Medical and sanitary antibacterial deodorizing polyethylene breathable film and preparation method thereof

Abstract

The invention relates to the technical field of medical breathable films, in particular to a medical and sanitary antibacterial deodorizing polyethylene breathable film and a preparation method thereof. The invention relates to an antibacterial deodorizing polyethylene breathable film for medical and sanitary use. The antibacterial deodorizing polyethylene breathable film is prepared by compounding metal ion doped mesoporous silica (MSN) with polyethylene (PE) breathable particles, the particle is prepared from 1-5 parts of a metal ion doped mesoporous silica nano antibacterial agent MSN and 100 parts of PE breathable particles. A resin matrix in the PE breathable particles is low-density polyethylene (LDPE) or linear low-density polyethylene (LLDPE); the inorganic filler for forming the microporous structure in the PE breathable particles comprises at least one of stearic acid modified calcium carbonate with the average particle size of 50-2000 nm, talcum powder, calcined shell powder, kaolin, silica fume, zeolite powder, titanium dioxide, silicon dioxide and glass powder. The PE breathable film has deodorizing, antibacterial and antistatic effects, is used in the field of medical non-woven fabrics, and reduces the bacterial infection risk of medical staff.

Description

Technical Field

[0001] This application relates to the technical field of medical breathable membranes, and particularly to a medical and sanitary antibacterial and deodorizing polyethylene breathable membrane and a preparation method thereof. Background Art

[0002] Polyethylene (PE) breathable membranes are applied in various fields due to their good high and low temperature resistance, corrosion resistance, high tensile strength, high waterproofness and softness, etc. PE is suitable for various processing methods, such as blow molding and thermoforming. In addition, due to the advantage of easy processing, it can be used to manufacture various plastic products, food packaging, disposable food containers, non-woven fabrics, industrial and household textiles. It can also be further processed into agricultural fabrics, medical textiles, cleaning cloths, sanitary products, outdoor anti-ultraviolet fabrics, tent fabrics and carpet surfaces, etc., making it a market with broad prospects.

[0003] The main components of polyethylene (PE) breathable membranes are PE particles and large particles of calcium carbonate. By mixing the two in a certain proportion, the corresponding PE breathable particles are prepared. After the PE breathable particles are made into a film, the calcium carbonate inside will cause the film to produce micropores, achieving the functions of air permeability and moisture permeability of the film. However, this type of breathable membrane will attract viruses and molds, which has raised concerns about safety and hygiene. For this reason, the inventor provides a medical and sanitary antibacterial and deodorizing polyethylene breathable membrane and a preparation method thereof. Summary of the Invention

[0004] In order to solve the problem that the existing polyethylene breathable membrane has poor antibacterial performance, which has raised concerns about safety and hygiene, the present invention provides a medical and sanitary antibacterial and deodorizing polyethylene breathable membrane and a preparation method thereof.

[0005] A medical and sanitary antibacterial and deodorizing polyethylene breathable membrane provided by the present invention is achieved through the following technical solutions:

[0006] A medical and sanitary antibacterial and deodorizing polyethylene breathable membrane is made of MSN-doped PE breathable particles; the MSN-doped PE breathable particles are made from the following raw materials in parts by weight: 1-5 parts of copper ion-doped mesoporous silica nano-antibacterial agent MSN, 100 parts of PE breathable particles.

[0007] Preferably, the resin matrix in the PE breathable particles is low-density polyethylene LDPE or linear low-density polyethylene LLDPE, and the addition amount of the inorganic filler in the PE breathable particles is 5-50 wt%.

[0008] Preferably, the inorganic filler for forming the microporous structure in the PE breathable particles includes at least one of calcium carbonate modified with stearic acid, talcum powder, calcined shell powder, kaolin, silica ash, zeolite powder, titanium dioxide, silicon dioxide, and glass powder with an average particle size of 50-2000 nm.

[0009] The PE breathable film in the present invention has deodorizing, antibacterial, and antistatic effects and is used in the field of medical non-woven fabrics to reduce the risk of bacterial infection for medical staff.

[0010] Preferably, the metal ion doped mesoporous silica nano-antibacterial agent MSN is doped with metal ions including Mn 2+ , Pb 2+ , Cu 2+ , Zn 2+ , Cu + , Zn 2+ , Fe 3+ , Fe 2+ , Ag + , Au + , Au 3+ and at least one of them; the particle size distribution of the mesoporous silica in the metal ion doped mesoporous silica nano-antibacterial agent MSN is 20-200 nm.

[0011] More preferably, the metal ion doped mesoporous silica nano-antibacterial agent MSN is doped with metal ions including Cu 2+ .

[0012] Preferably, the metal ion doped mesoporous silica nano-antibacterial agent MSN is prepared by a sol-gel method in one step using metal salts, sodium hydroxide, cetyltrimethylammonium bromide, and tetraethyl orthosilicate as raw materials.

[0013] More preferably, the preparation method of the metal ion doped mesoporous silica nano-antibacterial agent MSN is as follows: Step 1, prepare a metal hydroxide seed solution using metal salts, sodium hydroxide, and cetyltrimethylammonium bromide; Step 2, add tetraethyl orthosilicate to the metal hydroxide seed solution and react at 60-80 °C for 2-8 hours. The centrifuged solid is washed three times each with pure water and ethanol, dried, and pulverized to obtain the finished product MSN.

[0014] Preferably, the specific preparation method of the metal hydroxide seed solution in the first step is as follows: Prepare a metal salt solution with a concentration of 0.06 - 320 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, and a NaOH solution with a concentration of 0.5 - 1 mol / L for standby; then add 1 - 7 mL of the metal salt solution with a concentration of 0.06 - 320 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 - 65 °C, mix and stir for at least half an hour, then add 0.25 mL of the NaOH solution with a concentration of 0.5 - 1 mol / L, raise the temperature to 60 - 80 °C and continue to stir for at least half an hour to obtain the metal hydroxide seed solution.

[0015] Preferably, in the second step, add 1 - 2 mL of tetraethyl orthosilicate with a concentration of 15.0 - 20.0 g / L to the metal hydroxide seed solution prepared in the first step, react at 60 - 80 °C for 2 - 8 hours, wash the centrifuged solid matter three times each with pure water and ethanol, dry, and pulverize to obtain the finished product MSN.

