Antibacterial cleaning fabric and preparation method thereof

Abstract

The invention relates to the technical field of layered materials, in particular to an antibacterial cleaning fabric and a preparation method thereof. The defects that an existing cleaning fabric is poor in antibacterial property and mechanical property are overcome. The method comprises the following steps: firstly coating a bottom layer modified polyester fabric with a binder, then laminating a surface layer modified polyester fabric, and drying to obtain a multi-layer composite fabric; performing plasma treatment on the multi-layer composite fabric to obtain a post-treated fabric; carrying out dipping treatment on the post-treatment fabric, then carrying out UV curing, and then carrying out thermocuring, so as to obtain the antibacterial cleaning fabric. Wherein the bottom-layer modified polyester fabric is prepared from modified polyester fibers; the surface layer modified polyester fabric is prepared from polyester fibers, nano cerium dioxide, glycidyl methacrylate and the like; a binder of the bonding layer is prepared from a waterborne polyurethane binder, modified graphene oxide and the like. Through cooperation of multiple components and multiple processes, the finally prepared antibacterial cleaning fabric is high in antibacterial property and high in mechanical property.

Description

Technical Field

[0001] The present invention relates to the technical field of layered materials, and specifically to an antibacterial cleaning fabric and a preparation method thereof. Background Art

[0002] Polyethylene terephthalate (PET) fibers are widely used in the fields of clothing, home textiles, industrial textiles, etc. due to their high strength, wear resistance, good wrinkle resistance, and good chemical stability. In the field of cleaning fabrics, PET fibers have significant advantages. Their surfaces are smooth and flat, stains are not easily attached, which is convenient for cleaning and wiping, and they have good washability. After being washed multiple times, they can still maintain a stable structure and maintain the cleaning effect.

[0003] However, there are limitations when using single-layer PET fiber fabrics to make cleaning fabrics. For example, their functions are single, and it is difficult to simultaneously meet multiple requirements such as antibacterial and high water absorption. Moreover, in complex usage scenarios, their mechanical properties may not meet the requirements of long-term high-intensity use. By preparing multi-layer fiber fabrics and combining fibers with different properties, complementary advantages can be achieved, and the disadvantages of single-layer fabrics can be effectively overcome.

[0004] In the laboratory application environment, multi-layer PET fiber fabrics still face many challenges. Firstly, their antibacterial properties and antibacterial durability are insufficient, making it difficult to resist microbial contamination during experiments, and the antibacterial effect significantly decreases after being washed multiple times. Secondly, their mechanical properties are poor and cannot withstand external forces such as frequent pulling and friction during experimental operations, and are prone to breakage. Therefore, there is an urgent need to develop a PET layered fabric with excellent antibacterial properties, good mechanical properties, and moderate hygroscopicity to meet the strict requirements of the laboratory for antibacterial cleaning fabrics and ensure the safety and cleanliness of the experimental environment.

[0005] Therefore, an antibacterial cleaning fabric and a preparation method thereof are proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide an antibacterial cleaning fabric and a preparation method thereof. The present invention first coats a binder on the bottom modified PET fabric, then laminates the surface modified PET fabric and dries it to obtain a multi-layer composite fabric; the multi-layer composite fabric is subjected to plasma treatment to obtain a post-treatment fabric; the post-treatment fabric is subjected to impregnation treatment, then UV curing is carried out, and then thermal curing is carried out to obtain an antibacterial cleaning fabric; wherein, the bottom modified PET fabric is made of modified PET fibers; the surface modified PET fabric is made of PET fibers, nano-ceria, glycidyl methacrylate, etc.; the binder is made of a waterborne polyurethane binder, modified graphene oxide, etc.; the modified graphene oxide is made of graphene oxide and silver nitrate. Through the coordination of multiple components and multiple processes, the finally prepared antibacterial cleaning fabric has strong antibacterial properties and strong mechanical properties.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] On the one hand, the present invention provides a method for preparing an antibacterial cleaning fabric, specifically including the following steps:

[0009] First, coat the binder on the bottom modified polyester fabric, then laminate the surface modified polyester fabric and dry it to obtain a multi-layer composite fabric; perform plasma treatment on the multi-layer composite fabric to obtain a post-treatment fabric; perform impregnation treatment on the post-treatment fabric, first perform UV curing, and then perform thermal curing to obtain an antibacterial cleaning fabric;

[0010] The bottom modified polyester fabric includes modified polyester fibers; the surface modified polyester fabric includes polyester fibers, nano-ceria, (3-aminopropyl)triethoxysilane, and glycidyl methacrylate; the modified polyester fibers include polyester chips, nano-alumina, and phenyltrimethoxysilane; the binder includes a waterborne polyurethane binder, modified graphene oxide, and polycarbodiimide; the modified graphene oxide includes graphene oxide and silver nitrate.

[0011] Preferably, the preparation method of the binder is as follows: by weight, ultrasonically disperse the modified graphene oxide in deionized water, then mix it with the waterborne polyurethane binder and stir to obtain a mixed solution; add polycarbodiimide to the mixed solution and stir to obtain the binder. By weight, the weight ratio of the modified graphene oxide to polycarbodiimide is 2-3:1;

[0012] Among them, the preparation method of the modified graphene oxide is as follows: ultrasonically disperse the graphene oxide in deionized water, add ethylenediamine and stir for reaction for 2-3 hours to obtain a reaction solution; add an aqueous silver nitrate solution dissolved with 5-8 wt% to the reaction solution, stir, then add an aqueous sodium borohydride solution, stir for 1.5-2 hours, and then obtain the modified graphene oxide through centrifugation, washing, and drying.

