Multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, preparation method and application thereof
阅读说明：本技术 一种织物后整理用多功能纳米无机复合抗菌剂、制备方法及其应用 (Multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, preparation method and application thereof ) 是由 沈海红 付少海 赵硕 沈海华 于 2021-07-08 设计创作，主要内容包括：本发明公开了一种织物后整理用多功能纳米无机复合抗菌剂、制备方法及其应用,涉及织物抗菌技术领域。本发明提供的织物后整理用多功能纳米无机复合抗菌剂,用g-C-3N-4包覆纳米氧化锌,可以提高ZnO在可见光条件下的抗菌能力,扩大其应用范围；再进一步对g-C-3N-4包覆的纳米氧化锌进行羧基化,制得抗菌剂,这种抗菌剂通过后整理可直接与织物上的羟基反应,使得纳米氧化锌抗菌粒子最大程度的结合在织物上,同时纳米粒子与织物是通过化学键结合的,赋予织物持久抗菌性。本发明提供的织物抗菌整理方法,利用所述的织物后整理用多功能纳米无机复合抗菌剂对织物进行整理,方法简单,极大地提高了织物的耐水性和抗菌持久性。(The invention discloses a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, a preparation method and application thereof, and relates to the technical field of fabric antibacterial. The invention provides a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, which uses g-C 3 N 4 The coating of the nano zinc oxide can improve the antibacterial capability of ZnO under the condition of visible light and expand the application range of the ZnO; and further on g-C 3 N 4 The coated nano zinc oxide is carboxylated to prepare the antibacterial agent, the antibacterial agent can directly react with hydroxyl on the fabric through after-treatment, so that the nano zinc oxide antibacterial particles are combined on the fabric to the maximum extent, and meanwhile, the nano particles are combined with the fabric through chemical bonds to endow the fabric with lasting antibacterial property. The invention provides an antibacterial finishing method for fabrics, which is used for finishing the fabrics by using a multifunctional nano inorganic composite antibacterial agent for fabric after-finishingThe method is simple, and the water resistance and the antibacterial durability of the fabric are greatly improved.)
1. A preparation method of a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing is characterized by comprising the following steps:
s1, preparation of nano zinc oxide: crushing basic zinc carbonate, placing the crushed basic zinc carbonate in a muffle furnace for sintering treatment at the temperature of 350-650 ℃ for 30-90min to obtain a crude product, and crushing the crude product again to obtain rod-shaped nano zinc oxide;
S2，g-C3N4preparation of the dispersion: taking g-C3N4Putting the powder into deionized water, performing ultrasonic treatment for 18-36h, and centrifuging to remove undispersed g-C after the ultrasonic treatment is finished3N4Taking clear liquid to obtain g-C3N4A nanosheet dispersion;
S3，g-C3N4coated nano zinc oxide (g-C)3N4@ ZnO): dispersing nanometer zinc oxide in water, and mixing with water3N4Dropwise adding the nanosheet dispersion into the zinc oxide dispersion, stirring at room temperature for 50-60h, centrifuging after the reaction is finished to obtain precipitate, and drying the precipitate to obtain g-C3N4Coated nano zinc oxide, said g-C3N4The mass ratio of the zinc oxide to the nano zinc oxide is 1: 1.5-15;
S4，g-C3N4coated nano zinc oxide (g-C)3N4@ ZnO) surface carboxylation: g to C3N4Dispersing the @ ZnO powder in ultrapure water for ultrasonic treatment, adding concentrated nitric acid for ultrasonic treatment, heating to 115-120 ℃ after the ultrasonic treatment is finished, refluxing for 24 hours, cooling to room temperature, collecting precipitate, washing the precipitate with ultrapure water until the pH of the washing solution is neutral, and finally performing vacuum drying to obtain g-C with carboxylated surface3N4@ZnO。
2. The method for preparing a multifunctional nano inorganic composite antibacterial agent for fabric finishing as claimed in claim 1, wherein in step S4, the volume ratio of ultrapure water to concentrated nitric acid is 1: 1.
3. the method for preparing multifunctional nano inorganic composite antibacterial agent for fabric finishing as claimed in claim 1, wherein in step S4, g-C3N4@ ZnO powder is dispersed in ultrapure water and subjected to ultrasonic treatment for 1-2 h.
4. The method for preparing the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing according to claim 1, wherein in step S4, after concentrated nitric acid is added, ultrasonic treatment is carried out for 1-2 h.
5. The method for preparing the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing according to claim 1, wherein the g-C is3N4Is prepared by synthesizing g-C3N4The raw materials are placed in a corundum crucible, covered with a cover, placed in a muffle furnace, heated to 500-550 ℃ at the speed of 3-5 ℃/min for heat treatment for 4 hours, and naturally cooled to room temperature to obtain the g-C3N4。
6. The method for preparing multifunctional nano inorganic composite antibacterial agent for fabric finishing as claimed in claim 5, wherein the synthetic g-C3N4The raw material is at least one of cyanamide, dicyandiamide, melamine, urea and thiourea.
