. Example 1

[0024] Please continue to refer to Figure 3 、 Figure 4 , Figure 3 is the process flow chart of the embodiment of the present invention; Figure 4 are the key process parameters of atomic layer deposition in the embodiment of the present invention.

[0025] A manufacturing process of a three-proof bandage with fire resistance and anti-permeation includes: Step a. Pretreatment of the PAN pre-oxidized fabric layer: Provide the PAN pre-oxidized fabric and perform plasma cleaning using O2 plasma at a power of 100 W for 5 min to remove surface organic substances, increase the -OH active sites, and at the same time reduce the contact angle from 75° to <10°, improving the precursor adsorption rate; then treat it in a vacuum oven at 80 °C for 2 h to remove excess moisture and avoid moisture interfering with the reaction; Step b. Atomic layer deposition of the nanocomposite layer: Grow the nanocomposite layer on the fiber surface of the dried PAN pre-oxidized fabric through the atomic layer deposition process. The reaction precursors of Al2O3 are trimethylaluminum (TMA, Al(CH3)3) and water, with 50 cycles, and the reaction precursors of TiO2 are titanium isopropoxide (TTIP, Ti(OCH(CH3)2)4) and water, with 20 cycles. The reaction chamber temperature is 80 °C to avoid thermal deformation of the PAN fibers.

[0026] Deposition cycle (example): 1. TMA pulse: 0.1 s (introduce TMA vapor and adsorb it on the fiber surface) 2. Nitrogen purge: 5 s (remove unreacted precursors) 3. H2O pulse: 0.1 s (oxidize TMA to form a monolayer of Al2O3) 4. Nitrogen purge: 5 s 5. TTIP pulse: 0.2 s (deposit Ti atoms) Repeat the steps to complete the TiO2 layer; Cycle ratio: Al2O3:TiO2 = 3:1 (50 cycles of Al2O3 + 20 cycles of TiO2; Step c. Laser gradient micro-hole machining: Take out the PAN pre-oxidized fabric and place it in an ultraviolet picosecond laser device for laser gradient micro-hole machining to form a micro-hole array; Step d. Coating of the modified acrylic glue layer: Input the PAN pre-oxidized fabric into a coater and coat the modified acrylic glue layer using a gravure roll. The gravure roll has 180 lines / inch and a glue loading of 4.5 g / m², and perform hot pressing and gluing; Step e. Formation of the chitosan porous membrane: Provide drug-loaded electrospun PAN, and form a membrane through the phase separation method. Cast a film on the surface of the drug-loaded electrospun PAN using an aqueous acetic acid solution of chitosan in combination with a pore-forming agent. The film layer thickness is 100 μm, then immerse it in a NaOH coagulation bath with pH = 13 for 15 min, take it out and perform supercritical CO2 drying to obtain drug-loaded electrospun PAN with a chitosan porous membrane; Step f. Adhesion of the drug-loaded electrospun PAN layer: Adhere the drug-loaded electrospun PAN layer to the modified acrylic glue layer for cold pressing and lamination; the pressure is 0.1 MPa and it lasts for 1 min; Step g. Terminal sterilization, followed by packaging after sterilization using electron beam irradiation.

[0027] This process enables nanoscale precise control, is suitable for porous fiber substrates, and protects the PAN structure through a low-temperature process (<100°C). It has been measured that there is no corrosion after being soaked in 98% sulfuric acid for 4 hours. The tensile strength of the fiber is increased by 20%.

[0028] Preferably, after step b above, annealing is required in a nitrogen environment at 150°C for 1 hour to enhance the densification of the film layer. After annealing in step b, hexamethyldisilazane vapor is introduced to make the surface contact angle >100° for hydrophobic modification.

