CN114657763A

CN114657763A - Inorganic antibacterial coupling cotton fiber and application thereof

Info

Publication number: CN114657763A
Application number: CN202210341658.3A
Authority: CN
Inventors: 黄悦; 周忠华; 林曦; 王家雄
Original assignee: Fujian Yilai Industrial Co ltd; Xiamen University
Current assignee: Fujian Yilai Industrial Co ltd; Xiamen University
Priority date: 2022-04-02
Filing date: 2022-04-02
Publication date: 2022-06-24
Anticipated expiration: 2042-04-02
Also published as: CN114657763B

Abstract

The invention discloses an inorganic antibacterial coupling cotton fiber and application thereof. The inorganic antibacterial coupling cotton fiber comprises cotton loose fiber, inorganic salt particles and metal antibacterial nano particles; the cellulose molecules of the cotton loose fibers are in-situ grafted with hydroxylated inorganic salt particles, the inorganic salt particles are loaded with the metal antibacterial nanoparticles, the inorganic salt particles comprise phosphate or a mixture of phosphate and sulfate, and the metal antibacterial nanoparticles comprise Ag nanoparticles and also comprise Cu nanoparticles or Zn nanoparticles. The content of P element (atom%) in the cotton fiber is 1, the ratio of Ag/P/O element is 0.002-2.0/1/4.0-12.0 or the ratio of (Ag, Cu)/P/O element is 0.002-2.0/1/4.0-12.0 or the ratio of (Ag, Zn)/P/O element is 0.002-2.0/1/4.0-12.0, the ratio of (Na, K)/Ca/P/S element is 1-2/0.05-0.1/1/0.0-0.4, and Si is not contained.

Description

Inorganic antibacterial coupling cotton fiber and application thereof

Technical Field

The invention belongs to the technical field of cotton fibers and fabrics, and particularly relates to inorganic antibacterial coupling cotton fibers and application thereof, which are applied to antibacterial cotton yarns, cotton blended yarns, clothing, non-implanted medical textiles, health care fabrics and the like.

Background

The cotton loose fiber is raw cotton fiber or fiber obtained by combing and drawing raw cotton, and is raw material of cotton yarn, cotton blended yarn and clothing, non-implanted medical and health care fabric. The antibacterial fabric has the technical requirements of broad spectrum, high efficiency, washing resistance and environmental protection of the preparation method along with the improvement of living standard of people. Ag⁺、Cu⁺、Cu²⁺、Zn²⁺、Zr⁴⁺And the like, and the inorganic antibacterial agent has high safety and is widely applied. However, inorganic antibacterial agents are diffused and compatible with water, are not washable, and are mainly applied to disposable fabrics at present. The inorganic antibacterial agent is applied to the cotton loose fibers with great technical difficulty because the main component of the cotton loose fibers is organic cellulose, the linear macromolecular compound is formed by connecting glucose molecules, and the inorganic antibacterial agent is not chemically bonded, and the coupling technology of the inorganic antibacterial agent and the cotton loose fibers is complex and immature.

Chinese patent (publication No. CN102634977A) 'method for preparing antibacterial fiber and fabric by in-situ complexation method' and Chinese patent (publication No. CN103122581A) 'method for preparing antibacterial fiber by in-situ complexation method that the product has soft hand feeling' adopt silane coupling agent, add cotton fiber into silane coupling agent solution, put in air for reaction, lead the coupling agent to be polymerized and fixed on the fiber, and put the fiber after reaction in solution containing inorganic antibacterial ions for adsorption treatment. Chinese patent (publication No. CN112176728A) 'an antibacterial, antiviral and deodorant cotton fiber and its preparation method and application' metal ions contained in an inorganic antibacterial agent and phytic acid form an antibacterial complex, beta-cyclodextrin and the antibacterial complex are mixed and then mixed with the cotton fiber, and the cotton fiber and the beta-cyclodextrin in the beta-cyclodextrin/antibacterial agent complex are grafted and crosslinked. The products prepared in the prior art are not washable due to physical absorption or are difficult to release inorganic antibacterial ions due to complex formation, and the silane coupling agent or the beta-cyclodextrin and the phytic acid are organic matters, so that the products are easy to age and decompose due to sunlight irradiation, are not durable for long-term use and have poor long-term effect.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, provides inorganic antibacterial coupling cotton fiber and application thereof, and solves the problems in the background art.

The technical scheme adopted by the invention for solving the technical problems is as follows: the inorganic antibacterial coupling cotton fiber is characterized in that: the method comprises the following steps: comprises cotton loose fibers, inorganic salt particles and metal antibacterial nano particles; hydroxylated inorganic salt particles are grafted on cellulose molecules of the cotton loose fibers in situ, the metal antibacterial nanoparticles are loaded on the inorganic salt particles, the inorganic salt particles comprise phosphate, and the metal antibacterial nanoparticles comprise Ag nanoparticles.

In a preferred embodiment of the present invention, the inorganic salt particles are a mixture of phosphate and sulfate.

In a preferred embodiment of the present invention, the metal antibacterial nanoparticles further include Cu nanoparticles or Zn nanoparticles.

In a preferred embodiment of the present invention, the content of P element (atom%) in the cotton fiber is 1, and the ratio of Ag/P/O element is 0.002-2.0/1/4.0-12.0.

In a preferred embodiment of the present invention, the content of P element (atom%) in the cotton fiber is 1, the ratio of (Ag, Cu)/P/O element is 0.002-2.0/1/4.0-12.0 or the ratio of (Ag, Zn)/P/O element is 0.002-2.0/1/4.0-12.0.

In a preferred embodiment of the present invention, the ratio of (Na, K)/Ca/P/S element in the cotton fiber is 1-2/0.05-0.1/1/0.0-0.4 with the content of P element (atom%) as 1.

In a preferred embodiment of the invention, the cotton fibers do not contain Si.

In a preferred embodiment of the invention, the cotton fibers comprise cotton loose fibers or products containing cotton loose fibers.

