CN110959610A - Medical silver ion antibacterial film and preparation method thereof - Google Patents
Medical silver ion antibacterial film and preparation method thereof Download PDFInfo
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- CN110959610A CN110959610A CN201911377409.4A CN201911377409A CN110959610A CN 110959610 A CN110959610 A CN 110959610A CN 201911377409 A CN201911377409 A CN 201911377409A CN 110959610 A CN110959610 A CN 110959610A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
Abstract
The invention discloses a medical silver ion antibacterial film and a preparation method thereof, wherein the formula comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver salt and 0.1-3 parts of sodium borohydride; the invention takes polyvinyl alcohol as a reducing agent, reduces silver sulfate and silver nitrate in a polyvinyl alcohol system, and forms a coating stock solution by using a silver-containing polyvinyl alcohol solution; in the film forming process, the fixation of silver is realized by crosslinking polyvinyl alcohol, so that the reduced silver is uniformly dispersed; when in use, the silver is released by utilizing the acting force of the polyvinyl alcohol and water, namely the characteristic of swelling when meeting water, so as to achieve the antibacterial effect, and a dispersing agent is not required to be added, so that the production steps can be reduced, and the production cost can be reduced; the product obtained by the formula and the method has stable performance, excellent physical performance and lasting antibacterial effect.
Description
Technical Field
The invention relates to the field of medical materials, in particular to a medical silver ion antibacterial film and a preparation method thereof.
Background
Polyvinyl alcohol is a high molecular polymer with excellent performance, is widely applied to the fields of fiber, plastic, medical material surface modification, food contact packaging materials and the like, has excellent biodegradability and no toxicity, and is a new-generation environment-friendly plastic film material. The antibacterial material is a novel functional material and has good antibacterial and bactericidal properties. The antibacterial material is blended with polyvinyl alcohol to obtain a functional membrane material with broad antibacterial spectrum, long-acting effect, safety and stability, which is widely researched in recent years; in the method of the prior art, Ag and a dispersing agent are added into the membrane liquid for mixing, the processing is complex and the cost is high; the market needs a medical silver ion antibacterial film which does not need to add a dispersing agent, reduces the production steps and reduces the cost and a preparation method thereof.
In addition, the film made of pure polyvinyl alcohol material is easy to be oxidized because of two hydrogens on the carbon atom adjacent to the hydroxyl group of polyvinyl alcohol, and the oxidized structure is easy to be attacked by microorganisms, and further mildew and other phenomena occur.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a medical silver ion antibacterial film and a preparation method thereof, silver is reduced in a polyvinyl alcohol system, a dispersing agent is not required to be added, the production steps are reduced, the production cost is reduced, and the product obtained by the formula and the method has excellent physical properties and lasting antibacterial effect. Due to the existence of silver ions, the polyvinyl alcohol film has stable performance, is not easy to be corroded by microorganisms, and prolongs the service life of the product.
In order to achieve the above object, the present invention adopts the following technical solutions:
the medical silver ion antibacterial film comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver salt and 0.1-3 parts of sodium borohydride.
The medical silver ion antibacterial film comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver nitrate and 0.1-3 parts of sodium borohydride.
The medical silver ion antibacterial film comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.01-0.02 part of silver nitrate and 0.5-1.5 parts of sodium borohydride.
The medical silver ion antibacterial film comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.0083-0.037 part of silver sulfate and 0.1-3 parts of sodium borohydride.
The medical silver ion antibacterial film comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.0092-0.0184 part of silver sulfate and 0.5-1.5 parts of sodium borohydride.
In the medical silver ion antibacterial film, the plasticizer is urea.
A preparation method of a medical silver ion antibacterial film comprises the following steps:
preparing a reagent according to a formula, wherein the formula comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver nitrate or 0.0083-0.037 part of silver sulfate and 0.1-3 parts of sodium borohydride;
step two, preparing a premixed solution;
adding polyvinyl alcohol into water, and heating for dissolving;
dissolving urea into water, and dissolving the urea at room temperature;
dissolving sodium hydroxide into water, and dissolving at room temperature;
dissolving boric acid into water;
adding a silver salt into the second premixed solution, and dissolving at room temperature to obtain a first mixed solution;
dissolving sodium borohydride into the premixed solution III, and dissolving at room temperature to obtain a second mixed solution;
step five, keeping the preparation temperature of the coating stock solution at 70-100 ℃ through a temperature control system, adding the premix solution four, the first mixed solution and the second mixed solution into the premix solution one, and stirring for 2 hours at the speed of 200-;
NaBH4+AgNO3+3H2O＝Ag+NaNO3+H3BO3+3.5H2↑
or 2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O；
Sixthly, coating the coating stock solution on a high polymer substrate film such as polyethylene terephthalate and the like, and gradually crosslinking the coating stock solution into a solid at the temperature of lower than 70 ℃;
and seventhly, preparing a finished product of the medical silver ion antibacterial film through the processes of low-temperature drying, rolling, slitting and packaging.
