CN114346252A

CN114346252A - Nano silver colloidal solution, preparation method thereof and washing-resistant antibacterial antiviral fabric

Info

Publication number: CN114346252A
Application number: CN202111667442.8A
Authority: CN
Inventors: 徐思峻; 冯俊丹; 冯玲玲; 姚理荣
Original assignee: Nantong University
Current assignee: Nantong University
Priority date: 2021-12-30
Filing date: 2021-12-30
Publication date: 2022-04-15
Anticipated expiration: 2041-12-30
Also published as: CN114346252B

Abstract

The application discloses a nano-silver colloidal solution, a preparation method thereof and a washing-resistant antibacterial antiviral fabric, wherein the nano-silver colloidal solution is prepared by the following steps: mixing the solution of the long-chain branched spherical polyurethane with the metal precursor solution according to the volume ratio of 0.5: 1-100: 1, adding a reducing agent until a large amount of floating bubbles appear in the solution, and stirring to obtain the nano silver colloid solution with the average particle size of 1-100 nm. The long-chain branched spherical polyurethane has high water solubility, can form long-term stable nano micelle, has extremely strong adhesion performance, can adhere most of natural fibers and synthetic fibers, can be blended with paint for antibacterial and antiviral wall surfaces and wood coatings, has good film forming property and flexibility, good washability, washability resistance and weather resistance, has super-strong antibacterial and antiviral capacity, and can be used for developing reusable epidemic prevention medical instruments.

Description

Nano silver colloidal solution, preparation method thereof and washing-resistant antibacterial antiviral fabric

Technical Field

The invention belongs to the field of nano materials, and particularly relates to a nano silver colloidal solution, a preparation method thereof and a washing-resistant antibacterial antiviral fabric.

Background

Nanoparticles are also referred to as ultrafine particles, and mean nanoparticles having a particle diameter of 1 to 100 and formed by aggregating several to several tens of atoms. Nanoparticles have many special properties different from conventional solids, such as small size effect, surface effect, and macroscopic quantum tunneling effect. The nano metal particles have extremely strong antibacterial and antiviral abilities. For example, the nano silver has strong inhibiting and killing effects on gram-negative bacteria, gram-positive bacteria, mould and coronavirus, H1N1 and H3N 2. The nano metal can not generate pathogen to generate antibody or generate mutation, and can not interfere the normal immune function of human body. Therefore, the method has wide application prospect in the fields of functional textiles and epidemic situation protection.

The existing nano metal method mainly comprises a physical method and a chemical method. The physical method is simple to prepare, the particle size is uniform, but the corresponding equipment is high in price and the preparation cost is high; the chemical preparation method has low cost, but has the defects of uneven particle size, poor stability, easy oxidation, high irritation of a protective agent or a reducing agent or potential toxicity to a human body.

The existing antibacterial and antiviral nano metal colloid solution has the following problems: firstly, the nano metal solution has poor physical and chemical stability, is easy to precipitate, oxidize and digest, cannot resist high temperature and is limited in application in the field of reusable epidemic situation protection equipment; secondly, the adhesion of the nano metal is insufficient, and the nano metal lacks sufficient adhesion and universality on fabrics, walls, wood and plastics, so that the antibacterial and antiviral coating has insufficient washability, decontamination resistance (chlorine disinfectant or peroxide disinfectant) and durability, and cannot adapt to reusable epidemic prevention equipment. Thirdly, the treated fabric is stiff, thereby greatly influencing the comfort performance and the functional durability of the clothes. Fourthly, the hydrophilicity of the treated coating is increased, the polarization effect on the surfaces of epidemic-prevention base materials such as masks and protective clothing is reduced, and the electrostatic adsorption effect is reduced.

Disclosure of Invention

In order to better solve the technical problems, the invention provides a nano silver colloidal solution. The antibacterial and antiviral nano metal finishing agent for epidemic prevention developed by the invention has high solution stability, excellent high temperature resistance, oxidant disinfection performance and strong adhesion. The antimicrobial coating prepared has good flexibility, low specific surface energy (contact angle is more than 130 ℃) and good washing resistance and abrasion resistance.