[0016] Preferably, the metal salt in the metal salt solution is at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, cuprous chloride, zinc chloride, zinc nitrate, zinc acetylacetonate, ferrous sulfate, ferric chloride, ferric nitrate, ferric acetylacetonate, lead sulfate, lead chloride, lead nitrate, lead acetylacetonate, silver nitrate, and chloroauric acid.

[0017] Preferably, the solvent in the metal salt solution is water or a mixed solvent formed by water and at least one of alcohols, heptane, benzene, toluene, xylene, and acetone.

[0018] By adopting the above technical solutions, the synthesis of the metal ion-doped mesoporous silica nano-antibacterial agent MSN has a lower difficulty, less synthesis pollution, is convenient for realizing the industrial production of the nano-antibacterial agent MSN, and thus can reduce the production cost of the nano-antibacterial agent MSN and the production cost of the medical and hygienic antibacterial and deodorant polyethylene breathable film.

[0019] The preparation method of a medical and hygienic antibacterial and deodorant polyethylene breathable film provided by the present invention is achieved through the following technical solutions:

[0020] A preparation method of a medical and hygienic antibacterial and deodorant polyethylene breathable film includes the following steps:

[0021] Step 1, preparation of the metal ion-doped mesoporous silica nano-antibacterial agent MSN;

[0022] Step 2: Mix 1 - 5 parts of metal ion - doped mesoporous silica nano - antibacterial agent MSN with 100 parts of dried PE breathable particles at high speed until evenly mixed, and then put them into a twin - screw extruder for extrusion granulation. The temperature of the feeding section is 160 - 180°C, the plasticizing section is 160 - 180°C, the homogenizing section is 160 - 180°C, the rotational speed of the twin - screw is 60 - 72 r / min, and the die head temperature is 160 - 180°C to obtain MSN - doped PE breathable particles;

[0023] Step 3: Put the MSN - doped PE breathable particles into a twin - screw extruder. The temperature of the feeding section is 160 - 180°C, the plasticizing section is 160 - 180°C, the homogenizing section is 160 - 180°C, the rotational speed of the twin - screw is 80 - 100 r / min, and the die head temperature is 160 - 180°C. Place the obtained molten extruded material on a casting machine, and the rotational speed of the casting machine is 50 - 100 r / min to produce a medical and hygienic antibacterial and deodorizing polyethylene breathable film by horizontal stretching.

[0024] The preparation method of the present invention is relatively simple. The synthesis of the metal ion - doped mesoporous silica nano - antibacterial agent MSN has a relatively low difficulty, which is convenient for realizing batch production, reducing the production cost of the medical and hygienic antibacterial and deodorizing polyethylene breathable film, and thus enhancing the market competitiveness of the medical and hygienic antibacterial and deodorizing polyethylene breathable film.

[0025] The medical and hygienic antibacterial and deodorizing polyethylene breathable film in the present invention has an antibacterial property against Candida albicans ≥ 99%, an antibacterial property against Escherichia coli > 99%, an antibacterial property against Staphylococcus aureus > 99%, a deodorizing grade ≥ 2, an antistatic grade of 10 6 -10 9 Ω·cm, a water vapor transmission rate ≥ 1500 g / m 2 / 24h, and a hydrostatic pressure ≥ 500 mmH 2 0.

[0026] In summary, the present application has the following advantages:

[0027] 1. The PE breathable film in the present invention has deodorizing, antibacterial, and antistatic effects, and is used in the field of medical non - woven fabrics, reducing the risk of bacterial infection for medical staff.

[0028] 2. The preparation method of the present invention is relatively simple, with low operation difficulty, and is convenient for realizing batch production.

[0029] 3. The medical and hygienic antibacterial and deodorizing polyethylene breathable film in the present invention has an antibacterial property against Candida albicans ≥ 99%, an antibacterial property against Escherichia coli > 99%, an antibacterial property against Staphylococcus aureus > 99%, a deodorizing grade ≤ 2, an antistatic grade of 10 6 -10 9 Ω·cm, a water vapor transmission rate ≥ 1500 g / m 2 / 24h, hydrostatic pressure ≥ 500 mmHg 2 0. Description of the Drawings

[0030] Figure 1 It is the transmission electron microscope photograph of the metal-ion-free doped mesoporous silica nanoparticles in Preparation Example 15, with sizes of 20 and 200 nanometers respectively.

[0031] Figure 2 It is the TEM pictures (with a size of 100 nanometers) of the mesoporous MSN doped with different concentrations of Cu 2+ (a, b, c, d corresponding to 0.01, 0.1, 1.0, 10.0 mM respectively) in Preparation Examples 5 and 12 - 14.

[0032] Figure 3 It is the ultraviolet absorption spectra of the MSN doped with different metal ions (Mn 2+ , Pb 2+ , Cu 2+ , Zn 2+ , Cu 2+ , Zn 2+ , Fe 3+ ).

[0033] Figure 4 It is the schematic diagram of the preparation of the Cu 2+ -ion doped MSN nanoparticles in Preparation Example 5 of the present invention.

[0034] Figure 5 It is the dynamic light scattering diagram of the Cu 2+ -ion doped MSN nanoparticles in Preparation Example 5 of the present invention. Detailed Description of the Invention

[0035] In order to further understand the creativity and technological progress of the present invention, the preferred implementation schemes of the present invention will be discussed in detail below in combination with the examples and comparative examples. It should be noted that: the specific embodiments are only used to explain the technical solutions of the present invention, and they do not limit the present invention. Those skilled in the art can make modifications without creative contributions to the embodiments according to their needs after reading this specification, but as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

[0036] Examples

[0037] A medical and hygienic antibacterial and deodorizing polyethylene breathable film is prepared by extrusion casting of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made from the following raw materials in parts by weight: 1 - 5 parts of metal-ion-doped mesoporous silica nano-antibacterial agent MSN, 100 parts of PE breathable particles.

[0038] The resin matrix in the PE breathable particles is low-density polyethylene (LDPE) or linear low-density polyethylene (LLDPE), and the addition amount of the inorganic filler in the PE breathable particles is 5-50 wt%.

[0039] The inorganic filler used to form the microporous structure in the PE breathable particles includes at least one of calcium carbonate modified with stearic acid, talcum powder, calcined shell powder, kaolin, silica ash, zeolite powder, titanium dioxide, silicon dioxide, and glass powder with an average particle size of 50-500 nm. Preferably, the inorganic filler used to form the microporous structure in the PE breathable particles includes calcium carbonate modified with stearic acid with an average particle size of 50-2000 nm.

