WO2023279956A1 - Fibroin nano-silver antibacterial color-developing finishing agent, preparation method therefor, and application thereof - Google Patents

Fibroin nano-silver antibacterial color-developing finishing agent, preparation method therefor, and application thereof Download PDF

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WO2023279956A1
WO2023279956A1 PCT/CN2022/100281 CN2022100281W WO2023279956A1 WO 2023279956 A1 WO2023279956 A1 WO 2023279956A1 CN 2022100281 W CN2022100281 W CN 2022100281W WO 2023279956 A1 WO2023279956 A1 WO 2023279956A1
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silk fibroin
silver
antibacterial
nano
silk
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PCT/CN2022/100281
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French (fr)
Chinese (zh)
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李刚
刘静
赵泽宇
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南通纺织丝绸产业技术研究院
苏州大学
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Definitions

  • the invention belongs to the technical field of color-developing finishing agents, and relates to a silk fibroin nano-silver antibacterial color-developing finishing agent and a preparation method and application thereof.
  • Calotropis gigantea fiber is an extremely light natural plant fiber grown from the seed pappus of Calotropis fruit.
  • the fiber not only has an extremely smooth surface, crystal-like luster, and soft feel, Moreover, its super-large hollow cavity structure with a cross-section as high as 80-90% makes it have the same characteristics as kapok fiber, such as strong pressure resistance, strong heat retention, good sound insulation and high hygroscopicity.
  • the woven fabric has the smoothness of silk. Texture, and better air permeability, moisture absorption and warmth than cotton fabric.
  • the fiber also has excellent properties such as antibacterial, anti-moth and anti-mildew, and can be used as a potential thermal insulation material, water and oil absorption material, buoyant material, antibacterial and anti-mite material, etc. It is a textile fiber raw material that needs to be developed urgently.
  • Carlos antibacterial textiles can be obtained through two technical approaches, the method of functional finishing and the method of weaving directly with antibacterial fibers.
  • Most of the antibacterial fabrics directly woven with antibacterial fibers will destroy their natural antibacterial properties during textile processing, especially some high-temperature treatments, such as dyeing and scouring processes. After the textile is processed into a fabric, its antibacterial performance will be greatly reduced, and finally it is far from meeting the requirements of antibacterial fabrics; and the method of functional finishing, although it is easy to operate, can also achieve the purpose of antibacterial, but in the process of functional finishing
  • the added chemical reagents will damage the feel of the fabric, and its antibacterial persistence, stability and safety are poor.
  • the dyeing process is indispensable.
  • Many harmful chemicals are involved in the dyeing process, such as heavy metal salts such as chromium, lead or mercury. , titanium bronze salt dyes, potassium dichromate as mordant oxidizing agent, glutaraldehyde as crosslinking agent, etc., the discharged wastewater is very harmful to the environment and human beings.
  • the purpose of the present invention is to solve the problems in the prior art, and provide a silk fibroin nano-silver antibacterial and color-developing finishing agent and its preparation method and application.
  • the present invention firstly prepares a finishing agent capable of both antibacterial and color development, which can produce 3 colors and has antibacterial properties (using nano-silver to realize anti-bacteria, nano-silver has almost no toxic side effects, and the usage amount of nano-silver is controlled, It can be safely and safely applied in various fields, etc.), and then use it as a finishing agent to pad and finish Carlo silk fiber blended fabrics.
  • the finishing process is a new green and safe color development and antibacterial integrated treatment process.
  • the dyeing process and The combination of antibacterial finishing process reduces the textile processing process, protects the antibacterial properties of Carlo silk fiber itself, and greatly reduces the discharge of printing and dyeing wastewater. It is environmentally friendly and the final Carlo silk fabric is durable and stable. Excellent antibacterial properties, excellent wrinkle resistance and good hand feeling.
  • a preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent after first adding citric acid and ascorbic acid to the silk fibroin solution, adjusting its pH value to 3.6-5.6 , then adding AgNO3 crystals to obtain acidic silk fibroin silver nitrate solution (the reason why the "acidity" is controlled is because in a higher pH value (>8), the carboxyl group of citric acid free in the solution will be deprotonated), then add chitosan, Polyethylene glycol and manganese dioxide are blended to obtain a silk fibroin silver nitrate mixed solution.
  • the silk fibroin silver nitrate mixed solution is placed under a 10-60W LED lamp for 2-120 hours to obtain silk fibroin silver nitrate mixed solution.
  • Su nano silver antibacterial color finishing agent is added to the silk fibroin silver nitrate mixed solution.
  • the present invention uses silk fibroin, citric acid, ascorbic acid, chitosan, polyethylene glycol and manganese dioxide in the process of preparing silk fibroin nano silver antibacterial color-developing finishing agent, wherein:
  • silk fibroin As a natural polymer, silk fibroin has advantages in preparing nano-silver.
  • silk fibroin is a silk protein material, which is naturally pollution-free, safe and superior in performance.
  • it is reflected in the reduction of silk fibroin.
  • silver ions In the process of silver ions, it can act as a reducing agent and a protective agent at the same time (silk fibroin has a natural macromolecular structure, which can fix nano-silver in the framework of silk fibroin macromolecules, and the tyrosine residue has a strong supply Electronic properties, nano-silver will be well protected by silk fibroin molecules), and the impurity content in the prepared nano-silver solution is correspondingly less;
  • chitosan The molecular structure of chitosan is similar to that of cellulose, and it has good similar compatibility with cellulose fabrics. It is connected to cellulose fibers through hydrogen bonds. Its antibacterial properties can also be better combined with cellulose fabrics; although nano-silver has a wide antibacterial spectrum, it can kill infected bacteria and continue to contact and function with other bacteria, but the silver element in the air Instable, easy to oxidize and turn black, so the antibacterial and durability are poor, while chitosan antibacterial agents can destroy the cell membrane of bacteria, and the substances inside the cells leak out due to the destruction of the cell membrane, making the bacterial shape, cell There are obvious changes inside, so as to kill bacteria and achieve antibacterial effect, while the antibacterial performance of chitosan is greatly affected by the pH value of the environment, and has a strong antibacterial effect under acidic conditions, but in practical applications, most In some cases, chitosan is mainly used in neutral and alkaline environments, and its antibacterial effect is weakened.
  • the present invention combines the advantages of chitosan and silver ion antibacterial, and adopts inorganic silver-based antibacterial agent and natural chitosan These two antibacterial agents are compounded and provide acidic conditions (pH value to 3.6-5.6) for chitosan, so its antibacterial properties and stability are more durable;
  • ascorbic acid As an environmentally friendly reducing agent, ascorbic acid is cheap, easy to obtain, and has strong reducibility. It can quickly and thoroughly reduce silver ions in the solution to simple silver and grow, improving the conversion rate of silver ions. At the same time, due to its large solubility in water, it can ensure A small amount of reductant adsorbed on the surface of the gained nano-silver particle after the reaction can be removed by repeated washing, and it is a natural substance, non-toxic, and will not cause any pollution to the environment ; the prior art often adopts NaBH As the reductant of silver ions, On the one hand, the reducing ability of NaBH 4 is too strong, so it is difficult to control its reaction.
  • NaBH 4 is easy to decompose and unstable, it must be stored in alkaline solution. It is beneficial to industrial production.
  • NaBH 4 has certain toxicity, which not only pollutes the environment, but their residues in the product also greatly limit the application of synthesized silver nanoparticles in various fields;
  • Polyethylene glycol is used as a dispersant, and the elemental silver produced by the reaction is in-situ adsorbed and wrapped by the soft template polyethylene glycol, which effectively prevents the mutual combination and agglomeration of the initially formed particles, and utilizes its special crystallinity for silver nanoparticles.
  • the growth rate of different crystal planes can be adjusted by the selective adsorption of different crystal planes, so that the shape and particle size can be controlled, and it can induce and control the growth of particles.
  • polyethylene glycol contains hydroxyl groups, and has strong hydrophilicity and dispersion stability.
  • polyethylene glycol as a non-ionic surfactant, its water solubility, excellent stability, not easily affected by electrolytes, acids and alkalis, can be used as a dispersant through van der Waals Adsorbed on the surface of nano-silver to modify nano-silver and reduce the agglomeration of silver particles
  • polyethylene glycol as a green solvent, does not need to be removed from nano-silver colloid in the subsequent fabric antibacterial finishing process, and it also plays a role in adhesion
  • the role of the agent improves the bonding ability of nano-silver and Carlo silk fabrics; the prior art prepares nano-silver and often adopts PVP (polyvinylpyrrolidone) as a dispersant, but the amount of PVP is not easy to control (it is embodied in the small change of the added amount.
  • PVP polyvinylpyrrolidone
  • citric acid can disperse the solution, prevent precipitation, and ensure the vividness of dyeing.
  • Silk fibroin can also be better restored under acidic conditions.
  • citric acid can be dissolved in water to dissociate citrate ions, which can Form a strong complex with Ag + ions in the solution, thereby affecting the formation and growth of metal particles.
  • the migration of hydrogen atoms in citric acid will activate the electrons of its carboxyl oxygen atoms, and provide Ag( The 111) plane provides additional binding affinity, and the preferential binding of citric acid to Ag(111) can promote crystal growth along the Ag(100) surface, thereby promoting the reduction of silver ions to nanosilver;
  • manganese dioxide can oxidize with nano-silver particles, slow down the reduction of silver ions, and complex with citric acid through metal coordination.
  • Mn 2+ can not only combine with any lemon with -COOH on the surface of nano-silver
  • Acid groups are complexed by metal coordination, oxidizing hydroxy acids to carbonic acids, and can also complex with citrate groups on the surface of adjacent nano-silver. The two are mutually regulated, and the oxidation reaction of manganese dioxide and the reduction reaction of citric acid, etc. Continuously proceed and reach a state of dynamic equilibrium, thereby synergistically controlling the oxidation-reduction reaction to adjust the size of nano-silver particles.
  • the prior art prepares nano-silver often using H 2 O 2 as an oxidant, although it can etch nano-silver and adjust the morphology of the surface of nano-silver particles, but its chemical properties are unstable, easy to decompose and change color, especially in the metal silver Under the catalysis, thus affecting the effect;
  • the above reagents will have different effects on the color of silk fibroin nano silver, which can be obtained by adjusting the amount of silk fibroin, ascorbic acid, citric acid, chitosan, polyethylene glycol, manganese dioxide and controlling the light power and light time.
  • Silk Fibroin Nano Silver Finishing Agent in Desirable Colors can be obtained by adjusting the amount of silk fibroin, ascorbic acid, citric acid, chitosan, polyethylene glycol, manganese dioxide and controlling the light power and light time.
  • the molecular weight of chitosan is 150,000-300,000; the molecular weight of polyethylene glycol is 400-6,000.
  • the concentration of silk fibroin solution is 1-6wt%;
  • the concentration of citric acid is 5-20g/L, the concentration of ascorbic acid The concentration is 1-6wt%, the concentration of AgNO3 is 2-8mg /mL; in the silk fibroin silver nitrate mixed solution, the chitosan concentration is 5-15g/L, the volume of polyethylene glycol and silk fibroin silver nitrate solution The ratio is 2-8:10-20, and the concentration of manganese dioxide is 0.2-0.5mol/L.
  • LiBr lithium bromide
  • the present invention also provides a silk fibroin nano-silver antibacterial color-developing finishing agent prepared by the above-mentioned preparation method of a silk nano-silver antibacterial color-developing finishing agent, which is composed of nano-silver particles, silk fibroin, chitosan,
  • the dispersion liquid of polyethylene glycol and citric acid wherein, each nano-silver particle is regular in shape and uniform in size
  • the present invention adds citric acid in the preparation process, and the polycarboxylic acid on citric acid can complex the Ag in the nanometer , forming a strong complex, so that the reaction tends to be stable, forming regular shape, uniform size of nano-silver particles), nano-silver particles are firmly adsorbed on the hydrophilic segment in the silk fibroin molecule
  • the present invention utilizes silk fibroin tyrosine residues to reduce silver ions to obtain silk fibroin nano-silver aqueous solution, silk fibroin can be used as a
  • the particle size of the nano-silver particles is 10-100 nm, all of which are spherical structures, the particles are uniformly dispersed, and the particle size distribution range is narrow.
  • the silk fibroin nano-silver antibacterial and color-developing finishing agent as mentioned above, the silk fibroin nano-silver anti-bacterial color-developing finishing agent has excellent dispersibility, and the EDS energy spectrum and the transmission electron microscope figure show that the Ag element is evenly distributed;
  • the finishing agent has strong bactericidal properties, and the bacteriostatic rate against Escherichia coli and Staphylococcus aureus both reaches 99.9 ⁇ 0.1%.
  • the present invention also provides the application of the silk fibroin nano-silver antibacterial and color-developing finishing agent as described above. After the silk fibroin nano-silver antibacterial and color-developing finishing agent is dipped into the plasma-modified Carlo silk fiber blended fabric, it is first dried and then steamed. treatment to obtain silk fibroin nano-silver color-developing antibacterial functional Carlo silk fiber blended fabric;
  • Carlo silk fiber blended fabric is composed of Carlo silk fiber and cotton fiber
  • the temperature of the steam treatment is 100-120°C, and the time is 20-100min.
  • the steam treatment uses a high-pressure sterilizer. After the steam treatment, take out the fabric and dry it naturally for 12-24 hours. This treatment has the effect of fixing the color and can change the silk.
  • the property of plain protein can make the fabric have better hand feeling and anti-wrinkle performance.
  • the process of plasma modification is as follows: the Carlo silk fiber blended fabric is cleaned in deionized water for 10-20min, and then put into a low-temperature plasma treatment device after drying, using air, oxygen, nitrogen or Argon gas is used for plasma treatment of Carlo silk fiber blended fabric, the treatment power is 20-240W, and the treatment time is 1-10min;
  • the preparation process of Carlo silk fiber blended fabric is as follows: after cotton fiber is spun into combed cotton sliver, it is mixed with Carlo silk fiber according to the mass ratio of 8-6:2-4, and it is spun by ring spinning, compact spinning or rotary spinning.
  • the cup spinning method is used to weave into Carlo silk fiber blended fabric;
  • the padding is two-dipping and two-rolling (the whole process is soaked twice and squeezed twice), the soaking bath ratio is 1:10-100, the soaking time is 20-60min each time, and the soaking temperature is 30-45°C;
  • the drying temperature is 2-4cm/s, the pressure is 2-5Kg/cm 2 , the scrap rate is 80-90%, and the drying temperature is 60-80°C.
  • the silk fibroin nano-silver color development and antibacterial function Carlo silk fiber blended fabric has a moisture regain of 8.5-12.5%, a wrinkle recovery angle of 133-135°, and a bacteriostatic rate of 99.9% against E. coli.
  • the antibacterial rate of Escherichia coli reaches 90-95%
  • the antibacterial rate of Staphylococcus aureus reaches 99.9%
  • the antibacterial rate of Staphylococcus aureus reaches 55-60% after washing 20 times.
  • the present invention utilizes the reducibility of silk fibroin and ascorbic acid without adding any chemical reducing agent, which is safe and environmentally friendly, and the reaction is gentle, so that nano-silver particles with antibacterial function can be prepared in a controllable manner.
  • Adding chitosan can be well combined with silk
  • the silver ions and the lone pairs of electrons on the oxygen atoms and nitrogen atoms in chitosan can be chelated, which can reduce the amount of metal particles used to avoid heavy metal pollution.
  • the Carlo silk fiber and the combed cotton sliver are mixed according to the mass ratio of 2-4:8-6, and the Carlo silk with excellent quality is spun by three spinning methods: ring spinning, compact spinning and rotor spinning Fiber and combed sliver blended fabric, the spun blended fabric has excellent thermal performance and moisture absorption performance brought by the unique 80-90% hollowness of Carlos fiber, and then the Carlos fiber blended fabric is subjected to low temperature Plasma treatment, followed by the use of silk fibroin nano-silver antibacterial color-developing finishing agent to treat the Carlo silk fiber blended fabric, vacuum drying after two dipping and two rolling, so that the antibacterial color developing finishing agent and Carlo silk fiber blended fabric are combined by physical adsorption , through this combination method of extrusion, the fabric maintains good softness and air permeability, and at the same time, the nano-silver in the finishing agent is firmly attached to the yarn and even enters the pores of the yarn through padding treatment, and the anti-ultraviolet effect It
  • the silk fibroin nano-silver in the finishing agent of the present invention can present better physical and chemical stability, super strong bactericidal properties and extremely low biological toxicity due to quantum, small size effect and huge specific surface area;
  • the present invention can obtain 3 kinds of chromogenic antibacterial finishing agents by adjusting the consumption of reagents, and the bacteriostatic rate to Escherichia coli and Staphylococcus aureus is all higher, and all have good antibacterial washability;
  • the raw material in the present invention is natural plant fiber green and pollution-free, easy to pick and easy to get and cheap and can save textile cost;
  • the present invention integrates dyeing process and antibacterial finishing, has obtained multicolor antibacterial carlos fiber blended fabric
  • the Carlos fiber blended fabric of the present invention retains the crystal-like luster of the Carlos fiber, the advantages of soft feel, air permeability, hygroscopicity and warmth retention, and has long-acting antibacterial properties and color rendering properties. All in one.
