Antibacterial washable composite fabric and preparation process thereof

Abstract

The invention relates to the technical field of textile fabrics, in particular to an antibacterial washable composite fabric and a preparation process thereof. The preparation process comprises the following steps: preparing the tea tree oil composite microemulsion; preparing a tea tree oil dihydroxy silicon phthalocyanine composite liquid; preparing a blended fabric; and preparing the antibacterial washable composite fabric. Dihydroxy silicon phthalocyanine is used as a raw material; amino is introduced through 3-(dimethyl ethyoxyl silicon) n-propane, so that compounding of tea tree oil and dihydroxy silicon phthalocyanine is promoted, amino-modified dihydroxy silicon phthalocyanine is easier to polymerize with an oily solution, tea tree oil can directly destroy cell membranes of bacteria attached to the fabric, and dihydroxy silicon phthalocyanine can generate reactive oxygen species under the illumination condition, so that the bacteria can be killed, and the bacteria can be killed. And after the tea tree oil destroys the cell membranes of bacteria, the dihydroxy silicon phthalocyanine damages intracellular substances of the bacteria, and the bacteria can be attacked from a plurality of target spots at the same time through the combination of the dihydroxy silicon phthalocyanine and the tea tree oil, so that the antibacterial effect is remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of textile fabrics, and in particular to an antibacterial and washable composite fabric and a preparation process thereof. Background Art

[0002] Antibacterial washable fabric is a textile that has been specially treated or added with antibacterial ingredients, which can maintain good antibacterial properties after repeated washing. This fabric is widely used in medical, home, sportswear and other fields to provide long-lasting hygiene protection.

[0003] The prior art uses antibacterial agents on the surface of fabrics to improve the antibacterial properties of composite fabrics, such as metal ion antibacterial agents, which are mainly silver ions and zinc ions, etc. These ions can inhibit bacterial growth by destroying bacterial cell walls and cell membranes, and organic compound antibacterial agents, such as quaternary ammonium salts, triazines, pyridinethiones, etc. They can interfere with the metabolic process of bacteria and cause bacterial death. The antibacterial properties of existing antibacterial agents in laboratory environments are already very mature. However, when antibacterial agents are used on clothing fabrics, since clothing fabrics need to be washed daily, the antibacterial agents are often destroyed by the pH value changes of the water environment or the detergent environment after multiple washings, causing their antibacterial ability to disappear after multiple washings. Therefore, the present invention provides an antibacterial and washable composite fabric and its preparation process to solve the above problems. Summary of the invention

[0004] In view of the deficiencies in the prior art, the object of the present invention is to provide an antibacterial and washable composite fabric and a preparation process thereof.

[0005] A preparation process of an antibacterial washable composite fabric comprises the following steps: S1: Preparation of tea tree oil composite microemulsion Adding tea tree oil, an emulsifier and a co-emulsifier glycerol into deionized water to obtain a tea tree oil microemulsion, and then adding tetrabutylammonium hydroxide into the tea tree oil microemulsion, stirring, to obtain a tea tree oil composite microemulsion; S2: Preparation of tea tree oil dihydroxysilicon phthalocyanine composite liquid Pyridine is added to a reaction bottle, and then dihydroxysilicon phthalocyanine and 3-(dimethylethoxysilyl)-n-propane are added, and the reaction is heated, and the reaction product is evaporated to dryness by a rotary evaporator, and the obtained solid is dissolved in anhydrous ethanol, and then deionized water is added, and the supernatant is removed by centrifugation, and the precipitate is dried to obtain amino dihydroxysilicon phthalocyanine, and the tea tree oil composite microemulsion and anhydrous DMF are mixed, and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N-hydroxysuccinimide are added, stirred, and then the amino dihydroxysilicon phthalocyanine is added, reacted, and the lower precipitate is removed to obtain the tea tree oil dihydroxysilicon phthalocyanine composite liquid; S3: Preparation of blended fabrics N,N-dimethylacetamide and 4,4-diaminodiphenyl ether are mixed and stirred, and then pyromellitic anhydride and quaternized chitosan are added dropwise and stirred to obtain a precursor solution, the precursor solution is electrospun into yarn through an electrostatic spinning device to obtain a composite polyimide yarn, and the composite polyimide yarn is blended with cotton yarn to prepare a blended fabric; S4: Preparation of antibacterial and washable composite fabrics The blended fabric is alternately ultrasonically cleaned with deionized water and ethanol, the cleaned blended fabric is placed in oxygen plasma for treatment, then immersed in an APTES ethanol-water solution for reaction, washed, and dried to obtain a treated composite fabric, the treated composite fabric is immersed in a tea tree oil dihydroxysilicon phthalocyanine composite liquid, and naturally dried to obtain an antibacterial and washable composite fabric.

[0006] Furthermore, step S1 prepares tea tree oil composite microemulsion, comprising the following steps: S1.1: Add 1-3 parts by mass of tea tree oil, 1-3 parts by mass of emulsifier, and 0.5-1.5 parts by mass of co-emulsifier glycerol to 100-120 parts by volume of deionized water, stir evenly in a water bath at 40-50°C to completely dissolve, and then add 25-30 parts by volume of distilled water to obtain a tea tree oil microemulsion; S1.2: Add 24-26 parts by volume of tetrabutylammonium hydroxide to the tea tree oil microemulsion, and stir at a rotation speed of 400-500 r / min for 10-15 min to obtain a tea tree oil composite microemulsion.