[0040] The metal ions doped in the metal ion-doped mesoporous silica nano-antibacterial agent MSN are Mn 2+ , Pb 2+ , Cu 2 + , Zn 2+ , Cu + , Zn 2+ , Fe 3+ , Fe 2+ , Ag + , Au + and at least one of them. Preferably, the metal ions doped in the metal ion-doped mesoporous silica nano-antibacterial agent MSN are Cu 2+ .

[0041] The particle size distribution of the mesoporous silica in the metal ion-doped mesoporous silica nano-antibacterial agent MSN is 20-200 nm.

[0042] The metal ion-doped mesoporous silica nano-antibacterial agent MSN is prepared by a one-step sol-gel method using metal salts, sodium hydroxide, cetyltrimethylammonium bromide, and tetraethyl orthosilicate as raw materials.

[0043] The metal salts are at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, cuprous chloride, zinc chloride, zinc nitrate, zinc acetylacetonate, ferrous sulfate, ferric chloride, ferric nitrate, ferric acetylacetonate, lead sulfate, lead chloride, lead nitrate, lead acetylacetonate, silver nitrate, and chloroauric acid.

[0044] The preparation method of the metal ion-doped mesoporous silica nano-antibacterial agent MSN is as follows:

[0045] Step 1: Prepare a metal hydroxide seed solution using metal salts, sodium hydroxide, and cetyltrimethylammonium bromide;

[0046] Specifically, the specific preparation method of the metal hydroxide seed solution in Step 1 is as follows: First, prepare a metal salt solution with a concentration of 0.06 - 320 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, and a NaOH solution with a concentration of 0.5 - 1 mol / L respectively; then add 1 - 7 mL of the metal salt solution with a concentration of 0.06 - 320 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 - 65 °C, mix and stir for at least half an hour, then add 0.25 mL of the NaOH solution with a concentration of 0.5 - 1 mol / L, raise the temperature to 60 - 80 °C and continue to stir for at least half an hour to obtain the metal hydroxide seed solution;

[0047] The metal salt in the metal salt solution in Step 1 is at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, zinc chloride, zinc nitrate, zinc acetylacetonate, iron sulfate, iron chloride, iron nitrate, iron acetylacetonate, lead sulfate, lead chloride, lead nitrate, and lead acetylacetonate;

[0048] The solvent in the metal salt solution in Step 1 is water or a mixed solvent formed by water and at least one of alcohols, heptane, benzene, toluene, xylene, chloroform, ether, and acetone;

[0049] Step 2, add tetraethyl orthosilicate to the metal hydroxide seed solution, react at 60 - 80 °C for 2 - 8 h, wash the centrifuged solid with pure water and ethanol three times each, dry, and pulverize to obtain the finished product;

[0050] Specifically, in Step 2, add 1 - 2 mL of tetraethyl orthosilicate with a concentration of 15.0 - 20.0 g / L to the metal hydroxide seed solution prepared in Step 1, react at 60 - 80 °C for 2 - 8 h, wash the centrifuged solid with pure water and ethanol three times each, dry, and pulverize to obtain the finished product MSN.

[0051] A preparation method of a medical and hygienic antibacterial and deodorizing polyethylene breathable film includes the following steps:

[0052] Step 1, preparation of the metal ion - doped mesoporous silica nano - antibacterial agent MSN;

[0053] Step 2, mix 1 - 5 parts of the metal ion - doped mesoporous silica nano - antibacterial agent MSN with 100 parts of dried PE breathable particles at high speed and uniformly, put them into a twin - screw extruder for extrusion granulation, the feeding section is at 100 - 120 °C, the plasticizing section is at 120 - 140 °C, the homogenizing section is at 160 - 180 °C, the rotation speed of the twin - screw is 60 - 72 r / min, and the die head temperature is 160 - 180 °C to obtain MSN - doped PE breathable particles;

[0054] Step 3: The MSN-doped PE breathable particles are put into a twin-screw extruder. The feeding section is at 120 - 140°C, the plasticizing section is at 140 - 160°C, the homogenizing section is at 160 - 180°C, the rotational speed of the twin-screw is 80 - 100 r / min, the die head temperature is 160 - 180°C. The obtained molten extruded material is placed on a casting machine, and the rotational speed of the casting machine is 50 - 100 r / min. A medical and hygienic antibacterial and deodorizing polyethylene breathable film is prepared by horizontal stretching.

[0055] The obtained medical and hygienic antibacterial and deodorizing polyethylene breathable film has antibacterial performance against Candida albicans by Escherichia coli itself ≥ 99%, antibacterial performance against Escherichia coli > 99%, antibacterial performance against Staphylococcus aureus > 99%, deodorizing grade ≥ 2, antistatic grade 10 6 -10 9 Ω·cm, water vapor transmission rate ≥ 1500 g / m 2 / 24h, hydrostatic pressure ≥ 500 mmH 2 0.

[0056] Preparation Example 1: The preparation method of lead ion-doped mesoporous silica nano-antibacterial agent MSN is as follows:

[0057] S1. Respectively prepare an industrial-grade lead sulfate solution with a concentration of 50 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, a NaOH solution with a concentration of 27 g / L, and a tetraethyl orthosilicate solution with a concentration of 20.0 g / L;

[0058] S2. Add 1 mL of the industrial-grade lead sulfate solution with a concentration of 50 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at 60°C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of the NaOH solution with a concentration of 27 g / L, and raise the temperature to 60°C and continue stirring for half an hour to generate a lead hydroxide seed solution;

[0059] S3. Under stirring conditions, put 1.0 mL of the tetraethyl orthosilicate solution with a concentration of 20.0 g / L into the reaction kettle, and continue the reaction at 60°C for 4 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of the lead ion-doped mesoporous silica nano-antibacterial agent with precipitation at the lower layer;

[0060] S4. The crude product of lead ion-doped mesoporous silica nano-antibacterial agent in S3 is put into a reaction kettle filled with ethanol for cleaning. This process is carried out at 90 °C because there may be residual surfactants or pore-forming agents inside the nano-antibacterial agent. Stir and wash with ethanol for 4 hours. After this process ends, continue with the centrifugation operation. The filtrate is passed into other reaction kettles for ethanol distillation and recycling. The centrifuged blocky solid is then dried, crushed, and sieved to obtain the lead ion-doped mesoporous silica nano-antibacterial agent MSN.