In a preferred embodiment of the present invention, the preparation method of the inorganic antibacterial coupling cotton fiber comprises the following steps:

(1) mixing alkali metal phosphate and alkaline earth metal phosphate with water, adding silver salt or silver salt and an auxiliary agent, magnetically stirring for 1.5-2.5h, sealing, and heating and activating at 125 ℃ for 1.5-2.5h to form inorganic antibacterial sol; the silver salt is silver nitrate or silver sulfate; the auxiliary agent is copper nitrate or zinc nitrate;

(2) the inorganic antibacterial sol has the passing intensity of 0.1-0.5 mW/cm²Ultraviolet irradiation with the wavelength of 350-380 nm is carried out for 5-60 min, so that silver salt is aggregated into Ag nuclei through photolysis, and nucleated inorganic antibacterial sol is prepared;

(3) soaking cotton fibers in the nucleated inorganic antibacterial sol for 1-10 min, taking out, drying, and passing through the cotton fibers with the passing strength of 0.1-1.5 mW/cm²Ultraviolet irradiation with the wavelength of 350-380 nm is carried out for 30-60 min, so that inorganic phosphate particles are hydroxylated, and are subjected to dehydration and cellulose molecule in-situ grafting on the surface of cotton fibers; meanwhile, silver salt is photolyzed and reduced in situ on the surface of the phosphate inorganic particles to form Ag nano particles, and the Ag series phosphate-based inorganic antibacterial coupling cotton fiber is prepared.

The invention also provides the application of the inorganic antibacterial coupling cotton fiber, which is used for antibacterial cotton yarn, cotton blended yarn and clothing, non-implanted medical textile and health care fabric, and comprises cotton yarn or cotton blended yarn and the like which are prepared by taking cotton loose fiber as a raw material through the processes of carding, pre-drawing, drawing and rolling, drawing, roving, spinning, knotting and the like.

According to the invention, on the basis that each glucose unit in a cellulose molecular structure of cotton fibers has three free hydroxyl groups, on the basis that silver nitrate is decomposed and reduced by exposure to light, on the basis that phosphate has hydrophilicity per se, the surface hydroxylation of phosphate particles is promoted by light irradiation under the excitation of ultraviolet light irradiation on the surface of the cotton fibers ingeniously, and through dehydration between the hydroxyl groups of the phosphate particles subjected to surface hydroxylation and the hydroxyl groups on the glucose units of the cellulose molecules, as shown in figure 1, the phosphate particles are grafted with the cellulose molecules, and meanwhile, the decomposition and Ag decomposition are realized under the irradiation of the silver nitrate ultraviolet light⁺Reducing in situ on the surface of the phosphate particles and fixing on the surface of the phosphate particles. Silver nano-particle produced by decomposing and reducing silver nitrate with lightThe seeds and the cotton fibers are coupled through phosphate particles, and are not connected through organic matters; silver nano particles and phosphate particles generated by the decomposition and reduction of silver nitrate under the action of light are inorganic and can be firmly coupled together; the inorganic phosphate particles and the organic cellulose molecules are coupled by chemical bonds generated through dehydration, so that the inorganic antibacterial cotton fiber structure is a firmly coupled structure, as shown in fig. 2.

And simultaneously, under the irradiation of ultraviolet light, copper ions or zinc ions are photo-reduced into Cu nanoparticles or Zn nanoparticles by electrons generated by photo-decomposition of silver nitrate and Ag nanoparticles as cores. Ag nanoparticles and Cu nanoparticles or Zn nanoparticles are immobilized on the surface of phosphate particles.

The silver salt is silver nitrate, and the mass ratio of the alkali metal phosphate to the alkaline earth metal phosphate to the water to the silver nitrate is 6:0.5:100: 0.0013-1.3. When the auxiliary agent is copper nitrate, the mass ratio of the alkali metal phosphate to the alkaline earth metal phosphate to the water to the sum of silver nitrate and copper nitrate is 6:0.5:100: 0.0013-1.3, the ratio of silver nitrate is at least 0.001, and the ratio of copper nitrate is at least 0.0003; when the auxiliary agent is zinc nitrate, the mass ratio of the alkali metal phosphate to the alkaline earth metal phosphate to the water to the sum of the silver nitrate and the nitric acid is 6:0.5:100: 0.0016-1.6, the ratio of the silver nitrate is at least 0.001, and the ratio of the zinc nitrate is at least 0.0006.

The silver salt is silver sulfate, and the mass ratio of the alkali metal phosphate to the alkaline earth metal phosphate to the water to the silver sulfate is 6:0.5:100: 0.0023-2.3. When the auxiliary agent is copper nitrate, the mass ratio of the sum of the alkali metal phosphate, the alkaline earth metal phosphate, the water, the silver sulfate and the copper nitrate is 6:0.5:100: 0.0023-2.3, the ratio of the silver sulfate is at least 0.002, and the ratio of the copper nitrate is at least 0.0003; when the auxiliary agent is zinc nitrate, the mass ratio of the sum of the alkali metal phosphate, the alkaline earth metal phosphate, the water, the silver sulfate and the nitric acid is 6:0.5:100: 0.0026-2.6, the ratio of the silver sulfate is at least 0.002, and the ratio of the zinc nitrate is at least 0.0006.

In the step (2), the ultraviolet light source is installed above the liquid of the inorganic antibacterial sol, and the liquid height of the inorganic antibacterial sol is 1-10 cm. The irradiation time is 5-10 min when the silver salt is silver nitrate, and the irradiation time is 30-60 min when the silver salt is silver sulfate.

In the step (3), the ultraviolet intensity is 0.8-1.2 mW/cm²The irradiation time is 40-45 min.

In the preparation method, the silver nitrate or the silver sulfate is preferably heated in a sealed polytetrafluoroethylene container for 2 hours at 120 ℃ to ensure that the hydrothermal process is carried out, and the Ag in the antibacterial sol is silver nitrate or silver sulfate⁺Activation of nucleation before reduction to Ag particles; the sol passes through ultraviolet (185 nm-380 nm) with the ultraviolet intensity of 0.1-0.3 mW/cm²Irradiating for 5-10 min or 30-60 min to make silver nitrate or silver sulfate in antibacterial sol Ag⁺Light before being reduced into Ag nano particles is decomposed, aggregated and nucleated, meanwhile, the height of the sol is 1-10 cm, so that ultraviolet light irradiation is guaranteed, the height of the sol exceeds 10cm, and the ultraviolet light is difficult to irradiate; mixing the cotton loose fibers with the hydroxylated inorganic antibacterial sol, soaking for 1-10 min, taking out, spin-drying, and irradiating by ultraviolet (185-380 nm) (the optimal ultraviolet irradiation wavelength is 350-380 nm), and the optimal ultraviolet intensity is 0.8-1.2 mW/cm²And the irradiation time is optimally 40-45 min), and the method is characterized in that the surface hydroxylation of phosphate particles is promoted by light irradiation under the excitation of ultraviolet light irradiation on the surface of cotton fibers, the phosphate particles and cellulose molecules are grafted through dehydration between the hydroxyl of the phosphate particles subjected to surface hydroxylation and the hydroxyl on a glucose unit of the cellulose molecules, and meanwhile, the phosphate particles are decomposed and reduced in situ on the surfaces of the phosphate particles under the irradiation of silver nitrate or silver sulfate ultraviolet light and are fixed on the surfaces of the phosphate particles.