[0013] Preferably, the preparation method of the bottom modified polyester fabric is as follows: dissolve phenyltrimethoxysilane in a mixed solution of absolute ethanol and deionized water to obtain a silanol solution; add nano-alumina to the silanol solution, react and dry to obtain modified nano-alumina; by weight, mix polyester chips with 1-2 parts of the dried modified nano-alumina and stearic acid, and melt-blend, extrude, and cool and pelletize at a screw speed of 250-300 rpm to obtain modified polyester chips; the modified polyester chips are spun and twisted to obtain modified polyester fiber yarns with a linear density of 120-150 denier, and the modified polyester yarns are used to prepare a bottom polyester fiber fabric with a warp density of 120-150 ends per inch and a weft density of 80-110 ends per inch.

[0014] Preferably, the preparation method of the surface layer modified polyester fabric is as follows: polyester yarns with a linear density of 80-120 denier are prepared using polyester fibers, and a polyester fabric with a warp density of 100-150 threads per inch and a weft density of 70-110 threads per inch is prepared using the polyester yarns; the polyester fabric is subjected to functionalization treatment to obtain the surface layer modified polyester fabric.

[0015] Preferably, the functionalization treatment method is as follows: the polyester fiber fabric is immersed in a reaction solution composed of deionized water, potassium persulfate, and glycidyl methacrylate and reacted for 2-3 hours, then washed and dried to obtain pretreated polyester fibers; the pretreated polyester fibers are impregnated in a 1-2 wt% functionalized nano-ceria dispersion liquid, and then the surface layer modified polyester fabric is obtained through padding, drying, and re-heat treatment; the functionalized nano-ceria is obtained by reacting nano-ceria with dilute nitric acid for surface treatment and then reacting with (3-aminopropyl)triethoxysilane.

[0016] Preferably, the plasma treatment method is as follows: both sides of the multi-layer composite fabric are subjected to plasma treatment to obtain a post-treated fabric; the plasma treatment conditions are: the gas is a mixed gas of argon and oxygen, wherein the flow ratio of argon to oxygen is 7-8:2-3, the treatment power is 150-200 W, and the treatment time is 30-40 s.

[0017] Preferably, the preparation method of the antibacterial and cleaning fabric is as follows: the post-treated fabric is subjected to impregnation treatment, then UV curing is carried out first, and then thermal curing is carried out to obtain the antibacterial and cleaning fabric, wherein the UV curing conditions are a curing power of 110-130 W / cm; the thermal curing conditions are a thermal curing temperature of 130-150 °C and a thermal curing time of 5-7 min.

[0018] Preferably, the impregnation treatment method is as follows: by weight, 6-7 parts of methacryloyloxyethyl trimethyl ammonium chloride, 0.5-1 part of zinc acetate, 1-2 parts of epoxy cross-linking agent, 1-2 parts of perfluoroalkyl acrylate, and 0.3-0.5 part of photoinitiator are added to deionized water to prepare an impregnation solution, and the post-treated fabric is soaked in the impregnation solution for 4-6 min with a liquor pick-up rate of 80-90%; among them, the epoxy cross-linking agent is glycerol triglycidyl ether.

[0019] On the other hand, the present invention provides an antibacterial and cleaning fabric, which includes a surface layer modified polyester fabric, a bonding layer, and a bottom layer modified polyester fabric;

[0020] The surface layer modified polyester fabric includes polyester yarns, nano-ceria, and glycidyl methacrylate;

[0021] The bonding layer includes a binder, and the binder includes an aqueous polyurethane binder, modified graphene oxide, and polycarbodiimide cross-linking agent;

[0022] The bottom layer modified polyester fabric comprises polyester chips, nano-aluminum oxide, and phenyltrimethoxysilane;

[0023] The modified graphene oxide comprises graphene oxide and silver nitrate.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] 1. In the present invention, there is a synergistic antibacterial system mainly composed of modified graphene oxide and methacryloyloxyethyl trimethyl ammonium chloride, assisted by zinc acetate. The modified graphene oxide is located in the middle bonding layer, providing slow-release and highly efficient antibacterial properties, while enhancing the mechanical and corrosion resistance of the bonding layer. The surface layer is grafted with glycidyl methacrylate and loaded with modified nano-ceria to obtain antioxidant and partial antibacterial properties, and reactive sites are introduced. The quaternary ammonium salt is distributed on the surfaces and inside of the two layers by impregnation to directly kill bacteria. Multiple mechanisms cooperate to avoid the failure of a single component. The antibacterial system is fixed by the modified fiber skeleton and the intermediate layer matrix, and is bonded between the layers by an interfacial coupling agent to ensure resistance to chemical and mechanical damage. The impregnation penetrates evenly, and the UV-photothermal combined curing realizes the firm anchoring of the antibacterial components, ensuring the long-term durability of the function.

[0026] 2. In the present invention, the structure of the polyester surface layer fabric with appropriate denier and warp and weft density is convenient for subsequent plasma activation and the penetration of the impregnation liquid. The subsequent plasma increases the surface bonding points, and the impregnated functional components are firmly fixed by UV-photothermal curing, endowing the surface layer with durable antibacterial self-cleaning properties. The modified surface of the surface layer is strongly bonded to the intermediate layer, improving the overall mechanical properties.