[0061] The difference between Preparation Example 2 and Preparation Example 1 is as follows: The preparation method of zinc ion-doped mesoporous silica nano-antibacterial agent MSN is as follows:

[0062] S1. Respectively prepare an industrial-grade zinc sulfate solution with a concentration of 100 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, an NaOH solution with a concentration of 27 g / L, and a tetraethyl orthosilicate solution with a concentration of 20.0 g / L;

[0063] S2. Add 1 mL of the industrial-grade zinc sulfate solution with a concentration of 100 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of the NaOH solution with a concentration of 27 g / L, raise the temperature to 60 °C and continue stirring for half an hour to generate a zinc hydroxide seed solution;

[0064] S3. Under stirring conditions, add 1.0 mL of the tetraethyl orthosilicate solution with a concentration of 20.0 g / L into the reaction kettle, and continue to react at 60 °C for 4 hours. After the reaction ends, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of zinc ion-doped mesoporous silica nano-antibacterial agent with precipitation at the lower layer;

[0065] S4. The crude product of zinc ion-doped mesoporous silica nano-antibacterial agent in S3 is put into a reaction kettle filled with ethanol for cleaning. This process is carried out at 90 °C because there may be residual surfactants or pore-forming agents inside the nano-antibacterial agent. Stir and wash with ethanol for 4 hours. After this process ends, continue with the centrifugation operation. The filtrate is passed into other reaction kettles for ethanol distillation and recycling. The centrifuged blocky solid is then dried, crushed, and sieved to obtain the zinc ion-doped mesoporous silica nano-antibacterial agent MSN.

[0066] The difference between Preparation Example 3 and Preparation Example 1 is as follows: The preparation method of iron ion-doped mesoporous silica nano-antibacterial agent MSN is as follows:

[0067] S1. Prepare an industrial-grade ferric sulfate solution with a concentration of 150 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, an NaOH solution with a concentration of 27 g / L, and a tetraethyl orthosilicate solution with a concentration of 20.0 g / L respectively;

[0068] S2. Add 1 mL of the industrial-grade ferric sulfate solution with a concentration of 150 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of the NaOH solution with a concentration of 27 g / L, raise the temperature to 60 °C and continue stirring for half an hour to produce a ferric hydroxide seed solution;

[0069] S3. Under stirring conditions, put 1.0 mL of the tetraethyl orthosilicate solution with a concentration of 20.0 g / L into the reaction kettle, and continue to react at 60 °C for 4 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of iron ion-doped mesoporous silica nano-antibacterial agent with precipitation at the lower layer;

[0070] S4. Put the crude product of the iron ion-doped mesoporous silica nano-antibacterial agent in S3 into the reaction kettle filled with ethanol for cleaning. This process is carried out under the condition of 90 °C because there may be residual surfactants or pore-forming agents inside the nano-antibacterial agent. Stir and wash with ethanol for 4 hours. After this process is completed, continue with the centrifugation operation. The filtrate is introduced into other reaction kettles for ethanol distillation and recycling. The centrifuged blocky solid is then dried, crushed, and sieved to obtain the iron ion-doped mesoporous silica nano-antibacterial agent MSN.

[0071] The difference between Preparation Example 4 and Preparation Example 1 is that the preparation method of the manganese ion-doped mesoporous silica nano-antibacterial agent MSN is as follows:

[0072] S1. Prepare an industrial-grade manganese sulfate solution with a concentration of 100 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, an NaOH solution with a concentration of 27 g / L, and a tetraethyl orthosilicate solution with a concentration of 20.0 g / L respectively;

[0073] S2. Add 1 mL of the industrial-grade manganese sulfate solution with a concentration of 100 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of the NaOH solution with a concentration of 27 g / L, raise the temperature to 60 °C and continue stirring for half an hour to produce a manganese hydroxide seed solution;

[0074] S3. 1.0 mL of 20.0 g / L tetraethyl orthosilicate was added to the reactor under stirring and the reaction was continued at 60 ° C for 4 hours. After the reaction, the reaction solution in the reactor was cooled and centrifuged to obtain a crude manganese ion-doped mesoporous silica nano-antibacterial agent precipitated in the lower layer;

[0075] S4. The crude product of manganese ion-doped mesoporous silica nano-antibacterial agent in S3 is put into a reactor filled with ethanol for cleaning. The process is carried out at 90°C because there may be residual surfactants or porogens inside the nano-antibacterial agent. The agent is stirred and washed with ethanol for 4 hours. After the process is completed, the centrifugal operation is continued, and the filtrate is passed into other reactors for ethanol distillation and recovery. The block solid after centrifugation is then dried, crushed and sieved to obtain manganese ion-doped mesoporous silica nano-antibacterial agent MSN.

[0076] The difference between Preparation Example 5 and Preparation Example 1 is that the preparation method of the copper ion-doped mesoporous silica nano antibacterial agent MSN is as follows:

[0077] S1. An industrial-grade copper sulfate solution having a concentration of 160 g / L, a hexadecyltrimethylammonium bromide solution having a concentration of 13 g / L, a NaOH solution having a concentration of 27 g / L, and a tetraethyl orthosilicate solution having a concentration of 20.0 g / L were prepared;

[0078] S2. Add 1 mL of 160 g / L industrial-grade copper sulfate solution and 1.0 mL of 13 g / L hexadecyltrimethylammonium bromide solution to 100 mL of ultrapure water at 60 ° C, mix and stir for half an hour, add 0.25 mL of 27 g / L sodium hydroxide solution after thorough mixing, heat to 60 ° C and continue stirring for half an hour to generate a copper hydroxide seed solution;

[0079] S3. 1.0 mL of 20.0 g / L tetraethyl orthosilicate was added to the reactor under stirring and the reaction was continued at 60 ° C for 4 hours. After the reaction, the reaction solution in the reactor was cooled and centrifuged to obtain a crude copper ion-doped mesoporous silica nano-antibacterial agent precipitated in the lower layer;

[0080] S4. The crude copper ion-doped mesoporous silica nano-antibacterial agent in S3 is put into a reactor filled with ethanol for cleaning. The process is performed at 90°C because there may be residual surfactants or porogens inside the nano-antibacterial agent. The agent is stirred and washed with ethanol for 4 hours. After the process is completed, the centrifugal operation is continued, and the filtrate is passed into other reactors for ethanol distillation and recovery. The block solid after centrifugation is then dried, crushed and sieved to obtain the copper ion-doped mesoporous silica nano-antibacterial agent MSN.