  • Fig. 1 is the changing figure of the moisture regain of silk fibroin nano-silver color developing antibacterial function carlos fiber blended fabric of embodiment 7 ⁇ 9;
  • Fig. 2 is the change figure of the antibacterial rate of silk fibroin nano silver color developing antibacterial function carlos fiber blended fabric of embodiment 8;
  • Fig. 3 is the change figure of the wrinkle recovery angle of the silk fibroin nano silver color development antibacterial function carlos fiber blended fabric of embodiment 7 ⁇ 9;
  • Fig. 4 is the antibacterial performance characterization figure of the silk fibroin nano-silver antibacterial color-developing finishing agent that embodiment 1 makes (a among the figure is escherichia coli, and b is staphylococcus aureus);
  • Fig. 5 is the antibacterial performance characterization figure of the silk fibroin nano silver antibacterial color developing finishing agent that embodiment 2 makes (a among the figure is escherichia coli, b is staphylococcus aureus);
  • Fig. 6 is the antibacterial performance characterization figure of the silk fibroin nano silver antibacterial color-developing finishing agent that embodiment 3 makes (a among the figure is escherichia coli, b is staphylococcus aureus)
  • Fig. 7 is the surface morphology scanning electron microscope (SEM) figure and its silver element distribution figure of the silk fibroin nano silver color development antibacterial function carlos fiber blended fabric of embodiment 7;
  • Fig. 8 is the surface morphology scanning electron microscope (SEM) picture and its silver element distribution figure of the silk fibroin nano silver color development antibacterial function carlos fiber blended fabric of embodiment 8;
  • Fig. 9 is the surface morphology scanning electron microscope (SEM) figure and its silver element distribution figure of the silk fibroin nano silver color development antibacterial function carlos fiber blended fabric of embodiment 9;
  • Figure 10 is a transmission electron microscope (TEM) figure of the silk fibroin nanosilver antibacterial color-developing finishing agent prepared in Examples 1-3 (a in the figure is Example 1, b is Example 2, and c is Example 3).
  • TEM transmission electron microscope
  • a preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent the specific steps are as follows:
  • the preparation process of the silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 9.7mol/L, place it in an oven at 60°C for 4 hours, and shake it every 1 hour to obtain a silk solution with a concentration of 1 wt%. ;
  • step (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 3.6, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 15g/L, the concentration of ascorbic acid is 1wt%, and the concentration of AgNO3 is 4mg/mL;
  • step (2) Add chitosan (molecular weight is 150000), polyethylene glycol (molecular weight is 400) and manganese dioxide blend to obtain silk fibroin silver nitrate mixed solution in the silk fibroin silver nitrate solution that step (2) makes ;
  • the concentration of chitosan is 5g/L
  • the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 4:16
  • the concentration of manganese dioxide is 0.2mol/L;
  • step (3) Put the silk fibroin silver nitrate mixed solution prepared in step (3) under a 40W LED lamp for 2 hours to obtain a silk fibroin nano-silver antibacterial color-developing finishing agent showing iron yellow.
  • the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle Regular and uniform in size, the particle size of nano-silver particles is 10-30nm, nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, the amino groups on the surface of chitosan molecules and the surface of silk fibroin Hydrogen bonding is formed between carboxyl groups, and polyethylene glycol is adsorbed and wrapped by van der Waals force to wrap nano-silver particles, while its hydroxyl groups are combined with hydrophilic groups in silk fibroin molecules; Dispersion, EDS energy spectrum and transmission electron microscope show that the Ag element is evenly distributed; as shown in Figure 4, it can be clearly observed that there is no bacterial growth in the petri dish, and the silk fibroin nano-silver anti
  • a preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent the specific steps are as follows:
  • the preparation process of silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 8.4mol/L, place it in an oven at 60°C for 6 hours, and shake it every 1 hour to obtain a silk solution with a concentration of 3wt%. ;
  • step (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 4.4, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 5g/L, the concentration of ascorbic acid is 6wt%, and the concentration of AgNO3 is 6mg/mL;
  • step (3) Add chitosan (molecular weight is 300,000), polyethylene glycol (molecular weight is 6000) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ;
  • the concentration of chitosan is 15g/L
  • the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 2:18, and the concentration of manganese dioxide is 0.3mol/L;
  • step (3) Put the silk fibroin silver nitrate mixed solution prepared in step (3) under a 60W LED lamp for 48 hours to obtain a purple-red silk fibroin nano-silver antibacterial color-developing finishing agent.
  • the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle Regular and uniform in size, the particle size of nano-silver particles is 35-75nm, nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, the amino groups on the surface of chitosan molecules and the surface of silk fibroin Hydrogen bonding is formed between carboxyl groups, and polyethylene glycol is adsorbed and wrapped by van der Waals force to wrap nano-silver particles, while its hydroxyl groups are combined with hydrophilic groups in silk fibroin molecules; Dispersion, EDS energy spectrum and transmission electron microscope show that the Ag element is evenly distributed; as shown in Figure 5, it can be clearly observed that there is no bacterial growth in the petri dish, and the silk fibroin nano-silver
  • a preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent the specific steps are as follows:
  • the preparation process of silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 12mol/L, place it in an oven at 60° C. for 3 hours, and shake it every 1 hour to obtain a silk solution with a concentration of 6 wt%.
  • step (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 4, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 10g/L, the concentration of ascorbic acid is 4wt%, and the concentration of AgNO3 is 2mg/mL;
  • step (2) Add chitosan (molecular weight is 230000), polyethylene glycol (molecular weight is 3000) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ;
  • the concentration of chitosan is 10g/L
  • the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 8:12
  • the concentration of manganese dioxide is 0.5mol/L;
  • step (3) Place the silk fibroin silver nitrate mixed solution prepared in step (3) under a 10W LED lamp for 120 hours to obtain a military yellow silk fibroin nano silver antibacterial color-developing finishing agent.
  • the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle Regular and uniform in size, the particle size of nano-silver particles is 70-100nm, nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, the amino groups on the surface of chitosan molecules and the Hydrogen bonding is formed between carboxyl groups, and polyethylene glycol is adsorbed and wrapped by van der Waals force to wrap nano-silver particles, while its hydroxyl groups are combined with hydrophilic groups in silk fibroin molecules; Dispersion, EDS energy spectrum and transmission electron microscope show that Ag elements are evenly distributed; as shown in Figure 6, it can be clearly observed that there is no bacterial growth in the petri dish, and the silk fibroin nano-silver antibacterial and color-developing
  • a preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent the specific steps are as follows:
  • the preparation process of the silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 9mol/L, place it in an oven at 60°C for 4.5 hours, and shake it once every 1 hour to obtain a silk solution with a concentration of 2wt%. ;
  • step (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 5.6, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 8g/L, the concentration of ascorbic acid is 2wt%, the concentration of AgNO3 is 3.5mg/mL;
  • step (3) Add chitosan (molecular weight is 180,000), polyethylene glycol (molecular weight is 1500) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ;
  • the concentration of chitosan is 8g/L
  • the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 2:10
  • the concentration of manganese dioxide is 0.25mol/L;
  • the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle is regular and the size is uniform, The particle size of nano-silver particles is 20-40nm.
  • Nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, and the amino groups on the surface of chitosan molecules and the carboxyl groups on the surface of silk fibroin form a Hydrogen bonding, polyethylene glycol adsorbs and wraps nano-silver particles through van der Waals force, and its hydroxyl group combines with hydrophilic groups in silk fibroin molecules; silk nano-silver antibacterial color-developing finishing agent has excellent dispersibility, EDS can Spectrum and transmission electron micrographs show that the Ag element is evenly distributed; the silk fibroin nano-silver antibacterial and chromogenic finishing agent has super bactericidal properties, and the bacteriostatic rate against Escherichia coli and Staphylococcus aureus reaches 100%.
  • a preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent the specific steps are as follows:
  • the preparation process of silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 10.5mol/L, place it in an oven at 75°C for 3.5h, and shake it every 1h to obtain silk fibroin with a concentration of 4wt%. solution;
  • step (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 5.2, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 12g/L, the concentration of ascorbic acid is 3wt%, the concentration of AgNO3 is 7mg/mL;
  • step (3) Add chitosan (molecular weight is 250,000), polyethylene glycol (molecular weight is 3500) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ;
  • the concentration of chitosan is 12g/L
  • the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 5:15
  • the concentration of manganese dioxide is 0.4mol/L;
  • step (3) Put the silk fibroin silver nitrate mixed solution prepared in step (3) under a 30W LED lamp for 40 hours to obtain a silk fibroin nano-silver antibacterial and color-developing finishing agent showing iron yellow.
  • the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle is regular and the size is uniform, The particle size of nano-silver particles is 50-90nm.
  • Nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, and the amino groups on the surface of chitosan molecules and the carboxyl groups on the surface of silk fibroin form a Hydrogen bonding, polyethylene glycol adsorbs and wraps nano-silver particles through van der Waals force, and its hydroxyl group combines with hydrophilic groups in silk fibroin molecules; silk nano-silver antibacterial color-developing finishing agent has excellent dispersibility, EDS can Spectrum and transmission electron micrographs show that the Ag element is evenly distributed; the silk fibroin nano-silver antibacterial and color-developing finishing agent has super bactericidal properties, and the bacteriostatic rate against Escherichia coli and Staphylococcus aureus reaches 99.8%.
  • a preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent the specific steps are as follows:
  • the preparation process of the silk fibroin solution is as follows: take the degummed silk and soak it in a lithium bromide solution with a concentration of 11mol/L, place it in an oven at 80° C. for 3 hours, and shake it once every 1 hour to obtain a silk solution with a concentration of 5 wt%.
  • step (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 4.8, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 20g/L, the concentration of ascorbic acid is 5wt%, and the concentration of AgNO3 is 4.5mg/mL;
  • step (3) Add chitosan (molecular weight is 270,000), polyethylene glycol (molecular weight is 4000) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ;
  • the concentration of chitosan is 14g/L
  • the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 8:20
  • the concentration of manganese dioxide is 0.45mol/L;
  • the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle is regular and the size is uniform, The particle size of the nano-silver particles is 40-60nm, and the nano-silver particles are firmly adsorbed on the hydrophilic segment of the silk fibroin molecule, and the amino group on the surface of the chitosan molecule and the carboxyl group on the surface of the silk fibroin are formed.
  • the silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 1 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
  • the Carlo silk fiber blended fabric that step (1) is made is placed in deionized water and cleaned for 20min, puts into the low-temperature plasma treatment device after drying, uses air to carry out plasma treatment to Carlo silk fiber blended fabric, working temperature
  • the temperature is 15°C
  • the treatment power is 80W
  • the treatment time is 10min, so as to obtain the plasma-modified Carlo silk fiber blended fabric;
  • step (3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
  • the padding is two-dipping and two-rolling (soaking twice in the whole process and rolling twice), the soaking bath ratio is 1:20, the soaking time is 30min each time, the soaking temperature is 40°C; the rolling speed is 2cm/s, the pressure 2Kg/cm 2 , the scrap rate is 80%; the drying temperature is 60°C, and the drying time is 40min;
  • the steam treatment was done in an autoclave at a temperature of 120°C for 20 minutes. After the treatment, the fabric was taken out and air-dried for 24 hours.
  • the moisture regain of the silk fibroin nano-silver color-developing and antibacterial functional Carlo silk fiber blended fabric is 10.2%, and the wrinkle recovery angle is 135°.
  • the silver element in the fabric Evenly distributed on the surface, with strong antibacterial properties, the bacteriostatic rate of Escherichia coli reached 99.9%, after washing 20 times, the bacteriostatic rate of Escherichia coli reached 90%, and the bacteriostatic rate of Staphylococcus aureus reached 99.9%, After washing 20 times, the antibacterial rate to Staphylococcus aureus reaches 58%.
  • the silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 2 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
  • the Carlo silk fiber blended fabric prepared in step (1) is placed in deionized water and cleaned for 20 minutes, put into a low-temperature plasma treatment device after drying, and oxygen is used to carry out plasma treatment to the Carlo silk fiber blended fabric, and the working temperature
  • the temperature is 20°C
  • the processing power is 240W
  • the processing time is 1min, so as to obtain a plasma-modified Carlo silk fiber blended fabric;
  • step (3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
  • the padding is two-dipping and two-rolling (the whole process is soaked twice and squeezed twice), the soaking bath ratio is 1:10, the soaking time is 20min each time, the soaking temperature is 40°C; the rolling speed is 2cm/s, the pressure 3Kg/cm 2 , the scrap rate is 82%; the drying temperature is 60°C, and the drying time is 50min;
  • the steam treatment was done in an autoclave at a temperature of 100°C for 30 minutes. After treatment, the fabric was taken out and air-dried for 24 hours.
  • the moisture regain of the prepared silk fibroin nano-silver color-developing and antibacterial functional Carlo silk fiber blended fabric is 12.5%, and the wrinkle recovery angle is 133 °, as shown in Figure 2 and Figure 8, silver
  • the elements are evenly distributed on the fabric and have strong antibacterial properties.
  • the antibacterial rate against E. coli reaches 99.9%.
  • the antibacterial rate against E. coli reaches 92%, and the antibacterial rate against Staphylococcus aureus reaches 99.9%, the bacteriostatic rate to Staphylococcus aureus reaches 55% after washing 20 times.
  • the silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 3 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
  • the cotton fiber After the cotton fiber is spun into combed sliver, it is mixed with the Carlo silk fiber according to the mass ratio of 8:2, and the Carlo silk fiber blended fabric with a count of 40 is spun by the rotor spinning method;
  • the Carlo silk fiber blended fabric that step (1) makes is placed in deionized water and cleaned for 20min, puts into a low-temperature plasma treatment device after drying, and uses nitrogen to carry out plasma treatment to the Carlo silk fiber blended fabric, working temperature
  • the temperature is 25°C
  • the processing power is 120W
  • the processing time is 5min, so as to obtain a plasma-modified Carlo silk fiber blended fabric;
  • step (3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
  • the padding is two-dipping and two-rolling (soaking twice in the whole process, rolling twice), the soaking bath ratio is 1:40, the soaking time is 60min each time, the soaking temperature is 37°C; the rolling speed is 3cm/s, the pressure 3Kg/cm 2 , the scrap rate is 84%; the drying temperature is 60°C, and the drying time is 60min;
  • the steam treatment was done in an autoclave at a temperature of 120°C for 60 minutes. After the treatment, the fabric was taken out and air-dried for 24 hours.
  • the moisture regain of the prepared silk nano-silver color-developing and antibacterial Carlo silk fiber blended fabric is 8.5%, and the wrinkle recovery angle is 134 °, as shown in Figure 9, the silver element is in the fabric Evenly distributed on the surface, with strong antibacterial properties, the antibacterial rate of Escherichia coli reached 99.9%, after washing 20 times, the antibacterial rate of Escherichia coli reached 95%, and the antibacterial rate of Staphylococcus aureus reached 99.9%, After washing 20 times, the antibacterial rate to Staphylococcus aureus reaches 60%.
  • the silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 4 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
  • the Carlo silk fiber blended fabric that step (1) makes is placed in deionized water and cleaned for 10 minutes, puts into a low-temperature plasma treatment device after drying, and uses argon to carry out plasma treatment to the Carlo silk fiber blended fabric, and the work
  • the temperature is 30°C
  • the treatment power is 20W
  • the treatment time is 10min, so as to prepare the plasma-modified Carlo silk fiber blended fabric;
  • step (3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
  • the padding is two-dipping and two-rolling (soaking twice in the whole process and rolling twice), the soaking bath ratio is 1:60, the soaking time is 60min each time, the soaking temperature is 45°C; the rolling speed is 3cm/s, the pressure 4Kg/cm 2 , the scrap rate is 86%; the drying temperature is 70°C, and the drying time is 40min;
  • the steam treatment was performed in an autoclave at a temperature of 110°C for 120 minutes. After treatment, the fabric was taken out and air-dried for 12 hours.
  • the obtained silk fibroin nano-silver color-developing antibacterial function carlos fiber blended fabric has a moisture regain rate of 12.1%, a wrinkle recovery angle of 133°, and a bacteriostatic rate of 99.9% against Escherichia coli.
  • the bacteriostatic rate reaches 91%, and the bacteriostatic rate to Staphylococcus aureus reaches 99.9%, and the bacteriostatic rate to Staphylococcus aureus reaches 56% after washing 20 times.
