Antibacterial and degradable gloves and preparation method thereof

Abstract

The present invention relates to the field of medical protection technology, and specifically proposes an antibacterial and degradable glove and a preparation method thereof. The method prepares an antibacterial coating liquid by combining polylactic acid and hydroxyapatite nanocolumns, and prepares a degradable glove with an antibacterial surface layer by two dipping steps. The glove mainly utilizes the columnar structure formed by the hydroxyapatite nanocolumns on the surface of the glove to achieve physical destruction of bacteria, is independent of the release of chemical agents, has good antibacterial properties and long-lasting effect, and at the same time, uses polylactic acid as a substrate to make the glove have excellent degradability and meet environmental protection requirements.

Description

Technical Field

[0001] The present invention relates to the field of medical protection technology, and in particular to an antibacterial and degradable glove and a preparation method thereof. Background Art

[0002] With the increasing demand for protective equipment in the fields of medical treatment, food processing, laboratories and daily household use, antibacterial gloves have become a common protective product. Traditional antibacterial gloves usually achieve their antibacterial function by adding antibacterial agents, coatings or composite materials, and are widely used to prevent the spread of microorganisms such as bacteria and viruses.

[0003] In the prior art, common technical solutions for antibacterial gloves include: silver ion antibacterial gloves, copper ion antibacterial gloves, organic antibacterial agent antibacterial gloves, etc. Silver ions are widely used in the preparation of antibacterial gloves due to their excellent antibacterial properties. Silver ions can destroy the metabolic process of bacteria and inhibit their growth by binding to bacterial cell walls and proteins. However, the silver ion coating will gradually be consumed during long-term use, resulting in a weakening of the antibacterial effect. In addition, the continuous release of silver ions may induce bacterial resistance, and the degradation of silver ion materials in the environment may cause certain pollution. Similar to silver ions, copper ions also have strong antibacterial properties and can inhibit bacterial growth by changing the permeability and cell function of bacterial cell membranes. However, copper ions also face the challenge of antibacterial effect decaying over time, and copper ions are toxic to certain microorganisms and may have adverse effects on the ecological environment. The antibacterial effect is achieved by adding organic antibacterial agents (such as chlorobenzamide, etc.) to the glove material. Such antimicrobial gloves usually have good antimicrobial effects, but their antimicrobial properties gradually weaken during long-term use, and organic antimicrobial agents may cause potential health risks to the human body or the environment, such as allergic reactions or toxicity issues.

[0004] Although the above antibacterial glove technology has solved the short-term antibacterial needs to a certain extent, it still has some significant shortcomings, such as the gradual consumption of antibacterial agents, the development of drug resistance, environmental pollution and other issues. Especially in the scenario of long-term wear and frequent use, the existing antibacterial gloves often cannot maintain a lasting antibacterial effect. In addition, most of the antibacterial components used in traditional antibacterial gloves will gradually become ineffective or consumed during use, and cannot provide lasting antibacterial protection, and their degradation may cause environmental pollution.

[0005] Therefore, there is an urgent need for a new antimicrobial glove technology that can provide a long-lasting and highly effective antimicrobial effect while being biocompatible and environmentally friendly. Summary of the invention

[0006] In view of this, the present invention proposes an antibacterial and degradable glove and a preparation method thereof, aiming to provide a more reasonable antibacterial means and maintain good environmental friendliness while maintaining good short-term antibacterial needs.

[0007] The technical solution of the present invention is achieved as follows: The present invention provides a method for preparing antibacterial and degradable gloves, comprising the following steps:

[0008] Step 1, adding polylactic acid and an additive into an organic solvent, stirring and treating, to obtain a polylactic acid solution;

[0009] Step 2: adding hydroxyapatite nanocolumns to the polylactic acid solution, and subjecting the solution to ultrasonic high-speed stirring for 30-60 minutes at a stirring speed of 400-800 rpm to obtain an antibacterial coating liquid;

[0010] Step 3: Immerse the hand mold in the degassing polylactic acid solution to ensure that the solution evenly covers the surface of the mold, and then perform a first drying process. Immerse the hand mold after the first drying in the degassing antibacterial coating solution, and then perform a second drying process.