[0081] The difference between Preparation Example 6 and Preparation Example 5 lies in the following steps in the preparation method of copper ion-doped mesoporous silica nano-antibacterial agent MSN: S2. Add 2 mL of industrial-grade copper sulfate solution with a concentration of 160 g / L and 1.0 mL of cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of sodium hydroxide solution with a concentration of 27 g / L, heat up to 60 °C and continue stirring for half an hour to generate a copper hydroxide seed solution; S3. Under stirring conditions, add 1.0 mL of tetraethyl orthosilicate with a concentration of 20.0 g / L into the reaction kettle, and continue the reaction at 60 °C for 3.5 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of copper ion-doped mesoporous silica nano-antibacterial agent with precipitation at the lower layer. The remaining steps are the same.

[0082] The difference between Preparation Example 7 and Preparation Example 5 lies in the following steps in the preparation method of copper ion-doped mesoporous silica nano-antibacterial agent MSN: S2. Add 3 mL of industrial-grade copper sulfate solution with a concentration of 160 g / L and 1.0 mL of cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of sodium hydroxide solution with a concentration of 27 g / L, heat up to 60 °C and continue stirring for half an hour to generate a copper hydroxide seed solution; S3. Under stirring conditions, add 1.0 mL of tetraethyl orthosilicate with a concentration of 20.0 g / L into the reaction kettle, and continue the reaction at 60 °C for 3.5 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of copper ion-doped mesoporous silica nano-antibacterial agent with precipitation at the lower layer. The remaining steps are the same.

[0083] The difference between Preparation Example 8 and Preparation Example 5 lies in the following steps in the preparation method of copper ion-doped mesoporous silica nano-antibacterial agent MSN: S2. Add 4 mL of industrial-grade copper sulfate solution with a concentration of 160 g / L and 1.0 mL of cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of sodium hydroxide solution with a concentration of 27 g / L, heat up to 60 °C and continue stirring for half an hour to generate a copper hydroxide seed solution; S3. Under stirring conditions, add 1.0 mL of tetraethyl orthosilicate with a concentration of 20.0 g / L into the reaction kettle, and continue the reaction at 60 °C for 4 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of copper ion-doped mesoporous silica nano-antibacterial agent with precipitation at the lower layer. The remaining steps are the same.

[0084] The difference between Preparation Example 9 and Preparation Example 5 lies in: In the preparation method of the copper ion-doped mesoporous silica nano-antibacterial agent MSN, in S2, 5 mL of an industrial-grade copper sulfate solution with a concentration of 160 g / L and 1.0 mL of a cetyltrimethylammonium bromide solution with a concentration of 13 g / L are added to 100 mL of ultrapure water at a temperature of 60 °C, mixed and stirred for half an hour. After thorough mixing, 0.25 mL of a sodium hydroxide solution with a concentration of 27 g / L is added, and the temperature is raised to 60 °C and stirring is continued for half an hour to generate a copper hydroxide seed solution; in S3, 1.0 mL of tetraethyl orthosilicate with a concentration of 20.0 g / L is put into the reaction kettle under stirring conditions, and the reaction is continued at 60 °C for 2.5 hours. After the reaction is completed, the reaction solution in the reaction kettle is cooled and centrifuged to obtain the crude product of the copper ion-doped mesoporous silica nano-antibacterial agent with the precipitate at the lower layer. The remaining steps are the same.

[0085] The difference between Preparation Example 10 and Preparation Example 5 lies in: In the preparation method of the copper ion-doped mesoporous silica nano-antibacterial agent MSN, in S2, 6 mL of an industrial-grade copper sulfate solution with a concentration of 160 g / L and 1.0 mL of a cetyltrimethylammonium bromide solution with a concentration of 13 g / L are added to 100 mL of ultrapure water at a temperature of 60 °C, mixed and stirred for half an hour. After thorough mixing, 0.25 mL of a sodium hydroxide solution with a concentration of 27 g / L is added, and the temperature is raised to 60 °C and stirring is continued for half an hour to generate a copper hydroxide seed solution; in S3, 1.0 mL of tetraethyl orthosilicate with a concentration of 20.0 g / L is put into the reaction kettle under stirring conditions, and the reaction is continued at 60 °C for 3 hours. After the reaction is completed, the reaction solution in the reaction kettle is cooled and centrifuged to obtain the crude product of the copper ion-doped mesoporous silica nano-antibacterial agent with the precipitate at the lower layer. The remaining steps are the same.

[0086] The difference between Preparation Example 11 and Preparation Example 5 lies in: In the preparation method of the copper ion-doped mesoporous silica nano-antibacterial agent MSN, in S2, 7 mL of an industrial-grade copper sulfate solution with a concentration of 160 g / L and 1.0 mL of a cetyltrimethylammonium bromide solution with a concentration of 13 g / L are added to 100 mL of ultrapure water at a temperature of 60 °C, mixed and stirred for half an hour. After thorough mixing, 0.25 mL of a sodium hydroxide solution with a concentration of 27 g / L is added, and the temperature is raised to 60 °C and stirring is continued for half an hour to generate a copper hydroxide seed solution; in S3, 1.0 mL of tetraethyl orthosilicate with a concentration of 20.0 g / L is put into the reaction kettle under stirring conditions, and the reaction is continued at 60 °C for 5 hours. After the reaction is completed, the reaction solution in the reaction kettle is cooled and centrifuged to obtain the crude product of the copper ion-doped mesoporous silica nano-antibacterial agent with the precipitate at the lower layer. The remaining steps are the same.