Compared with the background technology, the technical scheme has the following advantages:

1. the inorganic antibacterial coupling cotton fiber has the following characteristics:

(1) the reasonable ratio of Ag/P/O, (Ag, Cu)/P/O or (Ag, Zn)/P/O elements ensures the antibacterial property;

under the condition of singly using silver nitrate or silver sulfate, the content (atom%) of a P element in the prepared cotton fiber is 1, and the ratio of Ag/P/O elements is 0.002-2.0/1/4.0-12.0; adding a copper nitrate auxiliary agent, wherein the ratio of (Ag, Cu)/P/O elements is 0.002-2.0/1/4.0-12.0, and the optimal ratio is 0.006-0.60/1/8-10; adding a zinc nitrate additive, wherein the ratio of (Ag, Zn)/P/O elements is 0.002-2.0/1/4.0-12.0, and the optimal ratio is 0.006-0.60/1/8-10; the characteristic ensures the antibacterial performance, the ratio of Ag or (Ag, Cu) to (Ag, Zn) is less than the lower limit value, the antibacterial performance is insufficient, and the ratio is higher than the upper limit value, which can affect the color of the cotton fiber;

aiming at the element proportion characteristic between P and O, the molecules of the cotton fibers contain O element, one part of the O element is from the cotton fibers, the other part of the O element is from phosphate particles, when the O element is less than 4, the phosphate particles coupled with the cotton fibers are less, and when the O element is higher than 12, the phosphate particles coupled with the cotton fibers are too much, so that the surfaces of the cotton fibers are easy to be sticky;

(2) the reasonable proportion of (Na, K)/Ca/P/S elements ensures the stability of coupling;

under the condition of using silver nitrate, the ratio of (Na, K)/Ca/P elements is 1-2/0.05-0.1/1; silver sulfate is used, the ratio of (Na, K)/Ca/P/S elements is 1-2/0.05-0.1/1/0.01-0.4, the characteristic ensures that inorganic phosphate particles and organic cellulose molecules are coupled through chemical bonds generated by dehydration, a small amount of S elements exist in the form of sulfate, and the sulfate and the phosphate are mixed, so that the coupling with the organic cellulose molecules is enhanced compared with the single phosphate;

(3) does not contain Si element;

the application of organic coupling agents is avoided, the anti-aging performance is excellent, and the antibacterial effect is still excellent after the washing for many times.

2. According to the invention, by utilizing the structural characteristics of cellulose molecules, the hydrophilicity of phosphate and the like, phosphate particles are grafted with the cellulose molecules skillfully on the surface of cotton fibers under the excitation of ultraviolet irradiation; decomposing Ag by ultraviolet light⁺Reducing in situ on the surface of the phosphate particles and fixing on the surface of the phosphate particles; with addition of auxiliaries, also by means of electrons generated by photolysis of silver salts and byAg nano particles are used as cores, and the Ag nano particles are photo-reduced into Cu nano particles or Zn nano particles. Ag nano particles and Cu nano particles or Zn nano particles are fixed on the surfaces of phosphate particles; the preparation method has the advantages of ingenious design, no need of strong acid and strong alkali, no generation of a large amount of waste liquid or harmful heavy metals, and environmental protection.

Drawings

FIG. 1 example 1 shows the dehydration chemical bonding of hydroxylated inorganic phosphate particles to cellulose molecules;

FIG. 2 is a schematic view showing the molecular structure of the inorganic antibacterial cotton loose fiber in example 1;

FIG. 3 EDS elemental analysis area of the surface of inorganic antibacterial cotton loose fibers of example 1;

Detailed Description

One, examples 1 to 6 are Ag-based phosphate-based environmentally friendly inorganic antibacterial coupled cotton fibers

Example 1:

6 parts of disodium hydrogen phosphate and 0.5 part of calcium hydrogen phosphate are mixed with 100 parts of water, and 0.13 part of silver nitrate is added. Stirring by magnetic force for 2 h. Transferring to a polytetrafluoroethylene container, sealing, and heating and activating at 120 ℃ for 2h to form inorganic antibacterial sol.

The inorganic antibacterial sol passes through ultraviolet (350 nm-380 nm) with the ultraviolet intensity of 0.1mW/cm²Irradiating with Ag⁺Nucleation is achieved by photolysis aggregation. While stirring magnetically, ultraviolet irradiation was performed. The ultraviolet light source is arranged above the sol liquid. The height of the sol was set to 6cm and the irradiation time was 5 min. Obtaining the Ag nucleated inorganic antibacterial sol.

Mixing cotton loose fiber with Ag nucleating inorganic antibacterial sol, soaking for 3min, taking out, drying, irradiating by ultraviolet (350-380 nm) with ultraviolet intensity of 1.0mW/cm²And the irradiation time was 40 min. Hydroxylating inorganic phosphate particles, and in-situ grafting the inorganic phosphate particles with cellulose molecules through dehydration on the surface of the cotton loose fibers, wherein AgNO is added₃And carrying out in-situ photolysis reduction on the surfaces of the phosphate inorganic particles to form Ag nano particles. Obtaining the environment-friendly inorganic antibacterial coupling cotton loose fiber.

The inorganic antibacterial coupling cotton loose fibers are subjected to elemental analysis on samples by adopting an Oxford INCA energy spectrometer (EDS) assembled on an SU-70 type scanning electron microscope, the areas of the EDS elemental analysis on the surfaces of the cotton loose fibers are shown in figure 3, at least five areas of each sample are tested, the average value is obtained, and the result is shown in table 1. The content of P element (atom%) is 1, and the ratio of Ag/P/O element is 0.067/1/9.4. The ratio of Na/Ca/P elements was 1.17/0.08/1. The content of Si is 0%, and Si element is not contained.

TABLE 1

Washing the inorganic antibacterial coupling cotton loose fiber for 50 times according to the washing method of the appendix C of FZ/T73023-2006; the antibacterial tests of staphylococcus aureus, escherichia coli and candida albicans are detected according to GB/T201510-; as a result, the antibacterial rate is more than or equal to 99.9 percent of staphylococcus aureus, more than or equal to 99.9 percent of escherichia coli and more than or equal to 99.9 percent of candida albicans, and the antibacterial level reaches the AAA level required by FZ/T73023 and 2006.