[0011] Step 4: baking the dried hand mold and then demoulding it to obtain the antibacterial and biodegradable gloves;

[0012] The length of the hydroxyapatite nanocolumn is 50-1000nm, and the aspect ratio is (5-50):1.

[0013] In order to overcome the defects and shortcomings of the antibacterial active ingredients in the prior art, the above-mentioned embodiment adopts a hydroxyapatite nanocolumn structure as an antibacterial modified component, breaking through the technical limitations of traditional antibacterial gloves that only rely on chemical agents or surface coatings, and improving the sustainability of the antibacterial effect and the performance of the gloves.

[0014] Specifically, hydroxyapatite nanocolumns have good biocompatibility. As an antibacterial active ingredient, adding them to the raw materials of polylactic acid gloves will not limit their safety in the medical field. At the same time, they will not have adverse effects on the environment during the biodegradation and recycling process. Secondly, hydroxyapatite nanocolumns can form nanocolumnar microstructures on the surface of the gloves. These nanocolumnar microstructures can physically destroy bacterial cells. When bacteria dock on the surface of the gloves, these tiny nanocolumnar structures can stretch and cut the bacteria, thereby destroying the cell membrane and ultimately killing the bacteria.

[0015] In some embodiments, the method for preparing hydroxyapatite nanorods comprises:

[0016] 0.5-2 mol / L sodium dihydrogen phosphate solution and 1-2 mol / L calcium chloride solution are mixed and stirred evenly, the pH value of the solution is adjusted to 9.0-10.0 with ammonia water, and 1-2 wt% of hexadecyltrimethylammonium bromide is added to the mixed solution;

[0017] Then the mixed solution is transferred to a hydrothermal reactor, heated to 150-200°C, and kept warm for 12-24 hours. After the reaction is completed, the mixture is cooled to 20-30°C, filtered and dried to obtain hydroxyapatite nanocolumns.

[0018] The molar ratio of sodium dihydrogen phosphate to calcium chloride is 1:(1-2).

[0019] In the above embodiment, hydroxyapatite nanocolumns are synthesized by a hydrothermal method, and hydroxyapatite is generated by a chemical reaction of sodium dihydrogen phosphate and calcium chloride, and hexadecyltrimethylammonium bromide is used as a template. This synthesis method can prepare hydroxyapatite nanocolumns with high dimensional stability and consistency.

[0020] In some embodiments, the hydroxyapatite nanocolumns are subjected to a loading composite treatment, the loading substrate of the composite treatment is dendritic silica, and after the composite treatment, the hydroxyapatite nanocolumns are loaded on the surface of the dendritic silica, and the average particle size of the dendritic silica is 50-500 nm.

[0021] In the above embodiment, by loading on the surface of dendritic silica, the verticality of the hydroxyapatite nanocolumns on the surface of the gloves can be improved, thereby enhancing its antibacterial effect. Dendritic silica has a rich surface structure, which is conducive to the directional arrangement of nanocolumns. Dendritic silica has a high specific surface area and can provide more attachment sites for nanocolumns, thereby improving the stability of the composite structure and the loading amount of nanocolumns.

[0022] In some embodiments, the composite treatment method includes: adding hydroxyapatite nanocolumns and dendritic silica to a chitosan solution, adding 0.01-0.1% glutaraldehyde by mass of the solution, and then ultrasonically stirring for 1-2 hours, filtering and drying at 60-80°C to obtain composite hydroxyapatite nanocolumns, wherein the mass ratio of hydroxyapatite nanocolumns to dendritic silica is 1: (1-3).