The nano silver colloid solution is prepared by the following steps:

mixing a solution of long-chain branched spherical polyurethane and a metal precursor solution at a volume ratio of 0.5: 1-100: 1 (preferably 1: 1-100: 1, preferably 1.5: 1-90: 1, preferably 2: 1-80: 1, preferably 4: 1-70: 1, preferably 5: 1-60: 1, preferably 6: 1-50: 1, preferably 7: 1-40: 1, preferably 8: 1-30: 1, preferably 9: 1-25: 1, preferably 10: 1-20: 1, preferably 10: 1-15: 1), adding a reducing agent (for example, dropping an aqueous solution of the reducing agent) until a large amount of floating bubbles appear in the solution, and stirring (for example, 5-600 min), so as to obtain a nano silver colloid solution with an average particle size of 1-100 nm. The concentration of the nano silver colloid solution can be 1-6000mg/L, and further 1-5000mg/L for example.

Preferably, the solution mass concentration of the long-chain branched spherical polyurethane is 10 g/L-150 g/L, preferably 11-100 g/L, preferably 12 g/L-95 g/L, more preferably 15 g/L-90 g/L, more preferably 20 g/L-80 g/L, more preferably 30 g/L-70 g/L, more preferably 40 g/L-60 g/L. The solution of the long-chain branched spherical polyurethane is preferably an aqueous solution of the long-chain branched spherical polyurethane.

Preferably, the mass concentration of the metal precursor solution (preferably aqueous solution) is 0.01-15 g/L, 0.1-12 g/L, preferably 0.5-10 g/L, more preferably 1-9 g/L, more preferably 2-8 g/L, more preferably 4-8 g/L, more preferably 5-8 g/L.

Preferably, the mass concentration of the aqueous solution of the reducing agent is 10g/L to 100g/L, preferably 12g/L to 95g/L, more preferably 15g/L to 90g/L, more preferably 20g/L to 80g/L, more preferably 30g/L to 70g/L, and more preferably 40g/L to 60 g/L.

Preferably, the dropwise addition is carried out at a temperature of from 10 ℃ to 90 ℃, preferably from 20 ℃ to 80 ℃, preferably from 30 ℃ to 70 ℃, preferably from 40 ℃ to 60 ℃.

The metal precursor solution is one or more selected from silver nitrate solution, silver perchlorate solution, silver sulfate solution, chloroauric acid solution and copper chloride solution; the reducing agent is one or more of glucose, fructose, vitamin C, sodium borohydride and hydrazine hydrate.

The preparation method of the long-chain branched spherical polyurethane comprises the following steps:

(1) uniformly blending polycaprolactone polyol and C4-C10 carboxylic acid (which reacts with the polycaprolactone polyol to form a soft segment) comprising at least two hydroxyl groups, and adding isophorone diisocyanate to react (for example, at 40-100 ℃ for 30 minutes to 8 hours, preferably at 60-90 ℃ for 1 to 3 hours, for example, at 85 ℃ for 2 hours);

(2) cooling the reaction system (e.g. to normal temperature or ambient temperature + -10 deg.C), adding solvent (one or more of alcohols such as ethanol, ketones such as acetone, ethers such as diethyl ether, esters such as ethyl acetate, and amides such as dimethylformamide) and stirring;

(3) subsequently adding a neutralizing agent such as an organic amine such as triethylamine to react (for example, for half an hour to 4 hours, for example, for 1 hour), adding water to emulsify, and fixing the solid content to 20 to 45 mass%, preferably 25 to 35 mass%, for example, 30 mass%;

(4) adding an amino-terminated hyperbranched polymer, and reacting the polyurethane with the terminal amino of the amino-terminated hyperbranched polymer to form the long-chain branched hyperbranched polyurethane.