Example 2:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogen phosphate with 6 parts of dipotassium hydrogen phosphate in example 1 had a P element content (atom%) of 1 and a ratio of Ag/P/O elements of 0.067/1/9.4. The ratio of K/Ca/P elements was 1.20/0.08/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 3:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 3 parts of dipotassium hydrogenphosphate and 3 parts of disodium hydrogenphosphate in example 1 had a P element content (atom%) of 1 and a ratio of Ag/P/O element of 0.067/1/9.4. The ratio of (Na, K)/Ca/P elements was 1.19/0.08/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing 50 times, and the obtained antibacterial grade is AAA grade.

Example 4:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.13 part of silver nitrate in example 1 with 0.0013 part of silver nitrate has the P element content (atom%) of 1 and the ratio of Ag/P/O element of 0.003/1/9.6. The ratio of Na/Ca/P elements was 1.18/0.09/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 20 times to obtain the grade AA.

Example 5:

0.13 part of silver nitrate in example 1 was replaced with 0.0026 part of silver nitrate to obtain an inorganic antibacterial cotton loose fiber having a P element content (atom%) of 1 and a ratio of Ag/P/O element of 0.007/1/9.5. The ratio of Na/Ca/P elements was 1.16/0.07/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 6:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.13 part of silver nitrate in example 1 with 1.3 parts of silver nitrate has the P element content (atom%) of 1 and the ratio of Ag/P/O element of 0.57/1/9.4. The ratio of Na/Ca/P elements was 1.17/0.08/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Second, examples 7 to 13 are Ag and Cu mixed phosphate-based environmentally friendly inorganic antibacterial coupled cotton fibers

Example 7:

6 parts of disodium hydrogen phosphate and 0.5 part of calcium hydrogen phosphate are mixed with 100 parts of water, and 0.10 part of silver nitrate and 0.03 part of copper nitrate are added. Stirring by magnetic force for 2 h. Transferring to a polytetrafluoroethylene container, sealing, and heating and activating at 120 ℃ for 2h to form inorganic antibacterial sol.

Made of loose cotton fibres and AgMixing the nucleated inorganic antibacterial sol, soaking for 3min, taking out, drying, irradiating by ultraviolet (350-380 nm) with ultraviolet intensity of 1.0mW/cm²And the irradiation time was 40 min. The method comprises the steps of hydroxylating inorganic phosphate particles, carrying out in-situ grafting with cellulose molecules through dehydration on the surfaces of cotton loose fibers, carrying out in-situ photolysis and reduction on silver nitrate on the surfaces of the inorganic phosphate particles to form Ag nano particles, carrying out photolysis on copper nitrate under ultraviolet irradiation, and carrying out photo-reduction on copper ions to obtain Cu nano particles through electrons generated through photolysis of the silver nitrate and Ag nano particles as cores under ultraviolet irradiation. Ag nanoparticles and Cu nanoparticles are immobilized on the surface of phosphate particles. Obtaining the environment-friendly inorganic antibacterial coupling cotton loose fiber.

The inorganic antibacterial coupled cotton loose fibers were subjected to elemental analysis on the samples using an Oxford INCA spectrometer (EDS) equipped with a scanning electron microscope model SU-70, and the results are shown in Table 2. The ratio of (Ag, Cu)/P/O element was 0.063/1/8.5, with the P element content (atom%) being 1. The ratio of Na/Ca/P elements was 1.21/0.066/1. The content of Si is 0%, and Si element is not contained.

TABLE 2

Washing inorganic antibacterial coupling cotton loose fibers for 50 times according to a washing method of the annex C of FZ/T73023-; the antibacterial tests of staphylococcus aureus, escherichia coli and candida albicans are detected according to GB/T201510-; as a result, the antibacterial rate is more than or equal to 99.9 percent of staphylococcus aureus, more than or equal to 99.9 percent of escherichia coli and more than or equal to 99.9 percent of candida albicans, and the antibacterial level reaches the AAA level required by FZ/T73023 and 2006.

Example 8:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 6 parts of dipotassium hydrogenphosphate in example 7 had a P element content (atom%) of 1 and a (Ag, Cu)/P/O element ratio of 0.061/1/9.0. The ratio of K/Ca/P elements was 1.10/0.068/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 9:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 3 parts of dipotassium hydrogenphosphate and 3 parts of disodium hydrogenphosphate in example 7 had a P element content (atom%) of 1 and a (Ag, Cu)/P/O element ratio of 0.066/1/8.6. The ratio of (Na, K)/Ca/P elements was 1.13/0.062/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 10:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.10 parts of silver nitrate and 0.03 parts of copper nitrate in example 7 with 0.001 parts of silver nitrate and 0.03 parts of copper nitrate had a P element content (atom%) of 1 and a ratio of (Ag, Cu)/P/O element of 0.017/1/8.6. The ratio of Na/Ca/P elements was 1.19/0.065/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 11:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.10 parts of silver nitrate and 0.03 parts of copper nitrate with 0.001 parts of silver nitrate and 0.0003 parts of copper nitrate in example 7 had a P element content (atom%) of 1 and a ratio of (Ag, Cu)/P/O elements of 0.002/1/8.8. The ratio of Na/Ca/P elements was 1.15/0.067/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 20 times to obtain the grade AA.

Example 12:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.10 parts of silver nitrate and 0.03 parts of copper nitrate with 0.002 parts of silver nitrate and 0.003 parts of copper nitrate in example 7 had a P element content (atom%) of 1 and a (Ag, Cu)/P/O element ratio of 0.006/1/8.4. The ratio of Na/Ca/P elements was 1.19/0.064/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 13:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.10 parts of silver nitrate and 0.03 parts of copper nitrate with 1 part of silver nitrate and 0.03 parts of copper nitrate in example 7 had a P element content (atom%) of 1 and a ratio of (Ag, Cu)/P/O element of 0.55/1/8.8. The ratio of Na/Ca/P elements was 1.18/0.068/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Comparative example 1:

the inorganic antibacterial cotton loose fiber obtained in example 7 in which 0.10 part of silver nitrate and 0.03 part of copper nitrate were replaced with 0.001 part of silver nitrate was such that the content of the element P (atom%) was 1 and the ratio of Ag/P/O element was 0.001/1/8.7. The ratio of Na/Ca/P elements was 1.16/0.066/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing for 10 times, and the obtained antibacterial grade is grade A, and the antibacterial performance is poor.