[0023] In the above embodiment, hydroxyapatite nanorods and dendritic silica are added to a chitosan solution, and glutaraldehyde is used as a cross-linking agent for compounding, and the cross-linking reaction between glutaraldehyde and chitosan is utilized to increase the stability and loading effect of the composite material. Through the cross-linking reaction, the loading structure of the nanorods on the surface of the dendritic silica can be ensured to be stable, and dissociation can be avoided during the dispersion and mixing process with the polylactic acid solution.

[0024] In some embodiments, the concentration of the chitosan solution is 1-2 wt %, and the pH value is 4.5-5.5.

[0025] The use of 1-2wt% chitosan solution can effectively improve the uniformity of the impregnation molding of hydroxyapatite and dendritic silica surfaces.

[0026] In some embodiments, the organic solvent is one of dichloromethane, chloroform and acetone, and the concentration of the polylactic acid solution is 10-20% (w / v).

[0027] In some embodiments, the auxiliary agent includes a plasticizer, and the plasticizer includes at least one of polyethylene glycol, trioctyl ester and dioctyl adipate. In the polylactic acid solution, the amount of the plasticizer is 5-20wt% of the polylactic acid.

[0028] In some embodiments, in the antibacterial coating solution, the amount of hydroxyapatite nanorods is 1-20 wt % of the polylactic acid.

[0029] In some embodiments, the first drying treatment is performed at a temperature of 30-40°C for 1-2 hours, the second drying treatment is performed at a temperature of 40-50°C for 1-2 hours, and the baking temperature is 60-70°C for 2-4 hours.

[0030] The second aspect of the present invention also provides an antibacterial and degradable glove prepared by the above preparation method.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] First, the present application uses hydroxyapatite nanorods as antibacterial active materials combined with polylactic acid, so that the surface of the gloves has excellent antibacterial properties. Hydroxyapatite nanorods can physically destroy bacterial cell membranes and increase stress on the bacterial surface through their unique nanostructure, thereby effectively killing bacteria.

[0033] Polylactic acid, as the main base material of gloves, can be decomposed in the environment, avoiding the pollution of the environment by traditional plastic gloves. Combined with antibacterial properties, the gloves not only provide medical protection functions, but also have environmental protection performance. In this way, the demand for degradable gloves in the medical and daily protection fields is effectively solved.

[0034] The present application also uses a double coating process, that is, the polylactic acid solution and the antibacterial coating liquid are coated on the surface of the hand model respectively, thereby enhancing the surface antibacterial property and mechanical strength of the gloves. The two layers of coating can give full play to the degradation performance of polylactic acid and the antibacterial effect of HAp nanocolumns, while avoiding the problems of uneven coating and non-persistent antibacterial performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0036] Figure 1 is a SEM image of the hydroxyapatite nanorods prepared in Example 2 of the present invention;

[0037] Figure 2 is a SEM image of the hydroxyapatite nanorods prepared in Example 7 of the present invention;

[0038] Figure 3 is a SEM image of the hydroxyapatite nanorods prepared in Example 8 of the present invention;

[0039] Figure 4 This is a SEM image of the hydroxyapatite nanorods prepared in Example 9 of the present invention. DETAILED DESCRIPTION

[0040] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the embodiments of the present invention belong. If the definitions set forth in this section are contrary to or otherwise inconsistent with the definitions set forth in the patents, patent applications, published patent applications, and other publications incorporated herein by reference, the definitions listed in this section take precedence over the definitions incorporated herein by reference.

[0042] Unless otherwise specified, the methods used in the following examples are all conventional methods. Unless otherwise specified, the materials, reagents and instruments used are all conventional materials, reagents and instruments in the art, and can be obtained by those skilled in the art through commercial channels.

[0043] When an amount, concentration or other value or parameter is expressed as a range, a preferred range or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including the range "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described herein, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range. In the present specification and claims, range definitions can be combined and / or interchanged, and if not otherwise stated, these ranges include all subranges contained therein.