  • the silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 5 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
  • the cotton fiber After the cotton fiber is spun into combed sliver, it is mixed with the Carlo silk fiber according to the mass ratio of 6:3, and the Carlo silk fiber blended fabric with a count of 40 is spun by the compact spinning method;
  • the Carlo silk fiber blended fabric that step (1) makes is placed in deionized water and cleaned for 13 minutes, puts into a low-temperature plasma treatment device after drying, and uses air to carry out plasma treatment to the Carlo silk fiber blended fabric, and the working temperature
  • the temperature is 35°C
  • the processing power is 50W
  • the processing time is 8min, so as to obtain a plasma-modified Carlo silk fiber blended fabric;
  • step (3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
  • the padding is two-dipping and two-rolling (soaking twice in the whole process, rolling twice), the soaking bath ratio is 1:80, the soaking time is 40min each time, the soaking temperature is 34°C; the rolling speed is 4cm/s, the pressure 4Kg/cm 2 , the excess rate is 88%; the drying temperature is 70°C, and the drying time is 50 minutes;
  • the steam treatment was done in an autoclave at a temperature of 105°C for 80 minutes. After treatment, the fabric was taken out and air-dried for 15 hours.
  • the obtained silk fibroin nano-silver color-developing antibacterial function carlos fiber blended fabric has a moisture regain rate of 10.9%, a wrinkle recovery angle of 134°, and a bacteriostatic rate of 99.9% against Escherichia coli.
  • the bacteriostatic rate reaches 94%, and the bacteriostatic rate to Staphylococcus aureus reaches 99.9%, and the bacteriostatic rate to Staphylococcus aureus reaches 57% after washing 20 times.
  • the antibacterial and color-developing finishing agent of silk fibroin nano-silver in Example 6 is used to prepare the silk fiber blended fabric with silk fibroin nano-silver color development and antibacterial function, and the specific steps are as follows:
  • the cotton fiber After the cotton fiber is spun into combed sliver, it is mixed with the Carlo silk fiber according to the mass ratio of 7:2, and the Carlo silk fiber blended fabric with a count of 32 is spun by the rotor spinning method;
  • the Carlo silk fiber blended fabric that step (1) makes is placed in deionized water and cleaned for 17min, puts into a low-temperature plasma treatment device after drying, and uses oxygen to carry out plasma treatment to the Carlo silk fiber blended fabric, working temperature
  • the temperature is 30°C
  • the processing power is 100W
  • the processing time is 6min, so as to obtain the plasma-modified Carlo silk fiber blended fabric;
  • step (3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
  • the padding is two-dipping and two-rolling (soaking twice in the whole process, rolling twice), the soaking bath ratio is 1:100, the soaking time is 20min each time, the soaking temperature is 30°C; the rolling speed is 4cm/s, the pressure 5Kg/cm 2 , the scrap rate is 90%; the drying temperature is 80°C, and the drying time is 60 minutes;
  • the steam treatment was done in an autoclave at a temperature of 115°C for 50 minutes. After the treatment, the fabric was taken out and air-dried for 18 hours.
  • the obtained silk fibroin nano-silver color-developing and antibacterial function Carlo silk fiber blended fabric has a moisture regain rate of 9.7%, a wrinkle recovery angle of 135°, and a bacteriostatic rate of 99.9% against Escherichia coli.
  • the bacteriostatic rate reaches 95%, and the bacteriostatic rate to Staphylococcus aureus reaches 99.9%, and the bacteriostatic rate to Staphylococcus aureus reaches 59% after washing 20 times.

Abstract

The present invention relates to a fibroin nano-silver antibacterial color-developing finishing agent, a preparation method therefor, and an application thereof. The preparation method comprises: first adding citric acid and ascorbic acid to a fibroin solution, then adjusting a pH value thereof, then adding an AgNO3 crystal to obtain a fibroin silver nitrate solution, then adding chitosan, polyethylene glycol, and manganese dioxide to the fibroin silver nitrate solution for blending to obtain a fibroin silver nitrate mixed solution, and finally placing the fibroin silver nitrate mixed solution under an LED lamp for illumination, to obtain an antibacterial color-developing finishing agent. The prepared finishing agent is a dispersion containing nano-silver particles, fibroin, chitosan, polyethylene glycol, and manganese dioxide. The application is: padding a plasma-modified Calotropis gigantea fiber blended fabric with an antibacterial color-developing finishing agent, then drying, and then performing water vapor treatment to obtain a Calotropis gigantea fiber blended fabric having fibroin nano-silver color-developing and antibacterial functions. The finishing agent of the present invention is capable of both resisting bacteria and developing colors, and a Calotropis gigantea fabric having durable and stable antibacterial properties, excellent wrinkle resistance, and good hand feeling can be produced.

Description

一种丝素纳米银抗菌显色整理剂及其制备方法和应用A kind of silk fibroin nano-silver antibacterial color-developing finishing agent and its preparation method and application 技术领域technical field
本发明属于显色整理剂技术领域，涉及一种丝素纳米银抗菌显色整理剂及其制备方法和应用。The invention belongs to the technical field of color-developing finishing agents, and relates to a silk fibroin nano-silver antibacterial color-developing finishing agent and a preparation method and application thereof.
背景技术Background technique
卡洛丝(Calotropis gigantea)纤维是从卡洛丝果实的种子冠毛上生长出来的一种质量极轻的天然植物纤维，该纤维不仅有极为光滑的表面，水晶般的光泽，柔软的手感，而且其横截面高达80～90％的超大中空腔结构使之与木棉纤维一样具有耐压性强、保暖性强、隔音性好和吸湿性大的特性，织成的面料既有丝绸的爽滑质感，又有比棉织物更好的透气性、吸湿性和保暖性。除此之外，该纤维还具有抗菌、防蛀和防霉等优秀性能，可以作为潜在的保暖材料、吸水吸油材料、浮力材料和抗菌防螨材料等，是一种亟待开发的纺织纤维原料。Calotropis gigantea fiber is an extremely light natural plant fiber grown from the seed pappus of Calotropis fruit. The fiber not only has an extremely smooth surface, crystal-like luster, and soft feel, Moreover, its super-large hollow cavity structure with a cross-section as high as 80-90% makes it have the same characteristics as kapok fiber, such as strong pressure resistance, strong heat retention, good sound insulation and high hygroscopicity. The woven fabric has the smoothness of silk. Texture, and better air permeability, moisture absorption and warmth than cotton fabric. In addition, the fiber also has excellent properties such as antibacterial, anti-moth and anti-mildew, and can be used as a potential thermal insulation material, water and oil absorption material, buoyant material, antibacterial and anti-mite material, etc. It is a textile fiber raw material that needs to be developed urgently.
对于面料，人们在要求其美观时尚和保暖御寒的同时，舒适性和功能性的要求更是放在了第一位。各种各样的多功能型面料及服装的研究也越来越多，例如具有导湿快干功能的运动衣、具有防风御寒和抗紫外等功能的户外运动服，还有一些具有抗静电、防辐射和抗菌等功能的多功能面料。针对一些内衣、家纺面料和卫生用品，具有抗菌防臭等性能是必不可少的，所以结合卡洛丝纤维的优秀性能，开发出一种美观舒适、绿色安全且长效抗菌的卡洛丝面料能带来极大的应用价值和经济效益。For fabrics, people put the requirements of comfort and functionality on the first place while requiring them to be beautiful, fashionable and warm and keep out the cold. There are more and more researches on various multi-functional fabrics and clothing, such as sportswear with moisture-wicking and quick-drying functions, outdoor sportswear with functions such as wind and cold protection and UV resistance, and some with antistatic, Multifunctional fabric with functions such as radiation protection and antibacterial. For some underwear, home textile fabrics and sanitary products, it is essential to have antibacterial and deodorant properties. Therefore, combined with the excellent performance of Carlo silk fiber, a beautiful, comfortable, green, safe and long-lasting antibacterial Carlo silk fabric can be developed. Bring great application value and economic benefits.
一般而言，卡洛丝抗菌纺织品可以通过两种技术途径获得，采用功能性整理的方法和直接采用抗菌纤维进行织制的方法。采用抗菌纤维直接纺织的抗菌面料多数在纺织加工过程中其天然的抗菌性能会被破坏，尤其是一些高温处理，例如染色、煮练工艺等，虽然卡洛丝纤维自身就具有抗菌性能，但经过纺织加工成为面料后它的抗菌性能会大大缩减，最终远远达不到抗菌面料的要求；而采用功能性整理的方法，虽然其操作方便，也可达到抗菌的目的，但是功能性整理过程中所加入的化学试剂会对织物的手感造成破坏，并且其抗菌的持久性、稳定性和安全性较差。一般而言，无论是功能性整理的方法还是直接采用抗菌纤维进行织制的方法染色工艺都是必不可少的，染色工艺中涉及到许多有害化学药品，例如铬、铅或者汞等重金属盐类、钛青铜盐类染料、重铬酸钾作媒染剂氧化剂、戊二醛作交联剂等等，所排放的废水都对环境和人类都存在着很大的危害。Generally speaking, Carlos antibacterial textiles can be obtained through two technical approaches, the method of functional finishing and the method of weaving directly with antibacterial fibers. Most of the antibacterial fabrics directly woven with antibacterial fibers will destroy their natural antibacterial properties during textile processing, especially some high-temperature treatments, such as dyeing and scouring processes. After the textile is processed into a fabric, its antibacterial performance will be greatly reduced, and finally it is far from meeting the requirements of antibacterial fabrics; and the method of functional finishing, although it is easy to operate, can also achieve the purpose of antibacterial, but in the process of functional finishing The added chemical reagents will damage the feel of the fabric, and its antibacterial persistence, stability and safety are poor. Generally speaking, whether it is the method of functional finishing or the method of directly weaving with antibacterial fibers, the dyeing process is indispensable. Many harmful chemicals are involved in the dyeing process, such as heavy metal salts such as chromium, lead or mercury. , titanium bronze salt dyes, potassium dichromate as mordant oxidizing agent, glutaraldehyde as crosslinking agent, etc., the discharged wastewater is very harmful to the environment and human beings.
如能研究一种既能抗菌又能显色还不会破坏织物的手感且抗菌的持久性、稳定性和安全性较好的整理剂将有望解决以上问题。If can study a kind of finishing agent that can not only be antibacterial but also can develop color and can not destroy the feel of fabric and antibacterial persistence, stability and safety are better, will hopefully solve the above problems.
发明内容Contents of the invention
本发明的目的是解决现有技术中的问题，提供一种丝素纳米银抗菌显色整理剂及其制备方法和应用。本发明先制备了一种既能抗菌又能显色的整理剂，其可产生3种颜色，且具有抗菌性能(利用纳米 银实现抗菌，纳米银几乎无毒副作用，控制纳米银的使用量，可以安全放心的在各个领域等方面应用)，再将其作为整理剂浸轧整理卡洛丝纤维混纺面料，整理工艺是一种全新绿色安全的显色抗菌一体化的处理工艺，将染色工艺和抗菌整理工艺结合，缩减了纺织加工流程，使卡洛丝纤维自身的抗菌性能得到保护，还大幅度减少了印染废水的排放，对环境生态友好，最终制得的卡洛丝面料具有持久和稳定的抗菌性、优异的抗皱性和良好的手感。The purpose of the present invention is to solve the problems in the prior art, and provide a silk fibroin nano-silver antibacterial and color-developing finishing agent and its preparation method and application. The present invention firstly prepares a finishing agent capable of both antibacterial and color development, which can produce 3 colors and has antibacterial properties (using nano-silver to realize anti-bacteria, nano-silver has almost no toxic side effects, and the usage amount of nano-silver is controlled, It can be safely and safely applied in various fields, etc.), and then use it as a finishing agent to pad and finish Carlo silk fiber blended fabrics. The finishing process is a new green and safe color development and antibacterial integrated treatment process. The dyeing process and The combination of antibacterial finishing process reduces the textile processing process, protects the antibacterial properties of Carlo silk fiber itself, and greatly reduces the discharge of printing and dyeing wastewater. It is environmentally friendly and the final Carlo silk fabric is durable and stable. Excellent antibacterial properties, excellent wrinkle resistance and good hand feeling.
为达到上述目的，本发明采用的技术方案如下：In order to achieve the above object, the technical scheme adopted in the present invention is as follows:
一种丝素纳米银抗菌显色整理剂的制备方法，首先向丝素溶液中加入柠檬酸和抗坏血酸后，调节其pH值至3.6-5.6，再加入AgNO 3晶体，得到酸性的丝素硝酸银溶液(之所以控制“酸性”是因为在较高的pH值(>8)中，柠檬酸游离在溶液中的羧基会被去质子化)，然后向丝素硝酸银溶液中加入壳聚糖、聚乙二醇和二氧化锰共混后得到丝素硝酸银混合溶液，最后利用丝素和抗坏血酸具有的还原性将丝素硝酸银混合溶液置于10-60W的LED灯下2-120h，得到丝素纳米银抗菌显色整理剂。 A preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent, after first adding citric acid and ascorbic acid to the silk fibroin solution, adjusting its pH value to 3.6-5.6 , then adding AgNO3 crystals to obtain acidic silk fibroin silver nitrate solution (the reason why the "acidity" is controlled is because in a higher pH value (>8), the carboxyl group of citric acid free in the solution will be deprotonated), then add chitosan, Polyethylene glycol and manganese dioxide are blended to obtain a silk fibroin silver nitrate mixed solution. Finally, using the reducing properties of silk fibroin and ascorbic acid, the silk fibroin silver nitrate mixed solution is placed under a 10-60W LED lamp for 2-120 hours to obtain silk fibroin silver nitrate mixed solution. Su nano silver antibacterial color finishing agent.