7. A multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. The fabric antibacterial finishing method applying the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing is characterized by comprising the following steps:
(1) cleaning the surface of the fabric: placing the fabric in 50-70 ℃ water for fully wetting, placing the fabric in 4-30g/L sodium hydroxide solution for soaking for about 10min-20min after squeezing out water, taking out the fabric and removing redundant water, then soaking the fabric in 4-30g/L sodium hydroxide solution, cooking for 1-2h by 100-102 ℃ constant temperature water bath, piling the fabric in a heat-preservation and moisture-preservation environment for 6-12h after cooking, washing for 2-3 times by 70-80 ℃ water, then washing for 3-4 times by 20-25 ℃ water, and placing the fabric at room temperature for airing;
wherein the hydroxyl content of the fabric is not less than 25 wt.%;
(2) antibacterial finishing of the fabric: by carboxylation of g-C3N4@ ZnO was dispersed in water, NaH was added2PO2Preparing aqueous solution to obtain dispersion; fully soaking the fabric in the dispersion, stirring for 1-2h in a water bath kettle at 50-70 ℃, taking out the fabric, pre-drying for 20-30min, roasting for 1-3min, fully washing and naturally drying to obtain the antibacterial fabric;
in the dispersion, g-C3N4@ ZnO concentration of 25g-50g/L, NaH2PO2The concentration is 40g-70 g/L;
said carboxylated g-C3N4@ ZnO is obtained by the production method described in any one of claims 1 to 6.
9. The antibacterial finishing method for fabric according to claim 8, characterized in that in the step (2), the pre-drying temperature is 60-80 ℃, the roasting temperature is 130-150 ℃, and the dosage ratio of the fabric (g) to the dispersion liquid (ml) is 1: 20-40.
10. An antibacterial fabric produced by the antibacterial finishing method of fabric as claimed in any one of claims 8 to 9.
Technical Field
The invention relates to the technical field of fabric antibacterial, in particular to a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, a preparation method and application thereof.
Background
With the improvement of living standard, people pay more and more attention to the quality of life, and people hope to obtain comfortable and safe clothes and a sanitary and healthy living environment. The wearing requirements of people are not only cold-proof and warm-keeping, but also fashionable, attractive, functional, safe and healthy textiles are gradually favored by people. Cotton, fiber and the like have the advantages of good air permeability, soft hand feeling, excellent hygroscopicity, reproducibility, biodegradability and the like, so that the natural fiber with the largest consumption is formed. The natural fiber is easy to absorb moisture, and can provide a large amount of nutrition for microorganisms under a proper temperature and humidity so as to enable the microorganisms to propagate in a large amount. In addition, sweat stains, grease and scurf which are continuously generated by the human body provide sufficient nutrient substances for bacteria on the fabrics, and the bred pathogenic bacteria can bring health risks to human beings through diet, wound infection and the like. Therefore, antibacterial textiles with excellent antibacterial performance, high efficiency, durability, safety and no toxicity are receiving more and more attention.
The production method of the antibacterial textile can be divided into three types: the first is natural antibiotic fiber of chitin or chitosan, the second is co-blending weaving method, that is, adding antibiotic agent into fiber production polymerization stage or spinning solution to prepare antibiotic fiber, and the third is functional finishing method, that is, post-processing method with antibiotic finishing agent to combine antibiotic agent with fiber fabric. The product made by blending and weaving method, the antibacterial agent is not only on the surface of the fiber, but also uniformly dispersed in the fiber, the antibacterial effect is relatively durable, the fabric hand feeling is good, but the method is mainly suitable for some fibers without reactive side groups, such as terylene, polypropylene fiber and the like. However, natural fibers such as cotton cannot be treated by this method because of some of the disadvantages of the natural fibers, and only after-finishing is performed. The mode of combining the finishing agent and the fabric in the current post-finishing process mainly has physical and chemical effects. The physical action is that the antibacterial agent is combined with the fabric through physical adsorption, and the combination mode enables the antibacterial agent to be easily separated from the surface of the fabric under washing conditions, so that the antibacterial effect is influenced. The chemical action is mostly graft modification, reactive groups are introduced on the fabric, but a large amount of hydroxyl contained in the fabric such as cotton fabric is converted into the reactive groups with limited quantity, and the antibacterial agent is further graft modified, so that the quantity of the graftable antibacterial agent is reduced, and the antibacterial effect is influenced.
Common antibacterial finishing agents include natural antibacterial agents, organic antibacterial agents, and inorganic antibacterial agents. The natural antibacterial agent is mainly derived from extracted substances of natural plants, is limited by processing conditions of raw materials, and cannot be marketed in a large scale. The organic antibacterial agent comprises bactericide ethanol, ammonium salt and the like, preservative formaldehyde, organic halogen compound, algaecide pyridine, alkyl halide and the like. The organic antibacterial agent has the characteristics of high sterilization speed, wide antibacterial range and the like, but has the defects of poor heat resistance, toxicity of dissolved substances, short service life and the like, so the use of the organic antibacterial agent has great limitation. The inorganic antibacterial agent mainly comprises metal, metal salt, photocatalytic antibacterial agent and the like, the inorganic antibacterial agent has the advantages of heat resistance, durability and the like, but has the problem that metal ions are harmful to human bodies, and the photocatalytic inorganic antibacterial agent is represented by TiO2And ZnO, but such antibacterial agents exhibit excellent antibacterial properties only under the action of ultraviolet light, and the application range of such antibacterial agents is limited due to limited ultraviolet energy in sunlight.
Disclosure of Invention
The invention aims to solve the technical problems that the antibacterial agent in the existing fabric is not easy to resist water and fall off, and the antibacterial performance of the photocatalytic inorganic antibacterial agent is limited, and provides a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, so that the prepared fabric has excellent antibacterial performance, good water washing resistance, safety and no toxicity.