[0044] Different from the antibacterial principle of existing antibacterial gloves, the antibacterial principle of hydroxyapatite (HAp) nanocolumns is mainly to achieve physical and chemical effects on bacteria through its special nanostructure and surface characteristics, leading to the destruction of bacterial cell membranes. Specifically, HAp nanocolumns have a special high specific surface area and nanoscale surface roughness. When these nanocolumns come into contact with bacteria, they can form mechanical pressure on the bacterial surface, especially when the nanocolumns are arranged vertically, they can contact the bacterial cells more directly. This surface morphology will increase the local stress of the bacterial cell membrane, leading to physical rupture or deformation of the membrane structure. When the size of HAp nanocolumns is between 50-1000nm, their length and shape enable them to penetrate the bacterial cell membrane like a "needle prick". The nanocolumns may directly contact the lipid bilayer of the bacterial cell, generate local mechanical stress, lead to the rupture of the bacterial cell membrane, and then release the internal substances of the cell, causing cell death. As the aspect ratio of the nanocolumns changes, their surface morphology can better contact with bacteria and increase the effect of antibacterial action. This effect is similar to that of other nanomaterials (such as nanosilver and nanocopper) that interact with bacteria in a physical way to achieve the purpose of antibacterial or bactericidal effects.

[0045] Secondly, the negative charge of HAp interacts with the charge on the surface of bacteria, enhancing the binding force between HAp and bacteria. Phospholipids are usually contained on bacterial cell membranes. These phospholipid components can interact with the negatively charged part of HAp, thereby affecting the structure and function of the cell membrane and enhancing the destructive effect on bacteria. The surface of HAp nanopillars contains calcium ions, which can exchange ions with some negatively charged molecules in the bacterial cell membrane and destroy the stability of the bacterial cell membrane. Especially for some Gram-negative bacteria, their outer membranes are rich in phospholipids. The calcium ions of HAp can exchange ions with phospholipids, reduce the integrity of the cell membrane, and thus expose the bacterial cells to the external environment, eventually leading to their death. In a humid environment, the hydroxyl groups on the surface of HAp can react with water to generate a certain amount of reactive oxygen species (ROS), such as hydrogen peroxide. These reactive oxygen species can oxidize the bacterial cell membrane, destroy its function, and eventually lead to bacterial death.

[0046] In order to further illustrate the technical effect of the technical solution of the biodegradable gloves of the present application, the applicant has designed different embodiments and comparative examples to verify the technical effect, as follows:

[0047] Example 1

[0048] This embodiment provides a technical solution of a polylactic acid glove having hydroxyapatite nanocolumns.

[0049] The raw materials include: polylactic acid, hydroxyapatite nanorods, and dioctyl adipate.

[0050] The hydroxyapatite nanorods were purchased, with an average length of 500 nm and an aspect ratio of 20:1.

[0051] The steps for preparing gloves are as follows:

[0052] 100 g of polylactic acid and 10 g of dioctyl adipate were added to 1 L of dichloromethane and stirred to obtain a polylactic acid solution with a mass concentration of 10% (w / v);

[0053] Take 500g of the prepared polylactic acid solution, add 50g of hydroxyapatite nanocolumns, and treat with ultrasonic stirring for 60min at a stirring speed of 600rpm to obtain an antibacterial coating liquid;

[0054] The hand mold was immersed in the degassing polylactic acid solution for 30 seconds, then taken out and dried at 35°C for 1.5 hours, immersed in the antibacterial coating solution again for 30 seconds, then taken out and dried at 45°C for 1.5 hours, and then baked at 65°C for 3 hours, demolded, and antibacterial and degradable gloves were obtained.

[0055] Example 2

[0056] This embodiment provides a technical solution of a polylactic acid glove having hydroxyapatite nanocolumns, wherein the hydroxyapatite nanocolumns are prepared.

[0057] The raw materials include: polylactic acid, hydroxyapatite nanorods, and dioctyl adipate.

