CN107964785B - Antibacterial silk product loaded with nanometer copper and preparation method thereof - Google Patents

Abstract

The invention discloses a antibacterial silk product loaded with nanometer copper and a preparation method thereof, which comprises the following steps: the silk product is immersed in a buffer solution containing Monascus, then added with a copper hydrochloric acid solution, subjected to ultraviolet reduction treatment after soaking, and finally cleaned, The antibacterial silk product loaded with nanometer copper is obtained by drying; while the invention can improve the broad-spectrum antibacterial performance of the silk fiber and its fabric, it can avoid harm to the human body and pollution to the environment. The preparation method of the invention is simple and easy to produce in batches, and the obtained antibacterial silk fiber product has excellent antibacterial property and long-lasting antibacterial performance.

Description

Antibacterial silk product loaded with nanometer copper and preparation method thereof

technical field

The invention relates to an antibacterial natural polymer fiber, in particular to an antibacterial silk product loaded with nanometer copper and a preparation method thereof.

Background technique

At present, domestic and foreign textile antibacterial treatment technologies can be roughly divided into two types: Prepare antibacterial fibers first, and then make various antibacterial fabrics; Fabrics are post-treated with various antimicrobial agents to obtain antimicrobial properties. In comparison, the fabric obtained by the first method has a long-lasting antibacterial effect and good washability, but it has high technical content, great difficulty, and a wide range of fields. The production process of antibacterial fibers is relatively complicated, and the requirements for antibacterial agents are high. And the processing process of the second method is relatively simple, but there are many three wastes in production, and its washability and antibacterial effect persistence are relatively poor. However, because the second method is easy to process and has a wide range of antibacterial agents to choose from. Textiles, whether they are raw fibers, yarns, fabrics, or even garments, can obtain antibacterial effects through post-finishing methods. Therefore, among all kinds of antibacterial fabrics currently on the market, most of them are post-finishing.

In the prior art, the methods of post-finishing processing include:

Use reactive resin to thermally fix the antibacterial agent on the surface of the fiber, such as diphenyl ether antibacterial and deodorant finishing agents such as Nonstack of Nippon Bobo and Sanityze of Gunji. It itself has no affinity for cellulose and needs to be combined with 2D resin or cyanaldehyde resin to improve its durability. Its deodorant and antibacterial mechanism is to inhibit the function of microbial cell membranes and cell walls.

The antibacterial agent is adsorbed and fixed on the surface of the fiber. Representative goods such as Odoyte of inner and outer cotton.

The antibacterial agent is immobilized by the demethanolization reaction of the trimethoxy group of the organosilicon quaternary ammonium salt and the hydroxyl group on the surface of the fiber. In this method, since the antibacterial agent is completely fixed, the antibacterial effect depends on the contact state between the active part of the antibacterial agent and the bacterial cell surface. Such as Viosil of Japan's Toyobo, Cransil of Cangfang, DC5700 of Dow Corning Corporation of the United States, etc.

Antibacterial finishing of silk by nano-silver finishing, silver-loaded zinc nano- _SiO2 finishing, chitosan finishing, etc.

Generally, the antibacterial agents used in post-textile finishing mainly include quaternary ammonium salts, organosilicon quaternary ammonium salts, chitin, chitosan, inorganic salts and natural product extracts, etc., but most of the antibacterial agents currently on the market have antibacterial Poor broad spectrum, poor washing resistance, unreliable safety and other problems. Although silver has a strong and broad antibacterial effect in antibacterial fabric finishing agents, in 2014, the US Natural Resources Defense Council (NRDC) announced restrictions on the use of nano silver in textiles. This is because people have gradually discovered that silver is not as safe as people think. On the one hand, silver ions or nano-silver enter the human body through the skin, and silver compounds are basically insoluble except silver nitrate, so it will cause the accumulation of heavy metals in the body, which will damage health in the long run.

At present, there are two main antibacterial modification methods of nano-silver: one is to synthesize nano-silver first, and then modify it on the surface of silk material; the other is to directly synthesize nano-silver in situ on the surface of silk material. However, the common problem of these two methods is that nano-silver only adheres to the surface of the silk material, its adhesion is low, and its bonding fastness is poor, which cannot meet the requirements of practical applications, so further application and promotion are greatly limited.