The C4-C10 carboxylic acid including at least two hydroxyl groups is preferably a C4-C8 carboxylic acid including at least two hydroxyl groups, and more preferably one or more selected from dimethylolpropionic acid, dimethylolbutyric acid and the like.

The number average molecular weight of the polycaprolactone polyol may be 1000-.

The neutralizing agent is used in an amount such that the C4-C10 carboxylic acid comprising at least two hydroxyl groups: the neutralizing agent is 1: 1.01-2.0, preferably 1: 1.02-1: 1.2 calculated by molar ratio.

The number average molecular weight of the amino-terminated hyperbranched polymer can be 300-15000, preferably 800-8000, preferably 1000-5000, and preferably 1000-3000.

The reaction formula is shown as follows:

in one embodiment, the polycaprolactone polyol, the C4-C10 carboxylic acid comprising at least two hydroxyl groups, isophorone diisocyanate, amino terminated hyperbranched polymer, are in a (1-10: 12): (10-30): (0.2-2), preferably (2-9): 12: (12-25): (0.4-1.8), preferably (3-7) 12: (15-22): (0.5-1.5), preferably (4-6) 12: (15-20): (0.6-1.2).

In one embodiment, the polycaprolactone polyol has a molecular weight of 1000-.

In one embodiment, the amino-terminated hyperbranched polymer has a molecular weight of 300-12000; the structure is as follows:

preferably, the amino-terminated hyperbranched polymer is prepared by the following method: reacting diethylenetriamine with a mixed solution of methyl acrylate and methanol at the temperature of 10-30 ℃ for 2-5 hours to obtain a light yellow transparent substance, then decompressing and removing the methanol at the temperature of 60-80 ℃, immediately heating to 130-145 ℃, continuing decompressing and reacting for 2-3 hours, and stopping the reaction to obtain the viscous light yellow amino-terminated hyperbranched polymer. The volume ratio of diethylenetriamine to methyl acrylate may be, for example, (0.8-2):1, further for example (0.9-1.5):1 or (1.08-1.2): the volume ratio of methanol to (diethylenetriamine to methyl acrylate blend) may be, for example, (2-0.9):1, further for example (1.5-1.05): 1.

the invention further provides a washing-resistant antibacterial antiviral fabric, which is prepared by the following steps:

soaking the fabric in the nano silver colloid solution, wherein the bath ratio is set as 1: 10-1: 50, then carrying out ultrasonic treatment for 10-20min at normal temperature;

secondly, rolling the fabric dry at normal temperature, and setting the liquid carrying rate to be 20-80%;

thirdly, the fabric is dried for 10 to 30min at the temperature of between 70 and 85 ℃, and finally is dried for 2 to 10min at the temperature of between 110 and 140 ℃.

The fabric is a knitted, woven, tatted or non-woven fabric formed by pure spinning or mutual blending of cotton, hemp, silk, terylene, chinlon, vinylon, aramid fiber, high-strength and high-modulus polyethylene fiber and carbon fiber. The concentration of the nano silver solution can be 1-5000mg/L, and the silver content of the prepared fabric is controlled to be 1-8000 mg/kg.

The invention has the advantages that:

1. the long-chain branched spherical polyurethane has the characteristics of high stability and low viscosity of hyperbranched polymer solution, and has the characteristic of easy crosslinking and film forming of waterborne polyurethane, so that the stability of the nano metal solution and the adhesion to materials are ensured.

2. The long-chain branched spherical polyurethane is spherical, can effectively encapsulate nano metal, can isolate external air through physical isolation, and has a reduction effect on an amide group inside, so that the chemical stability of the nano metal is ensured. When the nano metal is coated on the surface of the base material, the long-chain branched spherical polyurethane is mutually crosslinked to form a film so as to further isolate oxygen, thereby ensuring the oxidation resistance of the coating.

3. The prepared nano silver solution has good stability, the particle size of the nano silver is controllable (1-100nm), and the concentration of the solution can reach 6000 mg/L.

4. The super-high adhesiveness has strong adhesive effect on fabrics such as cotton and terylene, wooden furniture and walls, and can be blended with oil gas and woodware in any ratio.