[0007] Furthermore, step S2 prepares a tea tree oil dihydroxysilicon phthalocyanine composite solution, comprising the following steps: S2.1: Add 22-24 parts by volume of pyridine to a reaction bottle, then add 0.1-0.4 parts by mass of dihydroxysilicon phthalocyanine and 1-3 parts by volume of 3-(dimethylethoxysilyl)propane, heat to 140-150°C, react for 12-14 hours, evaporate the solvent from the reaction product by rotary evaporator, dissolve the obtained solid in 4-8 parts by volume of anhydrous ethanol, then add 4-8 parts by volume of deionized water, centrifuge at 4000-4200 r / min for 3-5 minutes, separate and remove the supernatant after centrifugation, and dry the precipitate at 60-70°C for 3-4 hours to obtain amino dihydroxysilicon phthalocyanine; S2.2: Mix 2-5 parts by volume of tea tree oil composite microemulsion and 10-15 parts by volume of anhydrous DMF and stir thoroughly until dissolved, then add 1.2-1.4 parts by mass of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 0.8-0.9 parts by mass of N-hydroxysuccinimide, stir at a speed of 150-200 r / min for 30-35 minutes, then add 0.2-0.4 parts by mass of aminodihydroxysilicon phthalocyanine, seal and heat to 40-45°C, react for 24-26 hours, dialyze the reacted solution for 46-48 hours, then centrifuge at a speed of 4000-4200 r / min for 3-5 minutes, remove the lower precipitate, and obtain a tea tree oil dihydroxysilicon phthalocyanine composite liquid.

[0008] Furthermore, step S3 of preparing the blended fabric comprises the following steps: S3.1: 14-16 parts by weight of N,N-dimethylacetamide and 1-3 parts by weight of 4,4-diaminodiphenyl ether are mixed and mechanically stirred for 15-20 minutes, and then 1-2 parts by weight of pyromellitic dianhydride and 1-3 parts by weight of quaternized chitosan are added dropwise within 2-2.5 hours, followed by stirring for 1-1.5 hours and standing for 12-13 hours to obtain a precursor solution; S3.2: The precursor solution is electrospun into filaments through an electrospinning device to obtain a composite polyimide yarn, which is blended with cotton yarn. The linear density is 14.6tex, the mass ratio of the composite polyimide yarn is 60-70%, and the mass ratio of the cotton yarn is 30-40%. A 29G large circular knitting machine is selected as the manufacturing equipment, and the fabric structure is a weft plain needle structure to prepare a blended fabric.

[0009] Furthermore, step S4 prepares the antibacterial and washable composite fabric, comprising the following steps: S4.1: The blended fabric is ultrasonically cleaned with deionized water and ethanol alternately for 15-20 minutes each time, and the cleaning is repeated 3 times and then blown dry with nitrogen. The cleaned blended fabric is placed in oxygen plasma for 3-5 minutes, and then immersed in APTES ethanol-water solution for reaction at 37-40°C for 24-26 hours. After the reaction is completed, the reaction product is washed with ethanol and water, and placed in an oven at 60-70°C for drying for 2-3 hours to obtain a treated composite fabric; S4.2: Soak the treated composite fabric in the tea tree oil dihydroxysilicon phthalocyanine composite solution for 6-8 minutes, take it out, and dry it naturally to obtain an antibacterial and washable composite fabric.

[0010] Furthermore, the emulsifier in step S1.1 is one of polyoxyethylene castor oil, Tween 80 and Kolliphor EL.

[0011] Furthermore, the rotation speed of the rotary evaporator in step S2.1 is 40-60 r / min and the temperature is 100-110°C.

[0012] Furthermore, the spinning voltage of the electrospinning in step S3.2 is set to 18 kV, the pushing speed is 30 uL / min, the time is set to 50 min, an 18G spinning nozzle needle is selected, and the distance from the needle tip to the receiver is 17 cm.

[0013] Furthermore, the APTES ethanol-water solution of step S4.1 is prepared by mixing (3-aminopropyl)triethoxysilane, ethanol and deionized water in a volume ratio of 1:8:1.

[0014] An antibacterial and washable composite fabric is prepared by the above-mentioned preparation process of the antibacterial and washable composite fabric.

[0015] Compared with the prior art, the present invention has at least the following beneficial effects: 1. The present invention uses dihydroxysilicon phthalocyanine as a raw material, introduces amino groups through 3-(dimethylethoxysilyl)-propane, thereby promoting the compounding of tea tree oil and dihydroxysilicon phthalocyanine. The amino-modified dihydroxysilicon phthalocyanine is more easily polymerized with an oily solution, so the amino-modified dihydroxysilicon phthalocyanine can be bonded with the tea tree oil composite microemulsion to construct a phthalocyanine-based photosensitizing emulsion. After the tea tree oil dihydroxysilicon phthalocyanine composite liquid is coated on the fabric, the tea tree oil can directly destroy the cell membrane of the bacteria attached to the fabric, and under light conditions, the dihydroxysilicon phthalocyanine will produce active oxygen species to attack the cell membrane and internal structure of the microorganism. After the tea tree oil destroys the cell membrane of the bacteria, the dihydroxysilicon phthalocyanine damages the intracellular substances of the bacteria. The combination of the two can attack the bacteria from multiple targets at the same time, significantly improving the antibacterial effect.