Contents of the invention

The purpose of the present invention is to disclose a simple and convenient method for preparing antibacterial natural silk products, endow natural polymer fibers with antibacterial functions, overcome the deficiencies in the prior art, provide an antibacterial fiber loaded with nano-copper and its preparation method, and expand its application field; in the antibacterial natural silk fiber of the present invention, copper compounds are all soluble, and the copper that enters the human body can also be excreted from the body along with metabolism. The third life element, and the human body does not need silver element, so the antibacterial natural silk fiber of the present invention overcomes the problems and defects of the existing silver preparation antibacterial fiber.

To achieve the above object, the technical solution of the present invention is,

A method for preparing antibacterial silk products loaded with nano-copper, comprising the following steps: the silk products are immersed in a buffer solution containing Monascus, then copper hydrochloric acid solution is added, after soaking, ultraviolet lamp irradiation reduction treatment is carried out, and finally the loaded silk products are obtained by washing and drying. Nano copper antibacterial silk products.

In the above technical scheme, the copper salt is one or more of copper nitrate, copper sulfate, copper acetate; the acid in the copper hydrochloric acid solution is sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid One; in the copper hydrochloric acid solution, the mass concentration of copper salt is 3%-20%.

In the above technical scheme, in the buffer solution containing Monascus, the mass concentration of Monascus is 0.5%-0.8%; the buffer is a phosphate buffer.

In the above technical solution, the soaking time is 20-30 minutes and the temperature is 10°C-15°C; the soaking time is 0.5-12 hours and the temperature is 0°C-5°C.

In the above technical scheme, the silk is one or more of mulberry silk, tussah silk, celestial silk, castor silk, and regenerated silk; the silk product is silk fiber, degummed or undegummed cocoon silk, raw silk, twisted silk One or more of filaments, braided threads, knitted fabrics, woven fabrics, non-woven fabrics, and braided fabrics.

In the above technical solution, preferably, when the ultraviolet lamp is irradiated for reduction treatment, the power is 1-100W, preferably the power of the ultraviolet lamp is 10-50W.

The present invention also discloses a nano-copper-loaded antibacterial silk product prepared according to the preparation method of the nano-copper-loaded antibacterial silk product; the nano-copper particles are adsorbed on the surface and inside of silk fibers; The mass content is 5%-20%; the particle size of the nano-copper is 1-200nm.

The invention also discloses the application of the antibacterial silk product loaded with nanometer copper in the preparation of antibacterial products.

The invention also discloses a preparation method of an antibacterial composite cotton thread, which comprises the following steps: immersing the degummed silk in a buffer solution containing Monascus, then adding copper hydrochloric acid solution, performing reduction treatment by ultraviolet lamp irradiation after soaking, and finally washing and drying The antibacterial silk loaded with nanometer copper is obtained; then the antibacterial composite cotton thread loaded with nanometer copper and clean cotton thread is blended to prepare antibacterial composite cotton thread, which can be used for wound hemostasis, etc. In general antibacterial composite cotton thread, the mass fraction of cotton thread is 75%-80%, and the blending method for existing technology.

The degummed silk is obtained by degumming and removing impurities. The obtained degummed silk is immersed in a buffer solution containing Monascus, and then soaked in a copper hydrochloric acid solution to promote the uniform penetration and adsorption of copper ions to the inside and outside of the silk, and then reduce the copper ions in situ to generate nano copper, and finally wash and dry the reacted silk to obtain antibacterial silk products loaded with nanometer copper.

In the preferred technical solution, the copper salt is copper nitrate with a mass concentration of 5%-20%; the acid in the copper hydrochloric acid solution is formic acid with a mass concentration of 90%-98%; Ultraviolet light irradiation is used as reduction treatment; under this optimal condition, not only the preparation time is shorter, but also the obtained silk fiber has excellent antibacterial properties.