And step five, keeping the preparation temperature of the coating stock solution at 80-90 ℃ through a temperature control system, adding the fourth premixed solution, the first mixed solution and the second mixed solution into the first premixed solution, and stirring for 2 hours at the speed of 200-300 revolutions per minute.
In the preparation method of the medical silver ion antibacterial film, the optimal temperature for preparing the coating stock solution is 85 ℃.
The invention has the advantages that:
the polyvinyl alcohol can be used as a carrier and also can be used as a dispersing agent of Ag, so that the process links are reduced, and the cost is reduced. The traditional process is to add the silver solution after oxidation and reduction into polyvinyl alcohol gel for gluing. For example, 480 yuan/kg of 4000ppm silver ion solution is sold on the market, namely, the actual content is 0.4%. The market price of the silver nitrate is only 2000 yuan/kg, the molar mass of the silver nitrate is 169.87g/mol, the actual silver content accounts for about 63.5 percent of the mass of the silver nitrate, and when the actual silver content is converted into 4000ppm, the price is about 12.6 yuan. According to the method of the traditional process, when 4000ppm is reached, the price of silver ions is 480 yuan; if the liquid phase of silver nitrate is continuously used for reducing the polyvinyl alcohol solution, the price of silver ions is about 12.6 yuan when the same reaches 4000 ppm. Therefore, the method has remarkable economic benefit.
Silver ion is used as an antibacterial agent, can effectively prevent the invasion of microorganisms and improve the stability of polyvinyl alcohol.
The three-dimensional network structure prevents silver particles from agglomerating, and can slowly release silver after meeting water to generate stable and continuous antibacterial action;
the generated polyvinyl alcohol membrane is a three-dimensional net structure, and the hydrophilicity is adjusted by adjusting the net aperture (polymerization degree);
the linear structure is converted into a three-dimensional network structure through crosslinking, so that the mechanical strength and elasticity of the membrane are improved;
sodium borohydride can be used as a reducing agent of Ag +, and also as a cross-linking agent of polyvinyl alcohol;
the activity of sodium borohydride is inhibited under alkaline conditions, so that the polyvinyl alcohol crosslinking reaction is slow, and the polymerization reaction is favorably and smoothly carried out;
the polyvinyl alcohol is baked at low temperature after the film is formed by the extension flow, so that the deformation of high polymer base material films such as polyethylene terephthalate and the like can be prevented, the integrity of the films is maintained, and the large-scale production is facilitated;
through optimization experiments, the formula preferably selects silver salt with the weight part of silver nitrate of 0.01-0.02 or sulfate of 0.0092-0.0184, and the formula within the range not only provides enough silver content, but also reduces the cost;
the preparation temperature of the coating stock solution is optimized by an optimization experiment, the temperature range is preferably 80-90 ℃, and the temperature in the range not only provides a proper reaction temperature, but also ensures the liquidity of the liquid.
Drawings
FIG. 1 is a SEM image of the surface structure of a silver ion antibacterial film obtained in example 8 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
A medical silver ion antibacterial film comprises 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver nitrate or 0.0083-0.037 part of silver sulfate and 0.1-3 parts of sodium borohydride. Preferably, the plasticizer is urea, and urea can be used as a plasticizer of polyvinyl alcohol and can promote dissolution of silver ions, but urea is not the only plasticizer, and can be one or more of aliphatic amines, alcamines, amides, alicyclic amines, aromatic amines, naphthalene amines, aliphatic alcohols, alicyclic alcohols, and aromatic alcohols, and it should be noted that the examples of the present invention are not exhaustive, and any plasticizer suitable for the formulation of the present invention is within the protection scope of the present invention.