[0058] The preparation method of hydroxyapatite nanocolumns is as follows: 1L of 1mol / L sodium dihydrogen phosphate solution and 1L of 2mol / L calcium chloride solution are mixed and stirred evenly, ammonia water is used to adjust the pH value of the solution to 9.0-10.0, and 1wt% of hexadecyltrimethylammonium bromide is added to the mixed solution;

[0059] The mixed solution was then transferred to a hydrothermal reactor, heated to 160°C, and kept warm for 18 hours. After the reaction was completed, the mixture was cooled to 25°C, filtered, and dried to obtain hydroxyapatite nanocolumns.

[0060] The average length of the obtained hydroxyapatite nanorods is 500 nm, and the aspect ratio is 20:1. The SEM image is shown in Figure 1 shown.

[0061] The steps for preparing gloves are as follows:

[0062] 100 g of polylactic acid and 10 g of dioctyl adipate were added to 1 L of dichloromethane and stirred to obtain a polylactic acid solution with a mass concentration of 10% (w / v);

[0063] Take 500g of the prepared polylactic acid solution, add 50g of hydroxyapatite nanocolumns, and treat with ultrasonic stirring for 60min at a stirring speed of 600rpm to obtain an antibacterial coating liquid;

[0064] The hand mold was immersed in the degassing polylactic acid solution for 30 seconds, then taken out and dried at 35°C for 1.5 hours, immersed in the antibacterial coating solution again for 30 seconds, then taken out and dried at 45°C for 1.5 hours, and then baked at 65°C for 3 hours, demolded, and antibacterial and degradable gloves were obtained.

[0065] Example 3

[0066] This embodiment provides a technical solution of a polylactic acid glove having hydroxyapatite nanocolumns, wherein the hydroxyapatite nanocolumns are prepared.

[0067] The raw materials include: polylactic acid, hydroxyapatite nanocolumn composite material, and dioctyl adipate.

[0068] The preparation method of the hydroxyapatite nanocolumn composite material is as follows: 1L of 1mol / L sodium dihydrogen phosphate solution and 1L of 2mol / L calcium chloride solution are mixed and stirred evenly, ammonia water is used to adjust the pH value of the solution to 9.5, and 1wt% of hexadecyltrimethylammonium bromide is added to the mixed solution;

[0069] The mixed solution was then transferred to a hydrothermal reactor, heated to 160°C, and kept warm for 18 hours. After the reaction was completed, the mixture was cooled to 25°C, filtered, and dried to obtain hydroxyapatite nanocolumns.

[0070] The average length of the obtained hydroxyapatite nanorods was 500 nm, and the aspect ratio was 20:1.

[0071] 100 g of hydroxyapatite nanocolumns and 200 g of dendritic silica with an average particle size of 100 nm were added to 1 L of chitosan solution with a mass concentration of 2% and a pH value of 5.0, and 0.1% of glutaraldehyde by mass of the solution was added, followed by ultrasonic stirring for 2 h. The mixture was filtered and dried at 70° C. to obtain a composite hydroxyapatite nanocolumn composite material.

[0072] The steps for preparing gloves are as follows:

[0073] 100 g of polylactic acid and 10 g of dioctyl adipate were added to 1 L of dichloromethane and stirred to obtain a polylactic acid solution with a mass concentration of 10% (w / v);

[0074] Take 500g of the prepared polylactic acid solution, add 50g of the hydroxyapatite nanocolumn composite material, and perform ultrasonic stirring for 60min at a stirring speed of 600rpm to obtain an antibacterial coating liquid;

[0075] The hand mold was immersed in the degassing polylactic acid solution for 30 seconds, then taken out and dried at 35°C for 1.5 hours, immersed in the antibacterial coating solution again for 30 seconds, then taken out and dried at 45°C for 1.5 hours, and then baked at 65°C for 3 hours, demolded, and antibacterial and degradable gloves were obtained.