本发明在制备丝素纳米银抗菌显色整理剂的过程中用到了丝素、柠檬酸、抗坏血酸、壳聚糖、聚乙二醇和二氧化锰，其中：The present invention uses silk fibroin, citric acid, ascorbic acid, chitosan, polyethylene glycol and manganese dioxide in the process of preparing silk fibroin nano silver antibacterial color-developing finishing agent, wherein:
丝素作为一种天然高聚物，用其来制备纳米银具有优势，一方面体现在丝素是蚕丝蛋白材料，天然无污染、安全性好且性能优越，另一方面体现在丝素在还原银离子的过程中，可同时起到还原剂和保护剂(丝素蛋白具有天然大分子结构，能将纳米银固定在丝素大分子的框架中，且酪氨酸残基具有很强的供电子性能，纳米银会受到丝素蛋白分子很好的保护)的作用，制备出的纳米银溶液中杂质含量也相应较少；As a natural polymer, silk fibroin has advantages in preparing nano-silver. On the one hand, silk fibroin is a silk protein material, which is naturally pollution-free, safe and superior in performance. On the other hand, it is reflected in the reduction of silk fibroin. In the process of silver ions, it can act as a reducing agent and a protective agent at the same time (silk fibroin has a natural macromolecular structure, which can fix nano-silver in the framework of silk fibroin macromolecules, and the tyrosine residue has a strong supply Electronic properties, nano-silver will be well protected by silk fibroin molecules), and the impurity content in the prepared nano-silver solution is correspondingly less;
壳聚糖的分子结构与纤维素类似，与纤维素织物具有很好的相似相容性，通过氢键与纤维素纤维连接，因此与丝素纳米银结合，不仅可以赋予显色整理剂更优异的抗菌性能，也能与结构为纤维素的卡洛丝面料更好的结合；虽然纳米银抗菌谱广，能够杀灭已感染的细菌并继续与其他细菌接触并发挥作用，但银元素在空气中不稳定，易氧化发黑，因而抗菌性和耐久性较差，而壳聚糖类抗菌剂能对细菌的细胞膜进行破坏，细胞内部物质因细胞膜的破坏而渗漏出来，使得细菌形态、细胞内部均发生明显变化，从而杀死细菌，达到抑菌效果，而壳聚糖的抗菌性能受到环境pH值的影响很大，在酸性条件下具有很强的抗菌效果，但是在实际应用中，大部分情况下壳聚糖主要用于中性及偏碱性的环境，其抗菌效果被削弱，本发明结合壳聚糖和银离子抗菌的优点，采用无机的银系抗菌剂与天然的壳聚糖这两种抗菌剂相复合,并且为壳聚糖提供了酸性条件(pH值至3.6-5.6)，因而其抗菌性和稳定性更加持久；The molecular structure of chitosan is similar to that of cellulose, and it has good similar compatibility with cellulose fabrics. It is connected to cellulose fibers through hydrogen bonds. Its antibacterial properties can also be better combined with cellulose fabrics; although nano-silver has a wide antibacterial spectrum, it can kill infected bacteria and continue to contact and function with other bacteria, but the silver element in the air Instable, easy to oxidize and turn black, so the antibacterial and durability are poor, while chitosan antibacterial agents can destroy the cell membrane of bacteria, and the substances inside the cells leak out due to the destruction of the cell membrane, making the bacterial shape, cell There are obvious changes inside, so as to kill bacteria and achieve antibacterial effect, while the antibacterial performance of chitosan is greatly affected by the pH value of the environment, and has a strong antibacterial effect under acidic conditions, but in practical applications, most In some cases, chitosan is mainly used in neutral and alkaline environments, and its antibacterial effect is weakened. The present invention combines the advantages of chitosan and silver ion antibacterial, and adopts inorganic silver-based antibacterial agent and natural chitosan These two antibacterial agents are compounded and provide acidic conditions (pH value to 3.6-5.6) for chitosan, so its antibacterial properties and stability are more durable;
抗坏血酸作为环保的还原剂，价廉易得、还原性强，能够迅速、彻底地将溶液中银离子还原成银单质并生长，提高银离子的转化率，同时由于其在水中较大的溶解度可以确保反应后所得纳米银颗粒表面吸附的少量还原剂能够通过多次洗涤除去，且其为天然物质，无毒，不会对环境造成任何污染；现有技 术常采用NaBH 4作为银离子的还原剂，一方面NaBH 4还原能力太强，不易对其反应进行调控，另一方面，由于NaBH 4很容易分解，不稳定，必须在碱性溶液中才能保存，保存时间段，需要现配现用，不利于工业化生产，此外NaBH 4有一定的毒性，不仅污染环境，它们在产物中的残留也极大限制了合成的纳米银颗粒在各个领域的应用； As an environmentally friendly reducing agent, ascorbic acid is cheap, easy to obtain, and has strong reducibility. It can quickly and thoroughly reduce silver ions in the solution to simple silver and grow, improving the conversion rate of silver ions. At the same time, due to its large solubility in water, it can ensure A small amount of reductant adsorbed on the surface of the gained nano-silver particle after the reaction can be removed by repeated washing, and it is a natural substance, non-toxic, and will not cause any pollution to the environment ; the prior art often adopts NaBH As the reductant of silver ions, On the one hand, the reducing ability of NaBH 4 is too strong, so it is difficult to control its reaction. On the other hand, because NaBH 4 is easy to decompose and unstable, it must be stored in alkaline solution. It is beneficial to industrial production. In addition, NaBH 4 has certain toxicity, which not only pollutes the environment, but their residues in the product also greatly limit the application of synthesized silver nanoparticles in various fields;
聚乙二醇作为分散剂，反应生成的单质银被软模板聚乙二醇原位吸附包裹，从而有效地阻止了初始形成的粒子间的相互结合、团聚，并利用其对银纳米颗粒特殊晶面的选择吸附来调节不同晶面的生长速度，从而使形貌和粒度可控，起到诱导、控制粒子生长的作用，同时聚乙二醇含有羟基，且亲水性较强，有分散稳定作用，能得到分散较好的球形粒子；聚乙二醇作为一种非离子型表面活性剂，它的水溶性、稳定性极好，不易受电解质及酸、碱影响，可作为分散剂通过范德华力吸附在纳米银表面来达到修饰纳米银，减少银颗粒的团聚；聚乙二醇作为绿色溶剂，在后续的织物抗菌整理过程中不需要从纳米银胶体中除去，此外它还起到了粘合剂的作用，提高了纳米银与卡洛丝面料的结合能力；现有技术制备纳米银时常采用PVP(聚乙烯吡咯烷酮)作为分散剂，但是PVP的量不易控制(具体体现在加入量的微小变化会导致反应体系产生巨大变化)，添加量稍少，不能起到较好的保护从而产生团聚现象，添加量稍多，过量的会将纳米银颗粒包裹，从而降低抗菌性，很难保证不同批次之间的稳定性，与其相比，聚乙二醇的量容易控制，有效避免了上述问题；Polyethylene glycol is used as a dispersant, and the elemental silver produced by the reaction is in-situ adsorbed and wrapped by the soft template polyethylene glycol, which effectively prevents the mutual combination and agglomeration of the initially formed particles, and utilizes its special crystallinity for silver nanoparticles. The growth rate of different crystal planes can be adjusted by the selective adsorption of different crystal planes, so that the shape and particle size can be controlled, and it can induce and control the growth of particles. At the same time, polyethylene glycol contains hydroxyl groups, and has strong hydrophilicity and dispersion stability. Function, can get better dispersed spherical particles; polyethylene glycol as a non-ionic surfactant, its water solubility, excellent stability, not easily affected by electrolytes, acids and alkalis, can be used as a dispersant through van der Waals Adsorbed on the surface of nano-silver to modify nano-silver and reduce the agglomeration of silver particles; polyethylene glycol, as a green solvent, does not need to be removed from nano-silver colloid in the subsequent fabric antibacterial finishing process, and it also plays a role in adhesion The role of the agent improves the bonding ability of nano-silver and Carlo silk fabrics; the prior art prepares nano-silver and often adopts PVP (polyvinylpyrrolidone) as a dispersant, but the amount of PVP is not easy to control (it is embodied in the small change of the added amount. It will lead to great changes in the reaction system), if the amount of addition is slightly small, it will not be able to play a good role in protection and cause agglomeration, if the amount of addition is slightly larger, the excessive amount will wrap the nano-silver particles, thereby reducing the antibacterial properties, it is difficult to guarantee different batches The stability between times, compared with it, the amount of polyethylene glycol is easy to control, effectively avoiding the above problems;
柠檬酸作为络合剂，可以分散溶液、防止产生沉淀、保证染色鲜艳度，丝素蛋白在酸性条件下也可以更好地还原，具体为：柠檬酸能溶于水解离出柠檬酸根离子，可与溶液中的Ag +离子形成强络合物，从而影响金属颗粒的形成和生长，在生成柠檬酸银的过程中柠檬酸内氢原子的迁移会激活其羧基氧原子的电子，并为Ag(111)平面提供了额外的结合亲和力，柠檬酸对Ag(111)的优先结合能促进沿Ag(100)表面的晶体生长，进而促进银离子还原成纳米银； As a complexing agent, citric acid can disperse the solution, prevent precipitation, and ensure the vividness of dyeing. Silk fibroin can also be better restored under acidic conditions. Specifically: citric acid can be dissolved in water to dissociate citrate ions, which can Form a strong complex with Ag + ions in the solution, thereby affecting the formation and growth of metal particles. During the generation of silver citrate, the migration of hydrogen atoms in citric acid will activate the electrons of its carboxyl oxygen atoms, and provide Ag( The 111) plane provides additional binding affinity, and the preferential binding of citric acid to Ag(111) can promote crystal growth along the Ag(100) surface, thereby promoting the reduction of silver ions to nanosilver;
二氧化锰作为氧化剂，能与纳米银颗粒发生氧化反应，减速银离子的还原，还能与柠檬酸通过金属配位作用络合，Mn 2+不仅可与任意一个纳米银表面带-COOH的柠檬酸根通过金属配位作用络合，氧化羟基酸成碳基酸，还可与邻近纳米银表面上的柠檬酸根络合，两者相互调节，二氧化锰发生的氧化反应与柠檬酸等的还原反应不断进行，并达到动态平衡的状态，从而协同控制氧化还原反应来调节纳米银颗粒的大小，此外，还能与还原性有机污染物发生氧化还原反应，降低其毒性，起到环境修复和净化的作用；现有技术制备纳米银时常采用H 2O 2作为氧化剂，虽然其能刻蚀纳米银，调节纳米银颗粒表面的形态，但是其化学性质不稳定，容易分解和变色，尤其在金属银的催化下，从而影响作用效果； As an oxidizing agent, manganese dioxide can oxidize with nano-silver particles, slow down the reduction of silver ions, and complex with citric acid through metal coordination. Mn 2+ can not only combine with any lemon with -COOH on the surface of nano-silver Acid groups are complexed by metal coordination, oxidizing hydroxy acids to carbonic acids, and can also complex with citrate groups on the surface of adjacent nano-silver. The two are mutually regulated, and the oxidation reaction of manganese dioxide and the reduction reaction of citric acid, etc. Continuously proceed and reach a state of dynamic equilibrium, thereby synergistically controlling the oxidation-reduction reaction to adjust the size of nano-silver particles. In addition, it can also undergo oxidation-reduction reactions with reducing organic pollutants to reduce their toxicity and play a role in environmental restoration and purification. Effect; the prior art prepares nano-silver often using H 2 O 2 as an oxidant, although it can etch nano-silver and adjust the morphology of the surface of nano-silver particles, but its chemical properties are unstable, easy to decompose and change color, especially in the metal silver Under the catalysis, thus affecting the effect;
以上这些试剂对丝素纳米银颜色会产生不同影响，可以通过调节丝素蛋白、抗坏血酸、柠檬酸、壳聚糖、聚乙二醇、二氧化锰的用量和控制光照功率、光照时间，从而得到理想颜色的丝素纳米银整理剂。The above reagents will have different effects on the color of silk fibroin nano silver, which can be obtained by adjusting the amount of silk fibroin, ascorbic acid, citric acid, chitosan, polyethylene glycol, manganese dioxide and controlling the light power and light time. Silk Fibroin Nano Silver Finishing Agent in Desirable Colors.
作为优选的技术方案：As a preferred technical solution:
如上所述的一种丝素纳米银抗菌显色整理剂的制备方法，壳聚糖的分子量为150000-300000；聚乙二醇的分子量为400-6000。According to the preparation method of the silk fibroin nano-silver antibacterial and color-developing finishing agent, the molecular weight of chitosan is 150,000-300,000; the molecular weight of polyethylene glycol is 400-6,000.
如上所述的一种丝素纳米银抗菌显色整理剂的制备方法，丝素溶液的浓度为1-6wt％；丝素硝酸银溶液中，柠檬酸的浓度为5-20g/L，抗坏血酸的浓度为1-6wt％，AgNO 3的浓度为2-8mg/mL；丝素硝酸银混合溶液中，壳聚糖的浓度为5-15g/L，聚乙二醇与丝素硝酸银溶液的体积比为2-8:10-20，二氧化锰的浓度为0.2-0.5mol/L。 The preparation method of a kind of silk fibroin nano-silver antibacterial color-developing finishing agent as mentioned above, the concentration of silk fibroin solution is 1-6wt%; In silk fibroin silver nitrate solution, the concentration of citric acid is 5-20g/L, the concentration of ascorbic acid The concentration is 1-6wt%, the concentration of AgNO3 is 2-8mg /mL; in the silk fibroin silver nitrate mixed solution, the chitosan concentration is 5-15g/L, the volume of polyethylene glycol and silk fibroin silver nitrate solution The ratio is 2-8:10-20, and the concentration of manganese dioxide is 0.2-0.5mol/L.
如上所述的一种丝素纳米银抗菌显色整理剂的制备方法，丝素溶液的制备过程为：取脱胶蚕丝浸润在浓度为8-12mol/L的溴化锂(LiBr)溶液中，置于40-80℃的烘箱中3-6h，每1h摇晃一次，得到丝素溶液。A kind of preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent as mentioned above, the preparation process of silk fibroin solution is: take degummed silk and soak in the lithium bromide (LiBr) solution that concentration is 8-12mol/L, place 40 Place in an oven at -80°C for 3-6 hours, and shake once every 1 hour to obtain a silk fibroin solution.
本发明还提供采用如上所述的一种丝素纳米银抗菌显色整理剂的制备方法制得的丝素纳米银抗菌显色整理剂，为含纳米银粒子、丝素蛋白、壳聚糖、聚乙二醇和柠檬酸的分散液，其中，各纳米银粒子的形状规则且尺寸大小均匀(本发明在制备过程中加入了柠檬酸，柠檬酸上的多元羧酸能够络合纳米中的Ag +，形成强配合物，从而使反应趋于稳定，形成形状规则、尺寸大小均匀的纳米银粒子)，纳米银粒子稳固地吸附在丝素蛋白分子中的亲水片段上(本发明利用丝素中的酪氨酸残基来还原银离子从而得到的丝素纳米银水溶液，丝素能够作为稳定剂和保护剂，从而纳米银粒子会稳固地吸附在丝素蛋白分子中的亲水片段上)，壳聚糖分子表面的氨基基团和丝素蛋白表面的羧基基团之间形成氢键结合，聚乙二醇通过范德华力吸附包裹纳米银粒子，同时其羟基与丝素蛋白分子中的亲水基团结合(聚乙二醇能够充分的包裹和分散纳米银粒子，使得纳米银粒子稳定的分布在溶胶中而不发生聚集，没有键位连接，但聚乙二醇会与丝素蛋白分子中的亲水片段结合，因为亲疏水的作用力可以使形成的纳米银粒子更加的稳定)。 The present invention also provides a silk fibroin nano-silver antibacterial color-developing finishing agent prepared by the above-mentioned preparation method of a silk nano-silver antibacterial color-developing finishing agent, which is composed of nano-silver particles, silk fibroin, chitosan, The dispersion liquid of polyethylene glycol and citric acid, wherein, each nano-silver particle is regular in shape and uniform in size (the present invention adds citric acid in the preparation process, and the polycarboxylic acid on citric acid can complex the Ag in the nanometer , forming a strong complex, so that the reaction tends to be stable, forming regular shape, uniform size of nano-silver particles), nano-silver particles are firmly adsorbed on the hydrophilic segment in the silk fibroin molecule (the present invention utilizes silk fibroin tyrosine residues to reduce silver ions to obtain silk fibroin nano-silver aqueous solution, silk fibroin can be used as a stabilizer and protective agent, so that the nano-silver particles will be firmly adsorbed on the hydrophilic segment of the silk fibroin molecule), Hydrogen bonding is formed between the amino groups on the surface of chitosan molecules and the carboxyl groups on the surface of silk fibroin, polyethylene glycol adsorbs and wraps nano-silver particles through Van der Waals force, and at the same time, its hydroxyl groups and the hydrophilic groups in silk fibroin molecules Group combination (polyethylene glycol can fully wrap and disperse nano-silver particles, so that nano-silver particles are stably distributed in the sol without aggregation, and there is no bond connection, but polyethylene glycol will combine with silk fibroin molecules The combination of hydrophilic fragments, because the hydrophilic and hydrophobic forces can make the formed silver nanoparticles more stable).
作为优选的技术方案：As a preferred technical solution:
如上所述的丝素纳米银抗菌显色整理剂，纳米银粒子的粒径为10-100nm，均为球形结构，粒子分散均匀，粒径分布范围较窄。In the silk fibroin nano-silver antibacterial and color-developing finishing agent mentioned above, the particle size of the nano-silver particles is 10-100 nm, all of which are spherical structures, the particles are uniformly dispersed, and the particle size distribution range is narrow.
如上所述的丝素纳米银抗菌显色整理剂，丝素纳米银抗菌显色整理剂具有优异的分散性，EDS能谱和透射电镜图中显示Ag元素分布均匀；丝素纳米银抗菌显色整理剂具有超强的杀菌性，对大肠杆菌和金黄色葡萄球菌的抑菌率都达到99.9±0.1％。The silk fibroin nano-silver antibacterial and color-developing finishing agent as mentioned above, the silk fibroin nano-silver anti-bacterial color-developing finishing agent has excellent dispersibility, and the EDS energy spectrum and the transmission electron microscope figure show that the Ag element is evenly distributed; The finishing agent has strong bactericidal properties, and the bacteriostatic rate against Escherichia coli and Staphylococcus aureus both reaches 99.9±0.1%.
本发明还提供如上所述的丝素纳米银抗菌显色整理剂的应用，将等离子体改性的卡洛丝纤维混纺面料浸轧丝素纳米银抗菌显色整理剂后先干燥再进行水蒸气处理，制得丝素纳米银显色抗菌功能卡洛丝纤维混纺面料；The present invention also provides the application of the silk fibroin nano-silver antibacterial and color-developing finishing agent as described above. After the silk fibroin nano-silver antibacterial and color-developing finishing agent is dipped into the plasma-modified Carlo silk fiber blended fabric, it is first dried and then steamed. treatment to obtain silk fibroin nano-silver color-developing antibacterial functional Carlo silk fiber blended fabric;
卡洛丝纤维混纺面料由卡洛丝纤维和棉纤维组成；Carlo silk fiber blended fabric is composed of Carlo silk fiber and cotton fiber;
水蒸气处理的温度为100-120℃，时间为20-100min，水蒸气处理采用高压灭菌锅，水蒸气处理后取 出面料自然风干12-24h，此处理起到了固色的作用且可以改变丝素蛋白性能，能使面料拥有更好的手感和抗皱性能。The temperature of the steam treatment is 100-120°C, and the time is 20-100min. The steam treatment uses a high-pressure sterilizer. After the steam treatment, take out the fabric and dry it naturally for 12-24 hours. This treatment has the effect of fixing the color and can change the silk. The property of plain protein can make the fabric have better hand feeling and anti-wrinkle performance.