In order to solve the above problems, the present invention proposes the following technical solutions:
the invention firstly synthesizes nano zinc oxide by a uniform precipitation method and then synthesizes g-C3N4，g-C3N4Dispersed in water to g-C3N4Coating nano zinc oxide with the dispersion liquidAnd then, carboxylating the coated product, and performing after-treatment on the carboxylated antibacterial agent and the fabric to obtain the antibacterial fabric. The method comprises the following specific steps:
in a first aspect, the invention provides a preparation method of a multifunctional nano inorganic composite antibacterial agent for fabric after-treatment, which comprises the following steps:
s1, preparation of nano zinc oxide: crushing basic zinc carbonate by using an airflow crusher, and sintering in a muffle furnace at 350-650 ℃ for 30-90min to obtain a crude product. And then carrying out jet milling on the obtained crude product again to obtain the final product of the rodlike nano zinc oxide. The obtained nanometer zinc oxide has average particle diameter of about 10-20nm and specific surface area of 50-70m2/g。
S2，g-C3N4Preparation of the dispersion: taking g-C3N4Putting the powder into deionized water, performing ultrasonic treatment for 18-36h, and centrifuging to remove undispersed g-C after the ultrasonic treatment is finished3N4Obtaining milk white g-C from clear liquid3N4A nanosheet dispersion;
S3，g-C3N4coated nano zinc oxide (g-C)3N4@ ZnO): dispersing nanometer zinc oxide in water, and mixing with water3N4Dropwise adding the nanosheet dispersion into the zinc oxide dispersion, stirring at room temperature for 50-60h, centrifuging after the reaction is finished to obtain precipitate, and drying the precipitate to obtain g-C3N4Coated nano zinc oxide, said g-C3N4The mass ratio of the zinc oxide to the nano zinc oxide is 1: 1.5-15;
S4，g-C3N4coated nano zinc oxide (g-C)3N4@ ZnO) surface carboxylation: g to C3N4Dispersing the @ ZnO powder in ultrapure water for ultrasonic treatment, adding concentrated nitric acid for ultrasonic treatment, heating to 115-120 ℃ after the ultrasonic treatment is finished, refluxing for 24 hours, cooling to room temperature, collecting precipitate, washing the precipitate with ultrapure water until the pH of the washing solution is neutral, and finally performing vacuum drying to obtain g-C with carboxylated surface3N4@ZnO。
Further, in step S3, the specific operation of drying the precipitate is drying at 60-80 ℃ for 18-30 h.
Further, in step S4, the volume ratio of ultrapure water to concentrated nitric acid is 1: 1.
further, in step S4, g-C3N4@ ZnO powder is dispersed in ultrapure water and subjected to ultrasonic treatment for 1-2 h.
Further, in step S4, after adding concentrated nitric acid, performing ultrasonic treatment for 1-2 h.
Further, the g-C3N4Is prepared by synthesizing g-C3N4The raw materials are placed in a corundum crucible, covered with a cover, placed in a muffle furnace, heated to 500-550 ℃ at the speed of 3-5 ℃/min for heat treatment for 4 hours, and naturally cooled to room temperature to obtain the g-C3N4Further grinding and pulverizing to obtain g-C3N4And (3) powder.
Further, the synthesis of g-C3N4The raw material is at least one of cyanamide, dicyandiamide, melamine, urea and thiourea.
In a second aspect, the invention provides a multifunctional nano inorganic composite antibacterial agent for fabric after-treatment, which is prepared by the preparation method of the first aspect.
In a third aspect, the invention also provides a fabric antibacterial finishing method applying the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, which comprises the following steps:
(1) cleaning the surface of the fabric: placing the fabric in 50-70 ℃ water for fully wetting, placing the fabric in 4-30g/L sodium hydroxide solution for soaking for about 10min-20min after squeezing out water, taking out the fabric and removing redundant water, then soaking the fabric in 4-30g/L sodium hydroxide solution, cooking for 1-2h by 100-102 ℃ constant temperature water bath, piling the fabric in a heat-preservation and moisture-preservation environment for 6-12h after cooking, washing for 2-3 times by 70-80 ℃ water, then washing for 3-4 times by 20-25 ℃ water, and placing the fabric at room temperature for airing;
wherein the hydroxyl content of the fabric must not be less than 25 wt.%;
(2) antibacterial finishing of the fabric: carboxylated g-C3N4@ ZnO was dispersed in water, NaH was added2PO2Preparing aqueous solution to obtain dispersion; fully soaking the fabric in the dispersion, stirring for 1-2h in a water bath kettle at 50-70 ℃, taking out the fabric, pre-drying for 20-30min, then roasting for 1-3min, fully washing again, and naturally airing to obtain the antibacterial fabric;
in the dispersion, g-C3N4@ ZnO concentration of 25g-50g/L, NaH2PO2The concentration is 40g-70 g/L;
said carboxylated g-C3N4@ ZnO is obtained by the production method described in any one of claims 1 to 6.
Further, in the step (1), a glass rod is used for continuously stirring in the cooking process so as to enable the fabric to be heated uniformly.
Further, in the step (2), the pre-drying temperature is 60-80 ℃, the roasting temperature is 130-150 ℃, and the use amount ratio of the fabric (g) to the dispersion liquid (ml) is 1: 20-40.
The invention also provides an antibacterial fabric prepared by the antibacterial finishing method of the fabric.