[0016] 2. The present invention combines N,N-dimethylacetamide, 4,4-diaminodiphenyl ether and quaternized chitosan to prepare a precursor solution, and uses the precursor solution to blend and spin into silk to prepare a blended fabric. N,N-dimethylacetamide and 4,4-diaminodiphenyl ether can be combined to form polyimide for spinning, and the introduced quaternized chitosan is spun to form a stable nano-composite material after chemical cross-linking. The addition of quaternized chitosan can significantly improve the mechanical properties of polyimide spinning, thereby improving the surface wear resistance and arrangement density of the fabric, preventing the fabric from becoming loose due to external force after washing with water, and improving the wash resistance of the composite fabric. In addition, the quaternized chitosan can also modify dihydroxysilicon phthalocyanine, so that the phthalocyanine-based photosensitizer with dihydroxysilicon phthalocyanine as the main active ingredient can still maintain chemical activity under different pH values ​​and temperature conditions, thereby improving the antibacterial property of the composite fabric after the tea tree oil dihydroxysilicon phthalocyanine composite liquid is coated on the composite fabric.

[0017] 3. The present invention also uses oxygen plasma to treat blended fabrics. The oxygen plasma mainly acts on the composite polyimide yarn in the blended fabrics. The surface energy of the treated polyimide material is increased, thereby improving the adhesion between the polyimide material and the tea tree oil dihydroxysilicon phthalocyanine composite liquid, so that the tea tree oil dihydroxysilicon phthalocyanine composite liquid can be better coated on the blended fabric. In addition, the active oxygen species in the oxygen plasma will undergo an oxidation reaction with the carbon chain on the surface of the polyimide to generate oxygen-containing functional groups, especially the content of hydroxyl and carboxyl groups is increased, making the tea tree oil more easily attached to the blended fabric. By embedding the tea tree oil and improving the adhesion of the polyimide material surface, the adhesion of the tea tree oil dihydroxysilicon phthalocyanine composite liquid is improved, making the coating of the composite fabric not easy to fall off, further improving the antibacterial performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The accompanying drawings, which are incorporated herein and constitute a part of the specification, illustrate embodiments of the present disclosure and, together with the description, further serve to explain the principles of the present disclosure and to enable those skilled in the relevant art to make and use the present disclosure.

[0019] Figure 1 This is a process flow chart for preparing the antibacterial and washable composite fabric used in an embodiment of the present invention. DETAILED DESCRIPTION

[0020] The following is a detailed description of an antibacterial washable composite fabric and its preparation process provided by the present invention in combination with the accompanying drawings and specific embodiments. At the same time, it is explained here that in order to make the embodiments more detailed, the following embodiments are the best and preferred embodiments, and those skilled in the art may also adopt other alternative methods to implement some known technologies; and the accompanying drawings are only for a more specific description of the embodiments, and are not intended to specifically limit the present invention.

[0021] Example

[0022] A preparation process of an antibacterial washable composite fabric, such as Figure 1 As shown, the following steps are included: S1: Preparation of tea tree oil composite microemulsion S1.1: Add 1 part by mass of tea tree oil, 1 part by mass of emulsifier polyoxyethylene castor oil, and 0.5 parts by mass of co-emulsifier glycerol to 100 parts by volume of deionized water, stir evenly in a water bath at 40°C to completely dissolve them, and then add 25 parts by volume of distilled water to obtain a tea tree oil microemulsion; S1.2: Add 24 parts by volume of tetrabutylammonium hydroxide to the tea tree oil microemulsion, and stir at a rotation speed of 400 r / min for 10 min to obtain a tea tree oil composite microemulsion.

[0023] S2: Preparation of tea tree oil dihydroxysilicon phthalocyanine composite liquid S2.1: Add 22 parts by volume of pyridine to a reaction bottle, then add 0.1 parts by mass of dihydroxysilicon phthalocyanine and 1 part by volume of 3-(dimethylethoxysilyl)propane, heat to 140°C, react for 12 hours, evaporate the reaction product to dryness of solvent by rotary evaporator, the speed of the rotary evaporator is 40r / min, the temperature is 100°C, the obtained solid is dissolved in 4 parts by volume of anhydrous ethanol, then add 4 parts by volume of deionized water, centrifuge at 4000r / min for 3 minutes, separate and remove the supernatant after centrifugation, and dry the precipitate at 60°C for 3 hours to obtain amino dihydroxysilicon phthalocyanine; S2.2: Mix 2 parts by volume of tea tree oil composite microemulsion and 10 parts by volume of anhydrous DMF and stir thoroughly until dissolved, then add 1.2 parts by mass of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 0.8 parts by mass of N-hydroxysuccinimide, stir at a speed of 150 r / min for 30 minutes, then add 0.2 parts by mass of amino dihydroxysilicon phthalocyanine, seal and heat to 40°C, react for 24 hours, dialyze the reacted solution for 46 hours, then centrifuge at a speed of 4000 r / min for 3 minutes, remove the lower layer of precipitate, and obtain a tea tree oil dihydroxysilicon phthalocyanine composite liquid.