[0029] In step c, the laser energy density of the outer layer holes is 2.5 J / cm², the laser energy density of the transition holes is 1.8 J / cm², and the laser energy density of the inner layer holes is 0.5 J / cm² to complete gradient drilling. Example 2

[0030] Step a. Pretreatment of the PAN pre-oxidized fabric layer, providing a PAN pre-oxidized fabric; Step b. Coating of the modified acrylic glue layer, inputting the PAN pre-oxidized fabric into a coater, and using a gravure roll to coat the modified acrylic glue layer. The gravure roll has 180 lines / inch and a glue loading of 4.5 g / m², followed by hot pressing and gluing; Step c. Formation of the chitosan porous membrane, providing drug-loaded electrospun PAN, forming a membrane through the phase separation method, casting a film on the surface of the drug-loaded electrospun PAN using a chitosan acetic acid aqueous solution in combination with a pore-forming agent. The film layer thickness is 100 μm, then it is immersed in a NaOH coagulation bath with pH = 13 for 15 minutes, taken out and dried using supercritical CO2 to obtain drug-loaded electrospun PAN with a chitosan porous membrane; Step d. Adhesion of the drug-loaded electrospun PAN layer, adhering the drug-loaded electrospun PAN layer to the modified acrylic glue layer for cold pressing and laminating; the pressure is 0.1 MPa and it lasts for 1 minute; Step e. Terminal sterilization, followed by packaging after sterilization using electron beam irradiation. Example 3

[0031] Step a. Pretreatment of the PAN pre-oxidized fabric layer, providing a PAN pre-oxidized fabric, performing plasma cleaning using O2 plasma with a power of 100 W for 5 minutes to remove surface organic substances and increase the -OH active sites; then treating in a vacuum oven at 80°C for 2 hours to remove excess moisture; Step b. Atomic layer deposition of the nanocomposite layer, growing a nanocomposite layer on the fiber surface of the dried PAN pre-oxidized fabric through the atomic layer deposition process. The reaction precursors of Al2O3 are trimethylaluminum and water, with 50 cycles, and the reaction precursors of TiO2 are isopropyl titanate and water, with 20 cycles. The reaction chamber temperature is 80°C.

[0032] Step c. Coating of the modified acrylic glue layer: Feed the PAN pre-oxidized fabric into a coater, and coat the modified acrylic glue layer using a gravure roll. The gravure roll has 180 lines per inch and a glue loading of 4.5 g / m², and then perform hot pressing and gluing. Step d. Molding of the chitosan porous membrane: Provide drug-loaded electrospun PAN, and form a membrane by the phase separation method. Cast a film on the surface of the drug-loaded electrospun PAN with a chitosan acetic acid aqueous solution in combination with a pore-forming agent. The film layer thickness is 100 μm, then immerse it in a NaOH coagulation bath with pH = 13 for 15 min, and take it out for supercritical CO2 drying to obtain drug-loaded electrospun PAN with a chitosan porous membrane. Step e. Adhesion of the drug-loaded electrospun PAN layer: Adhere the drug-loaded electrospun PAN layer to the modified acrylic glue layer for cold pressing and laminating; the pressure is 0.1 MPa and it lasts for 1 min. Step f. Terminal sterilization: Sterilize by electron beam irradiation and then package.

[0033] Perform a fire resistance and anti-permeation test on Examples 1-3. Figure 5 This is the fire resistance and anti-permeation test table in Example 1 of the present invention. Figure 6 This is the grading diagram of the determination criteria for Examples 1-3 of the present invention and Examples 2 and 3. It is measured that Example 1 meets the A-level standard, while Examples 2-3 are at the C-level standard. Therefore, in Example 1, the bandage itself has the best fire resistance and anti-permeation performance.

[0034] In summary, the present invention uses the PAN pre-oxidized fabric layer as the bandage body, which has the characteristics of fire resistance and flame retardancy. At the same time, a nano-composite layer is deposited on its surface to further enhance the chemical corrosion resistance and has a good anti-permeation effect; and the laser gradient micro-porous processing has a stronger rapid sweating and bacteria barrier effect, and the overall medical effect is stronger than that of ordinary three-proof bandages.

[0035] The above description shows and describes several preferred embodiments of the present invention. However, as mentioned above, it should be understood that the present invention is not limited to the form disclosed herein, should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be changed within the scope of the inventive concept described herein through the above teachings or the techniques or knowledge in related fields. And any changes and modifications made by those skilled in the art without departing from the spirit and scope of the present invention shall fall within the protection scope of the appended claims of the present invention.