Comparative example 2:

the inorganic antibacterial cotton loose fibers obtained in example 7 were obtained by replacing 0.10 part of silver nitrate and 0.03 part of copper nitrate with 0.003 part of copper nitrate, and had a P element content (atom%) of 1 and a Cu/P/O element ratio of 0.001/1/8.8. The ratio of Na/Ca/P elements is 1.15/0.068/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing for 10 times, and the obtained antibacterial grade is grade A, and the antibacterial performance is poor.

Example 11 compared to comparative example 1, the combination of Ag and Cu significantly improved the wash and antibacterial properties compared to Ag alone, requiring at least 0.001 parts silver nitrate and 0.0003 parts copper nitrate; example 11 compared to comparative example 2, the combination of Ag and Cu significantly improved the wash and antimicrobial properties compared to Cu alone, requiring at least 0.001 parts silver nitrate and 0.0003 parts copper nitrate.

Third, examples 14 to 20 are Ag and Zn mixed phosphate-based environment-friendly inorganic antibacterial coupled cotton fibers

Example 14:

6 parts of disodium hydrogen phosphate and 0.5 part of calcium hydrogen phosphate are mixed with 100 parts of water, and 0.10 part of silver nitrate and 0.06 part of zinc nitrate are added. Stirring by magnetic force for 2 h. Transferring to a polytetrafluoroethylene container, sealing, and heating and activating at 120 ℃ for 2h to form inorganic antibacterial sol.

The inorganic antibacterial sol passes through ultraviolet (350 nm-380 nm) with the ultraviolet intensity of 0.1mW/cm²Irradiating with Ag⁺Nucleation is performed by photolysis aggregation. While stirring magnetically, ultraviolet irradiation was performed. The ultraviolet light source is arranged above the sol liquid. The height of the sol was set to 6cm and the irradiation time was 5 min. Obtaining the Ag nucleated inorganic antibacterial sol.

Mixing the loose cotton fiber with Ag-nucleated inorganic antibacterial sol, soaking for 3min, taking out, drying, irradiating by ultraviolet (350-380 nm) with ultraviolet intensity of 1.0mW/cm²And the irradiation time was 40 min. The method comprises the steps of hydroxylating phosphate inorganic particles, carrying out in-situ grafting with cellulose molecules through dehydration on the surfaces of cotton loose fibers, carrying out in-situ photolysis and reduction on silver nitrate on the surfaces of the phosphate inorganic particles to form Ag nano particles, and carrying out photo-reduction on zinc ions to obtain the zinc nano particles through electrons generated through photolysis of the silver nitrate and Ag nano particles as cores under the irradiation of ultraviolet light. Ag nanoparticles and zinc nanoparticles are immobilized on the surface of the phosphate particles. Obtaining the environment-friendly inorganic antibacterial coupling cotton loose fiber.

The inorganic antibacterial coupling cotton loose fibers were subjected to elemental analysis on a sample using an Oxford INCA spectrometer (EDS) equipped with an SU-70 model scanning electron microscope, and the results are shown in Table 3. The ratio of (Ag, Zn)/P/O element was 0.089/1/9.2, with the P element content (atom%) as 1. The ratio of Na/Ca/P elements was 1.30/0.074/1. The content of Si is 0%, and Si element is not contained.

TABLE 3

Element	Atomic％
		OK	78.89
NaK	11.18
		MgK	0.00
AlK	0.00
		SiK	0.00
PK	8.54
		SK	0.00
KK	0.00
		CaK	0.63
TiK	0.00
		FeK	0.00
CuK	0.00
		ZnK	0.28
ZrL	0.00
		AgL	0.48
Totals	100.00

Example 15:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 6 parts of dipotassium hydrogenphosphate in example 14 had a P element content (atom%) of 1 and a (Ag, Zn)/P/O element ratio of 0.086/1/9.0. The ratio of K/Ca/P elements was 1.21/0.07/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 16:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 3 parts of dipotassium hydrogenphosphate and 3 parts of disodium hydrogenphosphate in example 14 had a P element content (atom%) of 1 and a (Ag, Zn)/P/O element ratio of 0.088/1/9.1. The ratio of (Na, K)/Ca/P elements is 1.28/0.074/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 17:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.10 parts of silver nitrate and 0.06 parts of zinc nitrate in example 14 with 0.001 parts of silver nitrate and 0.06 parts of zinc nitrate had a P element content (atom%) of 1 and a ratio of (Ag, Zn)/P/O element of 0.033/1/9.0. The ratio of Na/Ca/P elements was 1.29/0.075/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 18:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.10 parts of silver nitrate and 0.06 parts of zinc nitrate in example 14 with 0.001 parts of silver nitrate and 0.0006 parts of zinc nitrate had a P element content (atom%) of 1 and a ratio of (Ag, Zn)/P/O elements of 0.002/1/9.3. The ratio of Na/Ca/P elements is 1.30/0.075/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 20 times to obtain the grade AA.

Example 19:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.10 parts of silver nitrate and 0.06 parts of zinc nitrate in example 14 with 0.002 parts of silver nitrate and 0.006 parts of zinc nitrate had a P element content (atom%) of 1 and a ratio of (Ag, Zn)/P/O element of 0.006/1/9.1. The ratio of Na/Ca/P elements was 1.30/0.073/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 20:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.10 parts of silver nitrate and 0.06 parts of zinc nitrate in example 14 with 1 part of silver nitrate and 0.06 parts of zinc nitrate had a P element content (atom%) of 1 and a ratio of (Ag, Zn)/P/O elements of 0.56/1/9.2. The ratio of Na/Ca/P elements was 1.31/0.073/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Comparative example 3:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.10 part of silver nitrate and 0.06 part of zinc nitrate in example 14 with 0.006 part of zinc nitrate had a P element content (atom%) of 1 and a Zn/P/O element ratio of 0.001/1/9.0. The ratio of Na/Ca/P elements is 1.30/0.071/1. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing for 10 times, and the obtained antibacterial grade is grade A, and the antibacterial performance is poor.

Example 18 compared to comparative example 1, the combination of Ag and Zn significantly improved the wash and antimicrobial properties compared to Ag alone, requiring at least 0.001 parts silver nitrate and 0.0006 parts zinc nitrate; example 18 compared to comparative example 3, the combination of Ag and Zn significantly improved the wash and antimicrobial properties compared to Zn alone, requiring at least 0.001 parts silver nitrate and 0.0006 parts zinc nitrate.

Fourth, examples 21 to 26 are Ag-based sulfur-containing phosphate-based environmentally friendly inorganic antibacterial coupled cotton fibers

Example 21:

6 parts of disodium hydrogen phosphate and 0.5 part of calcium hydrogen phosphate are mixed with 100 parts of water, and 0.23 part of silver sulfate is added. Stirring by magnetic force for 2 h. Transferring to a polytetrafluoroethylene container, sealing, and heating and activating at 120 ℃ for 2h to form inorganic antibacterial sol.

