CN115652615A - Antibacterial and antistatic finishing agent, antistatic and antibacterial fabric and preparation method thereof - Google Patents
Antibacterial and antistatic finishing agent, antistatic and antibacterial fabric and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an antibacterial and antistatic finishing agent, an antistatic and antibacterial fabric and a preparation method thereof. The antistatic and antibacterial fabric consists of an inner layer and an outer layer, wherein the inner layer is made of antibacterial blended yarns and is formed by interweaving pure cotton yarns and bamboo charcoal fiber/Modal fiber blended yarns; the outer layer is made of antistatic blended yarns, and is formed by interweaving pure cotton yarns and carbon nano tube fiber/polyacrylonitrile fiber blended yarns. The blended yarns have the antibacterial and antistatic functions, and the good physical and mechanical properties of the fabric are also kept. The two layers of fabrics are woven by weft-knitted thread plain needles, and are bonded by adhesives and then treated by an antibacterial and antistatic finishing agent, so that the produced fabrics are good in stability, soft and comfortable, and have excellent antistatic and antibacterial properties.
Description
Background
With the progress of science and technology and the improvement of the living standard of people, people put more and higher requirements on the functionality of textiles in production and life. Besides the comfort, beauty, health and the like of the product, the functionality of the textile is also sought after by people. The textile has the characteristics of softness, heat preservation, moisture absorption, quick drying, water resistance, moisture permeability and the like; household and industrial textiles with the characteristics of flame retardance, static resistance, water resistance, ultraviolet resistance, bacteria resistance and the like are increasingly seen in the aspects of life.
The textile is easy to generate static electricity due to friction and induction in production, processing and use, is easy to bring potential safety hazards and has great harm to human bodies. In recent years, many people research antistatic fabrics, and finally find that the antistatic effect of the fabrics can be improved by enhancing the moisture absorption performance of the fabrics, because the static leakage amount of the fabrics is improved after the fabrics absorb moisture in the environment. However, after the moisture absorption performance of the fabric is enhanced, the fabric is in a relatively humid environment in an environment with high humidity, and the environment is suitable for bacteria growth, so that the fabric is easy to breed bacteria. However, the fabric after breeding bacteria is easy to generate some peculiar smell, and bacterial plaque is easy to form on the fabric when serious, thereby influencing the use of people.
CN 109130374B discloses an antistatic and antibacterial textile fabric and a preparation method thereof, wherein an inner layer fabric is composed of pure cotton fibers and antistatic yarns for interweaving, and an outer layer fabric is composed of bamboo fibers and cotton fibers; and after the two layers of fabrics are bonded, further soaking the two layers of fabrics in antistatic and antibacterial composite hydrosol, and then drying and baking the fabrics to obtain the antistatic and antibacterial textile fabrics. Although the fabric has the dual effects of static resistance and antibiosis, the selected fabric material has poor static resistance and antibiosis effects, silver ions are added into the prepared static resistance and antibiosis composite solution, the cost is higher, and the silver ions are easy to fall off after being washed by water for many times, so that the performance is reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention discloses an antibacterial and antistatic finishing agent, an antistatic and antibacterial fabric and a preparation method thereof. The two layers of fabrics are both woven by weft-knitted threaded plain knitting, and the produced fabrics are good in stability and excellent in antistatic and antibacterial properties.
The specific technical scheme of the invention is as follows:
a preparation method of the antistatic and antibacterial fabric comprises the following steps:
(1) By adopting weaving, pure cotton yarn and bamboo charcoal fiber/Modal fiber blended yarn are mixed according to the mass ratio of (60-70): (30-40) interweaving the fabric into an inner layer fabric; pure cotton yarn and carbon nano tube fiber/polyacrylonitrile fiber blended yarn are mixed according to the mass ratio (40-50): (10-20) interweaving into outer shell fabric; wherein 5-10 g of adhesive is coated on each square meter of inner layer fabric, the inner layer fabric and the outer layer fabric are bonded to obtain an untreated fabric, and the gram weight of the untreated fabric is 240-280 g/m 2 。
(2) 1g of bath ratio: (10-20) soaking the untreated fabric in 20-50 wt% of sodium hydroxide aqueous solution for 5-6 h, taking out, and washing to be neutral; then mixing the raw materials according to the bath ratio of 1g: (10-20) soaking the fabric treated by the sodium hydroxide aqueous solution into a 4-6 wt% sulfuric acid aqueous solution for 3-5 h, taking out, and washing to be neutral; then mixing the raw materials according to the bath ratio of 1g: (10-20) soaking the fabric subjected to sulfuric acid water-soluble treatment in the mixed solution, stirring at the temperature of 110-120 ℃ for 2-5 min at the stirring speed of 10r/min, finally washing to be neutral, and drying at the temperature of 60-70 ℃ for 60-72 h to obtain the pretreated fabric.
The mixed solution comprises sodium hydroxide, sodium silicate, sodium phosphate and water according to the mass ratio of (10-15): (5-10): (1-5): (50-60) mixing.
(3) Soaking the pretreated fabric into an antibacterial and antistatic finishing agent according to a bath ratio of 1g (5-10) mL, soaking twice and rolling twice, wherein the soaking time is 20-30 min each time, the rolling residue rate is 60-80% each time, prebaking at 130 ℃ for 2-3 min, and baking at 60-70 ℃ for 6-7 h to obtain the antistatic and antibacterial fabric.
Preferably, the inner layer fabric takes pure cotton yarns as warps and bamboo charcoal fiber/Modal fiber blended yarns as wefts.
Preferably, the outer fabric is made of pure cotton yarn as warp and carbon nanotube fiber/polyacrylonitrile fiber blended yarn as weft.
The mass ratio of the bamboo charcoal fiber to the Modal fiber is (15-20): (80-85); the mass ratio of the carbon nano tube fiber to the polyacrylonitrile fiber is (5-10): (90-95).