According to the technical solution of the present invention, firstly, the pure silk fibroin fiber is obtained through the process of degumming and impurity removal, so that the fiber meets the application requirements of subsequent textile and clothing, medical and sanitary applications; secondly, the monascus is adsorbed on the surface of the silk fiber and has a certain penetration Then, use an acidic solution to swell the silk, open the ion permeation channels inside and outside the silk, and promote the uniform penetration and fixation of copper ions and Monascus into the inside of the silk; secondly, use ultraviolet light to reduce the copper ions inside and outside the fiber in situ. Nano-copper, to obtain silk fibroin fibers with uniformly dispersed nano-copper inside and outside, and ultraviolet reduction can achieve the effect of avoiding chemical reagent residues; finally, the loaded nano-copper fibers are eluted to remove ions and organic solvents, and then dried to obtain loaded nano-copper Antibacterial silk products. The present invention combines the fluffy and porous structure of silk itself, and at the same time utilizes the swelling effect of acidic solvents to effectively open the ion permeation channels inside and outside the fiber, introduce metal copper ions into the fiber, and then directly reduce the copper ions in situ to nanometer through ultraviolet reduction. Copper, to achieve uniform dispersion and fixation of nano-copper, so as to obtain permanent antibacterial and water washing resistance. Compared with this, the existing technology only fixes nano-copper on the surface of the fiber, which has the problems of low loading rate, low fixation strength, and uneven dispersion. In particular, the characteristics of nano-copper itself are different from nano-silver and zinc, so it is difficult to It is better attached to the surface of the fiber, and it is more difficult to penetrate and be enriched inside the fiber. In the present invention, the silk is first treated with Monascus and then soaked in acid solution. In the presence of Monascus, the copper salt penetrates into the fiber better and Colonization after restoration.

Due to the use of the above-mentioned technical solutions, the present invention has the following advantages compared with the prior art:

(1) The present invention uses an acidic solvent to directly swell the natural fiber effectively, which fully opens the ion permeation channels inside and outside the fiber, and realizes the effective penetration and uniform dispersion of the copper ion of the nano-copper precursor into the interior of the natural fiber; solves the problem that the existing technology cannot Technical challenges in introducing metal ions into natural fibers.

(2) On the basis of uniformly dispersing metal copper ions inside and outside the natural fiber, in the presence of Monascus, the present invention realizes in-situ reduction of metal ions to generate nano-copper through ultraviolet light reduction, which not only keeps the generated nano-copper in good condition At the same time, most of the nano-copper is fixed inside the silk, and the function is long-lasting, which solves the problem of poor bonding fastness between functional molecules and fiber products.

(3) The diameter of the nano-copper particles prepared by the present invention is between 10 and 100 nm, the particle size is small, the size is uniform, and the antibacterial performance is excellent, especially the binding force between the nano-copper ions and the silk material is strong. , in-situ reduction to nano-copper, effectively avoiding the agglomeration of nano-silver, and achieving good dispersion of nano-copper.

(4) The method of the present invention has wide applicability, and is suitable for existing silk products such as degummed and undegummed cocoon silk, raw silk, twisted silk, braided thread, knitted fabric, woven fabric, nonwoven fabric, braided fabric; The prepared nano-copper antibacterial material, the nano-copper is uniformly dispersed inside and outside the material, such as inside and on the surface of the fiber, so it has durable or permanent antibacterial properties.

(5) The method of the present invention is simple, the process flow is short, and it is easy to mass-produce; especially, the treated antibacterial copper particles penetrate deep into the fiber without affecting the mechanical properties of the fiber, avoiding the influence of the prior art on the mechanical properties of silk, and solving the problem of The technical problem of the reverse ratio between antibacterial property and mechanical properties in the prior art is solved.

Description of drawings

Fig. 1 is the scanning electron micrograph of embodiment one untreated mulberry silk fiber (degummed silk);

Fig. 2 is a scanning electron micrograph of the antibacterially treated mulberry silk fiber (degummed silk) in Example 1.