The inorganic antibacterial sol passes through ultraviolet (350 nm-380 nm) with the ultraviolet intensity of 0.5mW/cm²Irradiating with Ag⁺Nucleation is achieved by photolysis aggregation. While stirring magnetically, ultraviolet irradiation was performed. The ultraviolet light source is arranged above the sol liquid. The height of the sol was set to 6cm and the irradiation time was 45 min. Obtaining the Ag nucleated inorganic antibacterial sol.

Mixing the loose cotton fiber with Ag-nucleated inorganic antibacterial sol, soaking for 3min, taking out, drying, irradiating by ultraviolet (350-380 nm) with ultraviolet intensity of 1.0mW/cm²And the irradiation time was 40 min. Hydroxylating inorganic phosphate particles, carrying out in-situ grafting with cellulose molecules through dehydration on the surfaces of the cotton loose fibers, and simultaneously carrying out in-situ photolysis reduction on the surfaces of the inorganic phosphate particles to form Ag nano particles. Obtaining the environment-friendly inorganic antibacterial coupling cotton loose fiber.

The inorganic antibacterial coupling cotton loose fibers were subjected to elemental analysis on a sample using an Oxford INCA spectrometer (EDS) equipped with an SU-70 model scanning electron microscope, and the results are shown in Table 4. The content of P element (atom%) is 1, and the ratio of Ag/P/O element is 0.07/1/9.52. The ratio of Na/Ca/P/S elements was 1.20/0.085/1/0.037. The content of Si is 0%, and Si element is not contained.

TABLE 4

Element	Atomic％
		OK	79.90
NaK	10.10
		MgK	0.00
AlK	0.00
		SiK	0.00
PK	8.39
		SK	0.31
KK	0.00
		CaK	0.71
TiK	0.00
		FeK	0.00
CuK	0.00
		ZnK	0.00
ZrL	0.00
		AgL	0.59
Totals	100.00

Example 22:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 6 parts of dipotassium hydrogenphosphate in example 21 had a P element content (atom%) of 1 and a ratio of Ag/P/O element of 0.07/1/9.5. The ratio of K/Ca/P/S elements was 1.20/0.09/1/0.04. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 23:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 3 parts of dipotassium hydrogenphosphate and 3 parts of disodium hydrogenphosphate in example 21 had a P element content (atom%) of 1 and a ratio of Ag/P/O element of 0.07/1/9.4. The ratio of Na/Ca/P/S elements was 1.19/0.086/1/0.039. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 24:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.23 part of silver sulfate in example 21 with 0.0023 part of silver sulfate had a P element content (atom%) of 1 and a ratio of Ag/P/O element of 0.003/1/9.5. The ratio of Na/Ca/P/S elements was 1.18/0.09/1/0.01. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 20 times to obtain the grade AA.

Example 25:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.23 part of silver sulfate in example 21 with 0.0046 part of silver sulfate had a P element content (atom%) of 1 and a Ag/P/O element ratio of 0.006/1/9.4. The ratio of Na/Ca/P/S elements was 1.18/0.07/1/0.011. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 26:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.23 part of silver sulfate in example 21 with 2.3 parts of silver sulfate had a P element content (atom%) of 1 and a ratio of Ag/P/O element of 0.60/1/9.3. The ratio of Na/Ca/P/S elements was 1.21/0.08/1/0.4. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Fifth, examples 27 to 33 are Ag and Cu mixed series sulfur-containing phosphate-based environmentally friendly inorganic antibacterial coupled cotton fibers

Example 27:

6 parts of disodium hydrogenphosphate and 0.5 part of calcium hydrogenphosphate are mixed with 100 parts of water, and 0.20 part of silver sulfate and 0.03 part of copper nitrate are added. Stirring by magnetic force for 2 h. Transferring to a polytetrafluoroethylene container, sealing, and heating and activating at 120 ℃ for 2h to form inorganic antibacterial sol.

The inorganic antibacterial sol passes through ultraviolet (350 nm-380 nm) with the ultraviolet intensity of 0.5mW/cm²Irradiating with Ag⁺Nucleation is achieved by photolysis aggregation. While stirring magnetically, ultraviolet irradiation was performed. The ultraviolet light source is arranged above the sol liquid. Sol gelThe height of (2) was set to 6cm, and the irradiation time was 45 min. To obtain the Ag nucleating inorganic antibacterial sol.

Mixing cotton loose fiber with Ag nucleating inorganic antibacterial sol, soaking for 3min, taking out, drying, irradiating by ultraviolet (350-380 nm) with ultraviolet intensity of 1.0mW/cm²And the irradiation time was 40 min. The phosphate inorganic particles are hydroxylated and are in-situ grafted with cellulose molecules through dehydration on the surface of the cotton loose fibers, meanwhile, silver sulfate is photolyzed and reduced in situ on the surface of the phosphate inorganic particles to form Ag nano particles, and simultaneously, copper ions are photo-reduced into Cu nano particles by electrons generated through photolysis of the silver sulfate and the Ag nano particles as cores under the irradiation of ultraviolet light. Ag nanoparticles and Cu nanoparticles are immobilized on the surface of phosphate particles. Obtaining the environment-friendly inorganic antibacterial coupling cotton loose fiber.

The inorganic antimicrobial coupled cotton loose fibers were subjected to elemental analysis on the samples using an Oxford INCA spectrometer (EDS) equipped with a scanning electron microscope model SU-70, the results of which are shown in Table 5. The ratio of (Ag, Cu)/P/O element was 0.09/1/9.8, with the P element content (atom%) being 1. The ratio of Na/Ca/P/S elements was 1.37/0.08/1/0.037. The content of Si is 0%, and Si element is not contained.