Preferably, the linear density of the bamboo charcoal fiber/Modal fiber blended yarn is 18.0-23.3tex, and the linear density of the carbon nanotube fiber/polyacrylonitrile fiber blended yarn is 15.2-15.8tex.
The adhesive is one or a mixture of two or more of cellulose ester, polyvinyl acetate, polyvinyl alcohol and polyacrylate; preferably, the adhesive is polyvinyl acetate.
Preferably, the weaving in the step (1) is weft knitting threaded flat knitting, a 1+1, 1+2 or 2+2 threaded weave structure is adopted, the antibacterial blended yarn and the antistatic blended yarn are front side loops, and the pure cotton yarn is back side loops. The more the number of turns of the front surface line, the better the antistatic and antibacterial effect of the fabric is, but the comfort level can be reduced. Further preferably, the fabric adopting the 1+1 threaded structure is comfortable and has good antistatic and antibacterial effects.
The preparation method of the antibacterial and antistatic finishing agent comprises the following steps:
s1, according to the mass portion, 0.2 to 2 portions of g-C 3 N 4 0.2 to 0.8 portion of CuSO 4 ·5H 2 O, 3.64 to 4.96 portions of chelating agent and 100 portions of water are mixed, stirred in a thermostatic water bath at 60 ℃ at the rotating speed of 60 to 100r/min, then 0.12 to 0.2 portion of ascorbic acid is added, after the reaction is carried out for 15 to 30min at the constant temperature of 60 ℃ at the rotating speed of 60 to 100r/min, 8 to 12 portions of 0.2M NaOH aqueous solution is dripped, wherein the dripping speed is 6 to 10s/g, cu is generated 2 O/g-C 3 N 4 Precipitating, continuously stirring for 8-12 min, centrifuging to obtain precipitate, washing, and drying at 40-60 deg.C to obtainTo Cu 2 O/g-C 3 N 4 。
S2, adding 0.5-2 parts of Cu 2 O/g-C 3 N 4 5-10 parts of initiator and 10-20 parts of water, and performing ultrasonic dispersion for 30-40 min at room temperature to obtain dispersion liquid, wherein the ultrasonic power is 400-800W, and the frequency is 30-60 kHz.
S3, adding 10-20 parts of coupling agent and 20-40 parts of quaternary ammonium organic matter into a three-neck flask, reacting for 12-14 min at 89-91 ℃ under the stirring condition of 200-400rpm, then adding 10-20 parts of dispersion prepared in the step S2, 1-3 parts of glucose, 10-20 parts of diluent, 20-30 parts of vinyl-terminated silicone oil and 5-10 parts of water, and continuously stirring and reacting for 4-5 h at 89-91 ℃ under the stirring condition of 200-400 rpm; naturally cooling to room temperature, adjusting the pH value to be 5-7 by using ascorbic acid, filtering, taking precipitate, washing and drying to obtain the Cu grafted by the organosilicon quaternary ammonium salt 2 O/g-C 3 N 4 An antistatic antimicrobial agent.
S4, grafting 1-10 parts of organosilicon quaternary ammonium salt to Cu 2 O/g-C 3 N 4 Mixing the antistatic antibacterial agent and 100 parts of water, and performing ultrasonic treatment for 30-40 min, wherein the ultrasonic power is 400-800W, and the frequency is 30-60 kHz, so as to obtain the antibacterial antistatic finishing agent.
The chelating agent is one or a mixture of two or more of cetyl trimethyl ammonium bromide, ethylene diamine tetraacetic acid and sodium stearate; preferably, the chelating agent is cetyl trimethyl ammonium bromide and ethylene diamine tetraacetic acid according to the mass ratio (8-12): (1-2) mixing.
The initiator is one of benzoyl peroxide, lauroyl peroxide, potassium persulfate and ammonium persulfate; preferably, the initiator is ammonium persulfate.
The coupling agent is one of silane coupling agents and phthalate coupling agents; preferably, the coupling agent is a silane coupling agent KH792.
The quaternary ammonium organic matter is one or a mixture of two or more of tetrabutylammonium hydrogen sulfate, hexadecyl dimethyl benzyl ammonium, dimethyl diallyl ammonium chloride and N, N-dimethyl ethanolamine; preferably, the quaternary ammonium organic substance is N, N-dimethylethanolamine.
The diluent is one of allyl glycidyl ether, acetone, cyclohexanone and n-butyl alcohol; preferably, the diluent is acetone.
The bamboo charcoal fiber has a loose and porous structure, has fine and porous molecules and strong adsorption capacity, can eliminate peculiar smell, inhibit bacteria and expel parasites, can remove dampness and absorb sweat when contacting with a human body, promotes blood circulation and metabolism of the human body, and relieves fatigue. The inner layer fabric is blended by cotton threads and bamboo charcoal fiber/Modal fiber blended yarns, so that the fabric has the advantages of no stimulation to human skin, health, environmental protection, strong antibacterial capability and low cost;
because the structure of the carbon nano tube fiber is the same as the lamellar structure of the graphite, the carbon nano tube fiber has good conductivity, can effectively reduce the aggregation of charges on the fabric, and the polyacrylonitrile has good weather resistance and chemical reagent resistance, and the antistatic agent has little influence on the fabric.
The antibacterial and antistatic functions are always a research focus of textiles, and common fabrics can generate static electricity due to friction along with walking of people so that clothes cling to bodies and are deformed, or the fabric contacts with electronic components in the production process of the electronic components to generate static electricity effect. The existence of static electricity also has certain damage to human bodies, such as the increase of the pH value of blood, the decrease of the calcium content in blood, the increase of the calcium content in urine, the increase of blood sugar, the decrease of the vitamin C content and the like caused by static electricity. The harm of bacteria to human bodies is not to mention that the antibacterial, bacteriostatic and sterilizing functions of various clothes contacted by people are the primary factors to consider especially.