The multifunctional nano inorganic composite antibacterial agent for fabric after-finishing provided by the invention has the following antibacterial principle:
zinc oxide is a wide bandgap semiconductor material that, when excited by ultraviolet light, generates free electrons with negative charges and holes with positive charges, the electrons transit from the valence band to the conduction band, and the holes remain in the valence band to form electron-hole pairs. The electrons and the holes are transferred to the surface of the zinc oxide to generate oxidation-reduction reaction to decompose bacteria and viruses so as to achieve the aim of sterilization. However, zinc oxide hardly absorbs visible light, electron-hole pairs are very easily recombined and undergo photo-corrosion. Graphite phase carbon nitride (g-C)3N4) Is an important visible light catalyst, but also has the problem of high recombination rate of photo-generated electron-hole pairs. However, the applicants have found that the use of g-C3N4Coating the positions of conduction band and valence band of nano zinc oxide and ZnO and g-C3N4The conduction band and the valence band of ZnO are matched in position, and the conduction band and the valence band of ZnO are respectively lower than g-C3N4Conduction and valence bands. Under the action of visible light, lightThe generated electrons move to the conduction band of ZnO, and the holes are accumulated in g-C3N4Effectively preventing the recombination of electron-hole pairs. Greatly improves the antibacterial capacity of ZnO under the condition of visible light and enlarges the application range of the ZnO.
The fabric of the invention is a fabric with hydroxyl content not less than 25 wt.%, such as cotton fabric or fiber fabric, blended fabric, etc. The main component of the fiber of the fabric is cellulose, the cellulose has a large number of hydrophilic groups of hydroxyl (-OH), the prior graft modification technology is adopted, and-SH, -NH is introduced into the fabric2Reactive groups, -COOH, etc., which establish chemical bonds or other forms of stable bonds with the nanoparticles to form the antimicrobial fabric. The fabric is changed into a reactive group through a chemical reaction, the process enables the number of the groups which become reactive on the fabric to be very limited, so that the number of the nano particles which are grafted by chemical bonding or other combination methods is also very limited, and the antibacterial performance is limited. Applicants have found that g-C3N4Has a graphene-like structure, which can generate oxidation reaction under the action of oxide to generate a graphene oxide-like substance, thereby generating carboxyl, g-C on the surface3N4The coated nano zinc oxide can directly react with hydroxyl on the fabric through after-treatment, so that the nano antibacterial particles are combined on the fabric to the maximum extent, and meanwhile, the nano particles are combined with the fabric by chemical bonds, so that the fabric has strong water resistance after the treatment, and the fabric is endowed with lasting antibacterial property.
Compared with the prior art, the invention can achieve the following technical effects:
the invention provides a method for preparing a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, which uses g-C3N4The coating of the nano zinc oxide can improve the antibacterial capability of ZnO under the condition of visible light and expand the application range of the ZnO; and further on g-C3N4The coated nano zinc oxide is carboxylated to ensure that the nano zinc oxide is rich in carboxyl to prepare the antibacterial agent, and the antibacterial agent can directly react with hydroxyl on the fabric through after-treatment to ensure that the nano zinc oxide antibacterial particles are combined to the maximum extentOn the fabric, the nano particles and the fabric are combined through carboxyl-hydroxyl chemical bonds, so that the fabric is endowed with durable antibacterial property.
The antibacterial finishing method for the fabric, provided by the invention, has the advantages that the fabric is finished by using the multifunctional nano inorganic composite antibacterial agent for the fabric after-finishing, the method is simple, and the water resistance and the antibacterial durability of the fabric are greatly improved.
The invention is realized by firstly preparing g-C3N4Coating the nano zinc oxide by using g-C after coating3N4Is oxidized to form g-C3N4The antibacterial finishing liquid is prepared by the method rich in carboxyl, and then the antibacterial finishing liquid and the fabric rich in hydroxyl are subjected to antibacterial finishing to obtain the antibacterial fabric. Because the antibacterial agent is more easily subjected to carboxylation and is combined with hydroxyl in the fabric by chemical bonds, the antibacterial fabric prepared by the method has stronger antibacterial property, antiviral property, water washing resistance, deodorization property and ultraviolet resistance, and also has a certain mildew-proof effect.
Drawings
FIG. 1 is a TEM image of nano zinc oxide in the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing prepared in example 1;
FIG. 2 is a laser particle size distribution diagram of nano zinc oxide in the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing prepared in example 1.
Detailed Description
The technical solutions in the embodiments will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, wherein like reference numerals represent like elements in the drawings. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Example one
The embodiment provides a preparation method of a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing and a method for performing cotton fabric antibacterial finishing by using the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing, and the method specifically comprises the following steps:
s1 preparation of nano zinc oxide: crushing the basic zinc carbonate by using an airflow crusher, placing the crushed basic zinc carbonate in a muffle furnace for sintering treatment at the temperature of 650 ℃ for 30min, and then performing airflow crushing on the obtained crude product again to obtain the final product of the rod-shaped nano zinc oxide. The obtained nanometer zinc oxide has average particle diameter of about 10-20nm and specific surface area of 50-70m2/g。
S2 g-C3N4The synthesis of (2): putting urea in a corundum crucible, covering the corundum crucible with a cover, putting the corundum crucible in a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 4 hours, naturally cooling to room temperature, and then grinding and crushing to obtain light yellow g-C3N4And (3) powder.
g-C3N4Preparation of the dispersion: taking 0.2g of g-C3N4Putting the powder into 1000ml deionized water, carrying out ultrasonic treatment for 24h, and centrifuging to remove g-C which cannot be dispersed in the deionized water after the ultrasonic treatment is finished3N4Obtaining milk white g-C from clear liquid3N4Nanosheet dispersion, g-C obtained3N4The concentration of the nanosheet dispersion was 0.07 g/L.
S3 g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO): dispersing 1g of nano zinc oxide in water, and mixing 8L of g-C3N4Adding the nano-sheet dispersion into zinc oxide dispersion dropwise, stirring for 50h at room temperature, centrifuging, and drying at 60 deg.C for 24h to obtain g-C3N4Coated nano zinc oxide.