[0027] 3. In the present invention, the modified polyester bottom layer fabric with appropriate denier and warp and weft density is used, and nano-aluminum oxide is introduced into the body to improve the inherent strength and acid and alkali corrosion resistance. The bottom layer serves as a structural skeleton to enhance the mechanical foundation of the fabric, and its open structure is conducive to the plasma activation of the outer surface. The impregnated epoxy crosslinking agent bonds to the bottom layer and the intermediate layer again during heat curing, ensuring that the high mechanical properties of the bottom layer are transmitted to the whole composite fabric.

[0028] 4. In the present invention, the composite fabric is subjected to plasma treatment to micro-etch both sides of the fabric and introduce active functional groups, increasing the surface bonding points. The epoxy crosslinking agent and perfluoroalkyl acrylate are introduced through the impregnation liquid, and UV-photothermal combined curing is used. The epoxy crosslinking agent forms an interfacial chemical bond bridge during heat curing, enhancing the interlayer bonding. The perfluoroalkyl acrylate is UV-cured to fix the fluorine-containing chain segments on the surface, endowing hydrophobic and oleophobic self-cleaning functions. The plasma treatment improves the bonding efficiency, and the dual curing cooperates to firmly anchor the functional components, enhancing the interlayer bonding strength and the overall structural stability, and improving the breaking strength, breaking elongation and corrosion resistance of the fabric. Description of the Drawings

[0029] Figure 1Schematic diagram of water contact angles for Example 1, Example 6, Examples 8 - 9, and Comparative Examples 10 - 16 of the present invention. Detailed implementation manners

[0030] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0031] Please refer to Figure 1 , the present invention provides an antibacterial cleaning fabric and a preparation method thereof, and the technical solutions are as follows:

[0032] Example 1

[0033] First, coat the binder on the bottom modified polyester fabric, then laminate the surface modified polyester fabric and dry it to obtain a multi-layer composite fabric; perform plasma treatment on the multi-layer composite fabric to obtain a post-treatment fabric; perform impregnation treatment on the post-treatment fabric, first perform UV curing, and then perform thermal curing to obtain an antibacterial cleaning fabric;

[0034] The bottom modified polyester fabric includes polyester fibers, nano-ceria, (3-aminopropyl)triethoxysilane, and glycidyl methacrylate; the surface modified polyester fabric includes modified polyester fibers; the modified polyester fibers include polyester chips, nano-alumina, and phenyltrimethoxysilane; the binder includes a waterborne polyurethane binder, modified graphene oxide, and polycarbodiimide; the modified graphene oxide includes graphene oxide and silver nitrate.

[0035] Preparation of modified graphene oxide

[0036] Add 10 parts of graphene oxide with an average particle size of 10 μm to 1500 parts of deionized water and ultrasonically disperse for 30 min. Add 1.5 parts of ethylenediamine and stir and react at 300 rpm and 80 °C for 2 hours to obtain a reaction solution; after the reaction solution is cooled to room temperature, add 20 parts of a 5 wt% silver nitrate aqueous solution to the reaction solution, stir for 30 min, then add 10 parts of a 2 wt% sodium borohydride aqueous solution, stir for 1.5 hours, and then obtain modified graphene oxide through centrifugation, washing, and drying.

[0037] Preparation of the binder

[0038] By weight, 10 parts of modified graphene oxide are ultrasonically dispersed in 100 parts of deionized water, and then mixed with 100 parts of a waterborne polyurethane binder and stirred at 800 rpm for 30 min to obtain a mixed solution. Then, 5 parts of polycarbodiimide are added to the mixed solution and stirred at 300 rpm for 10 min to obtain a binder. By weight, the weight ratio of modified graphene oxide to polycarbodiimide is 2:1.

[0039] Preparation of the bottom modified polyester fabric

[0040] 0.1 part of phenyltrimethoxysilane is dissolved in a mixed solution of 10 parts of absolute ethanol and 1 part of deionized water and hydrolyzed at room temperature for 30 min to obtain a silanol solution; 1 part of nano-aluminum oxide with an average particle size of 10 nm is added to the silanol solution, and after reacting for 1 h, it is centrifuged, and the solid precipitate is dried at 80 °C to obtain modified nano-aluminum oxide; by weight, 100 parts of polyester chips are mixed with 1 part of modified nano-aluminum oxide and 0.1 part of stearic acid, and then melt-blended, extruded, and cooled and pelletized at a screw temperature of 260 - 285 °C and a rotation speed of 250 rpm to obtain modified polyester chips; the modified polyester chips are spun at a spinning temperature of 285 °C, twisted, and then a modified polyester fiber yarn with a linear density of 120 denier is obtained. The modified polyester yarn is used to prepare a bottom polyester fiber fabric with a warp density of 120 picks per inch and a weft density of 80 picks per inch.

[0041] Preparation of the surface modified polyester fabric

[0042] Polyester yarn with a linear density of 80 denier is prepared using polyester fibers, and a polyester fabric with a warp density of 100 picks per inch and a weft density of 70 picks per inch is prepared using the polyester yarn; the polyester fabric is subjected to a functionalization treatment to obtain a surface modified polyester fabric.

[0043] Preparation of functionalized nano-ceria: 100 parts of nano-ceria powder with an average particle size of 30 nm are added to 200 parts of a 1% dilute nitric acid solution by mass, soaked and stirred for 30 minutes, and then activated nano-ceria is obtained by centrifugation and washing with deionized water. The activated nano-ceria is added to 1000 parts of absolute ethanol and ultrasonically dispersed for 15 minutes, and then 5 parts of (3-aminopropyl)triethoxysilane are added to the suspension. The reaction is carried out at 70 °C and 300 rpm for 6 hours; after the reaction is completed, the suspension is cooled to room temperature. It is centrifuged at high speed, washed, and dried at 60 °C for 12 hours to obtain functionalized nano-ceria.