The traditional antibacterial and antistatic finishing agent for clothes mostly only has a single antibacterial or antistatic effect, the antibacterial and antistatic performance of the fabric is improved, the antibacterial agent and the antistatic agent are required to be mixed and modulated firstly, the operation is troublesome, few antibacterial agents and antistatic agents have synergistic effect, the effect that one antibacterial agent is larger than one antistatic agent can be generated, even some antibacterial agents and antistatic agents can interfere with each other, the antibacterial and antistatic performance of the fabric is influenced, and great troubles are brought to the fabric manufacturer.
Therefore, the invention aims to develop the fabric antibacterial and antistatic finishing agent with lower cost and both antibacterial and antistatic functions, and the fabric antibacterial and antistatic finishing agent is applied to fabric finishing to obtain the high-performance antibacterial and antistatic fabric. Firstly, blended yarns with an antibacterial function and pure cotton are selected to be interwoven into an inner-layer fabric, and blended yarns with an antistatic function and pure cotton are selected to be interwoven into an outer-layer fabric. The bamboo carbon fiber and the carbon nano tube fiber in the fiber have natural antistatic and antibacterial capabilities, and the physical and mechanical properties of the fiber are improved by compounding the fiber, so that the comfort level of the fabric is not influenced; and secondly, the bamboo charcoal fiber and the carbon nano tube fiber have strong adsorption effect, and are favorable for enhancing the firmness of the antibacterial antistatic agent.
Secondly, the fabric is pretreated, and impurities such as starch, inorganic salt and the like on the cotton fiber serving as warp can be effectively removed by adopting an alkali and acid desizing method. Then sodium hydroxide, sodium silicate, sodium phosphate and water are used according to the mass ratio (10-15): (5-10): (1-5): (50-60) boiling the fabric with the solution, removing pectin substances, wax substances, nitrogen-containing substances, cottonseed hulls and the like, and ensuring the cleanness of the fabric. Finally, the alkali treatment is beneficial to forming a large number of hydroxyl groups on the surface of the fabric and is beneficial to grafting the organic silicon quaternary ammonium salt with Cu 2 O/g-C 3 N 4 The antistatic antibacterial agent is not easy to fall off by the reaction of silicon atoms on the organic quaternary ammonium salt and the silicon-oxygen covalent bond formed by the reaction of the silicon atoms on the organic quaternary ammonium salt.
Finally, a divalent copper reduction method is adopted, divalent copper ions are reduced into monovalent cuprous ions by the reduction effect of ascorbic acid, and cuprous oxide precipitates are obtained by adjusting the pH value. In this process we used a chelating agent with terminal chelating properties, one end of which is chelated with divalent copper ions and the other end anchored at g-C 3 N 4 The cuprous oxide is stabilized in g-C 3 N 4 Surface nucleation and crystallization; furthermore, the chelating agent is adopted to separate copper ions, so that the copper ions are not easy to polymerizeThe length of the cuprous oxide nanoparticle is equal to that of the cuprous oxide nanoparticle, and a cavity is formed in the crystallization process of the cuprous oxide to obtain the cuprous oxide nanoparticle with a multilayer core-shell structure. The unique core-shell structure can form multiple light refraction in the shell, absorb the digestive light and improve the utilization rate of sunlight. Meanwhile, the core-shell structure is also beneficial to the g-C 3 N 4 The surface forms a Mott Schottky junction to promote Cu 2 O/g-C 3 N 4 The conductivity and the photocatalytic sterilization performance of the composite material. The cuprous ions released by the cuprous oxide have strong sterilization effect and are combined with the g-C 3 N 4 The supported Mott Schottky junction further improves the photocatalytic sterilization performance, has double functions and shows extremely excellent sterilization capability. Mixing Cu 2 O/g-C 3 N 4 During the synthesis process of adding the organosilicon quaternary ammonium salt, the cuprous ions are in an electron-rich state and combined with the quaternary ammonium salt in an electron-deficient state to form a firm chemical bond, so that the organosilicon quaternary ammonium salt grafted Cu is obtained 2 O/g-C 3 N 4 The modified silicon-aluminum-copper-aluminum alloy is used as an antibacterial and antistatic finishing agent of fabric, and silicon atoms on the modified silicon-aluminum-copper alloy can be combined with hydroxyl on the surface of the fabric to form silicon-oxygen bonds, and Cu 2 O/g-C 3 N 4 The nitrogen atoms in the bamboo charcoal fiber can be crosslinked with carbon atoms on the surfaces of the bamboo charcoal fiber and the carbon nano tube fiber to form carbon-nitrogen single bonds or double bonds, so that the combination is firmer.
The invention has the beneficial effects that: according to the invention, the wear-resistant textile fabric with antistatic and antibacterial effects is prepared by adopting a dual antistatic technology and an antibacterial technology, so that the functionality of the fabric is improved, the defects of the prior art are overcome, and the production cost is reduced.
Detailed Description
In the present invention, all the equipment and materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
Pure cotton yarn, 18.5tex, dow cotton ltd.
Bamboo charcoal fiber, 1.6dtex, guangzhou Ruixin chemical Co., ltd.
Modal fiber, 2.0dtex, length: 30-40mm, lenzing, inc.
Carbon nanotube fiber, 1.8dtex, length: 10-30mm, beijing Germany island gold technologies, inc.
Polyacrylonitrile fiber, 1.5dtex, length: 30-40mm, shandong Hongyao engineering materials Co.
Vinyl terminated silicone oil, CAS No.: 68083-19-2, shanghai Kainen chemical Co., ltd.
Silane coupling agent KH792, CAS No.: 1760-24-3, tokyo siliconizing chemical company ltd.
Polyvinyl acetate, CAS No.: 9003-20-7, molecular weight: 150000.
g-C 3 N 4 and the goods number: JK-R1010, size: 1-10 μm, shanghai Crystal Biocide engineering Co., ltd.