S4 g-C3N4Coated nanoparticlesZinc oxide (g-C)3N4@ ZnO) surface carboxylation: 0.5g of g-C3N4@ ZnO powder is dispersed in 50ml of ultrapure water and subjected to ultrasonic treatment for 1 hour, then the solution is transferred into a 250ml round-bottom flask, concentrated nitric acid with the same volume is added for ultrasonic treatment for 1 hour, after the solution is heated and slightly boiled for reflux for 24 hours, the solution is cooled to room temperature, then the precipitate is collected by high-speed centrifugation, the precipitate is washed by ultrapure water until the pH of the washing solution is neutral, finally the solution is dried in vacuum, and the g-C with carboxylated surface is obtained by grinding3[email protected]。
S5 cleaning the surface of cotton fabric: placing a cotton fabric sample in 50 ℃ water for wetting, soaking the cotton fabric sample in 4g/L sodium hydroxide solution for about 10min after squeezing water, taking out the cotton fabric sample to remove excessive water, soaking the cotton fabric in the sodium hydroxide solution, cooking the cotton fabric sample in 100 ℃ constant-temperature water bath for 1.5h, continuously stirring the cotton fabric sample by using a glass rod in the cooking process, piling the cotton fabric sample in a heat-preservation and moisture-preservation environment for 8h after cooking, washing the cotton fabric sample by using hot water for 3 times after finishing, then washing the cotton fabric sample by using cold water for 3 times, and placing the cotton fabric sample at room temperature for airing.
S6 antibacterial finishing of cotton fabric: 50g of carboxylated g-C3N4@ ZnO was dispersed in 2L of water, and 40g/L of NaH was added2PO2Preparing aqueous solution to obtain dispersion; then, soaking the cotton fabric into the dispersion liquid, wherein the dosage ratio of the cotton fabric (g) to the dispersion liquid (ml) is 1: 30, magnetically stirring the mixture in a water bath kettle at the temperature of 60 ℃ for 1.5 hours, taking out the cotton fabric, putting the cotton fabric into an oven at the temperature of 70 ℃ for pre-drying for 20 minutes, then roasting the cotton fabric at the temperature of 130 ℃ for 3 minutes, fully washing the cotton fabric, and naturally airing the cotton fabric to obtain the antibacterial cotton fabric.
The TEM image of the nano zinc oxide of the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing prepared in this example is shown in fig. 1, and the laser particle size distribution diagram of the nano zinc oxide is shown in fig. 2.
Example two
The embodiment provides a preparation method of a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing and a method for performing cotton fabric antibacterial finishing by using the nano zinc oxide composite antibacterial agent, and the method specifically comprises the following steps:
s1 preparation of nano zinc oxide: crushing the basic zinc carbonate by using an airflow crusher, placing the crushed basic zinc carbonate in a muffle furnace for sintering treatment at the temperature of 500 ℃ for 50min, and then performing airflow crushing on the obtained crude product again to obtain the final product of the rod-shaped nano zinc oxide.
S2 g-C3N4The synthesis of (2): placing melamine in a corundum crucible, covering the corundum crucible with a cover, placing the corundum crucible in a muffle furnace, heating to 550 ℃ at the speed of 3 ℃/min, performing heat treatment for 4 hours, naturally cooling to room temperature, and grinding and crushing to obtain light yellow g-C3N4And (3) powder.
g-C3N4Preparation of the dispersion: taking 0.2g of g-C3N4Putting the powder into 1000ml deionized water, carrying out ultrasonic treatment for 24h, and centrifuging to remove g-C which cannot be dispersed in the deionized water after the ultrasonic treatment is finished3N4Obtaining milk white g-C from clear liquid3N4A nanosheet dispersion, the concentration of the resulting dispersion being 0.08 g/L.
S3 g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO): dispersing 5g of nano zinc oxide in water, and mixing 4L of g-C3N4Adding the nano-sheet dispersion into zinc oxide dispersion dropwise, stirring at room temperature for 60h, centrifuging, and drying at 80 deg.C for 24h to obtain g-C3N4Coated nano zinc oxide.
S4 g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO) surface carboxylation: 0.4 g-C3N4@ ZnO powder is dispersed in 50ml of ultrapure water and subjected to ultrasonic treatment for 1.5h, then the mixture is transferred into a 250ml round-bottom flask, 50ml of concentrated nitric acid is added and subjected to ultrasonic treatment for 1h, the mixture is heated and slightly boiled and refluxed for 24h, after the mixture is cooled to room temperature, precipitate is collected through high-speed centrifugation, the precipitate is washed by ultrapure water until the pH value of the washing liquid is neutral, and finally the precipitate is dried in vacuum, ground to obtain g-C with carboxylated surface3[email protected]。
S5 cleaning the surface of cotton fabric: placing a cotton fabric sample in 70 ℃ water for wetting, soaking the cotton fabric sample in 30g/L sodium hydroxide solution for about 20min after squeezing water, taking out the cotton fabric sample to remove excessive water, soaking the cotton fabric in the sodium hydroxide solution, steaming the cotton fabric in 100 ℃ constant-temperature water bath for 2h, continuously stirring the cotton fabric sample by using a glass rod in the steaming process, piling the cotton fabric sample in a heat-preservation and moisture-preservation environment for 8h after the steaming is finished, washing the cotton fabric sample by using hot water for 3 times, then washing the cotton fabric sample by using cold water for 3 times, and placing the cotton fabric sample at room temperature for airing.