作为优选的技术方案：As a preferred technical solution:
如上所述的应用，等离子体改性的过程为：将卡洛丝纤维混纺面料置于去离子水中清洗10-20min，晾干后放入低温等离子体处理装置中，使用空气、氧气、氮气或氩气对卡洛丝纤维混纺面料进行等离子体处理，处理功率为20-240W，处理时间为1-10min；As mentioned above, the process of plasma modification is as follows: the Carlo silk fiber blended fabric is cleaned in deionized water for 10-20min, and then put into a low-temperature plasma treatment device after drying, using air, oxygen, nitrogen or Argon gas is used for plasma treatment of Carlo silk fiber blended fabric, the treatment power is 20-240W, and the treatment time is 1-10min;
卡洛丝纤维混纺面料的制备过程为：将棉纤维纺成精梳棉条后，与卡洛丝纤维按照8-6:2-4的质量比进行混合，采用环锭纺、紧密纺或转杯纺纺纱方法纺织成卡洛丝纤维混纺面料；The preparation process of Carlo silk fiber blended fabric is as follows: after cotton fiber is spun into combed cotton sliver, it is mixed with Carlo silk fiber according to the mass ratio of 8-6:2-4, and it is spun by ring spinning, compact spinning or rotary spinning. The cup spinning method is used to weave into Carlo silk fiber blended fabric;
浸轧为二浸二轧(整个过程浸泡两次，挤轧两次)，浸泡浴比为1:10-100，每次浸泡时间为20-60min，浸泡温度为30-45℃；挤轧速度为2-4cm/s，压力为2-5Kg/cm 2，轧余率为80-90％；干燥的温度为60-80℃。 The padding is two-dipping and two-rolling (the whole process is soaked twice and squeezed twice), the soaking bath ratio is 1:10-100, the soaking time is 20-60min each time, and the soaking temperature is 30-45°C; The drying temperature is 2-4cm/s, the pressure is 2-5Kg/cm 2 , the scrap rate is 80-90%, and the drying temperature is 60-80°C.
如上所述的应用，丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率为8.5-12.5％，折皱回复角为133-135°，对大肠杆菌的抑菌率达到99.9％，洗涤20次后对大肠杆菌的抑菌率达到90-95％，对金黄色葡萄球菌的抑菌率达到99.9％，洗涤20次后对金黄色葡萄球菌的抑菌率达到55-60％。As mentioned above, the silk fibroin nano-silver color development and antibacterial function Carlo silk fiber blended fabric has a moisture regain of 8.5-12.5%, a wrinkle recovery angle of 133-135°, and a bacteriostatic rate of 99.9% against E. coli. After 20 times of washing, the antibacterial rate of Escherichia coli reaches 90-95%, the antibacterial rate of Staphylococcus aureus reaches 99.9%, and the antibacterial rate of Staphylococcus aureus reaches 55-60% after washing 20 times.
本发明的原理如下：Principle of the present invention is as follows:
本发明利用丝素蛋白和抗坏血酸的还原性可以不加任何化学还原剂，其安全环保，反应平缓，从而可控的来制备具有抗菌功能的纳米银粒子，加入壳聚糖可以很好的与丝素纳米金属粒子结合并发挥抗菌性能，并且银离子与壳聚糖中氧原子和氮原子上的孤对电子能发生螯合作用，可以减少金属粒子的使用量，以免造成重金属污染，通过调节丝素蛋白、抗坏血酸、柠檬酸、聚乙二醇、二氧化锰浓度和光照时间，可以使丝素纳米金属混合溶液呈现不同的颜色，将染色和抗菌同步进行并赋予织物一些抗皱性能和良好的手感等等，节省了能源，降低了废水的排放，具有十分巨大的应用价值和研究潜力。The present invention utilizes the reducibility of silk fibroin and ascorbic acid without adding any chemical reducing agent, which is safe and environmentally friendly, and the reaction is gentle, so that nano-silver particles with antibacterial function can be prepared in a controllable manner. Adding chitosan can be well combined with silk The silver ions and the lone pairs of electrons on the oxygen atoms and nitrogen atoms in chitosan can be chelated, which can reduce the amount of metal particles used to avoid heavy metal pollution. By adjusting the silk Fibroin, ascorbic acid, citric acid, polyethylene glycol, manganese dioxide concentration and light time can make the silk fibroin nano-metal mixed solution present different colors, simultaneously carry out dyeing and antibacterial and give the fabric some anti-wrinkle properties and good hand feeling etc., saving energy, reducing the discharge of waste water, and having very huge application value and research potential.
本发明首先将卡洛丝纤维和精梳棉条按照质量比2-4:8-6进行混合，用环锭纺、紧密纺、转杯纺三种纺纱方法纺得品质优良的卡洛丝纤维与精梳棉条混纺面料，纺制出来的混纺面料具有卡洛丝纤维特有的80-90％的中空度带来的优秀的保暖性能和吸湿性能，然后对卡洛丝纤维混纺面料进行低温等离子体处理，接着使用丝素纳米银抗菌显色整理剂处理卡洛丝纤维混纺面料，二浸二轧后真空干燥，使得抗菌显色整理剂和卡洛丝纤维混纺面料用物理吸附的方式结合，通过挤轧这种结合方式，使面料保持良好的柔软性和透气性，同时通过浸轧处理使整理剂中的纳米银牢固地附着在纱线上甚至进入纱线的孔隙中，抗紫外效果更加持久，同时使银离子持续释放，释放量高，且抗菌效果持久，最后对卡洛丝纤维混纺面料进行水蒸气处理，以改变丝素蛋白性能，使面料拥有更好的手感和抗皱性能。整个过程将染色工艺和抗菌整理工艺结合，大幅度减少了印染废水的排放，而整理剂中的丝素与壳聚糖，会在织物表面形成了一层丝素/壳聚糖薄膜，从而提高了织物的弹性，同时丝素大分子在纤维间形成交联键以及丝素在纤维 上成膜导致纤维表面或交织点发生粘接而导致织物抗弯性能增加，从而提高了面料的抗皱性，改善了面料的手感。壳聚糖加入后能够改善织物耐水洗、耐摩擦，并具有固色和增强的作用，可提高织物的坚牢度，减少皱缩率。前期研究证明采用壳聚糖处理后的织物具有滑爽光洁的外观，挺括的手感以及透气、吸湿和抗弯刚度，最终得到的显色抗菌功能的卡洛丝纤维混纺面料具有长效抗菌性、鲜艳的颜色、优良的抗皱性和良好的手感。In the present invention, firstly, the Carlo silk fiber and the combed cotton sliver are mixed according to the mass ratio of 2-4:8-6, and the Carlo silk with excellent quality is spun by three spinning methods: ring spinning, compact spinning and rotor spinning Fiber and combed sliver blended fabric, the spun blended fabric has excellent thermal performance and moisture absorption performance brought by the unique 80-90% hollowness of Carlos fiber, and then the Carlos fiber blended fabric is subjected to low temperature Plasma treatment, followed by the use of silk fibroin nano-silver antibacterial color-developing finishing agent to treat the Carlo silk fiber blended fabric, vacuum drying after two dipping and two rolling, so that the antibacterial color developing finishing agent and Carlo silk fiber blended fabric are combined by physical adsorption , through this combination method of extrusion, the fabric maintains good softness and air permeability, and at the same time, the nano-silver in the finishing agent is firmly attached to the yarn and even enters the pores of the yarn through padding treatment, and the anti-ultraviolet effect It is more durable, and at the same time, it makes the continuous release of silver ions, high release amount, and long-lasting antibacterial effect. Finally, steam treatment is performed on the Carlo silk fiber blended fabric to change the properties of silk fibroin, so that the fabric has better hand feeling and anti-wrinkle performance. The whole process combines dyeing process and antibacterial finishing process, which greatly reduces the discharge of printing and dyeing wastewater, and the silk fibroin and chitosan in the finishing agent will form a layer of silk fibroin/chitosan film on the surface of the fabric, thereby improving Improve the elasticity of the fabric, and at the same time, silk fibroin macromolecules form cross-linking bonds between fibers and silk fibroin forms a film on the fiber, resulting in bonding of the fiber surface or interweaving points, resulting in an increase in the bending resistance of the fabric, thereby improving the wrinkle resistance of the fabric. Improved the feel of the fabric. After adding chitosan, it can improve the washing resistance and friction resistance of the fabric, and has the effect of color fixation and reinforcement, which can improve the fastness of the fabric and reduce the shrinkage rate. Preliminary studies have proved that the fabric treated with chitosan has a smooth and smooth appearance, a crisp feel, breathability, moisture absorption, and bending stiffness. Bright colors, excellent wrinkle resistance and good hand feeling.
有益效果：Beneficial effect:
(1)本发明的整理剂中的丝素纳米银由于量子、小尺寸效应和极大的比表面积，可以呈现更佳的理化稳定性、超强的杀菌性和极低的生物毒性；(1) The silk fibroin nano-silver in the finishing agent of the present invention can present better physical and chemical stability, super strong bactericidal properties and extremely low biological toxicity due to quantum, small size effect and huge specific surface area;
(2)本发明通过调节试剂的用量可得到3种显色抗菌整理剂，对大肠杆菌和金黄色葡萄球菌的抑菌率都较高，且都具有良好的抗菌耐洗性；(2) The present invention can obtain 3 kinds of chromogenic antibacterial finishing agents by adjusting the consumption of reagents, and the bacteriostatic rate to Escherichia coli and Staphylococcus aureus is all higher, and all have good antibacterial washability;
(3)本发明的工艺操作简单，低温等离子体处理和水蒸汽处理均为绿色环保工艺；(3) The process of the present invention is simple to operate, and both low-temperature plasma treatment and water vapor treatment are green and environmentally friendly processes;
(4)本发明中的原料为天然植物纤维绿色无公害，采摘方便易得且价格低廉可节约纺织成本；(4) The raw material in the present invention is natural plant fiber green and pollution-free, easy to pick and easy to get and cheap and can save textile cost;
(5)本发明将染色工艺与抗菌整理一体化，得到了多色抗菌的卡洛丝纤维混纺面料；(5) the present invention integrates dyeing process and antibacterial finishing, has obtained multicolor antibacterial carlos fiber blended fabric;
(6)本发明的卡洛丝纤维混纺面料保留了卡洛丝纤维水晶般的光泽，柔软的手感以及透气性、吸湿性和保暖性等优点，并具有长效抗菌性及显色性能，集多功能化于一体。(6) The Carlos fiber blended fabric of the present invention retains the crystal-like luster of the Carlos fiber, the advantages of soft feel, air permeability, hygroscopicity and warmth retention, and has long-acting antibacterial properties and color rendering properties. All in one.
附图说明Description of drawings
图1为实施例7～9的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率的变化图；Fig. 1 is the changing figure of the moisture regain of silk fibroin nano-silver color developing antibacterial function carlos fiber blended fabric of embodiment 7～9;
图2为实施例8的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的抗菌率的变化图；Fig. 2 is the change figure of the antibacterial rate of silk fibroin nano silver color developing antibacterial function carlos fiber blended fabric of embodiment 8;
图3为实施例7～9的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的折皱回复角的变化图；Fig. 3 is the change figure of the wrinkle recovery angle of the silk fibroin nano silver color development antibacterial function carlos fiber blended fabric of embodiment 7～9;
图4为实施例1制得的丝素纳米银抗菌显色整理剂的抗菌性能表征图(图中a为大肠杆菌，b为金黄色葡萄球菌)；Fig. 4 is the antibacterial performance characterization figure of the silk fibroin nano-silver antibacterial color-developing finishing agent that embodiment 1 makes (a among the figure is escherichia coli, and b is staphylococcus aureus);
图5为实施例2制得的丝素纳米银抗菌显色整理剂的抗菌性能表征图(图中a为大肠杆菌，b为金黄色葡萄球菌)；Fig. 5 is the antibacterial performance characterization figure of the silk fibroin nano silver antibacterial color developing finishing agent that embodiment 2 makes (a among the figure is escherichia coli, b is staphylococcus aureus);
图6为实施例3制得的丝素纳米银抗菌显色整理剂的抗菌性能表征图(图中a为大肠杆菌，b为金黄色葡萄球菌)Fig. 6 is the antibacterial performance characterization figure of the silk fibroin nano silver antibacterial color-developing finishing agent that embodiment 3 makes (a among the figure is escherichia coli, b is staphylococcus aureus)
图7为实施例7的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的表面形态扫描电镜(SEM)图及其银元素分布图；Fig. 7 is the surface morphology scanning electron microscope (SEM) figure and its silver element distribution figure of the silk fibroin nano silver color development antibacterial function carlos fiber blended fabric of embodiment 7;
图8为实施例8的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的表面形态扫描电镜(SEM)图及其银元素分布图；Fig. 8 is the surface morphology scanning electron microscope (SEM) picture and its silver element distribution figure of the silk fibroin nano silver color development antibacterial function carlos fiber blended fabric of embodiment 8;
图9为实施例9的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的表面形态扫描电镜(SEM)图及其银元素分布图；Fig. 9 is the surface morphology scanning electron microscope (SEM) figure and its silver element distribution figure of the silk fibroin nano silver color development antibacterial function carlos fiber blended fabric of embodiment 9;
图10为实施例1～3制得的丝素纳米银抗菌显色整理剂的透射电镜(TEM)图(图中a为实施例1，b为实施例2，c为实施例3)。Figure 10 is a transmission electron microscope (TEM) figure of the silk fibroin nanosilver antibacterial color-developing finishing agent prepared in Examples 1-3 (a in the figure is Example 1, b is Example 2, and c is Example 3).
具体实施方式detailed description
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1Example 1
一种丝素纳米银抗菌显色整理剂的制备方法，具体步骤如下：A preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent, the specific steps are as follows:
(1)丝素溶液的制备过程为：取脱胶蚕丝浸润在浓度为9.7mol/L的溴化锂溶液中，置于60℃的烘箱中4h，每1h摇晃一次，得到浓度为1wt％的丝素溶液；(1) The preparation process of the silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 9.7mol/L, place it in an oven at 60°C for 4 hours, and shake it every 1 hour to obtain a silk solution with a concentration of 1 wt%. ;
(2)向步骤(1)制得的丝素溶液中加入柠檬酸和抗坏血酸后，调节其pH值至3.6，再加入AgNO 3晶体，得到丝素硝酸银溶液；丝素硝酸银溶液中，柠檬酸的浓度为15g/L，抗坏血酸的浓度为1wt％，AgNO 3的浓度为4mg/mL； (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 3.6, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 15g/L, the concentration of ascorbic acid is 1wt%, and the concentration of AgNO3 is 4mg/mL;
(3)向步骤(2)制得的丝素硝酸银溶液中加入壳聚糖(分子量为150000)、聚乙二醇(分子量为400)和二氧化锰共混后得到丝素硝酸银混合溶液；丝素硝酸银混合溶液中，壳聚糖的浓度为5g/L，聚乙二醇与丝素硝酸银溶液的体积比为4:16，二氧化锰的浓度为0.2mol/L；(3) Add chitosan (molecular weight is 150000), polyethylene glycol (molecular weight is 400) and manganese dioxide blend to obtain silk fibroin silver nitrate mixed solution in the silk fibroin silver nitrate solution that step (2) makes ; In the silk fibroin silver nitrate mixed solution, the concentration of chitosan is 5g/L, the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 4:16, and the concentration of manganese dioxide is 0.2mol/L;
(4)将步骤(3)制得的丝素硝酸银混合溶液置于40W的LED灯下2h，得到显铁黄色的丝素纳米银抗菌显色整理剂。(4) Put the silk fibroin silver nitrate mixed solution prepared in step (3) under a 40W LED lamp for 2 hours to obtain a silk fibroin nano-silver antibacterial color-developing finishing agent showing iron yellow.
如图10所示，制得的丝素纳米银抗菌显色整理剂为含纳米银粒子、丝素蛋白、壳聚糖、聚乙二醇和柠檬酸的分散液；其中，各纳米银粒子的形状规则且尺寸大小均匀，纳米银粒子的粒径为10-30nm，纳米银粒子稳固地吸附在丝素蛋白分子中的亲水片段上，壳聚糖分子表面的氨基基团和丝素蛋白表面的羧基基团之间形成氢键结合，聚乙二醇通过范德华力吸附包裹纳米银粒子，同时其羟基与丝素蛋白分子中的亲水基团结合；丝素纳米银抗菌显色整理剂具有优异的分散性，EDS能谱和透射电镜图中显示Ag元素分布均匀；如图4所示，可明显观察到培养皿中无细菌生长，丝素纳米银抗菌显色整理剂具有超强的杀菌性，对大肠杆菌和金黄色葡萄球菌的抑菌率都达到100％。As shown in Figure 10, the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle Regular and uniform in size, the particle size of nano-silver particles is 10-30nm, nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, the amino groups on the surface of chitosan molecules and the surface of silk fibroin Hydrogen bonding is formed between carboxyl groups, and polyethylene glycol is adsorbed and wrapped by van der Waals force to wrap nano-silver particles, while its hydroxyl groups are combined with hydrophilic groups in silk fibroin molecules; Dispersion, EDS energy spectrum and transmission electron microscope show that the Ag element is evenly distributed; as shown in Figure 4, it can be clearly observed that there is no bacterial growth in the petri dish, and the silk fibroin nano-silver antibacterial and color-developing finishing agent has super bactericidal properties , the bacteriostatic rate of Escherichia coli and Staphylococcus aureus all reached 100%.