The invention takes polyvinyl alcohol as a reducing agent, reduces silver sulfate and silver nitrate in a polyvinyl alcohol system, and forms a coating stock solution by using a silver-containing polyvinyl alcohol solution; in the film forming process, the fixation of silver is realized by crosslinking polyvinyl alcohol, so that the reduced silver is uniformly dispersed; when in use, the silver is released by utilizing the acting force of the polyvinyl alcohol and water, namely the characteristic of swelling when meeting water, thereby achieving the antibacterial effect.
A preparation method of a medical silver ion antibacterial film comprises the following steps:
preparing a reagent according to a formula, 25 parts of polyvinyl alcohol, 4.7 parts of urea, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver salt and 0.1-3 parts of sodium borohydride;
step two, preparing a premixed solution;
adding polyvinyl alcohol into water to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved;
in the formula: m (polyvinyl alcohol) is the mass of polyvinyl alcohol, and the unit is g or kg;
msilver saltsIs the silver salt mass in g;
MAgthe unit is the molar mass of Ag and the unit is g/mol;
the silver content is the silver content in polyvinyl alcohol, unit ppm;
Msilver saltsThe molar mass of the silver salt is given in g/mol.
Dissolving urea into water to form 100%, and dissolving at room temperature;
dissolving sodium hydroxide into water to form 100%, and dissolving at room temperature;
dissolving boric acid into water;
adding silver salt into the second premixed solution to form 100%, and dissolving at room temperature to obtain a first mixed solution;
dissolving sodium borohydride into the premixed solution III, and dissolving at room temperature to obtain a second mixed solution;
step five, keeping the preparation temperature of the coating stock solution at 70-100 ℃ through a temperature control system (deviation of 0.5 ℃), adding the premix solution four, the first mixed solution and the second mixed solution into the premix solution one, and stirring for 2 hours at the speed of 200-;
NaBH4+AgNO3+3H2O＝Ag+NaNO3+H3BO3+3.5H2↑
or 2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O；
Sixthly, coating the coating stock solution on a high polymer substrate film such as polyethylene terephthalate and the like, and gradually crosslinking the coating stock solution into a solid at the temperature of lower than 70 ℃;
and seventhly, preparing a finished product of the medical silver ion antibacterial film through the processes of low-temperature drying, rolling, slitting and packaging.
The following experiments are used for verifying the effect of the invention and carrying out optimization experiments;
samples were prepared according to the following examples.
Example 1
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, Ag2SO4Preparation of dilution liquid
3.32g of Ag2SO4Crystal (Ag)2SO40.0083 parts) was added to 39996.68g of the second premix obtained in the first step, 100% being formed and dissolved at room temperature.
Thirdly, preparing reducing diluent
4g of sodium borohydride was dissolved in 396g of the third premixed solution obtained in the first step, and the solution was dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of the 22.98kg of the premixed liquid obtained in the first step is reduced to 80 ℃, adding the fourth premixed liquid obtained in the first step and 40kg of the product Ag obtained in the second step2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 2
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, AgNO3Preparation of dilution liquid
3.60g of AgNO3Crystal (AgNO)30.009 parts) was added to 39996.40g of the second premix obtained in the first step to form 100%, which was dissolved at room temperature.
Thirdly, preparing reducing diluent
4g of sodium borohydride was dissolved in 396g of the third premixed solution obtained in the first step, and the solution was dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of 45.73kg of the premixed solution obtained in the first step is reduced to 80 ℃, adding the premixed solution obtained in the first step, and 40kg of the Ag product obtained in the second step2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
NaBH4+AgNO3+3H2O＝Ag+NaNO3+H3BO3+3.5H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 3
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, AgNO3Preparation of dilution liquid
3.60g of AgNO3Crystal (AgNO)30.009 parts) was added to 39996.40g of the second premix obtained in the first step to form 100%, which was dissolved at room temperature.
Thirdly, preparing reducing diluent
4g of sodium borohydride was dissolved in 396g of the third premixed solution obtained in the first step, and the solution was dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of 45.73kg of the premixed solution obtained in the first step is reduced to 85 ℃, adding the premixed solution obtained in the first step, and 40kg of the Ag product obtained in the second step2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
NaBH4+AgNO3+3H2O＝Ag+NaNO3+H3BO3+3.5H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 4
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, Ag2SO4Preparation of dilution liquid
3.32g of Ag2SO4Crystal (Ag)2SO40.0083 parts) was added to 39996.68g of the second premix obtained in the first step, 100% being formed and dissolved at room temperature.