S6 antibacterial finishing of cotton fabric: 50g of carboxylated g-C3N4@ ZnO was dispersed in 1L of water, and 70g/L of NaH was added2PO2Preparing aqueous solution to obtain dispersion; then, soaking the cotton fabric into the dispersion liquid, wherein the dosage ratio of the cotton fabric (g) to the dispersion liquid (ml) is 1: and 20, magnetically stirring for 2 hours in a water bath kettle at the temperature of 60 ℃, taking out the cotton fabric, putting the cotton fabric into an oven at the temperature of 80 ℃, pre-drying for 30 minutes, roasting for 1 minute at the temperature of 150 ℃, fully washing, and naturally airing to obtain the antibacterial cotton fabric.
EXAMPLE III
The embodiment provides a preparation method of a multifunctional nano inorganic composite antibacterial agent for fabric after-finishing and a fiber fabric antibacterial finishing method by using the nano zinc oxide composite antibacterial agent, and the preparation method specifically comprises the following steps:
s1 preparation of nano zinc oxide: crushing the basic zinc carbonate by using an airflow crusher, placing the crushed basic zinc carbonate in a muffle furnace for sintering treatment at the temperature of 400 ℃ for 80min, and then performing airflow crushing on the obtained crude product again to obtain the final product of the rod-shaped nano zinc oxide.
S2 g-C3N4The synthesis of (2): putting thiourea in a corundum crucible, covering the corundum crucible with a cover, putting the corundum crucible in a muffle furnace, heating to 540 ℃ at the speed of 4 ℃/min, performing heat treatment for 4 hours, naturally cooling to room temperature, and grinding and crushing to obtain light yellow g-C3N4And (3) powder.
g-C3N4Preparation of the dispersion: taking 0.2g of g-C3N4Putting the powder into 1000ml deionized water, carrying out ultrasonic treatment for 24h, and centrifuging to remove g-C which cannot be dispersed in the deionized water after the ultrasonic treatment is finished3N4Obtaining milk white g-C from clear liquid3N4Nanosheet dispersion, the concentration of the resulting dispersion being 0.075 g/L.
S3 g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO): dispersing 3g of nano zinc oxide in water, and mixing 14L of g-C3N4Adding the nano-sheet dispersion into zinc oxide dispersion dropwise, stirring at room temperature for 55h, centrifuging, and drying at 70 deg.C for 24h to obtain g-C3N4Coated nano zinc oxide.
S4 g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO) surface carboxylation: 0.2g of g-C3N4@ ZnO powder is dispersed in 50ml of ultrapure water and subjected to ultrasonic treatment for 1.5h, then the mixture is transferred into a 250ml round-bottom flask, concentrated nitric acid with the same volume is added for ultrasonic treatment for 1h, the mixture is heated and slightly boiled for reflux for 24h, after the mixture is cooled to room temperature, precipitate is collected by high-speed centrifugation, the precipitate is washed by ultrapure water until the pH of washing liquid is neutral, and finally the precipitate is dried in vacuum and ground to obtain g-C with carboxylated surface3[email protected]。
S5 surface cleaning of the fiber fabric: placing a cotton fabric sample in water of 60 ℃ for wetting, soaking the cotton fabric sample in a 10g/L sodium hydroxide solution for about 15min after squeezing water, taking out the cotton fabric sample to remove excessive water, soaking the cotton fabric in the sodium hydroxide solution, steaming the cotton fabric sample in a 100 ℃ constant-temperature water bath for 1h, continuously stirring the cotton fabric sample by using a glass rod in the steaming process, piling the cotton fabric sample in a heat-preservation and moisture-preservation environment for 10h after the steaming is finished, firstly washing the cotton fabric sample by using hot water for 3 times after the steaming is finished, then washing the cotton fabric sample by using cold water for 4 times, and placing the cotton fabric sample at room temperature for airing.
And (S6) antibacterial finishing of the fiber fabric: 30g of carboxylated g-C3N4@ ZnO was dispersed in 1L of water, and 60g/L of NaH was added2PO2Preparing aqueous solution to obtain dispersion; subsequently, the fiber fabric was immersed in the dispersion in a ratio of the amount of the fiber fabric (g) to the amount of the dispersion (ml) of 1: and 40, magnetically stirring the mixture in a water bath kettle at the temperature of 60 ℃ for 2 hours, taking out the fiber fabric, putting the fiber fabric into an oven at the temperature of 80 ℃ for pre-drying for 25 minutes, then roasting the fiber fabric at the temperature of 135 ℃ for 2 minutes, fully washing the fiber fabric, and naturally airing the fiber fabric to obtain the antibacterial fiber fabric.
Comparative example 1
S1 preparation of nano zinc oxide: the preparation conditions were the same as in S1 of example 1.
S2 surface carboxylation of nano zinc oxide: dispersing nanometer zinc oxide in absolute ethyl alcohol, adding oleic acid under the condition of violent stirring, and adding N2Under the protection of (1), reacting at constant temperature of 70 ℃ for 1h, and separatingAnd (3) taking the precipitate after centrifugation, washing the precipitate for 4 times by using ethanol, then washing the precipitate by using deionized water until the pH value of a washing solution is 7, dispersing the precipitate in water again, adding potassium permanganate to react for 2 hours at constant temperature, and washing the precipitate by using the deionized water after the reaction is finished to obtain the nano zinc oxide with the carboxylated surface.
S3 cleaning the surface of cotton fabric: the method and conditions were the same as those of S5 in example 1.