[0044] The polyester fiber fabric was immersed in a reaction solution composed of 500 parts of deionized water, 1 part of potassium persulfate and 50 parts of glycidyl methacrylate, reacted at 70 °C for 2 hours, washed with deionized water, and then dried at 60 °C to obtain pretreated polyester fiber; the pretreated polyester fiber was impregnated in a 1 wt% functionalized nano-ceria dispersion liquid, and then through padding, the liquor pickup was 90%, and after drying and then heat treatment, the surface layer modified polyester fabric was obtained.

[0045] Plasma treatment

[0046] Both sides of the multi-layer composite fabric were subjected to plasma treatment to obtain a post-treated fabric; the conditions of plasma treatment were: the gas was a mixed gas of argon and oxygen, wherein the flow ratio of argon to oxygen was 8:2, the treatment power was 150 W, and the treatment time was 60 s.

[0047] Preparation of antibacterial and cleaning fabric

[0048] The post-treated fabric was subjected to impregnation treatment. The method of impregnation treatment was: by weight, 6 parts of methacryloyloxyethyl trimethyl ammonium chloride, 0.5 part of zinc acetate, 1 part of epoxy crosslinking agent, 1 part of perfluoroalkyl acrylate, and 0.3 part of photoinitiator were added to deionized water to prepare an impregnation solution. The total amount of the impregnation solution was 100 parts, and the balance was deionized water. The post-treated fabric was soaked in the impregnation solution for 4 min, and the liquor pickup was 80%; among them, the epoxy crosslinking agent was glycerol triglycidyl ether. Then, it was first subjected to UV curing and then heat curing to obtain an antibacterial and cleaning fabric. Among them, the conditions of UV curing were a curing power of 110 W / cm; the conditions of heat curing were a heat curing temperature of 130 °C and a heat curing time of 5 min.

[0049] The difference between Example 2 and Example 1 was that the reaction time of graphene oxide and ethylenediamine was 2.5 h, the mass fraction of the silver nitrate aqueous solution was 6.5 wt%, an aqueous solution of sodium borohydride was added, and the stirring reaction was carried out for 1.7 hours; the weight ratio of modified graphene oxide to polycarbodiimide was 2.5:1, the dosage of methacryloyloxyethyl trimethyl ammonium chloride in the impregnation solution component was 6.5 parts, the dosage of zinc acetate in the impregnation solution component was 0.75 part, and the concentration of the functionalized nano-ceria dispersion liquid in the surface layer functionalized impregnation solution was 1.5 wt%.

[0050] The difference between Example 3 and Example 1 was that the reaction time of graphene oxide and ethylenediamine was 3 h, the mass fraction of the silver nitrate aqueous solution was 8 wt%, an aqueous solution of sodium borohydride was added, and the stirring reaction was carried out for 2 hours; the weight ratio of modified graphene oxide to polycarbodiimide was 3:1, the dosage of methacryloyloxyethyl trimethyl ammonium chloride in the impregnation solution component was 7 parts, the dosage of zinc acetate in the impregnation solution component was 1 part, and the concentration of the functionalized nano-ceria dispersion liquid in the surface layer functionalized impregnation solution was 2 wt%.

[0051] Example 4 is different from Example 2 in that the linear density of the surface layer polyester yarn is 100 denier, the warp density of the surface layer polyester fabric is 125 threads per inch, and the weft density of the surface layer polyester fabric is 90 threads per inch; the reaction time of the polyester fiber fabric immersed in the reaction solution is 2.5 hours.

[0052] Example 5 is different from Example 2 in that the linear density of the surface layer polyester yarn is 120 denier, the warp density of the surface layer polyester fabric is 150 threads per inch, and the weft density of the surface layer polyester fabric is 110 threads per inch; the reaction time of the polyester fiber fabric immersed in the reaction solution is 3 hours.

[0053] Example 6 is different from Example 4 in that the dosage of modified nano-alumina is 1.5 parts by weight relative to the polyester chip, the rotational speed of the melt blending screw is 275 rpm, the linear density of the bottom layer modified polyester fiber yarn is 135 denier, the warp density of the bottom layer modified polyester fabric is 140 threads per inch, and the weft density of the bottom layer modified polyester fabric is 90 threads per inch.

[0054] Example 7 is different from Example 4 in that the dosage of modified nano-alumina is 2 parts by weight relative to the polyester chip, the rotational speed of the melt blending screw is 300 rpm, the linear density of the bottom layer modified polyester fiber yarn is 150 denier, the warp density of the bottom layer modified polyester fabric is 150 threads per inch, and the weft density of the bottom layer modified polyester fabric is 110 threads per inch.

[0055] Example 8 is different from Example 6 in that the flow ratio of plasma gases argon and oxygen is 7.5:2.5, the plasma treatment power is 175 W, and the plasma treatment time is 75 s; the dosage of epoxy crosslinking agent in the impregnating solution component is 1.5 parts, the dosage of perfluoroalkyl acrylate in the impregnating solution component is 1.5 parts, the dosage of photoinitiator in the impregnating solution component is 0.4 part, the impregnation time is 5 min, and the squeeze ratio is 85%; the UV curing power is 120 W / cm; the thermal curing temperature is 140 °C and the thermal curing time is 6 min.