实施例2Example 2
一种丝素纳米银抗菌显色整理剂的制备方法，具体步骤如下：A preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent, the specific steps are as follows:
(1)丝素溶液的制备过程为：取脱胶蚕丝浸润在浓度为8.4mol/L的溴化锂溶液中，置于60℃的烘 箱中6h，每1h摇晃一次，得到浓度为3wt％的丝素溶液；(1) The preparation process of silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 8.4mol/L, place it in an oven at 60°C for 6 hours, and shake it every 1 hour to obtain a silk solution with a concentration of 3wt%. ;
(2)向步骤(1)制得的丝素溶液中加入柠檬酸和抗坏血酸后，调节其pH值至4.4，再加入AgNO 3晶体，得到丝素硝酸银溶液；丝素硝酸银溶液中，柠檬酸的浓度为5g/L，抗坏血酸的浓度为6wt％，AgNO 3的浓度为6mg/mL； (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 4.4, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 5g/L, the concentration of ascorbic acid is 6wt%, and the concentration of AgNO3 is 6mg/mL;
(3)向步骤(2)制得的丝素硝酸银溶液中加入壳聚糖(分子量为300000)、聚乙二醇(分子量为6000)和二氧化锰共混后得到丝素硝酸银混合溶液；丝素硝酸银混合溶液中，壳聚糖的浓度为15g/L，聚乙二醇与丝素硝酸银溶液的体积比为2:18，二氧化锰的浓度为0.3mol/L；(3) Add chitosan (molecular weight is 300,000), polyethylene glycol (molecular weight is 6000) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ; In the silk fibroin silver nitrate mixed solution, the concentration of chitosan is 15g/L, the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 2:18, and the concentration of manganese dioxide is 0.3mol/L;
(4)将步骤(3)制得的丝素硝酸银混合溶液置于60W的LED灯下48h，得到显紫红色的丝素纳米银抗菌显色整理剂。(4) Put the silk fibroin silver nitrate mixed solution prepared in step (3) under a 60W LED lamp for 48 hours to obtain a purple-red silk fibroin nano-silver antibacterial color-developing finishing agent.
如图10所示，制得的丝素纳米银抗菌显色整理剂为含纳米银粒子、丝素蛋白、壳聚糖、聚乙二醇和柠檬酸的分散液；其中，各纳米银粒子的形状规则且尺寸大小均匀，纳米银粒子的粒径为35-75nm，纳米银粒子稳固地吸附在丝素蛋白分子中的亲水片段上，壳聚糖分子表面的氨基基团和丝素蛋白表面的羧基基团之间形成氢键结合，聚乙二醇通过范德华力吸附包裹纳米银粒子，同时其羟基与丝素蛋白分子中的亲水基团结合；丝素纳米银抗菌显色整理剂具有优异的分散性，EDS能谱和透射电镜图中显示Ag元素分布均匀；如图5所示，可明显观察到培养皿中无细菌生长，丝素纳米银抗菌显色整理剂具有超强的杀菌性，对大肠杆菌和金黄色葡萄球菌的抑菌率都达到99.9％。As shown in Figure 10, the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle Regular and uniform in size, the particle size of nano-silver particles is 35-75nm, nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, the amino groups on the surface of chitosan molecules and the surface of silk fibroin Hydrogen bonding is formed between carboxyl groups, and polyethylene glycol is adsorbed and wrapped by van der Waals force to wrap nano-silver particles, while its hydroxyl groups are combined with hydrophilic groups in silk fibroin molecules; Dispersion, EDS energy spectrum and transmission electron microscope show that the Ag element is evenly distributed; as shown in Figure 5, it can be clearly observed that there is no bacterial growth in the petri dish, and the silk fibroin nano-silver antibacterial and color-developing finishing agent has super bactericidal properties , the antibacterial rate of Escherichia coli and Staphylococcus aureus reached 99.9%.
实施例3Example 3
一种丝素纳米银抗菌显色整理剂的制备方法，具体步骤如下：A preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent, the specific steps are as follows:
(1)丝素溶液的制备过程为：取脱胶蚕丝浸润在浓度为12mol/L的溴化锂溶液中，置于60℃的烘箱中3h，每1h摇晃一次，得到浓度为6wt％的丝素溶液；(1) The preparation process of silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 12mol/L, place it in an oven at 60° C. for 3 hours, and shake it every 1 hour to obtain a silk solution with a concentration of 6 wt%.
(2)向步骤(1)制得的丝素溶液中加入柠檬酸和抗坏血酸后，调节其pH值至4，再加入AgNO 3晶体，得到丝素硝酸银溶液；丝素硝酸银溶液中，柠檬酸的浓度为10g/L，抗坏血酸的浓度为4wt％，AgNO 3的浓度为2mg/mL； (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 4, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 10g/L, the concentration of ascorbic acid is 4wt%, and the concentration of AgNO3 is 2mg/mL;
(3)向步骤(2)制得的丝素硝酸银溶液中加入壳聚糖(分子量为230000)、聚乙二醇(分子量为3000)和二氧化锰共混后得到丝素硝酸银混合溶液；丝素硝酸银混合溶液中，壳聚糖的浓度为10g/L，聚乙二醇与丝素硝酸银溶液的体积比为8:12，二氧化锰的浓度为0.5mol/L；(3) Add chitosan (molecular weight is 230000), polyethylene glycol (molecular weight is 3000) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ; In the silk fibroin silver nitrate mixed solution, the concentration of chitosan is 10g/L, the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 8:12, and the concentration of manganese dioxide is 0.5mol/L;
(4)将步骤(3)制得的丝素硝酸银混合溶液置于10W的LED灯下120h，得到显军黄色的丝素纳米银抗菌显色整理剂。(4) Place the silk fibroin silver nitrate mixed solution prepared in step (3) under a 10W LED lamp for 120 hours to obtain a military yellow silk fibroin nano silver antibacterial color-developing finishing agent.
如图10所示，制得的丝素纳米银抗菌显色整理剂为含纳米银粒子、丝素蛋白、壳聚糖、聚乙二醇和柠檬酸的分散液；其中，各纳米银粒子的形状规则且尺寸大小均匀，纳米银粒子的粒径为70-100nm， 纳米银粒子稳固地吸附在丝素蛋白分子中的亲水片段上，壳聚糖分子表面的氨基基团和丝素蛋白表面的羧基基团之间形成氢键结合，聚乙二醇通过范德华力吸附包裹纳米银粒子，同时其羟基与丝素蛋白分子中的亲水基团结合；丝素纳米银抗菌显色整理剂具有优异的分散性，EDS能谱和透射电镜图中显示Ag元素分布均匀；如图6所示，可明显观察到培养皿中无细菌生长，丝素纳米银抗菌显色整理剂具有超强的杀菌性，对大肠杆菌和金黄色葡萄球菌的抑菌率都达到99.8％。As shown in Figure 10, the prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle Regular and uniform in size, the particle size of nano-silver particles is 70-100nm, nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, the amino groups on the surface of chitosan molecules and the Hydrogen bonding is formed between carboxyl groups, and polyethylene glycol is adsorbed and wrapped by van der Waals force to wrap nano-silver particles, while its hydroxyl groups are combined with hydrophilic groups in silk fibroin molecules; Dispersion, EDS energy spectrum and transmission electron microscope show that Ag elements are evenly distributed; as shown in Figure 6, it can be clearly observed that there is no bacterial growth in the petri dish, and the silk fibroin nano-silver antibacterial and color-developing finishing agent has super bactericidal properties , the antibacterial rate of Escherichia coli and Staphylococcus aureus reached 99.8%.
实施例4Example 4
一种丝素纳米银抗菌显色整理剂的制备方法，具体步骤如下：A preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent, the specific steps are as follows:
(1)丝素溶液的制备过程为：取脱胶蚕丝浸润在浓度为9mol/L的溴化锂溶液中，置于60℃的烘箱中4.5h，每1h摇晃一次，得到浓度为2wt％的丝素溶液；(1) The preparation process of the silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 9mol/L, place it in an oven at 60°C for 4.5 hours, and shake it once every 1 hour to obtain a silk solution with a concentration of 2wt%. ;
(2)向步骤(1)制得的丝素溶液中加入柠檬酸和抗坏血酸后，调节其pH值至5.6，再加入AgNO 3晶体，得到丝素硝酸银溶液；丝素硝酸银溶液中，柠檬酸的浓度为8g/L，抗坏血酸的浓度为2wt％，AgNO 3的浓度为3.5mg/mL； (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 5.6, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 8g/L, the concentration of ascorbic acid is 2wt%, the concentration of AgNO3 is 3.5mg/mL;
(3)向步骤(2)制得的丝素硝酸银溶液中加入壳聚糖(分子量为180000)、聚乙二醇(分子量为1500)和二氧化锰共混后得到丝素硝酸银混合溶液；丝素硝酸银混合溶液中，壳聚糖的浓度为8g/L，聚乙二醇与丝素硝酸银溶液的体积比为2:10，二氧化锰的浓度为0.25mol/L；(3) Add chitosan (molecular weight is 180,000), polyethylene glycol (molecular weight is 1500) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ; In the silk fibroin silver nitrate mixed solution, the concentration of chitosan is 8g/L, the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 2:10, and the concentration of manganese dioxide is 0.25mol/L;
(4)将步骤(3)制得的丝素硝酸银混合溶液置于20W的LED灯下25h，得到显军黄色的丝素纳米银抗菌显色整理剂。(4) Put the silk fibroin silver nitrate mixed solution prepared in the step (3) under a 20W LED lamp for 25 hours to obtain an antibacterial and color-developing finishing agent of silk fibroin nano-silver showing a military yellow color.
制得的丝素纳米银抗菌显色整理剂为含纳米银粒子、丝素蛋白、壳聚糖、聚乙二醇和柠檬酸的分散液；其中，各纳米银粒子的形状规则且尺寸大小均匀，纳米银粒子的粒径为20-40nm，纳米银粒子稳固地吸附在丝素蛋白分子中的亲水片段上，壳聚糖分子表面的氨基基团和丝素蛋白表面的羧基基团之间形成氢键结合，聚乙二醇通过范德华力吸附包裹纳米银粒子，同时其羟基与丝素蛋白分子中的亲水基团结合；丝素纳米银抗菌显色整理剂具有优异的分散性，EDS能谱和透射电镜图中显示Ag元素分布均匀；丝素纳米银抗菌显色整理剂具有超强的杀菌性，对大肠杆菌和金黄色葡萄球菌的抑菌率都达到100％。The prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle is regular and the size is uniform, The particle size of nano-silver particles is 20-40nm. Nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, and the amino groups on the surface of chitosan molecules and the carboxyl groups on the surface of silk fibroin form a Hydrogen bonding, polyethylene glycol adsorbs and wraps nano-silver particles through van der Waals force, and its hydroxyl group combines with hydrophilic groups in silk fibroin molecules; silk nano-silver antibacterial color-developing finishing agent has excellent dispersibility, EDS can Spectrum and transmission electron micrographs show that the Ag element is evenly distributed; the silk fibroin nano-silver antibacterial and chromogenic finishing agent has super bactericidal properties, and the bacteriostatic rate against Escherichia coli and Staphylococcus aureus reaches 100%.
实施例5Example 5
一种丝素纳米银抗菌显色整理剂的制备方法，具体步骤如下：A preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent, the specific steps are as follows:
(1)丝素溶液的制备过程为：取脱胶蚕丝浸润在浓度为10.5mol/L的溴化锂溶液中，置于75℃的烘箱中3.5h，每1h摇晃一次，得到浓度为4wt％的丝素溶液；(1) The preparation process of silk fibroin solution is as follows: soak degummed silk in a lithium bromide solution with a concentration of 10.5mol/L, place it in an oven at 75°C for 3.5h, and shake it every 1h to obtain silk fibroin with a concentration of 4wt%. solution;
(2)向步骤(1)制得的丝素溶液中加入柠檬酸和抗坏血酸后，调节其pH值至5.2，再加入AgNO 3晶体，得到丝素硝酸银溶液；丝素硝酸银溶液中，柠檬酸的浓度为12g/L，抗坏血酸的浓度为3wt％，AgNO 3的浓度为7mg/mL； (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 5.2, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 12g/L, the concentration of ascorbic acid is 3wt%, the concentration of AgNO3 is 7mg/mL;
(3)向步骤(2)制得的丝素硝酸银溶液中加入壳聚糖(分子量为250000)、聚乙二醇(分子量为3500)和二氧化锰共混后得到丝素硝酸银混合溶液；丝素硝酸银混合溶液中，壳聚糖的浓度为12g/L，聚乙二醇与丝素硝酸银溶液的体积比为5:15，二氧化锰的浓度为0.4mol/L；(3) Add chitosan (molecular weight is 250,000), polyethylene glycol (molecular weight is 3500) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ; In the silk fibroin silver nitrate mixed solution, the concentration of chitosan is 12g/L, the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 5:15, and the concentration of manganese dioxide is 0.4mol/L;
(4)将步骤(3)制得的丝素硝酸银混合溶液置于30W的LED灯下40h，得到显铁黄色的丝素纳米银抗菌显色整理剂。(4) Put the silk fibroin silver nitrate mixed solution prepared in step (3) under a 30W LED lamp for 40 hours to obtain a silk fibroin nano-silver antibacterial and color-developing finishing agent showing iron yellow.
制得的丝素纳米银抗菌显色整理剂为含纳米银粒子、丝素蛋白、壳聚糖、聚乙二醇和柠檬酸的分散液；其中，各纳米银粒子的形状规则且尺寸大小均匀，纳米银粒子的粒径为50-90nm，纳米银粒子稳固地吸附在丝素蛋白分子中的亲水片段上，壳聚糖分子表面的氨基基团和丝素蛋白表面的羧基基团之间形成氢键结合，聚乙二醇通过范德华力吸附包裹纳米银粒子，同时其羟基与丝素蛋白分子中的亲水基团结合；丝素纳米银抗菌显色整理剂具有优异的分散性，EDS能谱和透射电镜图中显示Ag元素分布均匀；丝素纳米银抗菌显色整理剂具有超强的杀菌性，对大肠杆菌和金黄色葡萄球菌的抑菌率都达到99.8％。The prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle is regular and the size is uniform, The particle size of nano-silver particles is 50-90nm. Nano-silver particles are firmly adsorbed on the hydrophilic segment of silk fibroin molecules, and the amino groups on the surface of chitosan molecules and the carboxyl groups on the surface of silk fibroin form a Hydrogen bonding, polyethylene glycol adsorbs and wraps nano-silver particles through van der Waals force, and its hydroxyl group combines with hydrophilic groups in silk fibroin molecules; silk nano-silver antibacterial color-developing finishing agent has excellent dispersibility, EDS can Spectrum and transmission electron micrographs show that the Ag element is evenly distributed; the silk fibroin nano-silver antibacterial and color-developing finishing agent has super bactericidal properties, and the bacteriostatic rate against Escherichia coli and Staphylococcus aureus reaches 99.8%.
实施例6Example 6
一种丝素纳米银抗菌显色整理剂的制备方法，具体步骤如下：A preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent, the specific steps are as follows:
(1)丝素溶液的制备过程为：取脱胶蚕丝浸润在浓度为11mol/L的溴化锂溶液中，置于80℃的烘箱中3h，每1h摇晃一次，得到浓度为5wt％的丝素溶液；(1) The preparation process of the silk fibroin solution is as follows: take the degummed silk and soak it in a lithium bromide solution with a concentration of 11mol/L, place it in an oven at 80° C. for 3 hours, and shake it once every 1 hour to obtain a silk solution with a concentration of 5 wt%.