Claims

1. A fire-resistant and anti-permeation triple-proof bandage, characterized in that, Comprising: A PAN pre-oxidized fabric layer, on the surface of which a nano-composite layer is grown on the fiber surface by atomic layer deposition; Micropore arrays are formed in the PAN pre-oxidized fabric layer by laser drilling. The pore diameters of the micropore arrays have a gradient and are divided into outer layer pores, transition layer pores, and inner layer pores; A modified acrylic glue layer coated on the inner surface of the PAN pre-oxidized fabric layer; A drug-loaded electrospun PAN layer adhered to the surface of the modified acrylic glue layer; and A chitosan porous membrane disposed on the surface of the drug-loaded electrospun PAN layer.

2. The fireproof and anti-permeation three-proof bandage according to claim 1, characterized in that, Wherein the nano-composite layer is deposited with an Al2O3 layer and a TiO2 layer by atomic layer deposition, and the overall thickness is 30 ± 2 nm.

3. The fireproof and anti-permeation three-proof bandage according to claim 1, characterized in that, Wherein the pore diameter of the outer layer pores decreases from 20 μm to 10 μm in gradient; the pore diameter of the transition layer pores decreases from 10 μm to 7 μm in gradient; the pore diameter of the inner layer pores decreases from 7 μm to 2 μm in gradient, and the pore depths of the three are the same.

4. The manufacturing process of a fireproof and anti-permeation three-proof bandage as described in claim 1, characterized in that, Comprising: Step a. Pretreatment of the PAN pre-oxidized fabric layer. Provide a PAN pre-oxidized fabric, perform plasma cleaning using O2 plasma with a power of 100 W for 5 min to remove surface organic substances and increase -OH active sites; then treat in a vacuum oven at 80 °C for 2 h to remove excess moisture; Step b. Deposition of the nano-composite layer by atomic layer deposition. The dried PAN pre-oxidized fabric is used to grow a nano-composite layer on its fiber surface by atomic layer deposition. The reaction precursors of Al2O3 are trimethylaluminum and water, with 50 cycles, and the reaction precursors of TiO2 are isopropyl titanate and water, with 20 cycles. The reaction chamber temperature is 80 °C; Step c. Laser gradient micropore processing. Take out the PAN pre-oxidized fabric and place it in an ultraviolet picosecond laser device for laser gradient micropore processing to form a micropore array; Step d. Coating of the modified acrylic glue layer. Input the PAN pre-oxidized fabric into a coater, and use a gravure roll to coat the modified acrylic glue layer. The gravure roll has 180 lines / inch and a glue loading of 4.5 g / m², and perform hot press gluing; Step e. Molding of the chitosan porous membrane. Provide drug-loaded electrospun PAN, and form a membrane by the phase separation method. Cast a film on the surface of the drug-loaded electrospun PAN with a chitosan acetic acid aqueous solution and a pore-forming agent. The film layer thickness is 100 μm, then immerse it in a NaOH coagulation bath with pH = 13 for 15 min, take it out and perform supercritical CO2 drying to obtain drug-loaded electrospun PAN with a chitosan porous membrane; Step f. Adhesion of the drug-loaded electrospun PAN layer. Adhere the drug-loaded electrospun PAN layer to the modified acrylic glue layer for cold press lamination; the pressure is 0.1 MPa and it lasts for 1 min; Step g. Terminal sterilization. Sterilize by electron beam irradiation and then package.

5. The manufacturing process of the fireproof and anti-permeation three-proof bandage according to claim 4, characterized in that, Wherein after step b, it is necessary to anneal in a nitrogen environment at 150 °C for 1 h to enhance the film layer density.

6. The manufacturing process of the fireproof and anti-permeation three-proof bandage according to claim 5, characterized in that, Wherein after annealing in step b, hexamethyldisilazane vapor is introduced to make the surface contact angle > 100°.

7. The manufacturing process of the fireproof, anti-permeation and three-proof bandage according to claim 4, characterized in that, Wherein in step c, the laser energy density of the outer layer pores is 2.5 J / cm², the laser energy density of the transition pores is 1.8 J / cm², and the laser energy density of the inner layer pores is 0.5 J / cm².

Images