Example 1
A preparation method of an antistatic and antibacterial fabric comprises the following steps:
(1) And (2) mixing bamboo charcoal fibers and Modal fibers according to a mass ratio of 13:87, performing mixed spinning to obtain bamboo charcoal fiber/Modal fiber blended yarns; carbon nanotube fiber and polyacrylonitrile fiber are mixed according to the mass ratio of 7:93 and carrying out mixed spinning to obtain the carbon nano tube fiber/polyacrylonitrile fiber mixed spinning yarn. The linear density of the bamboo carbon fiber/Modal fiber blended yarn is 20.0tex, and the linear density of the carbon nanotube fiber/polyacrylonitrile fiber blended yarn is 15.4tex.
(2) A double-faced circular weft knitting machine (Huaxing mechanical Co., ltd., zhoushan, model HX 211) is adopted to mix pure cotton yarn and bamboo charcoal fiber/Modal fiber blended yarn according to the mass ratio of 70:30 are interwoven into 1+1 inner layer fabric with a threaded structure; pure cotton yarn and carbon nanotube fiber/polyacrylonitrile fiber blended yarn are mixed according to the mass ratio of 40:15 are interwoven into 1+1 thread structure outer layer fabric; wherein 8g of adhesive is coated on each square meter of inner layer fabric, the inner layer fabric and the outer layer fabric are bonded to obtain an untreated fabric, and the gram weight of the untreated fabric is 261g/m 2 。
(3) 1g of bath ratio: 20mL of the untreated fabric is soaked in 40wt% of sodium hydroxide aqueous solution for 6 hours and washed to be neutral; then mixing the raw materials according to the bath ratio of 1g: soaking 20mL of the fabric treated by the sodium hydroxide aqueous solution into a 5wt% sulfuric acid aqueous solution for 3.5h, and washing to be neutral; then mixing the raw materials according to the bath ratio of 1g: and (2) immersing the fabric treated by the sulfuric acid aqueous solution into the mixed solution by 20mL, stirring at the temperature of 120 ℃ for 3min at the speed of 10r/min, finally washing to be neutral, and drying at the temperature of 70 ℃ for 60h to obtain the pretreated fabric.
The mixed solution is prepared from sodium hydroxide, sodium silicate, sodium phosphate and water according to a mass ratio of 15:5:5:60 are mixed to prepare the composition.
(4) 1g of bath ratio: and 8mL of the antistatic and antibacterial fabric is obtained by soaking the pretreated fabric into an antibacterial and antistatic finishing agent for two times and two rolls, wherein the soaking time is 30min each time, the rolling residue rate is 80% each time, prebaking is carried out for 3min at the temperature of 130 ℃, and then baking is carried out for 6h at the temperature of 70 ℃.
The preparation method of the antibacterial and antistatic finishing agent comprises the following steps:
s1, according to the mass portion, 1 portion of g-C 3 N 4 0.4 part of CuSO 4 ·5H 2 O, 4.21 parts of chelating agent and 100 parts of water are mixed, stirred in a constant-temperature water bath at the rotating speed of 80r/min and the temperature of 60 ℃, then 0.18 part of ascorbic acid is added, after the constant-temperature reaction at the rotating speed of 80r/min and the temperature of 60 ℃ for 20min, 10 parts of 0.2M NaOH aqueous solution is added dropwise, wherein the dropping speed is 8s/g, and Cu is generated 2 O/g-C 3 N 4 Precipitating, stirring for 10min, centrifuging, washing, and drying at 50 deg.C to obtain Cu 2 O/g-C 3 N 4 。
S2, adding 1.5 parts of Cu 2 O/g-C 3 N 4 6 parts of ammonium persulfate and 18 parts of water are mixed and ultrasonically dispersed for 35min to obtain dispersion liquid, wherein the ultrasonic power is 600W, and the frequency is 40kHz.
S3, adding 18 parts of silane coupling agent KH792 and 36 parts of N, N-dimethylethanolamine into a three-neck flask, reacting for 14min at 90 ℃ under the stirring condition of 200rpm, then adding 15 parts of dispersion liquid, 2 parts of glucose, 10 parts of acetone, 15 parts of vinyl-terminated silicone oil and 10 parts of water which are obtained in the step S2, stirring and reacting for 4.5h at 90 ℃ and 200rpm, naturally cooling to room temperature, adjusting the pH to be =6.5 by using ascorbic acid, filtering, washing and drying to obtain the Cu grafted with the organosilicon quaternary ammonium salt 2 O/g-C 3 N 4 Anti-static reactorAnd (4) a microbial inoculum.
S4, grafting 1 part of organosilicon quaternary ammonium salt to Cu 2 O/g-C 3 N 4 And mixing the antistatic antibacterial agent and 20 parts of water, and performing ultrasonic treatment for 30min, wherein the ultrasonic power is 600W, and the frequency is 40kHz, so as to obtain the antibacterial antistatic finishing agent.
The chelating agent is cetyl trimethyl ammonium bromide and ethylene diamine tetraacetic acid according to the mass ratio of 10:1.5 mixing.
Example 2
Essentially the same as example 1, except that: the preparation scheme of the antibacterial antistatic finishing agent is as follows:
s1, according to the mass portion, 1 portion of g-C 3 N 4 0.4 part of CuSO 4 ·5H 2 O, 4.21 parts of chelating agent and 100 parts of water are mixed, stirred in a constant-temperature water bath at the rotating speed of 80r/min and the temperature of 60 ℃, then 0.18 part of ascorbic acid is added, after the constant-temperature reaction at the rotating speed of 80r/min and the temperature of 60 ℃ for 20min, 10 parts of 0.2M NaOH aqueous solution is added dropwise, wherein the dropping speed is 8s/g, and Cu is generated 2 O/g-C 3 N 4 Precipitating, stirring for 10min, centrifuging, washing, and drying at 50 deg.C to obtain Cu 2 O/g-C 3 N 4 。
S2, adding 1 part of Cu 2 O/g-C 3 N 4 And mixing 20 parts of water with ultrasound for 30min, wherein the ultrasound power is 600W, and the frequency is 40kHz, so as to obtain the antibacterial antistatic finishing agent.