(2)向步骤(1)制得的丝素溶液中加入柠檬酸和抗坏血酸后，调节其pH值至4.8，再加入AgNO 3晶体，得到丝素硝酸银溶液；丝素硝酸银溶液中，柠檬酸的浓度为20g/L，抗坏血酸的浓度为5wt％，AgNO 3的浓度为4.5mg/mL； (2) After adding citric acid and ascorbic acid to the silk fibroin solution prepared in step (1), adjust its pH value to 4.8, then add AgNO 3 crystals to obtain a silk fibroin silver nitrate solution; in the silk fibroin silver nitrate solution, lemon The concentration of acid is 20g/L, the concentration of ascorbic acid is 5wt%, and the concentration of AgNO3 is 4.5mg/mL;
(3)向步骤(2)制得的丝素硝酸银溶液中加入壳聚糖(分子量为270000)、聚乙二醇(分子量为4000)和二氧化锰共混后得到丝素硝酸银混合溶液；丝素硝酸银混合溶液中，壳聚糖的浓度为14g/L，聚乙二醇与丝素硝酸银溶液的体积比为8:20，二氧化锰的浓度为0.45mol/L；(3) Add chitosan (molecular weight is 270,000), polyethylene glycol (molecular weight is 4000) and manganese dioxide to the silk fibroin silver nitrate solution that step (2) makes to obtain the silk fibroin silver nitrate mixed solution ; In the silk fibroin silver nitrate mixed solution, the concentration of chitosan is 14g/L, the volume ratio of polyethylene glycol and silk fibroin silver nitrate solution is 8:20, and the concentration of manganese dioxide is 0.45mol/L;
(4)将步骤(3)制得的丝素硝酸银混合溶液置于50W的LED灯下78h，得到显紫红色的丝素纳米银抗菌显色整理剂。(4) Put the silk fibroin silver nitrate mixed solution prepared in the step (3) under a 50W LED lamp for 78 hours to obtain a purplish red silk fibroin nano silver antibacterial color-developing finishing agent.
制得的丝素纳米银抗菌显色整理剂为含纳米银粒子、丝素蛋白、壳聚糖、聚乙二醇和柠檬酸的分散液；其中，各纳米银粒子的形状规则且尺寸大小均匀，纳米银粒子的粒径为40-60nm，纳米银粒子稳固地吸附在丝素蛋白分子中的亲水片段上，壳聚糖分子表面的氨基基团和丝素蛋白表面的羧基基团之间形成氢键结合，聚乙二醇通过范德华力吸附包裹纳米银粒子，同时其羟基与丝素蛋白分子中的亲水基团结合；丝素纳米银抗菌显色整理剂具有优异的分散性，EDS能谱和透射电镜图中显示Ag元素分布均匀；丝素纳米银抗菌显色整理剂具有超强的杀菌性，对大肠杆菌和金黄色葡萄球菌的抑菌率都达到99.9％。The prepared silk fibroin nano-silver antibacterial color-developing finishing agent is a dispersion liquid containing nano-silver particles, silk fibroin, chitosan, polyethylene glycol and citric acid; wherein, the shape of each nano-silver particle is regular and the size is uniform, The particle size of the nano-silver particles is 40-60nm, and the nano-silver particles are firmly adsorbed on the hydrophilic segment of the silk fibroin molecule, and the amino group on the surface of the chitosan molecule and the carboxyl group on the surface of the silk fibroin are formed. Hydrogen bonding, polyethylene glycol adsorbs and wraps nano-silver particles through van der Waals force, and its hydroxyl group combines with hydrophilic groups in silk fibroin molecules; silk nano-silver antibacterial color-developing finishing agent has excellent dispersibility, EDS can Spectrum and transmission electron micrographs show that the Ag element is evenly distributed; the silk fibroin nano-silver antibacterial and color-developing finishing agent has super bactericidal properties, and the bacteriostatic rate against Escherichia coli and Staphylococcus aureus reaches 99.9%.
实施例7Example 7
采用实施例1的丝素纳米银抗菌显色整理剂制备丝素纳米银显色抗菌功能卡洛丝纤维混纺面料，具体步骤如下：The silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 1 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
(1)卡洛丝纤维混纺面料的制备；(1) preparation of Carlo silk fiber blended fabric;
将棉纤维纺成精梳棉条后，与卡洛丝纤维按照7:3的质量比进行混合，采用环锭纺纺纱方法纺织成支数为32支的卡洛丝纤维混纺面料；After cotton fiber is spun into combed sliver, it is mixed with Carlo silk fiber according to the mass ratio of 7:3, adopts ring spinning spinning method to be spun into count and be 32 Carlo silk fiber blended fabrics;
(2)等离子体改性卡洛丝纤维混纺面料；(2) Plasma modified Carlo silk fiber blended fabric;
将步骤(1)制得的卡洛丝纤维混纺面料置于去离子水中清洗20min，晾干后放入低温等离子体处理装置中，使用空气对卡洛丝纤维混纺面料进行等离子体处理，工作温度为15℃，处理功率为80W，处理时间为10min，从而制得等离子体改性的卡洛丝纤维混纺面料；The Carlo silk fiber blended fabric that step (1) is made is placed in deionized water and cleaned for 20min, puts into the low-temperature plasma treatment device after drying, uses air to carry out plasma treatment to Carlo silk fiber blended fabric, working temperature The temperature is 15°C, the treatment power is 80W, and the treatment time is 10min, so as to obtain the plasma-modified Carlo silk fiber blended fabric;
(3)将步骤(2)制得的等离子体改性的卡洛丝纤维混纺面料浸轧丝素纳米银抗菌显色整理剂后先干燥再进行水蒸气处理，制得丝素纳米银显色抗菌功能卡洛丝纤维混纺面料；(3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
浸轧为二浸二轧(整个过程浸泡两次，挤轧两次)，浸泡浴比为1:20，每次浸泡时间为30min，浸泡温度为40℃；挤轧速度为2cm/s，压力为2Kg/cm 2，轧余率为80％；干燥的温度为60℃，干燥的时间为40min； The padding is two-dipping and two-rolling (soaking twice in the whole process and rolling twice), the soaking bath ratio is 1:20, the soaking time is 30min each time, the soaking temperature is 40°C; the rolling speed is 2cm/s, the pressure 2Kg/cm 2 , the scrap rate is 80%; the drying temperature is 60°C, and the drying time is 40min;
水蒸气处理采用高压灭菌锅，温度为120℃，时间为20min，处理后取出面料自然风干24h。The steam treatment was done in an autoclave at a temperature of 120°C for 20 minutes. After the treatment, the fabric was taken out and air-dried for 24 hours.
如图1、图3所示，制得的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率为10.2％，折皱回复角为135°，如图7所示，银元素在面料上均匀分布，具有很强的抗菌性能，对大肠杆菌的抑菌率达到99.9％，洗涤20次后对大肠杆菌的抑菌率达到90％，对金黄色葡萄球菌的抑菌率达到99.9％，洗涤20次后对金黄色葡萄球菌的抑菌率达到58％。As shown in Fig. 1 and Fig. 3, the moisture regain of the silk fibroin nano-silver color-developing and antibacterial functional Carlo silk fiber blended fabric is 10.2%, and the wrinkle recovery angle is 135°. As shown in Fig. 7, the silver element in the fabric Evenly distributed on the surface, with strong antibacterial properties, the bacteriostatic rate of Escherichia coli reached 99.9%, after washing 20 times, the bacteriostatic rate of Escherichia coli reached 90%, and the bacteriostatic rate of Staphylococcus aureus reached 99.9%, After washing 20 times, the antibacterial rate to Staphylococcus aureus reaches 58%.
实施例8Example 8
采用实施例2的丝素纳米银抗菌显色整理剂制备丝素纳米银显色抗菌功能卡洛丝纤维混纺面料，具体步骤如下：The silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 2 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
(1)卡洛丝纤维混纺面料的制备；(1) preparation of Carlo silk fiber blended fabric;
将棉纤维纺成精梳棉条后，与卡洛丝纤维按照6:4的质量比进行混合，采用紧密纺纺纱方法纺织成支数为21支的卡洛丝纤维混纺面料；After cotton fiber is spun into combed sliver, it is mixed with Carlo silk fiber according to the mass ratio of 6:4, adopts the compact spinning spinning method to be woven into count and be the Carlo silk fiber blended fabric of 21;
(2)等离子体改性卡洛丝纤维混纺面料；(2) Plasma modified Carlo silk fiber blended fabric;
将步骤(1)制得的卡洛丝纤维混纺面料置于去离子水中清洗20min，晾干后放入低温等离子体处理装置中，使用氧气对卡洛丝纤维混纺面料进行等离子体处理，工作温度为20℃，处理功率为240W，处理时间为1min，从而制得等离子体改性的卡洛丝纤维混纺面料；The Carlo silk fiber blended fabric prepared in step (1) is placed in deionized water and cleaned for 20 minutes, put into a low-temperature plasma treatment device after drying, and oxygen is used to carry out plasma treatment to the Carlo silk fiber blended fabric, and the working temperature The temperature is 20°C, the processing power is 240W, and the processing time is 1min, so as to obtain a plasma-modified Carlo silk fiber blended fabric;
(3)将步骤(2)制得的等离子体改性的卡洛丝纤维混纺面料浸轧丝素纳米银抗菌显色整理剂后先 干燥再进行水蒸气处理，制得丝素纳米银显色抗菌功能卡洛丝纤维混纺面料；(3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
浸轧为二浸二轧(整个过程浸泡两次，挤轧两次)，浸泡浴比为1:10，每次浸泡时间为20min，浸泡温度为40℃；挤轧速度为2cm/s，压力为3Kg/cm 2，轧余率为82％；干燥的温度为60℃，干燥的时间为50min； The padding is two-dipping and two-rolling (the whole process is soaked twice and squeezed twice), the soaking bath ratio is 1:10, the soaking time is 20min each time, the soaking temperature is 40°C; the rolling speed is 2cm/s, the pressure 3Kg/cm 2 , the scrap rate is 82%; the drying temperature is 60℃, and the drying time is 50min;
水蒸气处理采用高压灭菌锅，温度为100℃，时间为30min，处理后取出面料自然风干24h。The steam treatment was done in an autoclave at a temperature of 100°C for 30 minutes. After treatment, the fabric was taken out and air-dried for 24 hours.
如图1、图3所示，制得的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率为12.5％，折皱回复角为133°，如图2、图8所示，银元素在面料上均匀分布，具有很强的抗菌性能，对大肠杆菌的抑菌率达到99.9％，洗涤20次后对大肠杆菌的抑菌率达到92％，对金黄色葡萄球菌的抑菌率达到99.9％，洗涤20次后对金黄色葡萄球菌的抑菌率达到55％。As shown in Figure 1 and Figure 3, the moisture regain of the prepared silk fibroin nano-silver color-developing and antibacterial functional Carlo silk fiber blended fabric is 12.5%, and the wrinkle recovery angle is 133 °, as shown in Figure 2 and Figure 8, silver The elements are evenly distributed on the fabric and have strong antibacterial properties. The antibacterial rate against E. coli reaches 99.9%. After 20 washes, the antibacterial rate against E. coli reaches 92%, and the antibacterial rate against Staphylococcus aureus reaches 99.9%, the bacteriostatic rate to Staphylococcus aureus reaches 55% after washing 20 times.
实施例9Example 9
采用实施例3的丝素纳米银抗菌显色整理剂制备丝素纳米银显色抗菌功能卡洛丝纤维混纺面料，具体步骤如下：The silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 3 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
(1)卡洛丝纤维混纺面料的制备；(1) preparation of Carlo silk fiber blended fabric;
将棉纤维纺成精梳棉条后，与卡洛丝纤维按照8:2的质量比进行混合，采用转杯纺纺纱方法纺织成支数为40支的卡洛丝纤维混纺面料；After the cotton fiber is spun into combed sliver, it is mixed with the Carlo silk fiber according to the mass ratio of 8:2, and the Carlo silk fiber blended fabric with a count of 40 is spun by the rotor spinning method;
(2)等离子体改性卡洛丝纤维混纺面料；(2) Plasma modified Carlo silk fiber blended fabric;
将步骤(1)制得的卡洛丝纤维混纺面料置于去离子水中清洗20min，晾干后放入低温等离子体处理装置中，使用氮气对卡洛丝纤维混纺面料进行等离子体处理，工作温度为25℃，处理功率为120W，处理时间为5min，从而制得等离子体改性的卡洛丝纤维混纺面料；The Carlo silk fiber blended fabric that step (1) makes is placed in deionized water and cleaned for 20min, puts into a low-temperature plasma treatment device after drying, and uses nitrogen to carry out plasma treatment to the Carlo silk fiber blended fabric, working temperature The temperature is 25°C, the processing power is 120W, and the processing time is 5min, so as to obtain a plasma-modified Carlo silk fiber blended fabric;
(3)将步骤(2)制得的等离子体改性的卡洛丝纤维混纺面料浸轧丝素纳米银抗菌显色整理剂后先干燥再进行水蒸气处理，制得丝素纳米银显色抗菌功能卡洛丝纤维混纺面料；(3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
浸轧为二浸二轧(整个过程浸泡两次，挤轧两次)，浸泡浴比为1:40，每次浸泡时间为60min，浸泡温度为37℃；挤轧速度为3cm/s，压力为3Kg/cm 2，轧余率为84％；干燥的温度为60℃，干燥的时间为60min； The padding is two-dipping and two-rolling (soaking twice in the whole process, rolling twice), the soaking bath ratio is 1:40, the soaking time is 60min each time, the soaking temperature is 37°C; the rolling speed is 3cm/s, the pressure 3Kg/cm 2 , the scrap rate is 84%; the drying temperature is 60℃, and the drying time is 60min;
水蒸气处理采用高压灭菌锅，温度为120℃，时间为60min，处理后取出面料自然风干24h。The steam treatment was done in an autoclave at a temperature of 120°C for 60 minutes. After the treatment, the fabric was taken out and air-dried for 24 hours.
如图1、图3所示，制得的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率为8.5％，折皱回复角为134°，如图9所示，银元素在面料上均匀分布，具有很强的抗菌性能，对大肠杆菌的抑菌率达到99.9％，洗涤20次后对大肠杆菌的抑菌率达到95％，对金黄色葡萄球菌的抑菌率达到99.9％，洗涤20次后对金黄色葡萄球菌的抑菌率达到60％。As shown in Figure 1 and Figure 3, the moisture regain of the prepared silk nano-silver color-developing and antibacterial Carlo silk fiber blended fabric is 8.5%, and the wrinkle recovery angle is 134 °, as shown in Figure 9, the silver element is in the fabric Evenly distributed on the surface, with strong antibacterial properties, the antibacterial rate of Escherichia coli reached 99.9%, after washing 20 times, the antibacterial rate of Escherichia coli reached 95%, and the antibacterial rate of Staphylococcus aureus reached 99.9%, After washing 20 times, the antibacterial rate to Staphylococcus aureus reaches 60%.
实施例10Example 10
采用实施例4的丝素纳米银抗菌显色整理剂制备丝素纳米银显色抗菌功能卡洛丝纤维混纺面料，具体步骤如下：The silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 4 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
(1)卡洛丝纤维混纺面料的制备；(1) preparation of Carlo silk fiber blended fabric;
将棉纤维纺成精梳棉条后，与卡洛丝纤维按照8:4的质量比进行混合，采用环锭纺纺纱方法纺织成支数为21支的卡洛丝纤维混纺面料；After cotton fiber is spun into combed sliver, it is mixed with Carlo silk fiber according to the mass ratio of 8:4, adopts the ring spinning spinning method to be woven into count and be the Carlo silk fiber blended fabric of 21;
(2)等离子体改性卡洛丝纤维混纺面料；(2) Plasma modified Carlo silk fiber blended fabric;
将步骤(1)制得的卡洛丝纤维混纺面料置于去离子水中清洗10min，晾干后放入低温等离子体处理装置中，使用氩气对卡洛丝纤维混纺面料进行等离子体处理，工作温度为30℃，处理功率为20W，处理时间为10min，从而制得等离子体改性的卡洛丝纤维混纺面料；The Carlo silk fiber blended fabric that step (1) makes is placed in deionized water and cleaned for 10 minutes, puts into a low-temperature plasma treatment device after drying, and uses argon to carry out plasma treatment to the Carlo silk fiber blended fabric, and the work The temperature is 30°C, the treatment power is 20W, and the treatment time is 10min, so as to prepare the plasma-modified Carlo silk fiber blended fabric;
(3)将步骤(2)制得的等离子体改性的卡洛丝纤维混纺面料浸轧丝素纳米银抗菌显色整理剂后先干燥再进行水蒸气处理，制得丝素纳米银显色抗菌功能卡洛丝纤维混纺面料；(3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
浸轧为二浸二轧(整个过程浸泡两次，挤轧两次)，浸泡浴比为1:60，每次浸泡时间为60min，浸泡温度为45℃；挤轧速度为3cm/s，压力为4Kg/cm 2，轧余率为86％；干燥的温度为70℃，干燥的时间为40min； The padding is two-dipping and two-rolling (soaking twice in the whole process and rolling twice), the soaking bath ratio is 1:60, the soaking time is 60min each time, the soaking temperature is 45°C; the rolling speed is 3cm/s, the pressure 4Kg/cm 2 , the scrap rate is 86%; the drying temperature is 70°C, and the drying time is 40min;
水蒸气处理采用高压灭菌锅，温度为110℃，时间为120min，处理后取出面料自然风干12h。The steam treatment was performed in an autoclave at a temperature of 110°C for 120 minutes. After treatment, the fabric was taken out and air-dried for 12 hours.