[0076] Example 4

[0077] On the basis of Example 3, other conditions were kept unchanged, except that the average particle size of the dendritic silica used was 50 nm.

[0078] Example 5

[0079] On the basis of Example 3, other conditions were kept unchanged, except that the average particle size of the dendritic silica used was 200 nm.

[0080] Example 6

[0081] On the basis of Example 3, other conditions were kept unchanged, except that the average particle size of the dendritic silica used was 500 nm.

[0082] Example 7

[0083] On the basis of Example 3, other conditions were kept unchanged, except that in the preparation method of the hydroxyapatite nanocolumn composite material, the heating temperature was 150°C and the heat preservation treatment was 24 hours. The average length of the obtained hydroxyapatite nanocolumns was 50 nm, the aspect ratio was 10:1, and the SEM image was as follows: Figure 2 shown.

[0084] Example 8

[0085] On the basis of Example 3, other conditions were kept unchanged, except that in the preparation method of the hydroxyapatite nanocolumn composite material, the heating temperature was 200°C and the heat preservation treatment was 12 hours. The average length of the obtained hydroxyapatite nanocolumns was 800 nm, the aspect ratio was 40:1, and the SEM image was as follows: Figure 3 shown.

[0086] Example 9

[0087] On the basis of Example 3, other conditions were kept unchanged, except that in the preparation method of the hydroxyapatite nanocolumn composite material, the heating temperature was 200°C and the heat preservation treatment was 14 hours. The average length of the obtained hydroxyapatite nanocolumns was 1000nm, the aspect ratio was 50:1, and the SEM image was as follows: Figure 4 shown.

[0088] Example 10

[0089] On the basis of Example 3, other conditions were kept unchanged, except that the concentration of the chitosan solution was 1 wt % and the pH value was 4.5.

[0090] Embodiment 11

[0091] On the basis of Example 3, other conditions were kept unchanged, except that the concentration of the chitosan solution was 1 wt % and the pH value was 5.5.

[0092] Example 12

[0093] On the basis of Example 3, other conditions were kept unchanged, except that the mass of glutaraldehyde added was 0.01% of the mass of the solution.

[0094] Embodiment 13

[0095] On the basis of Example 3, other conditions were kept unchanged, and the only difference was that 100 g of hydroxyapatite nanocolumns and 200 g of nano-silicon dioxide particles with an average particle size of 100 nm were added to 1 L of chitosan solution with a mass concentration of 2% and a pH value of 5.0, 0.1% of glutaraldehyde by mass of the solution was added, and then ultrasonic stirring was performed for 2 h. After filtering, the mixture was dried at 70° C. to obtain a composite hydroxyapatite nanocolumn composite material.

[0096] Comparative Example 1

[0097] This comparative example provides a technical solution of a polylactic acid glove having hydroxyapatite nanoparticles.

[0098] The raw materials include: polylactic acid, hydroxyapatite nanoparticles and dioctyl adipate.

[0099] The hydroxyapatite nanoparticles were purchased and had an average particle size of 500 nm.

[0100] The steps for preparing gloves are as follows:

[0101] 100 g of polylactic acid and 10 g of dioctyl adipate were added to 1 L of dichloromethane and stirred to obtain a polylactic acid solution with a mass concentration of 10% (w / v);

[0102] Take 500g of the prepared polylactic acid solution, add 50g of hydroxyapatite nanoparticles, and treat with ultrasonic stirring for 60min at a stirring speed of 600rpm to obtain an antibacterial coating liquid;

[0103] The hand mold was immersed in the degassing polylactic acid solution for 30 seconds, then taken out and dried at 35°C for 1.5 hours, immersed in the antibacterial coating solution again for 30 seconds, then taken out and dried at 45°C for 1.5 hours, and then baked at 65°C for 3 hours, demolded, and antibacterial and degradable gloves were obtained.

[0104] Comparative Example 2

[0105] This comparative example provides a technical solution for a conventional polylactic acid glove.