5. The prepared antibacterial and antiviral material has excellent washing resistance, and a test structure shows that the antibacterial rate of the antibacterial and antiviral fabric after being washed for 100 times is more than or equal to 99.7 percent, and the inactivation rate of the antibacterial and antiviral fabric for H1N1, H3N2 and other viruses is more than 99 percent (when the loading capacity is more than or equal to 4000 mg/kg).

6. The prepared antibacterial and antiviral product has the advantages of high temperature resistance, oxidant sterilization and conventional detergent washing, excellent weather resistance and good flexibility, and can be widely applied to the fields of textile clothing for epidemic prevention, medical treatment and health, functional coatings and paints and the like.

Drawings

FIG. 1 is a UV spectrum of nano silver solution.

Fig. 2 is a distribution diagram of the particle size of the nano silver particles in the nano silver solution.

Fig. 3 is an SEM image of the nano silver particles.

FIG. 4 is an infrared image of the synthesized spherical polyurethane.

FIG. 5 is a zeta potential diagram of the synthesized spherical polyurethane.

Detailed Description

The present invention will be described in detail with reference to the following examples.

Example 1

Preparation of amino-terminated hyperbranched polymers: 540mL of diethylenetriamine was reacted with a mixed solution of 500mL of methyl acrylate and 1120mL of methanol at 10 ℃ to 30 ℃ for 3 hours to obtain a pale yellow transparent substance. Then, the methanol is removed under reduced pressure at the temperature of 80 ℃, the temperature is raised to 145 ℃, the reduced pressure reaction is continued for 3 hours, and the reaction is stopped, thus obtaining the viscous light yellow amino-terminated hyperbranched polymer compound with the weight-average molecular weight of about 7800.

0.2mol of polycaprolactone polyol (Mn 4000, Cystol chemical Co.) was uniformly blended with 1.2mol of 2, 2-dimethylolpropionic acid, 2mol of isophorone diisocyanate was added, and the mixture was reacted at 85 ℃ for 2 hours;

cooling the reaction system to normal temperature, adding 1.7mol of acetone, and violently stirring;

and then adding 1.32mol of triethylamine to react for 1 hour, adding water to quickly emulsify, and fixing the solid content to 30% to obtain the polyurethane.

And adding 0.2mol of prepared amino-terminated hyperbranched polymer into the polyurethane, and reacting the polyurethane with the terminal amino group of the amino-terminated hyperbranched polymer to form the long-chain branched hyperbranched polyurethane.

Preparing a nano colloidal silver solution by using long-chain branched hyperbranched polyurethane:

1. dissolving 5g of long-chain branched spherical polyurethane in 100ml of deionized water to obtain 50g/L of long-chain branched spherical polyurethane aqueous solution;

2. 1g of sodium borohydride was dissolved in 100ml of deionized water to obtain 10g/L of aqueous sodium borohydride solution.

3. Preparing a silver nitrate solution with the mass fraction of 7.87 g/L;

4. mixing 50g/L long-chain branched spherical polyurethane aqueous solution and 7.87g/L silver nitrate solution in a volume ratio of 10:1, then dropwise adding 10g/L sodium borohydride aqueous solution until a large amount of floating bubbles appear in the solution, and stirring for 1h at 20 ℃ to obtain the nano silver colloid solution with the particle size of 5-80 nm.

Treating the fabric with a nano-silver colloidal solution:

soaking the polyester fabric in 5000mg/L nano-silver solution at a bath ratio of 1:50, and performing ultrasonic treatment at normal temperature for 10-20 min;

rolling the fabric dry at normal temperature, setting the liquid carrying rate to be 80%, and setting the nano-silver loading to be 4000 mg/kg;

and finally, drying the fabric at 70-85 ℃ for 30min, and then baking at 120 ℃ for 10min to obtain the polyester fabric which is resistant to washing for 100 times, has 99% of antibacterial rate to escherichia coli and staphylococcus aureus and 99% of antiviral activity to influenza A viruses. And (3) antibacterial detection standard: GB/T20944.3-2008 section 3 evaluation of antibacterial properties of textiles: oscillation method (Vital energy); antiviral detection standard: ISO 18184: 2014 (E).