[0056] Example 9 is different from Example 6 in that the flow ratio of plasma gases argon and oxygen is 7:3, the plasma treatment power is 200 W, and the plasma treatment time is 90 s; the dosage of epoxy crosslinking agent in the impregnating solution component is 2 parts, the dosage of perfluoroalkyl acrylate in the impregnating solution component is 2 parts, the dosage of photoinitiator in the impregnating solution component is 0.5 part, the impregnation time is 6 min, and the squeeze ratio is 90%; the UV curing power is 130 W / cm; the thermal curing temperature is 150 °C and the thermal curing time is 7 min.

[0057] The only difference between Comparative Example 1 and Example 1 is that: in the preparation process of the binder, modified graphene oxide is not added.

[0058] The only difference between Comparative Example 2 and Example 1 is that: in the preparation process of the binder, graphene oxide is added.

[0059] The difference between Comparative Example 3 and Example 1 is only that: during the preparation of modified graphene oxide, it does not react with ethylenediamine and only reacts with silver nitrate.

[0060] The difference between Comparative Example 4 and Example 1 is only that: methylacryloyloxyethyl trimethyl ammonium chloride is not added to the impregnating solution.

[0061] The difference between Comparative Example 5 and Example 1 is only that: methylacryloyloxyethyl trimethyl ammonium chloride is not added to the impregnating solution, and the surface layer polyester fabric is not modified with functionalized nano-ceria.

[0062] The difference between Comparative Example 6 and Example 1 is only that: during the preparation of the surface layer modified polyester fabric, no pretreatment is carried out, and it is directly impregnated in the functionalized nano-ceria dispersion for reaction.

[0063] The difference between Comparative Example 7 and Example 1 is only that: the linear density of the polyester fiber during the preparation of the surface layer modified polyester fabric is 40 denier.

[0064] The difference between Comparative Example 8 and Example 1 is only that: during the preparation of the modified polyester fiber used for the bottom layer modified polyester fabric, modified nano-alumina is not added.

[0065] The difference between Comparative Example 9 and Example 1 is only that: the linear density of the modified polyester fiber during the preparation of the bottom layer modified polyester fabric is 60 denier.

[0066] The difference between Comparative Example 10 and Example 1 is only that: the multi-layer composite fabric is not subjected to plasma treatment.

[0067] The difference between Comparative Example 11 and Example 1 is only that: during plasma treatment, argon is used instead of the mixed gas.

[0068] The difference between Comparative Example 12 and Example 1 is only that: during plasma treatment, the treatment time is 90 s.

[0069] The difference between Comparative Example 13 and Example 1 is only that: an epoxy crosslinking agent is not added to the impregnating solution.

[0070] The difference between Comparative Example 14 and Example 1 is only that: perfluoroalkyl acrylate is not added to the impregnating solution.

[0071] The difference between Comparative Example 15 and Example 1 is only that: UV curing is used instead of thermal curing.

[0072] The difference between Comparative Example 16 and Example 1 is only that: thermal curing is used instead of UV curing.

[0073] Test Example 1

[0074] Test object: The antibacterial and cleaning fabrics prepared in Examples 1-5 and Comparative Examples 1-6 were tested.

[0075] Test method: The antibacterial rate test method refers to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method", and Escherichia coli is selected as the strain. The final test results are shown in Table 1.

[0076] Table 1 Antibacterial performance test results

[0077] Number Antibacterial Rate (%) Example 1 89.3 Example 2 90.5 Example 3 90.0 Example 4 91.1 Example 5 90.8 Comparative Example 1 75.2 Comparative Example 2 80.5 Comparative Example 3 78.9 Comparative Example 4 65.1 Comparative Example 5 58.7 Comparative Example 6 82.1

[0078] The synergistic antibacterial system integrates the slow-release effect of silver nanoparticles modified with graphene oxide in the intermediate layer and the rapid bactericidal effect of impregnated quaternary ammonium salts. The components are multi-point anchored in each layer by UV-photothermal combined curing, ensuring that the antibacterial components are not easily lost and inactivated. At the same time, nano-ceria can provide antioxidant properties, and the synergistic effect of each component and process realizes long-lasting and durable antibacterial.

[0079] In Comparative Example 1, modified graphene oxide was not added to the adhesive layer, and the intermediate layer lacked the multiple antibacterial mechanisms and slow-release fixation effects provided by modified graphene oxide, resulting in insufficient antibacterial ability contributed by this layer and weakened fixation effect on the impregnated antibacterial components. In Comparative Example 2, graphene oxide was added but not aminated, and the lack of positive charge and reactivity of amine groups on its surface affected the electrostatic adsorption with bacteria and the interaction with the polymer matrix and quaternary ammonium salts, resulting in reduced dispersion and poor fixation of graphene oxide, and the antibacterial efficiency and durability were affected. In Comparative Example 3, amine functional groups were not introduced during the preparation of modified graphene oxide, and the modified graphene oxide lost the positive charge adsorption effect and the ability to form chemical bonds with the matrix, and was not firmly fixed in the adhesive layer and was easy to fall off, and its contribution to long-term antibacterial and slow-release effects was significantly reduced. In Comparative Example 4, the impregnating solution did not contain methacryloyloxyethyltrimethylammonium chloride, and the main rapid bactericidal quaternary ammonium salt component was missing on the surface and inside of the fabric, and only relied on the antibacterial properties of a small amount of nano-ceria in the adhesive layer and the surface layer, resulting in insufficient overall antibacterial efficacy. In Comparative Example 5, both the quaternary ammonium salt and the modification of nano-ceria in the surface layer were missing, further reducing the antibacterial components of the fabric and lacking the auxiliary antibacterial property of the surface layer, and the antibacterial performance decreased significantly. In Comparative Example 6, the surface layer modification pretreatment was insufficient, affecting the grafting rate of glycidyl methacrylate, resulting in poor loading and easy falling off of nano-ceria, poor antioxidant and partial antibacterial durability of the surface layer, and weakened synergistic antibacterial effect.