[0106] The raw materials include: polylactic acid and dioctyl adipate.

[0107] The steps for preparing gloves are as follows:

[0108] 100 g of polylactic acid and 10 g of dioctyl adipate were added to 1 L of dichloromethane and stirred to obtain a polylactic acid solution with a mass concentration of 10% (w / v);

[0109] The hand mold was immersed in the degassing polylactic acid solution for 30 seconds, then taken out and dried at 35°C for 1.5 hours, immersed in the polylactic acid solution again for 30 seconds, then taken out and dried at 45°C for 1.5 hours, then baked at 65°C for 3 hours, demolded, and degradable gloves were obtained.

[0110] The gloves prepared in the above different embodiments and comparative examples were respectively subjected to antibacterial performance test, tensile strength test, wear resistance test and degradability test, and the specific methods are as follows:

[0111] 1. Tensile strength test: Use a universal material testing machine to perform a tensile test to measure the maximum tensile force and elongation. The tensile speed is 50 mm / min.

[0112] 2. Antibacterial performance test: Using the contact antibacterial test method, take glove membranes of the same size, use Staphylococcus aureus and Escherichia coli as test bacteria, and contact the surface of the glove membrane with a bacterial suspension of known concentration (10 7 CFU / ml), the contact test time is 24h, then the number of surviving bacteria on the surface of the glove membrane is measured and counted, and then the antibacterial rate is calculated.

[0113] 3. Long-term antibacterial test: Using the contact antibacterial test method, take glove membranes of the same size, use Staphylococcus aureus and Escherichia coli as test bacteria, and contact the surface of the glove membrane with a bacterial suspension of known concentration (10 7 CFU / ml), the contact test time was 2 weeks, and then the number of surviving bacteria on the surface of the glove membrane was measured and counted, and then the antibacterial rate was calculated.

[0114] In the above test method, the test surface is the surface formed by curing the antibacterial coating liquid.

[0115] The above examples and comparative examples were tested in three groups in parallel, and the results were averaged to obtain the data results shown in the following table:

[0116]

[0117] Hydroxyapatite nanocolumns are used in the above embodiments, so the antibacterial rate is much higher than that of conventional polylactic acid gloves, which shows the contribution of hydroxyapatite nanocolumns to the antibacterial performance of gloves. Among them, when only hydroxyapatite nanocolumns are used for improvement in Example 1 and Example 2, there is a certain difference in antibacterial performance compared with Example 3. The main reason is that when the hydroxyapatite nanocolumns are directly dispersed in the polylactic acid solution to form a film on the hand mold surface, the hydroxyapatite nanocolumns are easily attached to the surface of the polylactic acid film due to tension, so that the nanocolumn structure on the surface of the glove The structure is not prominent enough, the verticality is poor, and the stress damage to bacteria is limited. In Examples 3 and 4-12, dendritic nano-silica is used for composite modification, which significantly improves the antibacterial rate and long-term antibacterial rate compared with Examples 1 and 2. In Example 13, nano-silica particles of the same size are used for composite modification. Although the antibacterial rate is improved to a certain extent, it is significantly lower than that in Example 3. It can be seen that the use of dendritic silica is more effective in improving the antibacterial rate than the use of conventional spherical nano-silica.

[0118] Comparative Example 1 is based on Example 1, but the hydroxyapatite nanocolumn structure is replaced with ordinary hydroxyapatite nanoparticles of corresponding size. The corresponding prepared gloves not only have no antibacterial properties, but also have significantly lower tensile strength than that of Example 1. Comparative Example 2 uses conventional polylactic acid gloves. It can be seen that the polylactic acid gloves of the present invention have improved mechanical properties such as tensile strength compared with conventional polylactic acid gloves.

[0119] Therefore, the antibacterial and degradable gloves provided in the present application have good antibacterial properties and practicality, the raw materials used are low-cost and easy to prepare, and have good bioaffinity.