The ultraviolet spectrogram of the obtained nano silver solution is shown in fig. 1, the particle size distribution diagram of nano silver particles in the obtained nano silver solution is shown in fig. 2, the SEM chart of the obtained nano silver particles is shown in fig. 3, the infrared chart of the synthesized spherical polyurethane is shown in fig. 4, the polymer contains methyl and amide I, II and II, which are shown in the figure, the synthetic spherical polyurethane zeta potential is shown in fig. 5, as the hyperbranched polymer has positive charges in the solution, the surface potential of the synthesized polymer becomes negative (-30mV) after the reaction with long-chain branches, the fact that most of the amino groups with positive charges at the tail ends of the hyperbranched polymer are reacted to generate basically uncharged amide groups is proved, and the potential of the synthesized long-chain branched spherical polyurethane is determined by the long-chain branches with negative potential, so that the glue formed by the hyperbranched polymer is negative potential.

Example 2

1.5 g of the long chain branched spherical polyurethane prepared in example 1 was dissolved in 100ml of deionized water to obtain 50g/L of a long chain branched spherical polyurethane aqueous solution;

2. 2g of hydrazine hydrate is dissolved in 100ml of deionized water to obtain 20g/L of hydrazine hydrate aqueous solution;

3. preparing a silver nitrate solution with the mass fraction of 7.87 g/L;

4. mixing 50g/L long-chain branched spherical polyurethane aqueous solution and 7.87g/L silver nitrate solution in a volume ratio of 10:1, then dropwise adding 20g/L hydrazine hydrate aqueous solution until a large amount of floating bubbles appear in the solution, and stirring at 30 ℃ for 2 hours to obtain the nano silver colloid solution with the particle size of 5-80 nm.

5. Soaking the cotton fabric in 5000mg/L nano silver solution, wherein the bath ratio is set as 1:50, performing ultrasonic treatment at normal temperature for 10-20 min;

6. rolling the fabric dry at normal temperature, and setting the liquid carrying rate to be 80%;

7. and finally, drying the fabric at 70-85 ℃ for 30min, and then baking the fabric at 120 ℃ for 10min to obtain the dacron fabric which is resistant to washing for 100 times, has 99% of antibacterial rate to escherichia coli and staphylococcus aureus and 99% of antiviral activity to influenza A virus (antibacterial detection standard: GB/T20944.3-2008, evaluation No. 3 of antibacterial performance of textiles: oscillation method; antiviral detection standard: ISO 18184: 2014 (E)).

Example 3

2. dissolving 0.5g of sodium borohydride in 100ml of deionized water to obtain 5g/L of sodium borohydride aqueous solution;

3. preparing a silver nitrate solution with the mass fraction of 7.87 g/L;

4. mixing 50g/L long-chain branched spherical polyurethane aqueous solution and 7.87g/L silver nitrate solution in a volume ratio of 10:1, then dropwise adding 5g/L sodium borohydride aqueous solution until a large amount of floating bubbles appear in the solution, and stirring for 1h at 25 ℃ to obtain the nano-silver solution with the particle size of 5-80 nm.

5. Soaking the polyester fabric in 5000mg/L nano-silver solution, wherein the bath ratio is set as 1:50, performing ultrasonic treatment at normal temperature for 10-20 min;

6. rolling the fabric dry at normal temperature, and setting the liquid carrying rate to be 60%;

7. and finally, drying the fabric at 70-85 ℃ for 30min, and then baking at 120 ℃ for 10min to obtain the dacron fabric which is resistant to washing for 100 times, has 99% of antibacterial rate and 92% of antivirus (the antibacterial detection standard: GB/T20944.3-2008, part 3 of evaluation of antibacterial performance of textiles: oscillation method; the antivirus detection standard: ISO 18184: 2014 (E)).