Thirdly, preparing reducing diluent
4g of sodium borohydride was dissolved in 396g of the third premixed solution obtained in the first step, and the solution was dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of the first 22.98kg of the premixed liquid obtained in the first step is reduced to 85 ℃, the fourth premixed liquid obtained in the first step and 40kg of the product Ag obtained in the second step are added2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 5
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, Ag2SO4Preparation of dilution liquid
3.32g of Ag2SO4Crystal (Ag)2SO40.0083 parts) was added to 39996.68g of the second premix obtained in the first step, 100% being formed and dissolved at room temperature.
Thirdly, preparing reducing diluent
4g of sodium borohydride was dissolved in 396g of the third premixed solution obtained in the first step, and the solution was dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of the 22.98kg of the premixed liquid obtained in the first step is reduced to 90 ℃, adding the fourth premixed liquid obtained in the first step and 40kg of the product Ag obtained in the second step2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 6
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, Ag2SO4Preparation of dilution liquid
14.80g of Ag2SO4Crystal (Ag)2SO40.037 parts) was added to 39985.20g of the second premix obtained in the first step to form 100%, which was dissolved at room temperature.
Thirdly, preparing reducing diluent
4g of sodium borohydride was dissolved in 396g of the third premixed solution obtained in the first step, and the solution was dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of 102.43kg of the premixed solution obtained in the first step is reduced to 80 ℃, adding the premixed solution obtained in the first step, and 40kg of the Ag product obtained in the second step2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 7
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, Ag2SO4Preparation of dilution liquid
Mixing 6.60g of Ag2SO4Crystal (Ag)2SO40.0165 parts) was added to 39993.40g of the second premix obtained in the first step to form 100%, which was dissolved at room temperature.
Thirdly, preparing reducing diluent
12g of sodium borohydride was dissolved in 388g of the premix three obtained in the first step, and dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of 45.68kg of the premixed liquid obtained in the first step is reduced to 80 ℃, adding the premixed liquid obtained in the first step, and 40kg of the product Ag obtained in the second step2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 8
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, Ag2SO4Preparation of dilution liquid
Mixing 6.60g of Ag2SO4Crystal (Ag)2SO40.0165 parts) was added to 39993.40g of the second premix obtained in the first step to form 100%, which was dissolved at room temperature.
Thirdly, preparing reducing diluent
3.2g of sodium borohydride was dissolved in 396.8g of the premix three obtained in the first step, and dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of 45.68kg of the premixed liquid obtained in the first step is reduced to 85 ℃, adding the premixed liquid obtained in the first step, and 40kg of the product Ag obtained in the second step2SO4Diluent and 400g the reducing diluent obtained in the third step, and stirring at a speed of 200-300 rpm for 2 hours.
2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 9
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, AgNO3Preparation of dilution liquid
7.20g of AgNO3Crystal (AgNO)30.018 parts) was added to 39992.80g of the second premix obtained in the first step, 100% was formed and dissolved at room temperature.
Thirdly, preparing reducing diluent
6g of sodium borohydride was dissolved in 394g of the premix three obtained in the first step, and dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
To be firstCooling 91.47kg of the first premix obtained in step (A) to 80 deg.C, adding the fourth premix obtained in step (B) and 40kg of the second product Ag2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
NaBH4+AgNO3+3H2O＝Ag+NaNO3+H3BO3+3.5H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Example 10
First, preparing a premix
And (2) adding 25% of polyvinyl alcohol into 75% of water according to parts by weight to form 100%, and heating to 95 ℃ until the polyvinyl alcohol is fully dissolved.
And a second premix, in which 4.7% of urea was dissolved in 95.3% of water to 100%, and the mixture was dissolved at room temperature.
And thirdly, dissolving 0.6 percent of sodium hydroxide into 99.4 percent of water to form 100 percent, and dissolving at room temperature.
And fourthly, dissolving 0.25 percent of boric acid into 99.75 percent of water to form 100 percent, and dissolving at room temperature.
Second step, AgNO3Preparation of dilution liquid
7.20g of AgNO3Crystal (AgNO)30.018 parts) was added to 39992.80g of the second premix obtained in the first step, 100% was formed and dissolved at room temperature.