Detailed ways

The present invention will be further described below in conjunction with accompanying drawing and embodiment:

Embodiment one

Configure an aqueous solution of 90% formic acid by mass fraction, then add copper nitrate to the formic acid solution, and stir for 5 minutes in the dark to dissolve, and configure a copper nitrate formic acid solution with a mass concentration of 5%; immerse the natural degummed mulberry silk in red yeast rice with a mass concentration of 0.5% In the fungal phosphate buffer solution, add the above-mentioned copper nitrate formic acid solution after 20 minutes at 15°C, and keep it in the dark for 1h at a temperature of 4°C; irradiate the soaked silk with a UV lamp at a power of 10W for 12h; fully water the obtained silk After washing and natural drying, the antibacterial mulberry silk fiber product is obtained; after testing, the nano-copper content in the fiber is about 8wt%; X-ray diffraction test is carried out, and the X-ray diffraction angle 2θ is 43.53°, 50.24°, 74.91°, 89.88°, These characteristic diffraction angles are consistent with the peak value of the copper standard reference card No. 01-085-1326, so it is determined that a large amount of nano-copper exists inside the silk. The transmission electron microscope test also shows that there is uniform nano-copper dispersion in the fiber section; the silk is stretched before treatment. The strength is 420MPa, and after treatment it is 408Mpa, reaching more than 97% of that before treatment.

As shown in Figure 1, it is a scanning electron microscope image of untreated degummed silk. It can be seen from the figure that the surface of the silk fiber is smooth; Figure 2 is a scanning electron microscope image of the surface of degummed mulberry silk treated with antibacterial. In the figure, it can be seen that there are nano-copper with a diameter of about 50 nm on the surface of the silk , and the transmission electron microscope test also observed that there is uniform nano-copper dispersion on the fiber section; the X-ray diffraction test pattern shows characteristic diffraction peaks of nano-copper at 43.53°, 50.24°, 74.91°, and 89.88°. It shows that the method of the present invention successfully loads copper particles on the silk fiber, and most of the copper particles are inside the fiber and are not easy to be lost, as can be seen from the antibacterial performance after washing.

Embodiment two

Configure a mass fraction of 98% formic acid aqueous solution, then add copper sulfate pentahydrate to the formic acid solution, and magnetically stir in the dark for 15 minutes to dissolve, configure a copper sulfate formic acid solution with a mass concentration of 10%; immerse the natural degummed mulberry silk fiber with a mass concentration of 0.8% In the Monascus phosphate buffer solution of Monascus, add the above-mentioned copper sulfate formic acid solution after 30 minutes at 15°C, and keep it in the dark for 5h, at a temperature of 2°C; irradiate the soaked silk with a UV lamp, with a power of 30W, for 8h; The degummed mulberry silk is fully washed with water, and after natural drying, the antibacterial degummed mulberry silk is obtained; after testing, the nano-copper content in the fiber is about 12wt%; mechanical property tests show that the tensile strength reaches more than 95% of that before treatment.

The antibacterial test adopts the antibacterial fabric test method in the Textile Industry Standard of the People's Republic of China - Antibacterial Knitted Fabrics (FZ/T 73023-2006): Oscillating Flask Method.

Antibacterial effect test is carried out to embodiment one, embodiment two gained antibacterial silk fibers, test the antibacterial performance of the silk fiber without antibacterial treatment simultaneously, the results are shown in Table 1, the results show that degumming after antibacterial treatment and non-degumming mulberry silk all show Excellent antibacterial performance, after 50 times of standard washing, antibacterial silk still retains more than 86% of the antibacterial effect, indicating high antibacterial fastness.

Table 1 Antibacterial properties of mulberry silk fiber before and after treatment

Embodiment three

Configure mass fraction 80% trifluoroacetic acid ethanol solution, then add copper fluoride to the solution, avoid light and magnetically stir for 30min to dissolve, configure copper fluoride trifluoroacetic acid solution with mass concentration of 10%; immerse degummed natural tussah silk in mass concentration In the 0.6% Monascus phosphate buffer solution, add the above-mentioned copper fluoride trifluoroacetic acid solution at 10°C for 20 minutes, and keep it in the dark for 2 hours at a temperature of 1°C; irradiate the soaked silk with a UV lamp with a power of 50W , irradiated for 10 hours; the obtained degummed natural tussah silk was fully washed and dried naturally to obtain the antibacterial tussah silk fiber. After testing, the nano-copper content in the fiber is about 13wt%; X-ray diffraction test shows that a large amount of nano-copper exists inside the silk, and the X-ray diffraction test pattern shows the Nano-copper characteristic diffraction peak, transmission electron microscope test also observed uniform nano-copper dispersion on the fiber section; tensile strength reached more than 94% before treatment; Escherichia coli inhibition rate reached 99.3%, Bacillus subtilis inhibition rate reached 97.3%, golden grape The cocci inhibition rate reaches 97.4%. After 50 times of standard washing, the antibacterial silk still retains more than 85% of the antibacterial effect, which shows that the antibacterial fastness is high.