Example 4

The same as in example 1, except that 0.2mol of polycaprolactone polyol (Mn. RTM.4000, available from Cystol chemical Co.) was used and homogeneously blended with 1.2mol of 2, 2-dimethylolbutyric acid, and 2mol of isophorone diisocyanate was added and reacted at 85 ℃ for 2 hours.

Comparative example 1

0.2mol of polycaprolactone polyol (Mn 4000, Cystol chemical Co.) was uniformly blended with 1.2mol of dimethylolpropionic acid, 2mol of isophorone diisocyanate was added, and the reaction was carried out at 85 ℃ for 2 hours; 2. cooling the reaction system to normal temperature, adding 1.7mol of acetone, and violently stirring; 3. then adding 1.32mol of triethylamine to react for 1 hour, adding water to quickly emulsify, and fixing the solid content to 30%; 4. adding 0.2mol of hyperbranched polyester Hyper H203 for reaction to obtain the reaction product of the polyurethane and the hyperbranched polyester.

1. Dissolving 5g of the reaction product of the polyurethane and the hyperbranched polyester in 100ml of deionized water to obtain 50g/L aqueous solution;

3. Preparing a silver nitrate solution with the mass fraction of 7.87 g/L;

4. mixing 50g/L of the aqueous solution with 7.87g/L of silver nitrate solution in a volume ratio of 10:1, then dropwise adding 10g/L of sodium borohydride aqueous solution until a large amount of floating bubbles appear in the solution, and stirring for 1h at 25 ℃ to obtain the nano-silver solution with the particle size of 5-80 nm.

7. and finally, drying the fabric at 70-85 ℃ for 30min, and then baking the fabric at 120 ℃ for 10min to obtain the dacron fabric with 15 washing resistant times, 85% of antibacterial rate on escherichia coli and staphylococcus aureus and 87% of antiviral activity on influenza A virus. And (3) antibacterial detection standard: GB/T20944.3-2008 section 3 evaluation of antibacterial properties of textiles: oscillation method (Vital energy); antiviral detection standard: ISO 18184: 2014 (E). As can be seen from the above results, the washing endurance and the antibacterial effect using the nano-silver colloidal solution of the present invention are significantly superior to those of comparative example 1.

The preferred embodiments of the present invention have been described above, however, it should be understood that the above description is for illustrative purposes only and does not constitute any limitation of the present invention. Many modifications and equivalents may be made thereto without departing from the spirit and scope of the invention, and such modifications and equivalents are intended to be included within the scope of the invention.

Claims

1. A nano-silver colloidal solution, which is prepared by the following steps:

mixing a solution of long-chain branched spherical polyurethane with a metal precursor solution at a volume ratio of 0.5: 1-100: 1 (preferably 1: 1-100: 1, preferably 1.5: 1-90: 1, preferably 2: 1-80: 1, preferably 4: 1-70: 1, preferably 5: 1-60: 1, preferably 6: 1-50: 1, preferably 8: 1-30: 1, preferably 9: 1-25: 1, preferably 10: 1-20: 1, preferably 10: 1-15: 1), adding a reducing agent until a large amount of bubbles appear in the solution, and stirring to obtain a nano silver colloid solution with an average particle size of 1-100 nm.

2. The nano-silver colloid solution according to claim 1, wherein the solution mass concentration of the long-chain branched spherical polyurethane is 10g/L to 150g/L, preferably 11 g/L to 100g/L, preferably 12g/L to 95g/L, more preferably 15g/L to 90g/L, more preferably 20g/L to 80g/L, more preferably 30g/L to 70g/L, more preferably 40g/L to 60 g/L; and/or

The mass concentration of the metal precursor solution is 0.01-15 g/L, 0.1-12 g/L, preferably 0.5-10 g/L, more preferably 1-9 g/L, more preferably 2-8 g/L, more preferably 4-8 g/L, more preferably 5-8 g/L.