[0024] S3: Preparation of blended fabrics S3.1: 14 parts by mass of N,N-dimethylacetamide and 1 part by mass of 4,4-diaminodiphenyl ether were mixed and mechanically stirred for 15 minutes, and then 1 part by mass of pyromellitic dianhydride and 1 part by mass of quaternized chitosan were added dropwise within 2 hours, followed by stirring for 1 hour and standing for 12 hours to obtain a precursor solution; S3.2: The precursor solution is electrospun into filaments through an electrospinning device. The spinning voltage of the electrospinning is set to 18kV, the pushing speed is 30uL / min, the time is set to 50min, and an 18G spinning nozzle needle is selected. The distance from the needle tip to the receiver is 17cm to obtain a composite polyimide yarn. The composite polyimide yarn is blended with cotton thread with a linear density of 14.6tex, a composite polyimide yarn mass ratio of 70%, and a cotton thread mass ratio of 30%. A 29G large circular knitting machine is selected as the manufacturing equipment. The fabric structure is a weft plain needle structure to prepare a blended fabric.

[0025] S4: Preparation of antibacterial and washable composite fabrics S4.1: The blended fabric was ultrasonically cleaned alternately with deionized water and ethanol for 15 minutes each time, and the cleaning was repeated 3 times, and then dried with nitrogen. The cleaned blended fabric was placed in oxygen plasma for 3 minutes, and then immersed in APTES ethanol-water solution. The APTES ethanol-water solution was specifically prepared by mixing (3-aminopropyl) triethoxysilane, ethanol and deionized water in a volume ratio of 1:8:1, and reacted at 37°C for 24 hours. After the reaction, the reaction product was washed with ethanol and water, and placed in a 60°C oven for 2 hours to obtain a treated composite fabric; S4.2: Soak the treated composite fabric in the tea tree oil dihydroxysilicon phthalocyanine composite solution for 6 minutes, then take it out and dry it naturally to obtain an antibacterial and washable composite fabric. Example

[0026] A preparation process of an antibacterial washable composite fabric, such as Figure 1 As shown, the following steps are included: S1: Preparation of tea tree oil composite microemulsion S1.1: Add 3 parts by mass of tea tree oil, 3 parts by mass of emulsifier polyoxyethylene castor oil, and 1.5 parts by mass of co-emulsifier glycerol to 120 parts by volume of deionized water, stir evenly in a water bath at 50°C to completely dissolve them, and then add 30 parts by volume of distilled water to obtain a tea tree oil microemulsion; S1.2: Add 26 parts by volume of tetrabutylammonium hydroxide to the tea tree oil microemulsion, and stir at a rotation speed of 400 r / min for 10 min to obtain a tea tree oil composite microemulsion.

[0027] S2: Preparation of tea tree oil dihydroxysilicon phthalocyanine composite liquid S2.1: Add 24 parts by volume of pyridine to a reaction bottle, then add 0.4 parts by mass of dihydroxysilicon phthalocyanine and 1 part by volume of 3-(dimethylethoxysilyl)propane, heat to 140°C, react for 12 hours, evaporate the reaction product to dryness of solvent by rotary evaporator, the speed of the rotary evaporator is 40r / min, the temperature is 100°C, the obtained solid is dissolved in 8 parts by volume of anhydrous ethanol, then add 8 parts by volume of deionized water, centrifuge at 4000r / min for 3 minutes, separate and remove the supernatant after centrifugation, and dry the precipitate at 60°C for 3 hours to obtain amino dihydroxysilicon phthalocyanine; S2.2: Mix 5 parts by volume of tea tree oil composite microemulsion and 15 parts by volume of anhydrous DMF and stir thoroughly until dissolved, then add 1.4 parts by mass of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 0.9 parts by mass of N-hydroxysuccinimide, stir at a speed of 150 r / min for 30 minutes, then add 0.4 parts by mass of amino dihydroxysilicon phthalocyanine, seal and heat to 40°C, react for 24 hours, dialyze the reacted solution for 46 hours, then centrifuge at a speed of 4000 r / min for 3 minutes, remove the lower layer of precipitate, and obtain a tea tree oil dihydroxysilicon phthalocyanine composite liquid.

[0028] S3: Preparation of blended fabrics S3.1: 16 parts by mass of N,N-dimethylacetamide and 3 parts by mass of 4,4-diaminodiphenyl ether were mixed and mechanically stirred for 15 minutes, and then 2 parts by mass of pyromellitic anhydride and 3 parts by mass of quaternized chitosan were added dropwise within 2 hours, followed by stirring for 1 hour and standing for 12 hours to obtain a precursor solution; S3.2: The precursor solution is electrospun into filaments through an electrospinning device. The spinning voltage of the electrospinning is set to 18kV, the pushing speed is 30uL / min, the time is set to 50min, and an 18G spinning nozzle needle is selected. The distance from the needle tip to the receiver is 17cm to obtain a composite polyimide yarn. The composite polyimide yarn is blended with cotton thread with a linear density of 14.6tex, a composite polyimide yarn mass ratio of 60%, and a cotton thread mass ratio of 40%. A 29G large circular knitting machine is selected as the manufacturing equipment. The fabric structure is a weft plain needle structure to prepare a blended fabric.