The chelating agent is cetyl trimethyl ammonium bromide and ethylene diamine tetraacetic acid according to the mass ratio of 10:1.5 mixing.
Example 3
Essentially the same as example 1, except that: the preparation scheme of the antibacterial antistatic finishing agent is as follows:
s1, mixing 6 parts of ammonium persulfate and 18 parts of water by mass, and performing ultrasonic dispersion for 35min to obtain dispersion liquid, wherein the ultrasonic power is 600W, and the frequency is 40kHz.
S2, adding 18 parts of silane coupling agent KH792, 36 parts of N, N-dimethylethanolamine into a three-neck flask, reacting for 14min at 90 ℃ under the stirring condition of 200rpm, then adding 15 parts of dispersion liquid, 2 parts of glucose, 10 parts of acetone, 15 parts of vinyl-terminated silicone oil and 10 parts of water, keeping the temperature at 90 ℃ and the stirring speed of 200rpm, reacting for 4.5h, naturally cooling to room temperature, adjusting the pH =5 by using ascorbic acid, filtering, washing and drying to obtain the organic silicon quaternary ammonium salt.
And S3, mixing 1 part of organic silicon quaternary ammonium salt and 20 parts of water, and performing ultrasonic treatment for 30min, wherein the ultrasonic power is 600W, and the frequency is 40kHz, so as to obtain the antibacterial antistatic finishing agent.
Example 4
Essentially the same as example 1, except that: the preparation scheme of the antibacterial antistatic finishing agent is as follows:
s1, according to the mass portion, 1 portion of g-C 3 N 4 0.4 part of CuSO 4 ·5H 2 O, 4.21 parts of chelating agent and 100 parts of water are mixed, stirred in a constant-temperature water bath at the rotating speed of 80r/min and the temperature of 60 ℃, then 0.18 part of ascorbic acid is added, the mixture reacts for 20min at the constant temperature of 60 ℃ at the rotating speed of 80r/min, and 10 parts of 0.2M NaOH aqueous solution is added dropwise, wherein the dropping speed is 8s/g, so that Cu is generated 2 O/g-C 3 N 4 Precipitating, stirring for 10min, centrifuging, washing, and drying at 50 deg.C to obtain Cu 2 O/g-C 3 N 4 。
S2, mixing 6 parts of ammonium persulfate and 18 parts of water, and ultrasonically dispersing for 35min to obtain a dispersion liquid, wherein the ultrasonic power is 600W, and the frequency is 40kHz.
S3, adding 18 parts of silane coupling agent KH792, 36 parts of N, N-dimethylethanolamine into a three-neck flask, reacting for 14min at 90 ℃ under the stirring condition of 200rpm, then adding 15 parts of dispersion liquid, 2 parts of glucose, 10 parts of acetone, 15 parts of vinyl-terminated silicone oil and 10 parts of water which are obtained in the step S2, stirring and reacting for 4.5h at 90 ℃ and 200rpm, naturally cooling to room temperature, adjusting the pH =6.5 by using ascorbic acid, filtering, washing and drying to obtain the organosilicon quaternary ammonium salt.
S4, adding 0.15 part of Cu 2 O/g-C 3 N 4 0.85 part of organic silicon quaternary ammonium salt and 20 parts of water are mixed and subjected to ultrasonic treatment for 30min, wherein the ultrasonic power is 600W, and the frequency is 40kHz, so that the antibacterial antistatic finishing agent is obtained.
The chelating agent is cetyl trimethyl ammonium bromide and ethylene diamine tetraacetic acid according to the mass ratio of 10:1.5 mixing.
Example 5
Essentially the same as example 1, except that: the preparation scheme of the antibacterial antistatic finishing agent is as follows:
s1, according to the mass portion, 1 portion of g-C 3 N 4 0.4 part of CuSO 4 ·5H 2 O, 4.21 parts of chelating agent and 100 parts of water are mixed, stirred in a constant-temperature water bath at the rotating speed of 80r/min and the temperature of 60 ℃, then 0.18 part of ascorbic acid is added, after the constant-temperature reaction at the rotating speed of 80r/min and the temperature of 60 ℃ is carried out for 20min, 10 parts of 0.2M NaOH aqueous solution is added dropwise, wherein the dropping rate is 8s/g, and Cu is generated 2 O/g-C 3 N 4 Precipitating, stirring for 10min, centrifuging, washing, and drying at 50 deg.C to obtain Cu 2 O/g-C 3 N 4 。
S2, adding 1.5 parts of Cu 2 O/g-C 3 N 4 6 parts of ammonium persulfate and 18 parts of water are mixed and ultrasonically dispersed for 35min to obtain dispersion liquid, wherein the ultrasonic power is 600W, and the frequency is 40kHz.
S3, adding 18 parts of silane coupling agent KH792, 36 parts of N, N-dimethylethanolamine into a three-neck flask, reacting for 14min at 90 ℃ under the stirring condition of 200rpm, then adding 15 parts of dispersion liquid, 2 parts of glucose, 10 parts of acetone, 15 parts of vinyl-terminated silicone oil and 10 parts of water which are obtained in the step S2, stirring and reacting for 4.5h at 90 ℃ and 200rpm, naturally cooling to room temperature, adjusting the pH to be =6.5 by using ascorbic acid, filtering, washing and drying to obtain the Cu grafted with the organosilicon quaternary ammonium salt 2 O/g-C 3 N 4 An antistatic antimicrobial agent.
S4, grafting 1 part of organosilicon quaternary ammonium salt to Cu 2 O/g-C 3 N 4 And mixing the antistatic antibacterial agent and 20 parts of water, and performing ultrasonic treatment for 30min, wherein the ultrasonic power is 600W, and the frequency is 40kHz, so as to obtain the antibacterial antistatic finishing agent.
The chelating agent is ethylenediamine tetraacetic acid.