TABLE 5

Element	Atomic％
		OK	79.26
NaK	11.00
		MgK	0.00
AlK	0.00
		SiK	0.00
PK	8.05
		SK	0.30
KK	0.00
		CaK	0.66
TiK	0.00
		FeK	0.00
CuK	0.12
		ZnK	0.00
ZrL	0.00
		AgL	0.61
Totals	100.00

Example 28:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 6 parts of dipotassium hydrogenphosphate in example 27 had a P element content (atom%) of 1 and a (Ag, Cu)/P/O element ratio of 0.091/1/9.0. The ratio of K/Ca/P/S elements was 1.30/0.078/1/0.039. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 29:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 3 parts of dipotassium hydrogenphosphate and 3 parts of disodium hydrogenphosphate in example 27 had a P element content (atom%) of 1 and a ratio of (Ag, Cu)/P/O element of 0.089/1/9.6. The ratio of (Na, K)/Ca/P/S elements was 1.23/0.082/1/0.037. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 30:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 parts of silver sulfate and 0.03 parts of copper nitrate in example 27 with 0.002 parts of silver sulfate and 0.03 parts of copper nitrate had a P element content (atom%) of 1 and a ratio of (Ag, Cu)/P/O element of 0.018/1/8.9. The ratio of Na/Ca/P/S elements was 1.29/0.085/1/0.016. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 31:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 part of silver sulfate and 0.03 part of copper nitrate in example 27 with 0.002 part of silver sulfate and 0.0003 part of copper nitrate were found to have a ratio of (Ag, Cu)/P/O element of 0.002/1/9.6 in terms of P element content (atom%) of 1. The ratio of Na/Ca/P/S elements was 1.25/0.087/1/0.014. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 20 times to obtain the grade AA.

Example 32:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 parts of silver sulfate and 0.03 parts of copper nitrate with 0.002 parts of silver sulfate and 0.003 parts of copper nitrate in example 27 had a P element content (atom%) of 1 and a (Ag, Cu)/P/O element ratio of 0.006/1/9.4. The ratio of Na/Ca/P/S elements was 1.29/0.084/1/0.024. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 33:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 parts of silver sulfate and 0.03 parts of copper nitrate with 2 parts of silver sulfate and 0.03 parts of copper nitrate in example 27 had a P element content (atom%) of 1 and a ratio of (Ag, Cu)/P/O element of 0.53/1/9.8. The ratio of Na/Ca/P/S elements was 1.18/0.078/1/0.35. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Comparative example 4:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 part of silver sulfate and 0.03 part of copper nitrate in example 27 with 0.002 part of silver sulfate had a P element content (atom%) of 1 and a ratio of Ag/P/O element of 0.001/1/9.7. The ratio of Na/Ca/P/S elements was 1.26/0.076/1/0.013. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing for 10 times, and the obtained antibacterial grade is grade A, and the antibacterial performance is poor.

Comparative example 5:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 part of silver sulfate and 0.03 part of copper nitrate with 0.003 part of copper nitrate in example 27 had a P element content (atom%) of 1 and a Cu/P/O element ratio of 0.001/1/9.8. The ratio of Na/Ca/P/S elements was 1.25/0.086/1/0. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing for 10 times, and the obtained antibacterial grade is grade A, and the antibacterial performance is poor.

Example 31 compared to comparative example 4, the combination of Ag and Cu significantly improved the wash and antibacterial properties compared to Ag alone, requiring at least 0.002 parts silver sulfate and 0.0003 parts copper nitrate; example 31 compared to comparative example 5, the combination of Ag and Cu significantly improved the wash and antibacterial performance over Cu alone, requiring at least 0.002 parts silver sulfate and 0.0003 parts copper nitrate.

Sixthly, examples 34 to 40 are Ag and Zn mixed series sulfur-containing phosphate-based environment-friendly inorganic antibacterial coupling cotton fibers

Example 34:

6 parts of disodium hydrogenphosphate and 0.5 part of calcium hydrogenphosphate are mixed with 100 parts of water, and 0.20 part of silver sulfate and 0.06 part of zinc nitrate are added. Stirring by magnetic force for 2 h. Transferring to a polytetrafluoroethylene container, sealing, and heating and activating at 120 ℃ for 2h to form inorganic antibacterial sol.

The inorganic antibacterial sol passes through ultraviolet (350 nm-380 nm) with the ultraviolet intensity of 0.5mW/cm²Irradiating with Ag⁺Nucleation is achieved by photolysis aggregation. While stirring magnetically, ultraviolet irradiation was performed. The ultraviolet light source is arranged above the sol liquid. The height of the sol was set to 6cm and the irradiation time was 45 min. To obtain the Ag nucleating inorganic antibacterial sol.

Mixing cotton loose fiber with Ag nucleating inorganic antibacterial sol, soaking for 3min, taking out, drying, irradiating by ultraviolet (350-380 nm) with ultraviolet intensity of 1.0mW/cm²And the irradiation time was 40 min. The phosphate inorganic particles are hydroxylated and are in-situ grafted with cellulose molecules through dehydration on the surface of the cotton loose fibers, meanwhile, silver sulfate is photolyzed and reduced in situ on the surface of the phosphate inorganic particles to form Ag nano particles, and meanwhile, zinc ions are photo-reduced into Zn nano particles through electrons generated through photolysis of the silver sulfate and the Ag nano particles as cores under the irradiation of ultraviolet light. Ag nanoparticles and Zn nanoparticles are immobilized on the surface of phosphate particles. Obtaining the environment-friendly inorganic antibacterial coupling cotton loose fiber.

The inorganic antimicrobial coupled cotton loose fibers were subjected to elemental analysis on the samples using an Oxford INCA spectrometer (EDS) equipped with a scanning electron microscope model SU-70, the results of which are shown in Table 6. The ratio of (Ag, Zn)/P/O element was 0.104/1/9.4, with the P element content (atom%) as 1. The ratio of Na/Ca/P/S elements was 1.327/0.079/1/0.036. The content of Si is 0%, and Si element is not contained.

TABLE 6

Element	Atomic％
		OK	78.74
NaK	11.08
		MgK	0.00
AlK	0.00
		SiK	0.00
PK	8.35
		SK	0.30
KK	0.00
		CaK	0.66
TiK	0.00
		FeK	0.00
CuK	0.00
		ZnK	0.26
ZrL	0.00
		AgL	0.61
Totals	100.00

Washing inorganic antibacterial coupling cotton loose fibers for 50 times according to a washing method of the annex C of FZ/T73023-; the antibacterial tests of staphylococcus aureus, escherichia coli and candida albicans are detected according to GB/T201510-2008; as a result, the antibacterial rate is more than or equal to 99.9 percent of staphylococcus aureus, more than or equal to 99.9 percent of escherichia coli and more than or equal to 99.9 percent of candida albicans, and the antibacterial level reaches the AAA level required by FZ/T73023 and 2006.

Example 35:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 6 parts of dipotassium hydrogenphosphate in example 34 had a P element content (atom%) of 1 and a (Ag, Zn)/P/O element ratio of 0.096/1/9.1. The ratio of K/Ca/P/S elements was 1.31/0.078/1/0.038. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing 50 times, and the obtained antibacterial grade is AAA grade.