[0029] S4: Preparation of antibacterial and washable composite fabrics S4.1: The blended fabric was ultrasonically cleaned alternately with deionized water and ethanol for 15 minutes each time, and the cleaning was repeated 3 times, and then dried with nitrogen. The cleaned blended fabric was placed in oxygen plasma for 3 minutes, and then immersed in APTES ethanol-water solution. The APTES ethanol-water solution was specifically prepared by mixing (3-aminopropyl) triethoxysilane, ethanol and deionized water in a volume ratio of 1:8:1, and reacted at 37°C for 24 hours. After the reaction, the reaction product was washed with ethanol and water, and placed in a 60°C oven for 2 hours to obtain a treated composite fabric; S4.2: Soak the treated composite fabric in the tea tree oil dihydroxysilicon phthalocyanine composite solution for 6 minutes, then take it out and dry it naturally to obtain an antibacterial and washable composite fabric. Example

[0030] A preparation process of an antibacterial washable composite fabric, such as Figure 1 As shown, the following steps are included: S1: Preparation of tea tree oil composite microemulsion S1.1: Add 1 part by mass of tea tree oil, 1 part by mass of emulsifier polyoxyethylene castor oil, and 0.5 parts by mass of co-emulsifier glycerol to 100 parts by volume of deionized water, stir evenly in a water bath at 50°C to completely dissolve them, and then add 25 parts by volume of distilled water to obtain a tea tree oil microemulsion; S1.2: Add 24 parts by volume of tetrabutylammonium hydroxide to the tea tree oil microemulsion, and stir at a rotation speed of 500 r / min for 15 minutes to obtain a tea tree oil composite microemulsion.

[0031] S2: Preparation of tea tree oil dihydroxysilicon phthalocyanine composite liquid S2.1: Add 22 parts by volume of pyridine to a reaction bottle, then add 0.1 parts by mass of dihydroxysilicon phthalocyanine and 1 part by volume of 3-(dimethylethoxysilyl)propane, heat to 150°C, react for 14 hours, evaporate the reaction product to dryness of solvent by rotary evaporator, the speed of the rotary evaporator is 60r / min, the temperature is 110°C, the obtained solid is dissolved in 4 parts by volume of anhydrous ethanol, then add 4 parts by volume of deionized water, centrifuge at 4200r / min for 5 minutes, separate and remove the supernatant after centrifugation, and dry the precipitate at 65°C for 4 hours to obtain amino dihydroxysilicon phthalocyanine; S2.2: Mix 2 parts by volume of tea tree oil composite microemulsion and 10 parts by volume of anhydrous DMF and stir thoroughly until dissolved, then add 1.2 parts by mass of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 0.8 parts by mass of N-hydroxysuccinimide, stir at a speed of 200 r / min for 35 minutes, then add 0.2 parts by mass of amino dihydroxysilicon phthalocyanine, seal and heat to 45°C, react for 26 hours, dialyze the reacted solution for 48 hours, then centrifuge at a speed of 4200 r / min for 5 minutes, remove the lower layer of precipitate, and obtain a tea tree oil dihydroxysilicon phthalocyanine composite liquid.

[0032] S3: Preparation of blended fabrics S3.1: 14 parts by mass of N,N-dimethylacetamide and 1 part by mass of 4,4-diaminodiphenyl ether were mixed and mechanically stirred for 20 minutes, and then 1 part by mass of pyromellitic dianhydride and 1 part by mass of quaternized chitosan were added dropwise within 2 hours, followed by stirring for 1.5 hours and standing for 13 hours to obtain a precursor solution; S3.2: The precursor solution is electrospun into filaments through an electrospinning device. The spinning voltage of the electrospinning is set to 18kV, the pushing speed is 30uL / min, the time is set to 50min, and an 18G spinning nozzle needle is selected. The distance from the needle tip to the receiver is 17cm to obtain a composite polyimide yarn. The composite polyimide yarn is blended with cotton thread with a linear density of 14.6tex, a composite polyimide yarn mass ratio of 70%, and a cotton thread mass ratio of 30%. A 29G large circular knitting machine is selected as the manufacturing equipment. The fabric structure is a weft plain needle structure to prepare a blended fabric.

[0033] S4: Preparation of antibacterial and washable composite fabrics S4.1: The blended fabric is ultrasonically cleaned alternately with deionized water and ethanol for 20 minutes each time, and the cleaning is repeated 3 times and then dried with nitrogen. The cleaned blended fabric is placed in oxygen plasma for 5 minutes, and then immersed in APTES ethanol-water solution. The APTES ethanol-water solution is specifically prepared by mixing (3-aminopropyl) triethoxysilane, ethanol and deionized water in a volume ratio of 1:8:1, reacting at 40°C for 26 hours, and after the reaction, the reaction product is washed with ethanol and water, and placed in a 70°C oven for drying for 3 hours to obtain a treated composite fabric; S4.2: Soak the treated composite fabric in the tea tree oil dihydroxysilicon phthalocyanine composite solution for 8 minutes, then take it out and dry it naturally to obtain an antibacterial and washable composite fabric.