Embodiment four

Configure a mass fraction of 50% phosphoric acid methanol solution, then add copper nitrate to the solution, and magnetically stir in the dark for 5 minutes to dissolve, and configure a copper nitrate phosphoric acid solution with a mass concentration of 15%; the natural mulberry silk woven fabric is immersed in 0.6% red Aspergillus phosphate buffer solution, after 20 minutes at 10°C, add the above-mentioned copper nitrate phosphoric acid solution, and keep it in the dark for 5 hours at a temperature of 5°C; irradiate the soaked silk with a UV lamp at a power of 30W for 10 hours; the resulting silk fabric After fully washing and drying naturally, the antibacterial mulberry silk fabric is obtained; the nano-copper content in the fiber fabric is about 10wt% after testing; the inhibition rate of Escherichia coli reaches 98.2%, the inhibition rate of Bacillus subtilis reaches 97.2%, and the inhibition rate of Staphylococcus aureus reaches 97.9% , After 50 times of standard washing, the antibacterial silk still retains more than 83% of the antibacterial effect, indicating that the antibacterial fastness is high.

Embodiment five

Configure mass fraction 50% formic acid aqueous solution, then add copper chloride to the formic acid solution, avoid light and magnetically stir for 10 minutes to dissolve, configure the copper chloride formic acid solution with a mass concentration of 10%; immerse the natural castor silk raw silk with a mass concentration of 0.6% In the Monascus phosphate buffer solution, add the above-mentioned copper chloride formic acid solution after 20 minutes at 15°C, and let it stand in the dark for 12h, at a temperature of 3°C; irradiate the soaked silk with a UV lamp, with a power of 20W, for 8h; The obtained raw silk is fully washed and naturally dried to obtain antibacterial castor silkworm raw silk products; after testing, the nano-copper content in the fiber is about 10wt%; the tensile strength reaches more than 93% of that before treatment; the inhibition rate of Escherichia coli reaches 97.3%, and the bacteria The inhibition rate reaches 96.4%, and the inhibition rate of Staphylococcus aureus reaches 95.3%. After 50 times of standard washing, the antibacterial silk still retains more than 80% of the antibacterial effect, which shows that the antibacterial fastness is high.

Embodiment six

Configure a 30% sulfuric acid aqueous solution by mass fraction, then add copper nitrate to the solution, and stir for 20 minutes in the dark to dissolve, and configure a copper nitrate sulfuric acid solution with a mass concentration of 10%; immerse the natural mulberry silk braided wire into red yeast rice with a mass concentration of 0.6% In the mold phosphate buffer solution, after 25 minutes at 15°C, add the above-mentioned copper fluoride trifluoroacetic acid solution, and keep it in the dark for 10 hours at a temperature of 4°C; irradiate the soaked silk with a UV lamp at a power of 50W for 10 hours; The silk braided thread is fully washed and dried in vacuum to obtain the antibacterial mulberry silk braided thread; after testing, the nano-copper content in the fiber braided thread is about 8wt%; the inhibition rate of E. The inhibition rate reaches 99.1%. After 50 times of standard washing, the antibacterial silk still retains more than 90% of the antibacterial effect, which shows that the antibacterial fastness is high.

Embodiment seven

Configure an aqueous solution of 90% formic acid by mass fraction, then add copper nitrate to the formic acid solution, and stir for 5 minutes in the dark to dissolve, and configure a copper nitrate formic acid solution with a mass concentration of 5%; immerse the natural degummed mulberry silk in red yeast rice with a mass concentration of 0.5% In the fungal phosphate buffer solution, add the above-mentioned copper nitrate formic acid solution after 20 minutes at 15°C, and keep it in the dark for 1h at a temperature of 4°C; irradiate the soaked silk with a UV lamp at a power of 10W for 12h; fully water the obtained silk After washing and drying naturally, the antibacterial mulberry silk fiber is obtained; the antibacterial composite cotton thread is obtained by blending the antibacterial mulberry silk fiber with the cotton thread after ultraviolet disinfection, in which the mass fraction of the cotton thread is 80%, which is used in the animal wound hemostasis experiment, and the coagulation speed is increased by 30% , The use time is 40% longer than the existing gauze, and there is no sign of infection.