[0080] The common problem of these comparative examples lies in damaging or weakening the integrity of the synergistic antibacterial system or the fixation of antibacterial components in the fabric structure. Comparative Examples 1-3 mainly affect the function or fixation of the core antibacterial component, modified graphene oxide, in the intermediate bonding layer, resulting in insufficient antibacterial ability, slow-release effect, or poor durability. Comparative Examples 4 and 5 directly reduce or remove the important antibacterial components, quaternary ammonium salt and surface layer nano-ceria, on the surface and inside of the fabric, leading to a significant decrease in the overall antibacterial efficacy. Comparative Example 6 affects the fixation durability of the surface layer nano-ceria, weakening the antioxidant and partial antibacterial functions contributed by the surface layer. The absence or defect of these single components or processes breaks the balance of the multiple mechanisms of each component in the synergistic antibacterial system and their fixation and anchoring in the multi-layer structure, making the antibacterial components more likely to be lost during the washing process, resulting in a significant deterioration of the antibacterial performance of the fabric after 50 washes. This highlights the importance of each antibacterial component and its fixation in a specific layer and through a specific process.

[0081] Test Example 2

[0082] Test objects: The antibacterial cleaning fabrics prepared in Examples 1-2, Examples 4-5, and Comparative Examples 6-7 were tested.

[0083] Test methods: The tests for breaking strength and elongation at break were carried out with reference to ISO 9073-3-1989 "Textiles - Test methods for nonwovens - Part 3: Determination of tensile strength and elongation"; the test method for corrosion resistance was to first test the breaking strength before soaking the fabric, then immerse the fabric in a 2 wt% NaOH solution at 50 °C for 12 h, and test the breaking strength again after soaking. Calculate the breaking strength retention rate, where the breaking strength retention rate = (breaking strength before soaking - breaking strength after soaking) / breaking strength before soaking. The final test results are shown in Table 2.

[0084] Table 2 Test results of breaking strength, elongation at break, and corrosion resistance

[0085]

[0086]

[0087] In Comparative Example 6, insufficient surface layer modification pretreatment reduced the grafting rate of glycidyl methacrylate, decreased the number of reactive epoxy groups on the surface of the surface layer fibers, affected the firm loading of nano-ceria, and weakened the interfacial bonding between the nano-particles and the fibers. More importantly, the number of sites for chemical bonding between the surface layer and the interfacial coupling agent in the intermediate bonding layer and the impregnating solution decreased, resulting in a decline in the interlayer bonding strength. The embrittled interface caused poor stress transfer when the composite fabric was under tension, making it prone to delamination failure, reducing the overall breaking strength and elongation at break, and being prone to delamination damage and decreased corrosion resistance in a corrosive environment. In Comparative Example 7, the linear density of the polyester fibers in the surface layer was too low, the strength of the fiber body was weak, and the modification with antioxidant nano-ceria was difficult to make up for the insufficient basic strength. Plasma treatment might cause relatively large damage to overly fine fibers. The low strength of the fiber body limited the basic bearing capacity that the surface layer could provide as a component of the composite material, and the fabric structure composed of overly fine fibers might affect the effective bonding with the intermediate layer, jointly resulting in poor overall mechanical properties and corrosion resistance of the composite fabric.

[0088] Both of these comparative examples involve the effects of the modification and structural defects of the surface layer itself on the overall mechanical and corrosion resistance properties of the composite fabric, with different focuses. Comparative Example 6 emphasizes the importance of insufficient surface chemical modification of the surface layer in affecting the fixation of nano-particles and interlayer bonding, indicating that surface layer modification not only endows surface functions, but its firm connection with the intermediate layer is the key to improving the overall structural performance. Comparative Example 7 emphasizes the importance of the strength basis of the surface layer fibers. Even with good surface modification, an overly weak fiber body limits the upper limit of the overall performance. Both together illustrate that the surface layer needs to have sufficient fiber body strength and optimized surface chemical activity and structure to effectively bear stress in the composite structure and form a firm bond with the intermediate layer, thereby improving the overall breaking strength, elongation at break, and corrosion resistance of the fabric.

[0089] Test Example 3

[0090] Test object: Test the antibacterial and cleaning fabrics prepared in Example 1, Example 4, Example 6 - 7 and Comparative Example 8 - 9.

[0091] Test method: The test method refers to Test Example 2. The final test results are shown in Table 3.

[0092] Table 3 Test Results of Tensile Strength and Elongation at Break

[0093]

[0094]

[0095] The inherent strength and corrosion resistance of the bottom layer are improved through the bulk modification of nano-alumina. The bottom layer yarn fabric provides a mechanical skeleton. The bulk modification ensures the stability and durability of the basic structure. Its structure is adapted to subsequent plasma treatment and impregnating solution penetration, facilitating interfacial bonding.