Example 6
Essentially the same as example 1, except that: the preparation scheme of the antibacterial antistatic finishing agent is as follows:
s1, according to the mass portion, 1 portion of g-C 3 N 4 0.4 part of CuSO 4 ·5H 2 O、4.21 parts of chelating agent and 100 parts of water are mixed, stirred in a thermostatic water bath at the rotating speed of 80r/min and the temperature of 60 ℃, then 0.18 part of ascorbic acid is added, after the thermostatic reaction at the rotating speed of 80r/min and the temperature of 60 ℃ is carried out for 20min, 10 parts of 0.2M NaOH aqueous solution is added dropwise, wherein the dropping speed is 8s/g, and Cu is generated 2 O/g-C 3 N 4 Precipitating, stirring for 10min, centrifuging, washing, and drying at 50 deg.C to obtain Cu 2 O/g-C 3 N 4 。
S2, adding 1.5 parts of Cu 2 O/g-C 3 N 4 6 parts of ammonium persulfate and 18 parts of water are mixed and ultrasonically dispersed for 35min to obtain dispersion liquid, wherein the ultrasonic power is 600W, and the frequency is 40kHz.
S3, adding 18 parts of silane coupling agent KH792, 36 parts of N, N-dimethylethanolamine into a three-neck flask, reacting for 14min at 90 ℃ under the stirring condition of 200rpm, then adding 15 parts of dispersion liquid, 2 parts of glucose, 10 parts of acetone, 15 parts of vinyl-terminated silicone oil and 10 parts of water which are obtained in the step S2, stirring and reacting for 4.5h at 90 ℃ and 200rpm, naturally cooling to room temperature, adjusting the pH to be =6.5 by using ascorbic acid, filtering, washing and drying to obtain the Cu grafted with the organosilicon quaternary ammonium salt 2 O/g-C 3 N 4 An antistatic antimicrobial agent.
S4, grafting 1 part of organosilicon quaternary ammonium salt to Cu 2 O/g-C 3 N 4 And mixing the antistatic antibacterial agent and 20 parts of water, and performing ultrasonic treatment for 30min, wherein the ultrasonic power is 600W, and the frequency is 40kHz to obtain the antibacterial antistatic finishing agent.
The chelating agent is cetyl trimethyl ammonium bromide.
Example 7
Essentially the same as example 1, except that: the preparation scheme of the antibacterial antistatic finishing agent is as follows:
s1, according to the mass portion, 1 portion of g-C 3 N 4 0.4 part of CuSO 4 ·5H 2 O, 4.21 parts of chelating agent and 100 parts of water are mixed, stirred in a constant-temperature water bath at the rotating speed of 80r/min and the temperature of 60 ℃, then 0.18 part of ascorbic acid is added, after the constant-temperature reaction at the rotating speed of 80r/min and the temperature of 60 ℃ is carried out for 20min, 10 parts of 0.2M NaOH aqueous solution is added dropwise, wherein the dropping rate is 8s/g, and Cu is generated 2 O/g-C 3 N 4 Precipitating, stirring for 10min, centrifuging, washing, and drying at 50 deg.C to obtain Cu 2 O/g-C 3 N 4 。
S2, adding 1.5 parts of Cu 2 O/g-C 3 N 4 6 parts of ammonium persulfate and 18 parts of water are mixed and ultrasonically dispersed for 35min to obtain dispersion liquid, wherein the ultrasonic power is 600W, and the frequency is 40kHz.
S3, adding 18 parts of silane coupling agent KH792 and 36 parts of N, N-dimethylethanolamine into a three-neck flask, reacting for 14min at 90 ℃ under the stirring condition of 200rpm, then adding 15 parts of dispersion liquid, 10 parts of acetone, 15 parts of vinyl-terminated silicone oil and 10 parts of water, keeping the temperature of 90 ℃ and the stirring condition of 200rpm, reacting for 4.5h, naturally cooling to room temperature, adjusting the pH to be 6.5 with ascorbic acid, filtering, washing and drying to obtain the Cu grafted with organosilicon quaternary ammonium salt 2 O/g-C 3 N 4 An antistatic antimicrobial agent.
S4, grafting 1 part of organosilicon quaternary ammonium salt to Cu 2 O/g-C 3 N 4 And mixing the antistatic antibacterial agent and 20 parts of water, and performing ultrasonic treatment for 30min, wherein the ultrasonic power is 600W, and the frequency is 40kHz, so as to obtain the antibacterial antistatic finishing agent.
The chelating agent is cetyl trimethyl ammonium bromide and ethylene diamine tetraacetic acid according to the mass ratio of 10:1.5 mixing.
Comparative example
The standard sample is a double-sided circular weft knitting machine (Huaxing mechanical Co., ltd., zhoushan, model HX 211), and pure cotton yarns and bamboo charcoal fiber/Modal fiber blended yarns are blended according to the mass ratio of 70:30 are interwoven into 1+1 thread structure inner layer fabric; pure cotton yarn and carbon nanotube fiber/polyacrylonitrile fiber blended yarn are mixed according to the mass ratio of 40:15 are interwoven into an outer fabric with a threaded structure of 1+ 1. Coating 8g of polyvinyl acetate adhesive on each square meter of inner layer fabric, and bonding the inner layer fabric and the outer layer fabric to obtain a standard sample, wherein the gram weight of the standard sample is 261g/m 2 。
The linear density of the bamboo charcoal fiber/Modal fiber blended yarn is 20tex, and the mass ratio of the bamboo charcoal fiber to the Modal fiber is 13:87;
the carbon linear density of the carbon nano tube fiber/polyacrylonitrile fiber blended yarn is 15.4tex, and the mass ratio of the carbon nano tube to the polyacrylonitrile fiber is 7:93.
test example 1
Reference is made to GB/T12703.1-2008 evaluation of electrostatic properties of textiles section 1: electrostatic voltage half-life, evaluation of electrostatic properties of textiles section 2 of GB/T12703.2-2009: charge areal density the antistatic and antibacterial fabrics of the examples were subjected to antistatic tests as shown in table 1 using an LC K-305 fabric surface resistance tester and a faraday roller.