Thirdly, preparing reducing diluent
4g of sodium borohydride was dissolved in 396g of the third premixed solution obtained in the first step, and the solution was dissolved at room temperature.
Fourthly, preparing a coating stock solution (silver content 200ppm)
When the temperature of 91.47kg of the premixed solution obtained in the first step is reduced to 85 ℃, adding the premixed solution obtained in the first step, and 40kg of the Ag product obtained in the second step2SO4The diluent and 400g of the reducing diluent obtained in the third step were stirred at 200-.
NaBH4+AgNO3+3H2O＝Ag+NaNO3+H3BO3+3.5H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O
Fifthly, casting to form film
Coating the raw solution on a high molecular substrate film such as polyethylene terephthalate, and gradually crosslinking to solid at a temperature lower than 70 ℃.
And sixthly, drying at low temperature, rolling, cutting and packaging to obtain the finished product of the medical silver ion antibacterial film.
Comparative example 1
A medical silver ion antibacterial film was prepared in the same manner as in example 10, except that AgNO in the second step3The crystal mass was adjusted to 2.00g (0.005 parts), the sodium borohydride mass in the third step was adjusted to 0.036g (0.009 parts), the premix first mass in the fourth step was adjusted to 44.57kg (silver content 150ppm), and the premix first temperature in the fourth step was adjusted to 65 ℃, the solution was easily cured, resulting in uneven coating.
Comparative example 2
A medical silver ion antibacterial film was prepared in the same manner as in example 10, except that AgNO in the second step3The mass of the crystals was adjusted to 2.00g (0.005 parts), the mass of sodium borohydride in the third step was adjusted to 0.036g (0.009 parts), the mass of the premix in the fourth step was adjusted to 44.57kg (silver content 150ppm), and the temperature of the premix in the fourth step was adjusted to 105 ℃, so that a large amount of air bubbles were generated in the solution, and the coating process could not be normally performed.
The differences between the examples are shown in table 1 below:
the samples obtained in the above examples were tested as follows
Detection method
1 silver content
And measuring the silver content by adopting an atomic absorption spectrophotometer, wherein the error is +/-5%.
2 mechanical testing of the membranes
Tensile strength and elongation at break of the film were measured using a tensile machine.
3 film surface structure
Observing the surface structure of the membrane by adopting an SEM scanning electron microscope, wherein the generated polyvinyl alcohol membrane is a three-dimensional reticular structure as shown in figure 1, and the hydrophilicity is adjusted by adjusting the aperture (polymerization degree) of the mesh; the three-dimensional network structure prevents silver particles from agglomerating, and can slowly release silver after meeting water, thereby generating stable and continuous antibacterial action.
4 Water vapor Transmission Rate test
The water vapor transmission amount of the film was measured by a water vapor transmission amount measuring instrument.
5 test of antibacterial Properties
The antibacterial performance is measured according to AATCC 100-200;
an experimental report of the antibacterial performance of the silver ion antibacterial film;
1. the purpose is as follows: and (3) detecting the antibacterial performance of the silver ion antibacterial film.
2. Experimental apparatus: staphylococcus aureus, 0.9% normal saline, a culture dish, tweezers, an incubator, a pressure steam sterilization pot, a liquid-transfering gun head and a test tube.
3. The experimental steps are as follows: the test bacteria 24h slant culture was washed with 0.9% physiological saline, made into a bacterial suspension and counted. The test specimens were divided into 4 groups and placed in 4 sterilized tubes. And (3) taking the bacterial suspension, respectively dropwise adding 100 mu L of the bacterial suspension on each sample to be tested, uniformly coating and adding 1mL of physiological saline, starting timing, adding 5mL of physiological saline into each test tube after acting for 24 hours, fully and uniformly mixing, appropriately diluting, then taking 3 dilutions, respectively sucking 1mL of the diluted saline, placing the diluted saline in two plates, pouring 15mL of nutrient agar culture medium cooled to 40-45 ℃, rotating the plates to fully and uniformly mix, turning the plates after agar is solidified, culturing for 48 hours at 35 +/-2 ℃, and counting viable bacteria colonies.
4. The following experimental results were made for the sample according to example 8:
| initial amount of added bacteria | Bacterial count after 24h | Rate of sterilization |
| 1.02×106cfu | 8.15×103cfu | 99.2％ |
And (4) experimental conclusion: the sterilization rate of the sample product of example 8 after 24 hours reached 99.2%, and the test results of other samples are shown in table 2.