[0087] The difference between Preparation Example 12 and Preparation Example 5 lies in the following in the preparation method of the copper ion-doped mesoporous silica nano-antibacterial agent MSN: S1. Respectively prepare an industrial-grade cuprous chloride solution with a concentration of 0.06 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, an NaOH solution with a concentration of 27 g / L, and a tetraethyl orthosilicate solution with a concentration of 20.0 g / L; S2. Add 1 mL of the industrial-grade cuprous chloride solution with a concentration of 0.06 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60°C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of the NaOH solution with a concentration of 27 g / L, raise the temperature to 60°C and continue stirring for half an hour to generate a cuprous hydroxide seed solution; S3. Under stirring conditions, add 1.0 mL of the tetraethyl orthosilicate solution with a concentration of 20.0 g / L into the reaction kettle, and continue the reaction at 60°C for 4 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of the cuprous ion-doped mesoporous silica nano-antibacterial agent with precipitation at the lower layer. The remaining steps are the same.

[0088] The difference between Preparation Example 13 and Preparation Example 5 lies in the following in the preparation method of the copper ion-doped mesoporous silica nano-antibacterial agent MSN: S1. Respectively prepare an industrial-grade ferrous sulfate solution with a concentration of 150 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, an NaOH solution with a concentration of 27 g / L, and a tetraethyl orthosilicate solution with a concentration of 20.0 g / L; S2. Add 1 mL of the industrial-grade ferrous sulfate solution with a concentration of 150 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60°C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of the NaOH solution with a concentration of 27 g / L, raise the temperature to 60°C and continue stirring for half an hour to generate a ferrous hydroxide seed solution; S3. Under stirring conditions, add 1.0 mL of the tetraethyl orthosilicate solution with a concentration of 20.0 g / L into the reaction kettle, and continue the reaction at 60°C for 4 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of the ferrous ion-doped mesoporous silica nano-antibacterial agent with precipitation at the lower layer. The remaining steps are the same.

[0089] The difference between Preparation Example 14 and Preparation Example 5 lies in the following in the preparation method of the copper ion-doped mesoporous silica nano-antibacterial agent MSN: S1. Respectively prepare an industrial-grade silver nitrate solution with a concentration of 200 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, a NaOH solution with a concentration of 27 g / L, and a tetraethyl orthosilicate solution with a concentration of 20.0 g / L; S2. Add 1 mL of the industrial-grade silver nitrate solution with a concentration of 200 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of the NaOH solution with a concentration of 27 g / L, raise the temperature to 60 °C and continue stirring for half an hour to generate a silver hydroxide seed solution; S3. Under stirring conditions, add 1.0 mL of the tetraethyl orthosilicate solution with a concentration of 20.0 g / L into the reaction kettle, and continue the reaction at 60 °C for 4 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of the silver ion-doped mesoporous silica nano-antibacterial agent with the precipitate at the lower layer. The remaining steps are the same.

[0090] The difference between Preparation Example 15 and Preparation Example 1 lies in the following in the preparation method of the gold ion-doped mesoporous silica nano-antibacterial agent MSN:

[0091] S1. Respectively prepare an industrial-grade chloroauric acid solution with a concentration of 170 g / L, a cetyltrimethylammonium bromide solution with a concentration of 13 g / L, a NaOH solution with a concentration of 27 g / L, and a tetraethyl orthosilicate solution with a concentration of 20.0 g / L;

[0092] S2. Add 1 mL of the industrial-grade chloroauric acid solution with a concentration of 170 g / L and 1.0 mL of the cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C, mix and stir for half an hour. After thorough mixing, add 0.25 mL of the NaOH solution with a concentration of 27 g / L, raise the temperature to 60 °C and continue stirring for half an hour to generate a gold hydroxide seed solution;

[0093] S3. Under stirring conditions, add 1.0 mL of the tetraethyl orthosilicate solution with a concentration of 20.0 g / L into the reaction kettle, and continue the reaction at 60 °C for 4 hours. After the reaction is completed, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of the gold ion-doped mesoporous silica nano-antibacterial agent with the precipitate at the lower layer;

[0094] S4. The crude product of the gold ion-doped mesoporous silica nano-antibacterial agent in S3 is put into a reaction kettle filled with ethanol for cleaning. This process is carried out at 90 °C because there may be residual surfactants or pore-forming agents inside the nano-antibacterial agent. Stir and wash with ethanol for 4 hours. After this process ends, continue with the centrifugation operation. The filtrate is passed into other reaction kettles for ethanol distillation and recycling. The centrifuged massive solid is then dried, crushed, and sieved to obtain the gold ion-doped mesoporous silica nano-antibacterial agent MSN.

[0095] Preparation Example 16: Preparation method of metal ion-free doped mesoporous silica: S1. Prepare cetyltrimethylammonium bromide solution with a concentration of 13 g / L, NaOH solution with a concentration of 27 g / L, and tetraethyl orthosilicate solution with a concentration of 20.0 g / L respectively; S2. Add 1.0 mL of cetyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water at a temperature of 60 °C. After stirring for half an hour, add 0.25 mL of NaOH solution with a concentration of 27 g / L, heat up to 60 °C and continue stirring for half an hour. Under stirring conditions, put 1.0 mL of tetraethyl orthosilicate solution with a concentration of 20.0 g / L into the reaction kettle and continue to react at 60 °C for 4 h. After the reaction ends, cool and centrifuge the reaction solution in the reaction kettle to obtain the crude product of metal ion-free doped mesoporous silica with white precipitate at the bottom layer. The remaining steps are the same.

[0096] Specific preferred implementation plan

[0097] Example 1: A medical and hygienic antibacterial and deodorizing polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 5 and 100 parts of PE breathable particles (source: Changzhou Shuangcheng, model BM07).

[0098] A preparation method of a medical and hygienic antibacterial and deodorizing polyethylene breathable film includes the following steps:

[0099] Step 1, refer to Preparation Example 5 for the preparation of the copper ion-doped mesoporous silica nano-antibacterial agent MSN;

[0100] Step 2, mix 2 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 1 with 100 parts of dried PE breathable particles at high speed and uniformly, and put them into a twin-screw extruder for extrusion granulation. The feeding section is at 170 °C, the plasticizing section is at 165 °C, the homogenizing section is at 175 °C, the rotation speed of the twin-screw is 72 r / min, and the die head temperature is 175 °C to obtain MSN-doped PE breathable particles;

[0101] Step 3: The MSN-doped PE breathable particles are put into a twin-screw extruder. The feeding section is at 180°C, the plasticizing section is at 180°C, the homogenizing section is at 180°C, the rotational speed of the twin-screw is 80 r / min, and the die head temperature is 180°C. The obtained molten extruded material is placed on a casting machine, and the rotational speed of the casting machine is 100 r / min, and a medical and health antibacterial and deodorant polyethylene breathable film is prepared by horizontal stretching.