Table 1: antistatic performance test of antistatic and antibacterial fabric
| Resistivity of 10 6 Ω | Static voltage/V | Half life/s | |
| Standard sample | 3.14 | 282 | 1.19 |
| Example 1 | 0.24 | 194 | 0.81 |
| Example 2 | 2.48 | 256 | 1.08 |
| Example 3 | 0.86 | 217 | 0.95 |
| Example 4 | 0.74 | 209 | 0.92 |
| Example 5 | 0.29 | 198 | 0.83 |
| Example 6 | 0.28 | 197 | 0.82 |
| Example 7 | 0.29 | 199 | 0.83 |
As can be seen from the results in Table 1, the composite fabric has lower resistance without being soaked in the finishing liquid. The antistatic ability of the treated finishing liquid is greatly improved. This is because the prepared finishing liquid is Cu grafted by organosilicon quaternary ammonium salt 2 O/g-C 3 N 4 Antistatic antimicrobial agent of quaternary ammonium salt positive charge N + The fabric is positioned at the outer side and can generate positive ions, most of fiber products are electronegative, and quaternary ammonium salt nitrogen positive ions are neutralized with surface charges of electronegative textiles, so that the antistatic property of the textiles is improved; from example 2 and example 3It is seen that the grafted quaternary silicone ammonium salt, however, cu, is the primary antistatic effect 2 O/g-C 3 N 4 Also has a certain antistatic effect due to the hollow core-shell structure of cuprous oxide and g-C 3 N 4 Forming a mott schottky junction, enhancing its electrical conductivity. Example 4 shows that Cu is simply added 2 O/g-C 3 N 4 The performance of the antibacterial antistatic finishing agent prepared by mixing with the organosilicon quaternary ammonium salt is similar to that of the organosilicon quaternary ammonium salt used alone because the organosilicon quaternary ammonium salt is not similar to Cu 2 O/g-C 3 N 4 Grafting, the organosilicon quaternary ammonium salt is difficult to absorb the electron enriched by cuprous oxide, and the electron is rapidly led out. Meanwhile, the surface of the textile is hydrophilic after being finished by the organic silicon quaternary ammonium salt, so that the textile is endowed with soft hand feeling, and after being subjected to friction, the surface charges of the textile are greatly reduced, so that static electricity can be eliminated, and an antistatic effect is achieved. Examples 5 and 6, which use ethylenediaminetetraacetic acid and ethylenediaminetetraacetic acid as chelating agents for copper ions, respectively, alone, exhibited slightly less conductivity than the chelating agents formulated with cetyltrimethylammonium bromide and ethylenediaminetetraacetic acid, since ethylenediaminetetraacetic acid was easily anchored at g-C, compared to cetyltrimethylammonium bromide 3 N 4 Above, cuprous oxide is in g-C 3 N 4 The surface is nucleated and crystallized, and the hexadecyl trimethyl ammonium bromide has a long chain structure, so that the distance between copper ions can be increased, and a unique core-shell structure is formed when cuprous oxide is crystallized. High-performance cuprous oxide with a core-shell structure cannot be obtained by singly using the ethylenediamine tetraacetic acid, and the cuprous oxide load rate is not high by singly using the ethylenediamine tetraacetic acid. Two chelating agents are compounded, so that the core-shell structure of the cuprous oxide is maintained, and the g-C content of the cuprous oxide is improved 3 N 4 The amount of surface loading. The cuprous oxide core-shell structure prepared by using hexadecyl trimethyl ammonium bromide as a chelating agent is more complete, and a potential difference can be formed between the core and the shell to enrich more electrons. Example 7 No addition of glucose reducing agent during grafting of Quaternary ammonium Silicone salt, resulting in the Oxidation of cuprous oxide to cupric oxide, which is rich in cupric oxide as compared to cuprous oxideThe ability to collect electrons is weak. In addition, silicon in the organosilicon quaternary ammonium salt can form a silicon-oxygen covalent bond with hydroxyl on the surface of the fabric, so that the firmness is greatly increased.
Test example 2
Reference is made to GB/T20944.3-2008 < evaluation of antibacterial properties of textiles section 3: the antistatic and antibacterial fabrics in the examples were subjected to antibacterial tests using Escherichia coli (ATCC 11229) and Staphylococcus aureus (ATCC 6538) according to the shaking method, and the test results are shown in table 2.
Table 2: antibacterial performance test of antistatic antibacterial fabric
The results in table 2 show that the composite fabric before being treated with the finishing liquid has certain antibacterial performance, and the antibacterial performance of the composite fabric is comparable to that of other similar products. After the finishing liquid is used for treatment, the antibacterial property of the fabric is greatly improved due to the g-C adopted by people 3 N 4 Is visible light-responsive photocatalyst, can be sterilized by photocatalysis under room light, and is prepared by sterilizing in Cu 2 O-loaded to form Cu 2 O/g-C 3 N 4 And then, a Mott Schottky junction is formed, and the photocatalytic sterilization performance of the material is further improved. In addition, cuprous ions released by cuprous oxide have a strong sterilization effect, and positive charges of the organosilicon quaternary ammonium salt can be adsorbed to the outer side of cells of electronegative bacteria through electrostatic adsorption, so that cell membranes are broken, and cell death is caused. As can be seen from examples 2, 3 and 4, the main sterilization effect is Cu 2 O/g-C 3 N 4 However, cu 2 O/g-C 3 N 4 With organosilicon quaternary ammonium salts, without grafting, the properties cannot be optimized by acting alone, since quaternary ammonium saltsCapable of generating positive ions, quaternary ammonium salts and Cu 2 O/g-C 3 N 4 After grafting, photo-generated electrons enriched by cuprous oxide can be quickly consumed, the recombination efficiency of electron holes is reduced, and the photocatalytic sterilization performance is improved. The sterilization effects of the examples 5 and 6 are reduced, and the reason is that the cuprous oxide hollow core-shell structure prepared by singly adopting ethylene diamine tetraacetic acid or hexadecyl trimethyl ammonium bromide as the chelating agent of the copper ions is slightly poor or the cuprous oxide loading rate is low, so that the photocatalytic sterilization performance of the cuprous oxide hollow core-shell structure is influenced. Example 7 cuprous oxide was oxidized to cupric oxide due to no addition of reducing agent, which sum g-C 3 N 4 No Mort Schottky junction is formed between the two parts, so that the photocatalytic sterilization performance of the copper is influenced, and the sterilization effect of the cupric ions released by the cupric oxide is slightly inferior to that of the cuprous ions.