Comparative example one

Configure an aqueous solution of formic acid with a mass fraction of 98%, then add copper sulfate pentahydrate to the formic acid solution, stir for 15 minutes in the dark to dissolve, and configure a copper sulfate formic acid solution with a mass concentration of 10%; immerse the natural degummed mulberry silk fiber in the phosphate buffer After 30 minutes at 10°C, add the above-mentioned copper sulfate formic acid solution, and keep it in the dark for 5 hours at a temperature of 4°C; irradiate the soaked silk with a UV lamp at a power of 50W for 10 hours; wash the obtained degummed mulberry silk with water, and dry it naturally Afterwards, the antibacterial degummed mulberry silk was obtained; the mechanical property test showed that the tensile strength reached 82% of that before treatment, and the nano-copper content in the fiber was detected to be about 0.1wt%; the inhibition rate of Escherichia coli was 45.1%, and the inhibition rate of subtilis reached 32.5% , the inhibition rate of Staphylococcus aureus reached 25.4%, and after 50 times of standard washing, the antibacterial silk had almost no antibacterial effect.

Comparative example two

Configure a mass fraction of 98% formic acid aqueous solution, then add copper sulfate pentahydrate to the formic acid solution, avoid light and magnetically stir for 15 minutes to dissolve, configure a copper sulfate formic acid solution with a mass concentration of 20%; immerse the natural degummed mulberry silk fiber with a mass concentration of 1.2% In the Monascus phosphate buffer solution, add the above-mentioned copper sulfate formic acid solution after 30 minutes at 15°C, and let it stand in the dark for 5 hours, at a temperature of 2°C; irradiate the soaked silk with a UV lamp, with a power of 50W, for 10h; The degummed mulberry silk was fully washed with water, and after natural drying, the antibacterial degummed mulberry silk was obtained; the mechanical properties test showed that the tensile strength reached 60% of that before treatment, and the nano-copper content in the fiber was about 1.6wt% after testing; the inhibition rate of Escherichia coli reached 62.2 %, the inhibition rate of Bacteria subtilis reached 57.1%, and the inhibition rate of Staphylococcus aureus reached 43.6%. After 50 times of standard washing, the antibacterial silk retained 8% of the antibacterial effect.

Claims (3)

1. A preparation method for loading nano-copper antibacterial silk products is characterized in that, comprising the following steps, the silk products are immersed in the buffer solution containing Monascus, then copper hydrochloric acid solution is added, after soaking, ultraviolet lamp irradiation reduction treatment is carried out, and finally After cleaning and drying, nano-copper antibacterial silk products are obtained; the copper salt is one or more of copper nitrate, copper sulfate, and copper acetate; the acid in the copper hydrochloric acid solution is sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, One of acetic acid and trifluoroacetic acid; in the copper hydrochloric acid solution, the mass concentration of copper salt is 3%-20%; in the buffer solution containing Monascus, the mass concentration of Monascus is 0.5%- 0.8%; the buffer is phosphate buffer; the soaking time is 20-30 minutes, the temperature is 10°C-15°C; the soaking time is 0.5-12 hours, the temperature is 0°C-5°C ; When the ultraviolet lamp is irradiated for reduction treatment, the power is 1-100W. 2. The preparation method of nano-copper-loaded antibacterial silk products according to claim 1, wherein the silk is one or more of mulberry silk, tussah silk, celestial silk, castor silk, and regenerated silk. 3. according to the preparation method of the described antibacterial silk product of loading nanometer copper of claim 1, it is characterized in that, described silk product is silk fiber, degumming or not degumming cocoon silk, raw silk, twisted thread silk, braided thread, knitted fabric, machine One or more of fabrics, nonwovens, and braids.