[0034] Comparative Example 1: Comparative Example 1 is an antibacterial and washable fabric on the market.

[0035] Comparative Example 2: Compared with Example 1, the difference of Comparative Example 2 is that tea tree oil composite microemulsion is not added in step S2.2, specifically: "S2.2: Add 1.2 parts by mass of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 0.8 parts by mass of N-hydroxysuccinimide to 10 parts by volume of anhydrous DMF, mix and stir, stir at a speed of 150 r / min for 30 minutes, then add 0.2 parts by mass of amino dihydroxysilicon phthalocyanine, seal and heat to 40°C, react for 24 hours, dialyze the reacted solution for 46 hours, then centrifuge at a speed of 4000 r / min for 3 minutes, remove the lower precipitate, and obtain a dihydroxysilicon phthalocyanine composite liquid", and in step S4.2, dihydroxysilicon phthalocyanine composite liquid is used instead of tea tree oil dihydroxysilicon phthalocyanine composite liquid, and the other steps remain unchanged. The prepared antibacterial and washable composite fabric is recorded as Comparative Example 2.

[0036] Comparative Example 3: Compared with Example 1, the difference of Comparative Example 3 is that no quaternized chitosan is added in step S3.1, specifically: "S3.1: Mix 14 parts by mass of N,N-dimethylacetamide and 1 part by mass of 4,4-diaminodiphenyl ether and mechanically stir for 15 minutes, then add 1 part by mass of isomellitic dianhydride within 2 hours, then stir for 1 hour, and let stand for 12 hours to obtain a precursor solution", and the other steps remain unchanged. The prepared antibacterial and washable composite fabric is recorded as Comparative Example 3.

[0037] Comparative Example 4: Compared with Example 1, the difference of Comparative Example 4 is that step S2.1 is not performed, and in step S2.2, aminodihydroxysilicon phthalocyanine is not added, but phenothiazine is added, specifically: "S2: Preparation of tea tree oil phenothiazine composite liquid S2.1: 2 parts by volume of tea tree oil composite microemulsion and 10 parts by volume of anhydrous DMF were mixed and stirred thoroughly until dissolved, and then 1.2 parts by mass of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 0.8 parts by mass of N-hydroxysuccinimide were added, and stirred at a speed of 150 r / min for 30 min, and then 0.2 parts by mass of phenothiazine were added. After sealing, the mixture was heated to 40°C and reacted for 24 h. The reacted solution was dialyzed for 46 h, and then centrifuged at a speed of 4000 r / min for 3 min to remove the lower precipitate to obtain a tea tree oil phenothiazine composite liquid. The other steps remained unchanged, and the prepared antibacterial and washable composite fabric was recorded as Comparative Example 4.

[0038] Comparative Example 5: Compared with Example 1, the difference of Comparative Example 5 is that in step S4.1, the blended fabric is not placed in oxygen plasma for treatment, specifically: "S4.1: The blended fabric is ultrasonically cleaned alternately with deionized water and ethanol, each cleaning is for 15 minutes, repeated 3 times, and then blown dry with nitrogen, and then immersed in APTES ethanol-water solution, reacted at 37°C for 24 hours, and after the reaction is completed, the reaction product is washed with ethanol and water, and placed in a 60°C oven for 2 hours to obtain a treated composite fabric", and the other steps remain unchanged. The prepared antibacterial and washable composite fabric is recorded as Comparative Example 5.

[0039] The antibacterial properties of Examples 1-3 and Comparative Examples 1-5 were tested according to the national standard GB / T20944.3-2008 "Evaluation of Antibacterial Properties of Textiles Part 3: Oscillation Method". Bacterial species: Escherichia coli ATCC25922, Staphylococcus aureus ATCC6538. The specific antibacterial rate test results are shown in Table 1.

[0040] Table 1

[0041] Examples 1-3 and Comparative Examples 1-5 were placed in a solution containing 5 g / L of detergent (bath ratio 1:50), washed at 50°C for 5 min, then rinsed with clean water, and spun dry once. After repeated washing 20 times, the fabrics were dried at 85°C, and the tear strength loss of the fabrics was measured after being placed in the atmosphere for 24 hours. After washing 20 times, Examples 1-3 and Comparative Examples 1-5 were again subjected to the antibacterial test described in GB / T20944.3-2008 "Evaluation of Antibacterial Properties of Textiles Part 3: Oscillation Method", as shown in Table 2.

[0042] Table 2

[0043] The antibacterial rates of Staphylococcus aureus and Escherichia coli in Examples 1-3 during the initial test were both 99%, indicating that the antibacterial performance was excellent. After washing 20 times, the tear strength loss of the examples did not exceed 20%, and the antibacterial rate was above 68%. Although the initial antibacterial rate of Comparative Example 1 was also 98%, the tear strength loss reached 21.4% after washing 20 times, and the antibacterial rates of Staphylococcus aureus and Escherichia coli decreased to 44.6% and 51.6%, respectively. It can be seen that the examples have better wash resistance than commercially available products, and still maintain better antibacterial performance after washing.