[0120] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing antibacterial and degradable gloves, characterized in that: The steps include: Step 1, adding polylactic acid and an additive into an organic solvent, stirring and treating, to obtain a polylactic acid solution; Step 2: adding hydroxyapatite nanocolumns to the polylactic acid solution, and subjecting the solution to ultrasonic high-speed stirring for 30-60 minutes at a stirring speed of 400-800 rpm to obtain an antibacterial coating liquid; Step 3: Immerse the hand mold in the degassing polylactic acid solution to ensure that the solution evenly covers the surface of the mold, and then perform a first drying process. Immerse the hand mold after the first drying in the degassing antibacterial coating solution, and then perform a second drying process. Step 4: baking the dried hand mold and then demoulding it to obtain the antibacterial and biodegradable gloves; The length of the hydroxyapatite nanocolumns is 50-1000 nm, and the aspect ratio is (5-50):

1. In the antibacterial coating liquid, the amount of the hydroxyapatite nanocolumns is 1-20 wt % of the polylactic acid.

2. The method for preparing the antibacterial and degradable gloves according to claim 1, characterized in that: The preparation method of hydroxyapatite nanocolumns comprises: Mix 0.5-2 mol / L sodium dihydrogen phosphate solution and 1-2 mol / L calcium chloride solution and stir evenly, adjust the pH value of the solution to 9.0-10.0 with ammonia water, and add 1-2% of hexadecyltrimethylammonium bromide to the mixed solution; Then the mixed solution is transferred to a hydrothermal reactor, heated to 150-200°C, and kept warm for 12-24 hours. After the reaction is completed, the mixture is cooled to 20-30°C, filtered and dried to obtain hydroxyapatite nanocolumns. The molar ratio of sodium dihydrogen phosphate to calcium chloride is 1:(1-2).

3. The method for preparing the antibacterial and degradable gloves according to claim 1, characterized in that: The hydroxyapatite nanocolumns are subjected to a loading composite treatment, the loading substrate of the composite treatment is dendritic silicon dioxide, and after the composite treatment, the hydroxyapatite nanocolumns are loaded on the surface of the dendritic silicon dioxide, and the average particle size of the dendritic silicon dioxide is 50-500nm.

4. The method for preparing the antibacterial and degradable gloves according to claim 3, characterized in that: The composite treatment method comprises: adding hydroxyapatite nanocolumns and dendritic silica into a chitosan solution, adding glutaraldehyde at a mass percentage of 0.01-0.1% of the solution, and then ultrasonically stirring for 1-2 hours, filtering and drying at 60-80° C. to obtain composite hydroxyapatite nanocolumns, wherein the mass ratio of hydroxyapatite nanocolumns to dendritic silica is 1:(1-3).

5. The method for preparing the antibacterial and degradable gloves according to claim 4, characterized in that: The concentration of the chitosan solution is 1-2wt%, and the pH value is 4.5-5.

5.

6. The method for preparing the antibacterial and degradable gloves according to claim 1, characterized in that: The organic solvent is one of dichloromethane, chloroform and acetone, and the concentration of the polylactic acid solution is 10-20% (w / v).

7. The method for preparing the antibacterial and degradable gloves according to claim 1, characterized in that: The auxiliary agent includes a plasticizer, and the plasticizer includes at least one of polyethylene glycol, trioctyl ester and dioctyl adipate. In the polylactic acid solution, the amount of the plasticizer is 5-20wt% of the polylactic acid.

8. The method for preparing the antibacterial and degradable gloves according to claim 1, characterized in that: The temperature of the first drying treatment is 30-40°C and the time is 1-2h. The temperature of the second drying treatment is 40-50°C and the time is 1-2h. The temperature of the baking molding is 60-70°C and the baking time is 2-4h.

9. An antibacterial and degradable glove, characterized in that: The preparation method is described in any one of claims 1 to 8.

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