[0096] In Comparative Example 8, modified nano-aluminum oxide was not added during the preparation of the bottom-layer modified polyester fiber, and the bottom-layer fiber body lacked the enhancement of nanoparticles and the corrosion inhibition effect. Modified nano-aluminum oxide is the core component for enhancing the inherent strength and corrosion resistance retention rate of the bottom layer. The absence of nano-aluminum oxide results in a lower strength of the bottom layer, and it is more prone to degradation in an acidic or alkaline environment, with a rapid attenuation of mechanical properties. As the main structural framework, the insufficient performance of the bottom layer directly limits the overall breaking strength and corrosion resistance of the composite fabric. In Comparative Example 9, the linear density of the bottom-layer modified polyester fiber is too low, and the strength basis of the fiber body is weak. Although the nano-aluminum oxide modification of the fiber body is carried out, the low linear density of the fiber limits the absolute strength that the bottom-layer fabric can provide. The insufficient strength of the bottom-layer body is the key factor restricting the overall breaking strength and corrosion resistance of the composite fabric.

[0097] Both of these comparative examples involve the influence of the bottom-layer body modification on the overall mechanical and corrosion resistance properties of the composite fabric. In Comparative Example 8, the core component nano-aluminum oxide that provides body enhancement and corrosion inhibition was directly removed, resulting in a significant decline in the basic performance of the bottom layer, thereby affecting the whole. Comparative Example 9 indicates that even with body modification, the selection of the linear density of the bottom-layer fiber is crucial. An overly low linear density will limit the effectiveness of the body modification, resulting in insufficient strength of the bottom-layer body and being unable to provide a sufficiently solid structural support for the composite fabric. Both together illustrate that enhancing the inherent properties of the fiber through bottom-layer body modification is the basis for enhancing the overall mechanical properties and corrosion resistance of the composite fabric, and the parameter selection of the bottom-layer fiber itself is very important for the effect of graft modification.

[0098] Test Example 4

[0099] Test object: Test the antibacterial and cleaning fabrics prepared in Example 1, Example 6, Example 8 - 9, and Comparative Examples 10 - 16.

[0100] Test method: For the water contact angle test method, refer to GB / T42694—2023 "Testing and Evaluation of the Surface Anti-wetting Performance of Textiles - Contact Angle and Rolling Angle Method", and for the remaining test methods, refer to Test Examples 1 - 2. The final test results are shown in Table 4 and Figure 1 as follows.

[0101] Table 4 Comprehensive Performance Test Results Table

[0102]

[0103]

[0104] Plasma treatment etches the fabric surface and activates the fabric surface to increase bonding sites. Functional components such as epoxy crosslinkers and fluorinated acrylates in the impregnation solution penetrate into it. UV curing quickly fixes the self-cleaning components, and thermal curing prompts the crosslinker to form chemical bond bridges to strengthen the interlayers. The combined process and components synergistically improve the comprehensive performance of the material.

[0105] Comparative Example 10 lacks plasma treatment, and the outer surface of the fabric lacks microscopic etching structure and active functional groups such as hydroxyl and carboxyl. These active sites are targets for subsequent fixation of epoxy groups of epoxy crosslinkers with double bonds of acrylates of photocurable components such as perfluoroalkyl acrylates and methacryloyloxyethyl trimethyl ammonium chloride through covalent bonds. The lack of anchor points leads to loose fixation of functional components, mainly physical adsorption, easy to fall off, and impaired self-cleaning, antibacterial durability and interface bonding. Comparative Example 11 has improper plasma gas, and argon lacks the ability to introduce hydroxyl and carboxyl groups, which affects the efficiency of thermal ring-opening reaction of epoxy groups of epoxy crosslinkers, and the strength of chemical bonding is limited. Comparative Example 12 The plasma time is too long, which damages the fiber body structure and affects the overall mechanics. Comparative Example 13 lacks epoxy crosslinkers, that is, lacks bridging molecules with multiple epoxy groups. Epoxy should react with the hydroxyl, carboxyl, amine groups of each layer of substrate and the active hydrogen groups introduced by plasma to form ether bonds or ester bonds to construct a covalent bond network during thermal curing. The lack of epoxy crosslinker leads to a lack of strong curing chemical bridging between layers, weak bonding strength, easy delamination, and poor mechanical corrosion resistance. Comparative Example 14 lacks perfluoroalkyl acrylate, has no fluorinated segments, and loses the self-cleaning function. Comparative Example 15 is only UV-cured, and the epoxy reaction efficiency of the heat-activated epoxy crosslinker is extremely low, and an effective bond bridge cannot be formed, resulting in weak interlayer bonding. Comparative Example 16 is only thermally cured, the photoinitiator is not activated, the double bonds in the perfluoroalkyl acrylate and methacryloyloxyethyltrimethylammonium chloride molecules are not polymerized, the functional components are not firmly fixed, easy to lose, and the self-cleaning antibacterial durability is poor. These link defects destroy the synergy of the system, the functional components are not firmly fixed, the interface bonding is weak, or specific functions are missing, causing the overall performance to deteriorate.

[0106] These comparative examples cover defects in multiple aspects such as plasma treatment, impregnation liquid components and curing process. Plasma treatment is a prerequisite for the effective bonding of subsequent functional components. Improper parameters or missing treatment will affect the surface activation effect and fiber state. The epoxy crosslinker and perfluoroalkyl acrylate in the impregnation liquid are the core components for achieving interfacial bonding and self-cleaning functions. Their absence directly leads to the loss of the corresponding functions. UV light and thermal combined curing is a key process to ensure that these functional components and interfacial coupling agents can be firmly fixed and form chemical bond bridges in their most suitable way. A single curing method is not enough to achieve effective fixation and interface strengthening of multiple components. Any defect in these links will break the synergy of the entire system, resulting in loose fixation of functional components, weakened interlayer bonding or inability to achieve specific functions, thereby causing a decline in the overall performance of the fabric.