[0044] The initial antibacterial rates of comparative example 2 were 92.6% and 91.5%, and the antibacterial rates of Staphylococcus aureus and Escherichia coli decreased to 42.1% and 48.9% after washing 20 times. The initial antibacterial rates of comparative example 4 were 93.3% and 89.2%, and the antibacterial rates of Staphylococcus aureus and Escherichia coli decreased to 55.3% and 47.2% after washing 20 times. It can be seen that the introduction of tea tree oil can combine with dihydroxysilicon phthalocyanine to form an antibacterial layer with better antibacterial effect and more durable. The antibacterial effect will decrease if tea tree oil is not introduced or dihydroxysilicon phthalocyanine is not used. The tear strength loss of comparative example 2 is 22.5%, and the tear strength loss of comparative example 4 is 22.4%. It can be seen that the combination of tea tree oil and dihydroxysilicon phthalocyanine has a positive effect on the antibacterial properties and washability of the composite fabric.

[0045] The initial antibacterial rates of comparative example 3 were 94.1% and 93.6%, and the tear strength loss was 25.1%. The initial antibacterial rates of comparative example 4 were 93.3% and 89.2%. It can be seen that the addition of quaternized chitosan and its combination with polyimide prepared from N, N-dimethylacetamide and 4,4-diaminodiphenyl ether significantly improved the antibacterial rate.

[0046] The tear strength loss of Comparative Example 3 is 25.1%, and the tear strength loss of Comparative Example 4 is 22.4%. It can be seen that without the addition of quaternized chitosan and the polyimide prepared with N, N-dimethylacetamide and 4, 4-diaminodiphenyl ether, the washing resistance will decrease to a certain extent, and due to the decrease in washing resistance, the degree of tear strength loss increases. After washing 20 times, the antibacterial rate against Staphylococcus aureus and Escherichia coli also decreases, which is lower than that of the embodiment.

[0047] The initial antibacterial rates of Comparative Example 5 were 93.7% and 94.4%, the tear strength loss was 24.3%, and the antibacterial rates against Staphylococcus aureus and Escherichia coli after washing 20 times were 32.9% and 39.6%, respectively. It can be seen that without oxygen plasma treatment, the antibacterial coating formed by the tea tree oil dihydroxysilicon phthalocyanine composite liquid of the composite fabric has a decreased performance in combination with the blended fabric, resulting in a significant decrease in its antibacterial performance after washing 20 times.

[0048] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A preparation process of an antibacterial and washable composite fabric, characterized in that: The steps include: S1: Preparation of tea tree oil composite microemulsion Adding tea tree oil, an emulsifier and a co-emulsifier glycerol into deionized water to obtain a tea tree oil microemulsion, and then adding tetrabutylammonium hydroxide into the tea tree oil microemulsion, stirring, to obtain a tea tree oil composite microemulsion; S2: Preparation of tea tree oil dihydroxysilicon phthalocyanine composite liquid Pyridine is added to a reaction bottle, and then dihydroxysilicon phthalocyanine and 3-(dimethylethoxysilyl)-n-propane are added, and the reaction is heated, and the reaction product is evaporated to dryness by a rotary evaporator, and the obtained solid is dissolved in anhydrous ethanol, and then deionized water is added, and the supernatant is removed by centrifugation, and the precipitate is dried to obtain amino dihydroxysilicon phthalocyanine, and the tea tree oil composite microemulsion and anhydrous DMF are mixed, and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and N-hydroxysuccinimide are added, stirred, and then the amino dihydroxysilicon phthalocyanine is added, reacted, and the lower precipitate is removed to obtain the tea tree oil dihydroxysilicon phthalocyanine composite liquid; S3: Preparation of blended fabrics N,N-dimethylacetamide and 4,4-diaminodiphenyl ether are mixed and stirred, and then pyromellitic anhydride and quaternized chitosan are added dropwise and stirred to obtain a precursor solution, the precursor solution is electrospun into yarn through an electrostatic spinning device to obtain a composite polyimide yarn, and the composite polyimide yarn is blended with cotton yarn to prepare a blended fabric; S4: Preparation of antibacterial and washable composite fabrics The blended fabric is alternately ultrasonically cleaned with deionized water and ethanol, the cleaned blended fabric is placed in oxygen plasma for treatment, then immersed in an APTES ethanol-water solution for reaction, washed, and dried to obtain a treated composite fabric, the treated composite fabric is immersed in a tea tree oil dihydroxysilicon phthalocyanine composite liquid, and naturally dried to obtain an antibacterial and washable composite fabric.