S4 antibacterial finishing of cotton fabric: 50g of nano zinc oxide with carboxylated surface is dispersed in 2L of water, and then 40g/L of NaH is added2PO2Preparing aqueous solution to obtain dispersion; immersing a cotton fabric into the dispersion liquid, wherein the dosage ratio of the cotton fabric (g) to the dispersion liquid (ml) is 1: 30, magnetically stirring in a water bath kettle at 60 ℃ for 1.5h, taking out the cotton fabric, putting the cotton fabric into an oven at 70 ℃ for pre-drying for 20min, then roasting at 130 ℃ for 3min, fully washing and naturally drying.
That is, the nano zinc oxide antibacterial agent of comparative example 1 does not contain g-C3N4。
Comparative example 2
S1 preparation of nano zinc oxide: the preparation conditions were the same as in S1 of example 1.
S2 g-C3N4The synthesis of (2): the preparation conditions were the same as in S2 of example 1.
S3 g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO): the preparation conditions were the same as in S3 of example 1.
S4 cleaning the surface of cotton fabric: the method and conditions were the same as those of S5 in example 1.
S5 antibacterial finishing of cotton fabric: 50g of carboxylated g-C3N4@ ZnO was dispersed in 2L of water, and 40g/L of NaH was added2PO2Preparing aqueous solution to obtain dispersion; then, soaking the cotton fabric into the dispersion liquid, wherein the dosage ratio of the cotton fabric (g) to the dispersion liquid (ml) is 1: 30, magnetically stirring the mixture in a water bath kettle at the temperature of 60 ℃ for 1.5 hours, taking out the cotton fabric, putting the cotton fabric into an oven at the temperature of 70 ℃ for pre-drying for 20 minutes, then roasting the cotton fabric at the temperature of 130 ℃ for 3 minutes, fully washing the cotton fabric, and naturally airing the cotton fabric.
That is, comparative example 2 lacks g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO) surface carboxylationAnd (5) carrying out the following steps.
Comparative example 3
S1 preparation of nano zinc oxide: the preparation conditions were the same as in S1 of example 1.
S2 g-C3N4The synthesis of (2): the preparation conditions were the same as in S2 of example 1.
S3 g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO): the preparation conditions were the same as in S3 of example 1.
S4 cleaning the surface of cotton fabric: the method and conditions were the same as those of S5 in example 1.
S5 surface carboxylation of cotton fabric: soaking cotton fabric in citric acid and NaH2PO2The dosage ratio of the cotton fabric (g) to the mixed solution (ml) is 1: 30. magnetically stirring in a water bath at 60 deg.C for a while, taking out, pre-baking at 80 deg.C in an oven, washing with water, and air drying.
S6 antibacterial finishing of cotton fabric: soaking the cotton fabric with the surface carboxylated in finishing liquid, wherein the finishing liquid is prepared from g-C3N4Coated nano zinc oxide (g-C)3N4@ ZnO) in water, the cotton fabric (g) and finishing liquor (ml) being 1: and 40, magnetically stirring the mixture in a water bath kettle at the temperature of 60 ℃ for 1.5 hours, taking out the cotton fabric, putting the cotton fabric into an oven at the temperature of 70 ℃ for pre-drying for 20 minutes, then roasting the cotton fabric at the temperature of 130 ℃ for 3 minutes, fully washing the cotton fabric, and naturally airing the cotton fabric to obtain the antibacterial cotton fabric.
That is, the nano zinc oxide antibacterial agent of comparative example 3 was not surface-carboxylated, but surface-carboxylated for cotton fabric.
In order to further prove that the antibacterial effect of the fabric obtained by the preparation method of the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing provided by the invention and the fabric antibacterial finishing method by utilizing the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing is tested as follows:
firstly, antibacterial property test
The antibacterial test method is based on the oscillation method of FZ/T73023-2006, halo method.
An oscillation method: sample preparation: 0.75g +/-0.05 g of the fabric obtained in the experiments of examples 1-3 and comparative examples 1-3 is accurately weighed and folded into square samples with the side length of 5mm, two blank samples and one fabric sample without antibacterial finishing are prepared in each group of experiments, and each group of samples is wrapped by small paper pieces. The sample is sterilized. The test specimens were tested according to the test standards, and the test results after 50 water washes are shown in table 1 below:
TABLE 1 results of the test of antibacterial property by the oscillation method
Name of sample
Antibacterial rate of Escherichia coli
Staphylococcus aureus bacteriostasis rate
Bacteriostasis rate of candida albicans
Example 1
97％
99％
98％
Example 2
96％
98％
97％
Example 3
93％
99％
94％
Comparative example 1
39％
35％
25％
Comparative example 2
10％
12％
15％
Comparative example 3
71％
82％
69％
Halo method: the standard blank and the antibacterial fabric samples of examples 1 to 3 and comparative examples 1 to 3 were washed once according to the standard, and 4 to 6 test samples of 1.5cm x 1.5cm each were sterilized and tested according to the test standards, and the test results were in accordance with the index of dissolution safety. The test results are given in table 2 below:
TABLE 2 halo method bacteriostasis zone width test results
Note: the calculation formula of the width of the inhibition zone is as follows: d ═ T-R)/2; in the formula, D is the width of the bacteriostatic zone and the unit is millimeter; t is the total width of the outer edge of the bacteriostatic zone, and the unit is millimeter; r is the total width of the sample in millimeters.
Judging whether the sample is the dissolution type antibacterial fabric: the width D of the inhibition zone is more than 1mm, and the fabric can be judged as a dissolution type antibacterial fabric; the width D of the inhibition zone is less than or equal to 1mm, and the fabric can be judged to be a non-dissolution type antibacterial fabric.