[0102] The difference between Example 2 and Example 1 is that the medical and health antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the zinc ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 2 and 100 parts of PE breathable particles.

[0103] The difference between Example 3 and Example 1 is that the medical and health antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the iron ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 3 and 100 parts of PE breathable particles.

[0104] The difference between Example 4 and Example 1 is that the medical and health antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the manganese ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 4 and 100 parts of PE breathable particles.

[0105] The difference between Example 5 and Example 1 is that the medical and health antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the lead ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 1 and 100 parts of PE breathable particles.

[0106] The difference between Example 6 and Example 1 is that the medical and health antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 0.1 part of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 5 and 100 parts of PE breathable particles.

[0107] The difference between Example 7 and Example 1 is that the medical and health antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 0.5 part of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 5 and 100 parts of PE breathable particles.

[0108] Example 8 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made of 1.0 part of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 5 and 100 parts of PE breathable particles.

[0109] Example 9 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made of 5 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 5 and 100 parts of PE breathable particles.

[0110] Example 10 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made of 6 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 5 and 100 parts of PE breathable particles.

[0111] Example 11 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made of 2 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 6 and 100 parts of PE breathable particles.

[0112] Example 12 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made of 2 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 7 and 100 parts of PE breathable particles.

[0113] Example 13 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made of 2 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 8 and 100 parts of PE breathable particles.

[0114] Example 14 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made of 2 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 9 and 100 parts of PE breathable particles.

[0115] Example 15 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN-doped PE breathable particles are made of 2 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 10 and 100 parts of PE breathable particles.

[0116] Example 16 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 11 and 100 parts of PE breathable particles.

[0117] Example 17 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the cuprous ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 12 and 100 parts of PE breathable particles.

[0118] Example 18 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the ferrous ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 13 and 100 parts of PE breathable particles.

[0119] Example 19 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the silver ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 14 and 100 parts of PE breathable particles.

[0120] Example 20 is different from Example 1 in that the medical and hygienic antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of the gold ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 15 and 100 parts of PE breathable particles.

[0121] The difference between Control Group A and Example 1 is that the polyethylene breathable film is prepared from PE breathable particles (Changzhou Shuangcheng Model BM07).

[0122] The difference between Control Group B and Example 1 is that the medical and hygienic antibacterial and deodorant polyethylene breathable film is prepared from non-ion-doped mesoporous silica-doped PE breathable particles. The non-ion-doped mesoporous silica-doped PE breathable particles are prepared from 2 parts of non-ion-doped mesoporous silica in Preparation Example 16 and 100 parts of PE breathable particles.

[0123] The difference between Comparative Example 1 and Example 1 is that the medical and hygienic antibacterial and deodorant polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of an inorganic antibacterial agent and 100 parts of PE breathable particles. The inorganic antibacterial agent is nano copper powder with an average particle size of 200 nm.

[0124] The difference between Comparative Example 2 and Example 1 is that the medical and hygienic antibacterial and deodorizing polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 2 parts of organic antibacterial agent and 100 parts of PE breathable particles. The organic antibacterial agent is benzethonium chloride (quaternary ammonium salt organic antibacterial agent).

[0125] The difference between Comparative Example 3 and Example 1 is that the medical and hygienic antibacterial and deodorizing polyethylene breathable film is prepared from MSN-doped PE breathable particles. The MSN-doped PE breathable particles are prepared from 0.05 part of the copper ion-doped mesoporous silica nano-antibacterial agent MSN in Preparation Example 5 and 100 parts of PE breathable particles.

[0126] Performance detection test:

[0127] 1. Test method for antibacterial activity value: Determined according to ISO 18184.

[0128] 2. Test method for antibacterial rate: Determined according to GB / T 20944.2-2007. The sample sterilization method is autoclaving. The contact culture time between the sample and the bacterial solution is 18 h. The control sample is a common PE breathable film. The colony concentrations are Staphylococcus aureus ATCC 6538: 2.0×105 CFU / mL; Escherichia coli 8099: 1.9×105 CFU / mL; Candida albicans ATCC10231: 1.6×105 CFU / mL. The judgment criterion is that when the bacteriostatic value ≥ 2 or the antibacterial rate ≥ 99%, it is proved that it has bacteriostatic effect) determination.

[0129] 3. Test method for deodorization grade: Determined according to GB / T 33610.1-2019.

[0130] 4. Test method for antistatic grade: Determined according to GB / T 12703-91. If the resistivity of the PE breathable film < 10 9 ohm·cm (Ω·cm), it is considered that it has antistatic performance and is OK. If the resistivity of the PE breathable film > 10 9 ohm·cm (Ω·cm), it is considered that it does not have antistatic performance and is NG.

[0131] 5. Test method for water vapor transmission rate: Determined according to GB / T 19082-2023.

[0132] 6. Test method for tensile fracture stress: Determined according to GB / T 19082-2023.

[0133] 7. Test method for hydrostatic pressure: Determined according to GB / T 19082-2023.

[0134] Table 1: Experimental result table of copper ion-doped mesoporous nano-silica with different concentrations

[0135]

[0136]

[0137] Table 2: Antibacterial and deodorizing parameter table of PE breathable films in Examples 1 - 20, control group, and Comparative Examples 1 - 4

[0138]

[0139]

[0140] Table 3: Waterproof and breathable parameter table of PE breathable films in Examples 1 - 20, control group, and Comparative Examples 1 - 4

[0141]

[0142]

[0143] Combined with Examples 1 - 14, control groups A - B, and Comparative Examples 1 - 3 and combined with Tables 2 - 3, it can be seen that the PE breathable film in the present invention has deodorizing, antibacterial, and antistatic effects, and is used in the field of medical non-woven fabrics to reduce the risk of bacterial infection for medical staff.

[0144] In summary, for the medical antibacterial and deodorizing polyethylene breathable film in the present invention, the antibacterial performance against Escherichia coli ≥ 99%, the antibacterial performance against Staphylococcus aureus ≥ 99%, the deodorizing grade ≥ 2, the antistatic grade 10 6 -10 9 Ω·cm, the water vapor transmission rate ≥ 1500 g / m 2 / 24h, and the hydrostatic pressure ≥ 500 mmH 2 0.