TABLE 2
And (4) analyzing results:
the antibacterial film prepared by the formula and the method has the advantages of stable performance, high silver content, good physical property, good antibacterial performance and lasting antibiosis.
Through optimization experiments, the silver salt is preferably 0.01-0.02 part by weight of silver nitrate or 0.0092-0.0184 part by weight of silver sulfate, and the optimal formula is 0.018 part by weight of silver nitrate or 0.0165 part by weight of silver sulfate.
Through optimization experiments, the weight part of sodium borohydride is preferably 0.5-1.5, and the optimal formula is 0.8-1.2.
The preparation temperature of the coating stock solution is optimized by an optimization experiment, the optimal temperature range is 80-90 ℃, and the optimal temperature is 85 ℃.
The invention provides a medical silver ion antibacterial film and a preparation method thereof, silver is reduced in a polyvinyl alcohol system, a dispersing agent is not required to be added, the production steps are reduced, the production cost is reduced, and the obtained product has stable performance, excellent physical properties and lasting antibacterial effect.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.
Claims (9)
1. The medical silver ion antibacterial film is characterized by comprising the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver salt and 0.1-3 parts of sodium borohydride.
2. The medical silver ion antibacterial film as claimed in claim 1, wherein the formula comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver nitrate and 0.1-3 parts of sodium borohydride.
3. The medical silver ion antibacterial film as claimed in claim 2, wherein the formula comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.01-0.02 part of silver nitrate and 0.5-1.5 parts of sodium borohydride.
4. The medical silver ion antibacterial film as claimed in claim 1, wherein the formula comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.0083-0.037 part of silver sulfate and 0.1-3 parts of sodium borohydride.
5. The medical silver ion antibacterial film as claimed in claim 4, wherein the formula comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.0092-0.0184 part of silver sulfate and 0.5-1.5 parts of sodium borohydride.
6. The medical silver ion antibacterial film according to claim 1, wherein the plasticizer is urea.
7. A preparation method of a medical silver ion antibacterial film is characterized by comprising the following steps:
preparing a reagent according to a formula, wherein the formula comprises the following components in parts by mass: 25 parts of polyvinyl alcohol, 4.7 parts of plasticizer, 0.6 part of sodium hydroxide, 0.25 part of boric acid, 0.009-0.04 part of silver nitrate or 0.0083-0.037 part of silver sulfate and 0.1-3 parts of sodium borohydride;
step two, preparing a premixed solution;
adding polyvinyl alcohol into water, and heating for dissolving;
dissolving urea into water, and dissolving the urea at room temperature;
dissolving sodium hydroxide into water, and dissolving at room temperature;
dissolving boric acid into water;
adding a silver salt into the second premixed solution, and dissolving at room temperature to obtain a first mixed solution;
dissolving sodium borohydride into the premixed solution III, and dissolving at room temperature to obtain a second mixed solution;
step five, keeping the preparation temperature of the coating stock solution at 70-100 ℃ through a temperature control system, adding the premix solution four, the first mixed solution and the second mixed solution into the premix solution one, and stirring for 2 hours at the speed of 200-;
NaBH4+AgNO3+3H2O＝Ag+NaNO3+H3BO3+3.5H2↑
or 2NaBH4+Ag2SO4+6H2O＝2Ag+Na2SO4+2H3BO3+7H2↑
4H3BO3+2NaOH＝Na2B4O7+7H2O；
Sixthly, coating the coating stock solution on a high polymer substrate film such as polyethylene terephthalate and the like, and gradually crosslinking the coating stock solution into a solid at the temperature of lower than 70 ℃;
and seventhly, preparing a finished product of the medical silver ion antibacterial film through the processes of low-temperature drying, rolling, slitting and packaging.
8. The method for preparing a medical silver ion antibacterial film as claimed in claim 7, wherein in the fifth step, the temperature of the coating stock solution is maintained at 80-90 ℃ by a temperature control system, the fourth premixed solution, the first mixed solution and the second mixed solution are added into the first premixed solution, and the stirring is carried out at the speed of 200-.
9. The method for preparing a medical silver ion antibacterial film according to claim 8, wherein the optimal temperature for preparing the coating stock solution is 85 ℃.
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