Second, antiviral test
Antiviral test standards are in accordance with ISO 18184: 2014(E)
Sample preparation: the fabrics obtained in examples 1-3 and comparative examples 1-3 were accurately weighed to 0.4 + -0.05 g, cut into 50mm x 50mm pieces of cloth, six for each group, and nine blanks were cut for reference. The tests were performed according to the standard and the test results are given in table 3 below:
TABLE 3 antiviral Performance test results
Third, mildew resistance test
Mildew-proof test standard based on GB/T24346-2009 culture dish method
Sample preparation: the sheets obtained in examples 1 to 3 and comparative examples 1 to 3 were cut into pieces, and after the medium in the petri dish was solidified, a sample was placed on the surface of the medium, and 1ml of spore solution was aspirated by a pipette and uniformly distributed to be inoculated on the entire surface of the sample. And (4) covering the dish cover after the surface moisture of the sample is slightly dry, and making three parallel samples for each sample. The test strains are Aspergillus niger, Trichoderma viride, Penicillium funiculosum and Chaetomium globosum. The mildew-proof effect of the unwashed and 10-time washed fabrics is tested, and the test results are shown in the following table 4:
TABLE 4 results of the test of the mildew resistance
Name of sample
Unwashed mildew resistance rating
Mildew resistance rating after 10 washes
Example 1
0
0
Example 2
0
0
Example 3
0
0
Comparative example 1
3
4
Comparative example 2
0
2
Comparative example 3
0
1
Rating standard: level 0-no obvious mold growth under magnifier; grade 1-the mold growth is rare or local, the coverage area on the sample surface is less than 10%; level 2-the area of coverage of the mould on the surface of the sample is less than 30% (10% -30%); grade 3-the area of mould coverage on the sample surface is less than 60% (30% -60%); grade 4-the area of mould coverage on the sample surface reached or exceeded 60%.
Fourth, deodorizing Performance test
The deodorization performance test is based on GB/T33610.2-2017
The fabrics obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to deodorizing performance test using ammonia (concentration 28%), hydrogen sulfide (standard gas diluted with nitrogen gas at a concentration of 100. mu.L/L), acetic acid (purity 99.7%), test cloth pieces at a rate of 10cm x 10cm, and a test time of 2 hours. The test results are given in table 5 below:
TABLE 5 deodorant Performance test results
Fifth, ultraviolet resistance test
Ultraviolet resistance test is based on GB/T18830-2009
The multifunctional nano inorganic composite antibacterial agent for fabric after-finishing obtained in example 1 was used to perform fabric antibacterial finishing on polyester (fabric 1), polyester and rayon mixed fiber fabric (fabric 2) according to the fabric antibacterial finishing method of example 1. And respectively carrying out ultraviolet resistance tests on the finished fabrics 1 and 2 and the unfinished fabrics 1 and 2. Meanwhile, the test results according to comparative examples 1 to 3 are shown in the following Table 6:
TABLE 6 ultraviolet resistance test results
Note: when the UPF of the sample is > 40 and T (UVA)AVIf the percentage is less than 5%, the product can be called as 'ultraviolet-proof product', and the single item is judged to be 'in line' in table 6, otherwise, the product is 'not in line'.
The test results show that the fabric obtained by the preparation method of the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing provided by the invention and the method for performing fabric antibacterial finishing by using the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing has stronger antibacterial and antiviral properties: washing resistance 50 times of bacteriostasis rate>90 percent, the antibacterial effect accords with AAA level, and the antibacterial property of the antibacterial agent is strong in water washing resistance; the antiviral activity rate of influenza virus H1N1 and H3N2 is more than 90 percent; all in oneThe mildew-proof grade is 0 grade; the reduction rate of main odor components such as ammonia, hydrogen sulfide, acetic acid (acetic acid) and the like in sweat smell, body smell, smoke smell and the like reaches about 90 percent; ultraviolet protection index UPF rating>50 (ultraviolet transmittance T (UVA))AVLess than or equal to 2.5 percent) and has excellent ultraviolet protection effect.
In addition, the fabric obtained by the preparation method of the multifunctional nano inorganic composite antibacterial agent for fabric after-treatment and the fabric antibacterial finishing method by utilizing the multifunctional nano inorganic composite antibacterial agent for fabric after-treatment provided by the invention has no adverse effect on the whiteness, color, strength, hand feeling, air permeability and 50-100 times washing resistance of the fabric, and has washing fastness and dry cleaning resistance at 150 ℃.
Under the use concentration, the multifunctional nano inorganic composite antibacterial agent for fabric after-finishing provided by the invention meets the dissolution safety index (the width D of a bacteriostatic zone is less than or equal to 5mm), the results of multiple skin irritation, acute eye irritation and corrosivity tests are nonirritant, and the acute oral toxicity test belongs to the actual nontoxic level; has no irritation to human body and skin and mucosa, has no adverse effect such as discomfort, does not contain heavy metal and halogen, is green, healthy and environment-friendly, and meets the standards of Ministry of health.
In summary, the example of the present invention begins with g-C3N4Coating the nano zinc oxide by using g-C after coating3N4Is oxidized to form g-C3N4The antibacterial finishing liquid is prepared by the method rich in carboxyl, and then the antibacterial finishing liquid and the fabric rich in hydroxyl are subjected to antibacterial finishing to obtain the antibacterial fabric. Because the antibacterial agent is more easily subjected to carboxylation and is combined with hydroxyl in the fabric by chemical bonds, the antibacterial fabric prepared by the method has stronger antibacterial property, antiviral property, water washing resistance, deodorization property and ultraviolet resistance, and also has a certain mildew-proof effect.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
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