2. The preparation process of the antibacterial and washable composite fabric according to claim 1, characterized in that: Step S1 prepares tea tree oil composite microemulsion, comprising the following steps: S1.1: Add 1-3 parts by mass of tea tree oil, 1-3 parts by mass of emulsifier, and 0.5-1.5 parts by mass of co-emulsifier glycerol to 100-120 parts by volume of deionized water, stir evenly in a water bath at 40-50°C to completely dissolve, and then add 25-30 parts by volume of distilled water to obtain a tea tree oil microemulsion; S1.2: Add 24-26 parts by volume of tetrabutylammonium hydroxide to the tea tree oil microemulsion, and stir at a rotation speed of 400-500 r / min for 10-15 min to obtain a tea tree oil composite microemulsion.

3. The preparation process of the antibacterial and washable composite fabric according to claim 2, characterized in that: Step S2 prepares a tea tree oil dihydroxysilicon phthalocyanine composite liquid, comprising the following steps: S2.1: Add 22-24 parts by volume of pyridine to a reaction bottle, then add 0.1-0.4 parts by mass of dihydroxysilicon phthalocyanine and 1-3 parts by volume of 3-(dimethylethoxysilyl)propane, heat to 140-150°C, react for 12-14 hours, evaporate the solvent from the reaction product by rotary evaporator, dissolve the obtained solid in 4-8 parts by volume of anhydrous ethanol, then add 4-8 parts by volume of deionized water, centrifuge at 4000-4200 r / min for 3-5 minutes, separate and remove the supernatant after centrifugation, and dry the precipitate at 60-70°C for 3-4 hours to obtain amino dihydroxysilicon phthalocyanine; S2.2: Mix 2-5 parts by volume of tea tree oil composite microemulsion and 10-15 parts by volume of anhydrous DMF and stir thoroughly until dissolved, then add 1.2-1.4 parts by mass of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 0.8-0.9 parts by mass of N-hydroxysuccinimide, stir at a speed of 150-200 r / min for 30-35 minutes, then add 0.2-0.4 parts by mass of aminodihydroxysilicon phthalocyanine, seal and heat to 40-45°C, react for 24-26 hours, dialyze the reacted solution for 46-48 hours, then centrifuge at a speed of 4000-4200 r / min for 3-5 minutes, remove the lower precipitate, and obtain a tea tree oil dihydroxysilicon phthalocyanine composite liquid.

4. The process for preparing an antibacterial and washable composite fabric according to claim 3, characterized in that: Step S3 prepares the blended fabric, comprising the following steps: S3.1: 14-16 parts by weight of N,N-dimethylacetamide and 1-3 parts by weight of 4,4-diaminodiphenyl ether are mixed and mechanically stirred for 15-20 minutes, and then 1-2 parts by weight of pyromellitic dianhydride and 1-3 parts by weight of quaternized chitosan are added dropwise within 2-2.5 hours, followed by stirring for 1-1.5 hours and standing for 12-13 hours to obtain a precursor solution; S3.2: The precursor solution is electrospun into filaments through an electrospinning device to obtain a composite polyimide yarn, which is blended with cotton yarn. The linear density is 14.6tex, the mass ratio of the composite polyimide yarn is 60-70%, and the mass ratio of the cotton yarn is 30-40%. A 29G large circular knitting machine is selected as the manufacturing equipment, and the fabric structure is a weft plain needle structure to prepare a blended fabric.

5. The process for preparing an antibacterial and washable composite fabric according to claim 4, characterized in that: Step S4 is to prepare an antibacterial and washable composite fabric, comprising the following steps: S4.1: The blended fabric is ultrasonically cleaned with deionized water and ethanol alternately for 15-20 minutes each time, and the cleaning is repeated 3 times and then blown dry with nitrogen. The cleaned blended fabric is placed in oxygen plasma for 3-5 minutes, and then immersed in APTES ethanol-water solution for reaction at 37-40°C for 24-26 hours. After the reaction is completed, the reaction product is washed with ethanol and water, and placed in an oven at 60-70°C for drying for 2-3 hours to obtain a treated composite fabric; S4.2: Soak the treated composite fabric in the tea tree oil dihydroxysilicon phthalocyanine composite solution for 6-8 minutes, take it out, and dry it naturally to obtain an antibacterial and washable composite fabric.

6. The process for preparing an antibacterial and washable composite fabric according to claim 5, characterized in that: The emulsifier in step S1.1 is one of polyoxyethylene castor oil, Tween 80 and Kolliphor EL.

7. The process for preparing an antibacterial and washable composite fabric according to claim 3, characterized in that: The rotation speed of the rotary evaporator in step S2.1 is 40-60 r / min and the temperature is 100-110°C.

8. The process for preparing an antibacterial and washable composite fabric according to claim 4, characterized in that: The spinning voltage of the electrospinning in step S3.2 was set to 18 kV, the pushing speed was 30 uL / min, the time was set to 50 min, an 18G spinning nozzle needle was selected, and the distance from the needle tip to the receiver was 17 cm.

9. The process for preparing an antibacterial and washable composite fabric according to claim 5, characterized in that: The APTES ethanol-water solution of step S4.1 is specifically prepared by mixing (3-aminopropyl)triethoxysilane, ethanol and deionized water in a volume ratio of 1:8:

1.

10. An antibacterial and washable composite fabric, which is prepared by the preparation process of the antibacterial and washable composite fabric according to any one of claims 1 to 9.

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