3. The nano-silver colloidal solution according to claim 1 or 2, wherein the reducing agent is used in the form of an aqueous solution having a mass concentration of 10 to 100g/L, preferably 12 to 95g/L, more preferably 15 to 90g/L, more preferably 20 to 80g/L, more preferably 30 to 70g/L, more preferably 40 to 60 g/L;

preferably, the addition of the reducing agent is carried out at a temperature of from 10 ℃ to 90 ℃, preferably from 20 ℃ to 80 ℃, preferably from 30 ℃ to 70 ℃, preferably from 40 ℃ to 60 ℃.

4. The nano-silver colloidal solution according to any one of claims 1 to 3, wherein the metal precursor solution is one or more selected from the group consisting of a silver nitrate solution, a silver perchlorate solution, a silver sulfate solution, a chloroauric acid solution, and a copper chloride solution; and/or

The reducing agent is one or more of glucose, fructose, vitamin C, sodium borohydride and hydrazine hydrate.

5. The nanosilver colloidal solution of any of claims 1-4, wherein the preparation method of the long chain branched globular polyurethane is as follows:

(1) uniformly blending polycaprolactone polyol and C4-C10 carboxylic acid (preferably selected from dimethylolpropionic acid and/or dimethylolbutyric acid) comprising at least two hydroxyl groups, and adding isophorone diisocyanate for reaction;

6. The nanosilver colloidal solution of claim 5, wherein the number average molecular weight of the polycaprolactone polyol is 1000-;

the number average molecular weight of the amino-terminated hyperbranched polymer is 300-15000, preferably 800-8000, preferably 1000-5000, and preferably 1000-3000.

7. The nano-silver colloidal solution according to claim 5, wherein the neutralizing agent is used in an amount such that the ratio of the C4-C10 carboxylic acid comprising at least two hydroxyl groups: the neutralizing agent is 1: 1.01-2.0, preferably 1: 1.02-1: 1.2 calculated by molar ratio.

8. The nanosilver colloidal solution of claim 5, wherein the polycaprolactone polyol, the C4-C10 carboxylic acid comprising at least two hydroxyl groups, isophorone diisocyanate, and the amino-terminated hyperbranched polymer are present in a molar ratio of (1-10) 12: (10-30): (0.2-2), preferably (2-9): 12: (12-25): (0.4-1.8), preferably (3-7) 12: (15-22): (0.5-1.5), preferably (4-6) 12: (15-20): (0.6-1.2).

9. The nano-silver colloidal solution according to claim 5, wherein the amino-terminated hyperbranched polymer has a molecular structure of:

preferably, the amino-terminated hyperbranched polymer molecule is prepared by: reacting diethylenetriamine with a mixed solution of methyl acrylate and methanol at the temperature of 10-30 ℃ for 2-5 hours to obtain a light yellow transparent substance, then decompressing and removing the methanol at the temperature of 60-80 ℃, immediately heating to 130-145 ℃, continuing decompressing and reacting for 2-3 hours, and stopping the reaction to obtain a viscous light yellow amino-terminated hyperbranched polymer;

preferably, the volume ratio of diethylenetriamine to methyl acrylate is (1.08-1.2): the volume ratio of methanol to (diethylenetriamine and methyl acrylate blend) is as follows: (1.5-1.05): 1.

10. a wash-durable antibacterial and antiviral fabric is prepared by the following steps:

soaking the fabric in the nano-silver solution, wherein the bath ratio is set as 1: 10-1: 50, then carrying out ultrasonic treatment for 10-20min at normal temperature;

thirdly, drying the fabric at 70-85 ℃ for 10-30min, and finally baking at 110-140 ℃ for 2-10 min;

preferably, the fabric is a knitted, woven, tatted or non-woven fabric formed by pure spinning or mutual blending of cotton, hemp, silk, terylene, chinlon, vinylon, aramid, high-strength high-modulus polyethylene fiber and carbon fiber;

preferably, the concentration of the nano silver solution is 1-5000mg/L, and the silver content of the prepared fabric is controlled to be 1-8000 mg/kg.