Claims

1. An antibacterial and deodorizing polyethylene breathable membrane for medical and health use, characterized in that: The medical antibacterial and deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles; the MSN-doped PE breathable particles are made of the following raw materials in parts by weight: 1-5 parts of metal ion-doped mesoporous silica nano antibacterial agent MSN, 100 parts of PE breathable particles; The resin matrix in the PE breathable particles is low-density polyethylene LDPE or linear low-density polyethylene LLDPE, the addition amount of inorganic filler in the PE breathable particles is 5-50wt%, and the inorganic filler in the PE breathable particles used to form a microporous structure includes at least one of stearic acid-modified calcium carbonate, talcum powder, calcined shell powder, kaolin, silica ash, zeolite powder, titanium dioxide, silicon dioxide, and glass powder with an average particle size of 50-2000nm.

2. The antibacterial and deodorizing polyethylene breathable membrane for medical and health use according to claim 1, characterized in that: The metal ion doped in the metal ion doped mesoporous silica nano antibacterial agent MSN is Mn 2+ , Pb 2+ , Cu 2+ 、Zn 2+ , Cu + , Cu 2+ 、Zn 2+ , Fe 3+ , Fe 2+ 、Ag + 、Au + At least one of the following: the particle size distribution of the mesoporous silica in the metal ion-doped mesoporous silica nano antibacterial agent MSN is 20-200 nm.

3. The antibacterial and deodorizing polyethylene breathable membrane for medical and health use according to claim 2, characterized in that: The metal ion doped in the metal ion doped mesoporous silica nano antibacterial agent MSN is Cu 2+ .

4. The antibacterial and deodorizing polyethylene breathable membrane for medical and health use according to claim 1, characterized in that: The metal ion-doped mesoporous silica nano antibacterial agent MSN is prepared in one step by a sol-gel method using metal salt, sodium hydroxide, hexadecyltrimethylammonium bromide and ethyl orthosilicate as raw materials.

5. The antibacterial and deodorizing polyethylene breathable membrane for medical and health use according to claim 4, characterized in that: The preparation method of the metal ion-doped mesoporous silica nano antibacterial agent MSN is as follows: step 1, preparing a metal hydroxide seed solution using a metal salt, sodium hydroxide and hexadecyltrimethylammonium bromide; step 2, adding tetraethyl orthosilicate to the metal hydroxide seed solution, reacting at 60-80° C. for 2-8 hours, centrifuging the obtained solid, washing it three times with pure water and ethanol respectively, drying it, and crushing it to obtain a finished product MSN.

6. The antibacterial and deodorizing polyethylene breathable membrane for medical and health use according to claim 5, characterized in that: The specific preparation method of the metal hydroxide seed solution in the step 1 is as follows: prepare a concentrated metal salt solution with a concentration of 0.06-320 g / L, a hexadecyltrimethylammonium bromide solution with a concentration of 13 g / L, and a NaOH solution with a concentration of 0.5-1 mol / L, and set them aside; then add 1-7 mL of the metal salt solution with a concentration of 0.06-320 g / L and 1.0 mL of the hexadecyltrimethylammonium bromide solution with a concentration of 13 g / L to 100 mL of ultrapure water with a temperature of 60-65° C., mix and stir for at least half an hour, then add 0.25 mL of the NaOH solution with a concentration of 0.5-1 mol / L, heat to 60-80° C. and continue stirring for at least half an hour, to obtain the metal hydroxide seed solution.

7. The antibacterial and deodorizing polyethylene breathable membrane for medical and health use according to claim 6, characterized in that: In the step 2, 1-2 mL of tetraethyl orthosilicate with a concentration of 15.0-20.0 g / L is added to the metal hydroxide seed solution prepared in the step 1, and the mixture is reacted at 60-80° C. for 2-8 hours. The solid obtained by centrifugation is washed three times with pure water and ethanol respectively, dried, and crushed to obtain the finished MSN.

8. The antibacterial and deodorizing polyethylene breathable membrane for medical and health use according to claim 6, characterized in that: The metal salt in the metal salt solution is at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, cuprous chloride, zinc chloride, zinc nitrate, zinc acetylacetonate, ferrous sulfate, ferric chloride, ferric nitrate, ferric acetylacetonate, lead sulfate, lead chloride, lead nitrate, lead acetylacetonate, silver nitrate, and chloroauric acid; the solvent in the metal salt solution is water or a mixed solvent formed by water and at least one of alcohols, heptane, benzene, toluene, xylene, and acetone.

9. A method for preparing an antibacterial and deodorizing polyethylene breathable film for medical and health use according to any one of claims 1 to 8, characterized in that: The following steps are involved: Step 1, preparation of metal ion-doped mesoporous silica nano-antibacterial agent MSN; Step 2: 1-5 parts of metal ion-doped mesoporous silica nano-antibacterial agent MSN and 100 parts of PE breathable particles that have been dried are mixed evenly at high speed, and put into a twin-screw extruder for extrusion granulation, with a feeding section of 160-180° C., a plasticizing section of 160-180° C., a homogenizing section of 160-180° C., a twin-screw speed of 60-72 r / min, and a die head temperature of 160-180° C. to obtain MSN-doped PE breathable particles; Step three, the MSN-doped PE breathable particles are put into a twin-screw extruder, the feeding section is 160-180°C, the plasticizing section is 160-180°C, the homogenizing section is 160-180°C, the twin-screw speed is 80-100r / min, the die head temperature is 160-180°C, and the obtained molten extruded material is placed in a casting machine with a casting machine speed of 50-100r / min, and horizontally stretched to obtain an antibacterial and deodorizing polyethylene breathable film for medical use.

10. The method for preparing the antibacterial and deodorizing polyethylene breathable film for medical and health use according to claim 6, characterized in that: The antibacterial and deodorizing polyethylene breathable membrane for medical use in step 3 has an antibacterial performance against Candida albicans ≥ 99%, an antibacterial performance against Escherichia coli > 99%, an antibacterial performance against Staphylococcus aureus > 99%, a deodorizing level ≥ 2, and an antistatic level 10 6 -10 9 Ω·cm, water vapor transmission ≥1500g / m 2 / 24h, hydrostatic pressure ≥500mmH20.

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