制得的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率为12.1％，折皱回复角为133°，对大肠杆菌的抑菌率达到99.9％，洗涤20次后对大肠杆菌的抑菌率达到91％，对金黄色葡萄球菌的抑菌率达到99.9％，洗涤20次后对金黄色葡萄球菌的抑菌率达到56％。The obtained silk fibroin nano-silver color-developing antibacterial function carlos fiber blended fabric has a moisture regain rate of 12.1%, a wrinkle recovery angle of 133°, and a bacteriostatic rate of 99.9% against Escherichia coli. The bacteriostatic rate reaches 91%, and the bacteriostatic rate to Staphylococcus aureus reaches 99.9%, and the bacteriostatic rate to Staphylococcus aureus reaches 56% after washing 20 times.
实施例11Example 11
采用实施例5的丝素纳米银抗菌显色整理剂制备丝素纳米银显色抗菌功能卡洛丝纤维混纺面料，具体步骤如下：The silk fibroin nano-silver antibacterial and color-developing finishing agent of Example 5 is used to prepare the silk fibroin nano-silver color-developing antibacterial function Carlo silk fiber blended fabric, and the specific steps are as follows:
(1)卡洛丝纤维混纺面料的制备；(1) preparation of Carlo silk fiber blended fabric;
将棉纤维纺成精梳棉条后，与卡洛丝纤维按照6:3的质量比进行混合，采用紧密纺纺纱方法纺织成支数为40支的卡洛丝纤维混纺面料；After the cotton fiber is spun into combed sliver, it is mixed with the Carlo silk fiber according to the mass ratio of 6:3, and the Carlo silk fiber blended fabric with a count of 40 is spun by the compact spinning method;
(2)等离子体改性卡洛丝纤维混纺面料；(2) Plasma modified Carlo silk fiber blended fabric;
将步骤(1)制得的卡洛丝纤维混纺面料置于去离子水中清洗13min，晾干后放入低温等离子体处理装置中，使用空气对卡洛丝纤维混纺面料进行等离子体处理，工作温度为35℃，处理功率为50W，处理时间为8min，从而制得等离子体改性的卡洛丝纤维混纺面料；The Carlo silk fiber blended fabric that step (1) makes is placed in deionized water and cleaned for 13 minutes, puts into a low-temperature plasma treatment device after drying, and uses air to carry out plasma treatment to the Carlo silk fiber blended fabric, and the working temperature The temperature is 35°C, the processing power is 50W, and the processing time is 8min, so as to obtain a plasma-modified Carlo silk fiber blended fabric;
(3)将步骤(2)制得的等离子体改性的卡洛丝纤维混纺面料浸轧丝素纳米银抗菌显色整理剂后先干燥再进行水蒸气处理，制得丝素纳米银显色抗菌功能卡洛丝纤维混纺面料；(3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
浸轧为二浸二轧(整个过程浸泡两次，挤轧两次)，浸泡浴比为1:80，每次浸泡时间为40min，浸泡温度为34℃；挤轧速度为4cm/s，压力为4Kg/cm 2，轧余率为88％；干燥的温度为70℃，干燥的时间为50min； The padding is two-dipping and two-rolling (soaking twice in the whole process, rolling twice), the soaking bath ratio is 1:80, the soaking time is 40min each time, the soaking temperature is 34°C; the rolling speed is 4cm/s, the pressure 4Kg/cm 2 , the excess rate is 88%; the drying temperature is 70°C, and the drying time is 50 minutes;
水蒸气处理采用高压灭菌锅，温度为105℃，时间为80min，处理后取出面料自然风干15h。The steam treatment was done in an autoclave at a temperature of 105°C for 80 minutes. After treatment, the fabric was taken out and air-dried for 15 hours.
制得的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率为10.9％，折皱回复角为134°，对大肠杆菌的抑菌率达到99.9％，洗涤20次后对大肠杆菌的抑菌率达到94％，对金黄色葡萄球菌的抑菌率达到99.9％，洗涤20次后对金黄色葡萄球菌的抑菌率达到57％。The obtained silk fibroin nano-silver color-developing antibacterial function carlos fiber blended fabric has a moisture regain rate of 10.9%, a wrinkle recovery angle of 134°, and a bacteriostatic rate of 99.9% against Escherichia coli. The bacteriostatic rate reaches 94%, and the bacteriostatic rate to Staphylococcus aureus reaches 99.9%, and the bacteriostatic rate to Staphylococcus aureus reaches 57% after washing 20 times.
实施例12Example 12
采用实施例6的丝素纳米银抗菌显色整理剂制备丝素纳米银显色抗菌功能卡洛丝纤维混纺面料，具体步骤如下：The antibacterial and color-developing finishing agent of silk fibroin nano-silver in Example 6 is used to prepare the silk fiber blended fabric with silk fibroin nano-silver color development and antibacterial function, and the specific steps are as follows:
(1)卡洛丝纤维混纺面料的制备；(1) preparation of Carlo silk fiber blended fabric;
将棉纤维纺成精梳棉条后，与卡洛丝纤维按照7:2的质量比进行混合，采用转杯纺纺纱方法纺织成支数为32支的卡洛丝纤维混纺面料；After the cotton fiber is spun into combed sliver, it is mixed with the Carlo silk fiber according to the mass ratio of 7:2, and the Carlo silk fiber blended fabric with a count of 32 is spun by the rotor spinning method;
(2)等离子体改性卡洛丝纤维混纺面料；(2) Plasma modified Carlo silk fiber blended fabric;
将步骤(1)制得的卡洛丝纤维混纺面料置于去离子水中清洗17min，晾干后放入低温等离子体处理装置中，使用氧气对卡洛丝纤维混纺面料进行等离子体处理，工作温度为30℃，处理功率为100W，处理时间为6min，从而制得等离子体改性的卡洛丝纤维混纺面料；The Carlo silk fiber blended fabric that step (1) makes is placed in deionized water and cleaned for 17min, puts into a low-temperature plasma treatment device after drying, and uses oxygen to carry out plasma treatment to the Carlo silk fiber blended fabric, working temperature The temperature is 30°C, the processing power is 100W, and the processing time is 6min, so as to obtain the plasma-modified Carlo silk fiber blended fabric;
(3)将步骤(2)制得的等离子体改性的卡洛丝纤维混纺面料浸轧丝素纳米银抗菌显色整理剂后先干燥再进行水蒸气处理，制得丝素纳米银显色抗菌功能卡洛丝纤维混纺面料；(3) Dipping the silk fibroin nano-silver antibacterial and color-developing finishing agent on the plasma-modified carlos fiber blended fabric prepared in step (2) and then drying it with water vapor to obtain the color-developing silk fibroin nano-silver Antibacterial functional Carlo silk fiber blended fabric;
浸轧为二浸二轧(整个过程浸泡两次，挤轧两次)，浸泡浴比为1:100，每次浸泡时间为20min，浸泡温度为30℃；挤轧速度为4cm/s，压力为5Kg/cm 2，轧余率为90％；干燥的温度为80℃，干燥的时间为60min； The padding is two-dipping and two-rolling (soaking twice in the whole process, rolling twice), the soaking bath ratio is 1:100, the soaking time is 20min each time, the soaking temperature is 30°C; the rolling speed is 4cm/s, the pressure 5Kg/cm 2 , the scrap rate is 90%; the drying temperature is 80°C, and the drying time is 60 minutes;
水蒸气处理采用高压灭菌锅，温度为115℃，时间为50min，处理后取出面料自然风干18h。The steam treatment was done in an autoclave at a temperature of 115°C for 50 minutes. After the treatment, the fabric was taken out and air-dried for 18 hours.
制得的丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率为9.7％，折皱回复角为135°，对大肠杆菌的抑菌率达到99.9％，洗涤20次后对大肠杆菌的抑菌率达到95％，对金黄色葡萄球菌的抑菌率达到99.9％，洗涤20次后对金黄色葡萄球菌的抑菌率达到59％。The obtained silk fibroin nano-silver color-developing and antibacterial function Carlo silk fiber blended fabric has a moisture regain rate of 9.7%, a wrinkle recovery angle of 135°, and a bacteriostatic rate of 99.9% against Escherichia coli. The bacteriostatic rate reaches 95%, and the bacteriostatic rate to Staphylococcus aureus reaches 99.9%, and the bacteriostatic rate to Staphylococcus aureus reaches 59% after washing 20 times.

Claims (10)

  1. 一种丝素纳米银抗菌显色整理剂的制备方法，其特征在于，首先向丝素溶液中加入柠檬酸和抗坏血酸后，调节其pH值至3.6-5.6，再加入AgNO 3晶体，得到丝素硝酸银溶液，然后向丝素硝酸银溶液中加入壳聚糖、聚乙二醇和二氧化锰共混后得到丝素硝酸银混合溶液，最后将丝素硝酸银混合溶液置于10-60W的LED灯下2-120h，得到丝素纳米银抗菌显色整理剂。 A preparation method of silk fibroin nano-silver antibacterial color-developing finishing agent, it is characterized in that, after first adding citric acid and ascorbic acid to silk fibroin solution, adjust its pH value to 3.6-5.6, then add AgNO 3 crystals, obtain silk fibroin Silver nitrate solution, then add chitosan, polyethylene glycol and manganese dioxide to the silk fibroin silver nitrate solution to blend to obtain a silk fibroin silver nitrate mixed solution, and finally place the silk fibroin silver nitrate mixed solution in a 10-60W LED Under the light for 2-120h, the silk fibroin nano silver antibacterial and color-developing finishing agent is obtained.
  2. 根据权利要求1所述的一种丝素纳米银抗菌显色整理剂的制备方法，其特征在于，壳聚糖的分子量为150000-300000；聚乙二醇的分子量为400-6000。The preparation method of a kind of silk fibroin nano-silver antibacterial color developing finishing agent according to claim 1, is characterized in that, the molecular weight of chitosan is 150000-300000; The molecular weight of polyethylene glycol is 400-6000.
  3. 根据权利要求1所述的一种丝素纳米银抗菌显色整理剂的制备方法，其特征在于，丝素溶液的浓度为1-6wt％；丝素硝酸银溶液中，柠檬酸的浓度为5-20g/L，抗坏血酸的浓度为1-6wt％，AgNO 3的浓度为2-8mg/mL；丝素硝酸银混合溶液中，壳聚糖的浓度为5-15g/L，聚乙二醇与丝素硝酸银溶液的体积比为2-8:10-20，二氧化锰的浓度为0.2-0.5mol/L。 The preparation method of a kind of silk fibroin nano-silver antibacterial color-developing finishing agent according to claim 1, is characterized in that, the concentration of silk fibroin solution is 1-6wt%; In silk fibroin silver nitrate solution, the concentration of citric acid is 5 -20g/L, the concentration of ascorbic acid is 1-6wt%, the concentration of AgNO3 is 2-8mg /mL; in the silk fibroin silver nitrate mixed solution, the concentration of chitosan is 5-15g/L, polyethylene glycol and The volume ratio of silk fibroin silver nitrate solution is 2-8:10-20, and the concentration of manganese dioxide is 0.2-0.5mol/L.
  4. 根据权利要求1所述的一种丝素纳米银抗菌显色整理剂的制备方法，其特征在于，丝素溶液的制备过程为：取脱胶蚕丝浸润在浓度为8-12mol/L的溴化锂溶液中，置于40-80℃的烘箱中3-6h，每1h摇晃一次，得到丝素溶液。The preparation method of a kind of silk fibroin nano-silver antibacterial and color-developing finishing agent according to claim 1, is characterized in that, the preparation process of silk fibroin solution is: take degummed silk and soak in the lithium bromide solution that concentration is 8-12mol/L , placed in an oven at 40-80° C. for 3-6 hours, and shaken every 1 hour to obtain a silk fibroin solution.
  5. 采用如权利要求1～4任一项所述的一种丝素纳米银抗菌显色整理剂的制备方法制得的丝素纳米银抗菌显色整理剂，其特征在于，为含纳米银粒子、丝素蛋白、壳聚糖、聚乙二醇和柠檬酸的分散液。The silk fibroin nano-silver antibacterial color-developing finishing agent that adopts the preparation method of a kind of silk fibroin nano-silver antibacterial color-developing finishing agent as described in any one of claims 1 to 4 is characterized in that, contains nano-silver particles, Dispersion of silk fibroin, chitosan, polyethylene glycol and citric acid.
  6. 根据权利要求5所述的丝素纳米银抗菌显色整理剂，其特征在于，纳米银粒子的粒径为10-100nm。The silk fibroin nano-silver antibacterial and color-developing finishing agent according to claim 5, characterized in that the particle diameter of the nano-silver particles is 10-100nm.
  7. 根据权利要求5所述的丝素纳米银抗菌显色整理剂，其特征在于，丝素纳米银抗菌显色整理剂对大肠杆菌和金黄色葡萄球菌的抑菌率都达到99.9±0.1％。The silk fibroin nano-silver antibacterial and color-developing finishing agent according to claim 5, characterized in that the antibacterial rate of the silk fibroin nano-silver antibacterial and color-developing finishing agent to both Escherichia coli and Staphylococcus aureus reaches 99.9±0.1%.
  8. 如权利要求5～7任一项所述的丝素纳米银抗菌显色整理剂的应用，其特征在于，将等离子体改性的卡洛丝纤维混纺面料浸轧丝素纳米银抗菌显色整理剂后先干燥再进行水蒸气处理，制得丝素纳米银显色抗菌功能卡洛丝纤维混纺面料；The application of the silk fibroin nano-silver antibacterial and color-developing finishing agent as described in any one of claims 5 to 7, characterized in that the plasma-modified Carlo silk fiber blended fabric is pad-rolled with silk fibroin nano-silver antibacterial and color-developing finishing After the agent is dried first and then treated with water vapor, the silk fiber blended fabric with color development and antibacterial function of silk fibroin nano-silver is obtained;
    卡洛丝纤维混纺面料由卡洛丝纤维和棉纤维组成；Carlo silk fiber blended fabric is composed of Carlo silk fiber and cotton fiber;
    水蒸气处理的温度为100-120℃，时间为20-100min。The temperature of steam treatment is 100-120° C., and the time is 20-100 minutes.
  9. 根据权利要求8所述的应用，其特征在于，等离子体改性的过程为：将卡洛丝纤维混纺面料置于去离子水中清洗10-20min，晾干后放入低温等离子体处理装置中，使用空气、氧气、氮气或氩气对卡洛丝纤维混纺面料进行等离子体处理，处理功率为20-240W，处理时间为1-10min；According to the application according to claim 8, it is characterized in that the process of plasma modification is as follows: placing the Carlo silk fiber blended fabric in deionized water and cleaning it for 10-20 minutes, putting it into a low-temperature plasma treatment device after drying, Use air, oxygen, nitrogen or argon to conduct plasma treatment on Carlo silk fiber blended fabrics, the treatment power is 20-240W, and the treatment time is 1-10min;
    卡洛丝纤维混纺面料的制备过程为：将棉纤维纺成精梳棉条后，与卡洛丝纤维按照8-6:2-4的质量比进行混合，采用环锭纺、紧密纺或转杯纺纺纱方法纺织成卡洛丝纤维混纺面料；The preparation process of Carlo silk fiber blended fabric is as follows: after cotton fiber is spun into combed cotton sliver, it is mixed with Carlo silk fiber according to the mass ratio of 8-6:2-4, and it is spun by ring spinning, compact spinning or rotary spinning. The cup spinning method is used to weave into Carlo silk fiber blended fabric;
    浸轧为二浸二轧，浸泡浴比为1:10-100，每次浸泡时间为20-60min，浸泡温度为30-45℃；The padding is two dipping and two rolling, the soaking bath ratio is 1:10-100, the soaking time is 20-60min each time, and the soaking temperature is 30-45°C;
    挤轧速度为2-4cm/s，压力为2-5Kg/cm 2，轧余率为80-90％；干燥的温度为60-80℃。 The extrusion speed is 2-4cm/s, the pressure is 2-5Kg/cm 2 , the scrap ratio is 80-90%; the drying temperature is 60-80°C.
  10. 根据权利要求9所述的应用，其特征在于，丝素纳米银显色抗菌功能卡洛丝纤维混纺面料的回潮率为8.5-12.5％，折皱回复角为133-135°，对大肠杆菌的抑菌率达到99.9％，洗涤20次后对大肠杆菌的抑菌率达到90-95％，对金黄色葡萄球菌的抑菌率达到99.9％，洗涤20次后对金黄色葡萄球菌的抑菌率达到55-60％。According to the application according to claim 9, it is characterized in that the moisture regain of silk fibroin nano-silver color-developing and antibacterial functional Carlo silk fiber blended fabric is 8.5-12.5%, the wrinkle recovery angle is 133-135°, and the antibacterial effect on Escherichia coli The bacteria rate reaches 99.9%. After 20 times of washing, the bacteriostatic rate of Escherichia coli reaches 90-95%, and the bacteriostatic rate of Staphylococcus aureus reaches 99.9%. 55-60%.
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