Example 36:

the inorganic antibacterial cotton loose fibers obtained by replacing 6 parts of disodium hydrogenphosphate with 3 parts of dipotassium hydrogenphosphate and 3 parts of disodium hydrogenphosphate in example 34 had a P element content (atom%) of 1 and a (Ag, Zn)/P/O element ratio of 0.095/1/9.2. The ratio of (Na, K)/Ca/P/S elements is 1.33/0.081/1/0.037. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing 50 times, and the obtained antibacterial grade is AAA grade.

Example 37:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 part of silver sulfate and 0.06 part of zinc nitrate in example 34 with 0.002 part of silver sulfate and 0.06 part of zinc nitrate had a P element content (atom%) of 1 and a (Ag, Zn)/P/O element ratio of 0.032/1/9.4. The ratio of Na/Ca/P/S elements was 1.30/0.081/1/0.016. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 38:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 part of silver sulfate and 0.06 part of zinc nitrate in example 34 with 0.002 part of silver sulfate and 0.0006 part of zinc nitrate had a P element content (atom%) of 1 and a (Ag, Zn)/P/O element ratio of 0.003/1/9.3. The ratio of Na/Ca/P/S elements was 1.30/0.08/1/0.014. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 20 times to obtain the grade AA.

Example 39:

the inorganic antibacterial cotton loose fiber obtained by replacing 0.20 parts of silver sulfate and 0.06 parts of zinc nitrate in example 34 with 0.002 parts of silver sulfate and 0.006 parts of zinc nitrate had a P element content (atom%) of 1 and a (Ag, Zn)/P/O element ratio of 0.006/1/9.4. The ratio of Na/Ca/P/S elements was 1.31/0.078/1/0.014. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Example 40:

the inorganic antibacterial cotton loose fibers obtained by replacing 0.20 part of silver sulfate and 0.06 part of zinc nitrate in example 34 with 2 parts of silver sulfate and 0.06 part of zinc nitrate had a P element content (atom%) of 1 and a ratio of (Ag, Zn)/P/O element of 0.57/1/9.6. The ratio of Na/Ca/P/S elements was 1.32/0.078/1/0.37. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: and washing for 50 times, wherein the obtained antibacterial grade is AAA grade.

Comparative example 6:

0.20 part of silver sulfate and 0.06 part of zinc nitrate in example 34 were replaced with 0.006 part of zinc nitrate to obtain an inorganic antibacterial cotton loose fiber having a P element content (atom%) of 1 and a Zn/P/O element ratio of 0.001/1/9.3. The ratio of Na/Ca/P/S elements was 1.30/0.08/1/0. The content of Si is 0%, and Si element is not contained. Wash fastness and antibacterial properties: washing for 10 times, and the obtained antibacterial grade is grade A, and the antibacterial performance is poor.

Example 38 compared to comparative example 4, the combination of Ag and Zn significantly improved the wash and antibacterial performance over Ag alone, requiring at least 0.002 parts silver sulfate and 0.0006 parts zinc nitrate; example 38 compared to comparative example 6, the combination of Ag and Zn significantly improved the wash and antimicrobial properties compared to Zn alone, requiring at least 0.002 parts silver sulfate and 0.0006 parts zinc nitrate.

The inorganic antibacterial coupling cotton fiber has excellent washing resistance, antibacterial performance and ageing resistance, is not limited to cotton loose fiber, and can be also suitable for cotton yarns or cotton blended yarns prepared by combing, pre-drawing, strip-and-roll, drawing, roving, spun yarn, knotting and other processes by taking the cotton loose fiber as a raw material. The antibacterial cotton yarn is applied to antibacterial cotton yarn, cotton blended yarn, clothing, non-implanted medical textiles, health care fabrics and the like.

The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Inorganic antibiotic coupling cotton fiber, its characterized in that: the method comprises the following steps: comprises cotton loose fibers, inorganic salt particles and metal antibacterial nano particles; hydroxylated inorganic salt particles are grafted on cellulose molecules of the cotton loose fibers in situ, the metal antibacterial nanoparticles are loaded on the inorganic salt particles, the inorganic salt particles comprise phosphate, and the metal antibacterial nanoparticles comprise Ag nanoparticles.

2. The inorganic antimicrobial coupling cotton fiber of claim 1, wherein: the inorganic salt particles are a mixture of phosphate and sulfate.

3. The inorganic antimicrobial coupling cotton fiber of claim 1, wherein: the metal antibacterial nanoparticles further comprise Cu nanoparticles or Zn nanoparticles.

4. The inorganic antimicrobial coupling cotton fiber of claim 1, wherein: the content of P element (atom%) in the cotton fiber is 1, and the ratio of Ag/P/O element is 0.002-2.0/1/4.0-12.0.

5. The inorganic antimicrobial coupling cotton fiber of claim 3, wherein: the content of P element (atom%) in the cotton fiber is 1, the ratio of (Ag, Cu)/P/O element is 0.002-2.0/1/4.0-12.0 or the ratio of (Ag, Zn)/P/O element is 0.002-2.0/1/4.0-12.0.

6. The inorganic antimicrobial coupling cotton fiber of claim 2, wherein: the ratio of (Na, K)/Ca/P/S element in the cotton fiber is 1-2/0.05-0.1/1/0.0-0.4 with the content of P element (atom%) as 1.

7. The inorganic antimicrobial coupling cotton fiber of claim 1, wherein: cotton fibers do not contain Si.

8. The inorganic antimicrobial coupling cotton fiber of claim 1, wherein: the cotton fibers include cotton loose fibers or products containing cotton loose fibers.

9. The inorganic antimicrobial coupling cotton fiber of claim 1, wherein: the preparation method comprises the following steps:

(3) soaking cotton fibers in the nucleated inorganic antibacterial sol for 1-10 min, taking out, drying, and passing through the cotton fibers with the passing strength of 0.1-1.5 mW/cm²Ultraviolet irradiation with the wavelength of 350-380 nm is carried out for 30-60 min, so that inorganic phosphate particles are hydroxylated, and are subjected to dehydration and cellulose molecule in-situ grafting on the surface of cotton fibers; meanwhile, silver salt is photolyzed and reduced in situ on the surface of the inorganic phosphate particles to form Ag nano particles, and the Ag series phosphate-based inorganic antibacterial coupling cotton fiber is prepared.

10. Use of an inorganic antimicrobial coupled cotton fiber according to any of claims 1 to 9, wherein: can be used in antibacterial cotton yarn, cotton blended yarn, clothing, non-implanted medical textile, and health care fabric.