Claims (9)
1. The preparation method of the antibacterial and antistatic finishing agent is characterized by comprising the following steps:
s1, mixing g-C 3 N 4 、CuSO 4 ·5H 2 Mixing O, chelating agent and water, adding ascorbic acid, and adding NaOH to obtain Cu 2 O/g-C 3 N 4 ；
S2, mixing Cu 2 O/g-C 3 N 4 Mixing and reacting an initiator, water, a coupling agent, a quaternary ammonium organic matter, glucose, a diluent, vinyl-terminated silicone oil and water to obtain the organosilicon quaternary ammonium grafted Cu 2 O/g-C 3 N 4 An antistatic antimicrobial agent;
s3, grafting organic silicon quaternary ammonium salt to Cu 2 O/g-C 3 N 4 And mixing the antistatic antibacterial agent and water, and performing ultrasonic treatment to obtain the finishing agent.
2. The method for preparing the antibacterial antistatic finishing agent as claimed in claim 1, characterized by comprising the following steps:
s1, according to the mass portion, 0.2 to 2 portions of g-C 3 N 4 0.2 to 0.8 portion of CuSO 4 ·5H 2 O, 3.64 to 4.96 portions of chelating agent and 100 portions of water are mixed at the rotating speed of 60 to 100r/min and the rotating speed of 60 to 100r/minStirring in a constant temperature water bath, then adding 0.12-0.2 part of ascorbic acid, reacting at the constant temperature of 60 ℃ for 15-30 min at the rotating speed of 60-100 r/min, then dropwise adding 8-12 parts of 0.2M NaOH aqueous solution, wherein the dropwise adding speed is 6-10 s/g, and generating Cu 2 O/g-C 3 N 4 Precipitating, continuously stirring for 8-12 min, centrifuging to obtain precipitate, washing, and drying at 40-60 ℃ to obtain Cu 2 O/g-C 3 N 4 ；
S2, adding 0.5-2 parts of Cu 2 O/g-C 3 N 4 5-10 parts of initiator and 10-20 parts of water, and ultrasonically dispersing for 30-40 min at room temperature to obtain dispersion liquid, wherein the ultrasonic power is 400-800W, and the frequency is 30-60 kHz;
s3, adding 10-20 parts of coupling agent and 20-40 parts of quaternary ammonium organic matter into a three-neck flask, reacting at 89-91 ℃ for 12-14 min under the stirring condition of 200-400rpm, then adding 10-20 parts of dispersion prepared in the step S2, 1-3 parts of glucose, 10-20 parts of diluent, 20-30 parts of vinyl-terminated silicone oil and 5-10 parts of water, keeping the temperature at 89-91 ℃, continuously stirring and reacting for 4-5 h, naturally cooling to room temperature, adjusting the pH = 5-7 with ascorbic acid, filtering, taking precipitate, washing and drying to obtain the Cu grafted with the organic silicon quaternary ammonium salt 2 O/g-C 3 N 4 An antistatic antimicrobial agent;
s4, grafting 1-10 parts of organosilicon quaternary ammonium salt to Cu 2 O/g-C 3 N 4 Mixing the antistatic antibacterial agent and 100 parts of water, and performing ultrasonic treatment for 30-40 min, wherein the ultrasonic power is 400-800W, and the frequency is 30-60 kHz, so as to obtain the antibacterial antistatic finishing agent.
3. The method for preparing an antibacterial and antistatic finishing agent as claimed in claim 1 or 2, characterized in that the chelating agent is one or a mixture of two or more of cetyl trimethyl ammonium bromide, ethylene diamine tetraacetic acid and sodium stearate.
4. The method for preparing an antibacterial and antistatic finishing agent according to claim 1 or 2, wherein the quaternary ammonium organic substance is one or a mixture of two or more of tetrabutylammonium hydrogen sulfate, hexadecyldimethylbenzylammonium, dimethyldiallylammonium chloride and N, N-dimethylethanolamine.
5. The method for preparing an antibacterial and antistatic finishing agent according to claim 1 or 2, characterized in that the initiator is one or a mixture of two or more of benzoyl peroxide, lauroyl peroxide, potassium persulfate and ammonium persulfate.
6. The method for preparing the antibacterial and antistatic finishing agent as claimed in claim 1 or 2, characterized in that the coupling agent is one of silane coupling agents and phthalate coupling agents.
7. An antibacterial and antistatic finishing agent, which is characterized by being prepared by the preparation method of the antibacterial and antistatic finishing agent as claimed in any one of claims 1 to 6.
8. The preparation method of the antistatic and antibacterial fabric is characterized by comprising the following steps of:
(1) Interweaving pure cotton yarns and bamboo charcoal fiber/Modal fiber blended yarns into inner-layer fabric; interweaving pure cotton yarns and carbon nanotube fiber/polyacrylonitrile fiber blended yarns into outer-layer fabrics; bonding the fabric through an adhesive to obtain an untreated fabric;
(2) Carrying out strong alkali washing, strong acid washing and weak alkali washing on the untreated fabric to obtain a pretreated fabric;
(3) And (3) immersing the pretreated fabric into the antibacterial and antistatic finishing agent according to claim 7 for treatment, and drying to obtain the antistatic and antibacterial fabric.
9. An antistatic and antibacterial fabric, characterized by being prepared by the method for preparing the antistatic and antibacterial fabric according to claim 8.
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