[0107] Although embodiments of the present invention have been shown and described, those of ordinary skill in the art will appreciate that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing an antibacterial cleaning fabric, characterized in that: Specifically, it includes the following steps: The antibacterial and cleaning fabric includes a bottom modified polyester fabric, a bonding layer, and a surface modified polyester fabric; the binder is first coated on the bottom modified polyester fabric, and then the surface modified polyester fabric is laminated to obtain a multi-layer composite fabric; the multi-layer composite fabric is subjected to plasma treatment to obtain a post-treatment fabric; the post-treatment fabric is subjected to impregnation treatment and then first subjected to UV curing and then thermal curing to obtain the antibacterial and cleaning fabric; The bottom modified polyester fabric is made of modified polyester fibers; the surface modified polyester fabric is made of polyester yarns, nano-ceria, and glycidyl methacrylate; the modified polyester fibers are made of polyester chips, nano-alumina, and phenyltrimethoxysilane; the binder is made of a waterborne polyurethane binder and modified graphene oxide; the modified graphene oxide is made of graphene oxide and silver nitrate.

2. The preparation method of an antibacterial cleaning fabric according to claim 1, characterized in that: The preparation method of the bonding layer is as follows: the modified graphene oxide is ultrasonically dispersed in deionized water and then mixed with the waterborne polyurethane binder and stirred to obtain a mixed solution; polycarbodiimide is added to the mixed solution and stirred to obtain the binder; the binder is coated on the bottom modified polyester fabric to obtain the bonding layer; Among them, the preparation method of the modified graphene oxide is as follows: the graphene oxide is ultrasonically dispersed in deionized water, ethylenediamine is added and stirred to react to obtain a reaction solution; an aqueous silver nitrate solution is added to the reaction solution, stirred, and then an aqueous sodium borohydride solution is added, and after stirring and reacting, it is centrifuged, washed, and dried to obtain the modified graphene oxide.

3. The preparation method of an antibacterial cleaning fabric according to claim 1, characterized in that: The preparation method of the bottom modified polyester fabric is as follows: phenyltrimethoxysilane is dissolved in a mixed solution of anhydrous ethanol and deionized water to obtain a silanol solution; nano-alumina is added to the silanol solution, and after reaction, it is dried to obtain modified nano-alumina; the polyester chips are melt-blended, extruded, and cooled and pelletized with the modified nano-alumina and stearic acid to obtain modified polyester chips; the modified polyester chips are spun and twisted to obtain modified polyester fiber yarns, and the modified polyester fiber yarns are used to prepare the bottom polyester fiber fabric.

4. The preparation method of an antibacterial cleaning fabric according to claim 1, characterized in that: The preparation method of the surface modified polyester fabric is as follows: polyester fibers are used to prepare the polyester yarns with a linear density of 80-120 denier, and the polyester fabric is prepared with the polyester yarns; the polyester fabric is subjected to functionalization treatment to obtain the surface modified polyester fabric.

5. The preparation method of an antibacterial cleaning fabric according to claim 4, characterized in that: The method of the functionalization treatment is as follows: the polyester fabric is immersed in a reaction solution composed of deionized water, potassium persulfate, and glycidyl methacrylate, reacted, washed, and dried to obtain pretreated polyester fibers; the pretreated polyester fibers are impregnated in a functionalized nano-ceria dispersion liquid, and then obtained by padding, drying, and then heat treatment the surface modified polyester fabric; the functionalized nano-ceria is obtained by surface treatment of the nano-ceria with dilute nitric acid and reaction with (3-aminopropyl)triethoxysilane.

6. The preparation method of an antibacterial cleaning fabric according to claim 1, wherein: The method of the plasma treatment is as follows: both sides of the multi-layer composite fabric are subjected to the plasma treatment to obtain a post-treatment fabric; the conditions of the plasma treatment are: the gas is a mixed gas of argon and oxygen.

7. The preparation method of an antibacterial cleaning fabric according to claim 1, characterized in that: The preparation method of the antibacterial and cleaning fabric is as follows: the post-treatment fabric is subjected to impregnation treatment, then subjected to the UV curing, and then subjected to the thermal curing to obtain the antibacterial and cleaning fabric.

8. The preparation method of an antibacterial cleaning fabric according to claim 7, wherein: The method of the impregnation treatment is as follows: methylacryloyloxyethyl trimethyl ammonium chloride, zinc acetate, epoxy crosslinking agent, perfluoroalkyl acrylate, and photoinitiator are added to deionized water to prepare an impregnating solution, and the post-treatment fabric is immersed in the impregnating solution; wherein, the epoxy crosslinking agent is glycerol triglycidyl ether.

9. An antibacterial cleaning fabric according to claim 1, characterized in that: The antibacterial and cleaning fabric comprises a surface layer modified polyester fabric, an adhesive layer, and a bottom layer modified polyester fabric; The surface layer modified polyester fabric comprises polyester yarns, nano cerium dioxide, and glycidyl methacrylate; The adhesive layer comprises an adhesive, and the adhesive comprises an aqueous polyurethane adhesive, modified graphene oxide, and polycarbodiimide crosslinking agent; The bottom layer modified polyester fabric comprises polyester chips, nano alumina, and phenyltrimethoxysilane; The modified graphene oxide comprises graphene oxide and silver nitrate.

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