Low-ammonia deproteinized latex medical examination glove and preparation method thereof

Abstract

The invention relates to the technical field of preparation of low-ammonia deproteinized latex medical examination gloves, in particular to a low-ammonia deproteinized latex medical examination glove and a preparation method thereof.The method comprises the following steps that hevea brasiliensis juice is sieved, aminopeptidase and ficin are added, acetic acid is added to terminate enzymolysis, centrifugal concentration and vacuum distillation are performed, gingerol is added, and the low-ammonia deproteinized latex medical examination glove is obtained; graphene and hexagonal boron nitride are subjected to ultrasonic treatment, polylactic acid and glycerin are added, water bath stirring is carried out, latex and the dispersion are mixed, N-octyl-N-trimethyl chitosan is added, stirring is carried out, then 2, 6-butylated hydroxytoluene is added, a ceramic mold subjected to plasma cleaning is soaked in a coagulator and dried, the ceramic mold is soaked in 30% of composite latex and 50% of composite latex, edge curling and standing are carried out after drying, and the ceramic mold is obtained. And preheating the glove base body, electrostatically spraying the multifunctional coating liquid, curing and then carrying out ultraviolet radiation. Therefore, the problems that the low-ammonia deproteinized latex medical examination gloves are high in sensitization, poor in mechanical strength, not easy to degrade, uncomfortable to wear and the like are solved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of low-ammonia deproteinized latex medical examination gloves, in particular to a low-ammonia deproteinized latex medical examination glove and a preparation method thereof. BACKGROUND

[0002] As a medical protection product, the performance of the low-ammonia deproteinized latex medical examination glove is directly related to the health of medical staff and the quality of medical work. With the continuous development of the medical field, the demand for high-quality low-ammonia deproteinized latex medical examination gloves is increasing. In 2024, the market size of medical latex examination gloves in China reached 4.58 billion yuan, and it is expected to exceed 6.8 billion yuan in 2025, with an annual compound growth rate of about 12.4%. At present, the low-ammonia deproteinized latex medical examination glove has a high use rate and is used in a high-risk environment. Therefore, the preparation technology of the low-ammonia deproteinized latex medical examination glove needs to be upgraded and improved. Meanwhile, N-octyl-N-trimethyl chitosan is a functional chitosan derivative obtained by chemical modification, which has the biocompatibility of natural macromolecules and specific physicochemical properties, and becomes the core candidate of a new generation of low-ammonia deproteinized latex medical examination gloves.

[0003] However, the current low-ammonia deproteinized latex medical examination glove manufacturing technology is facing the core challenge that the low-ammonia deproteinized latex glove has the problems of high allergenicity, poor mechanical strength, difficulty in degradation, and poor wearing comfort due to residual allergenic proteins, molecular chain breakage, and insufficient vulcanization, which seriously restricts the economic and technological development of the low-ammonia deproteinized latex medical examination glove industry. SUMMARY

[0004] The application provides a low-ammonia deproteinized latex medical examination glove and a preparation method thereof, thereby solving the problems of high allergenicity, poor mechanical strength, difficulty in degradation, and poor wearing comfort of the low-ammonia deproteinized latex medical examination glove.

[0005] The first aspect embodiment of the application provides a low-ammonia deproteinized latex medical examination glove, which is composed of modified low-ammonia deproteinized latex, graphene-poly-lactic acid reinforced dispersion, functional additives, and a surface functional coating.

[0006] The second aspect embodiment of the application provides a preparation method of a low-ammonia deproteinized latex medical examination glove, which comprises the following steps: (1) Rubber tree juice 1800-1900 parts, sieve, add 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate, stir for 30 minutes, add aminopeptidase and ficin, add 6-7 parts of 10% KOH solution, stir at 45°C at 50 r / min for 6h, adjust pH to 7.5-8.0, add 19-20 parts of 1% acetic acid to terminate the enzymatic hydrolysis, centrifugal concentration to dry rubber content 60%, vacuum distillation, add 0.5 parts of gingerol, to obtain low ammonia deproteinized latex.

[0007] It can be understood that, in the embodiments of the present application, the impurities in the rubber tree juice are removed by screening to purify the raw material, potassium laurate and sodium dodecyl sulfate are used as surfactants to stabilize the latex particles by emulsification and dispersion, prevent agglomeration, aminopeptidase and ficin are used to hydrolyze the proteins in the juice to achieve deproteinization under the conditions of suitable temperature of 45°C, alkaline pH of 7.5-8.0 and stirring to promote contact, 10% KOH solution is used to adjust the pH to provide an alkaline environment for the enzymatic hydrolysis, 1% acetic acid is used to deactivate the enzyme by changing the pH to terminate the reaction, centrifugal concentration is used to separate and concentrate by centrifugal force, vacuum distillation is used to dehydrate under low pressure to make the dry rubber content reach 60%, and gingerol is used as a stabilizer to improve the stability of the low ammonia deproteinized latex.

[0008] (2) Ultrasonic treatment of graphene 0.05-0.1 parts and hexagonal boron nitride 0.05-0.1 parts in ethanol solution, add polylactic acid 15-20 parts and glycerol 3 parts, stir in 60°C water bath for 2 hours to form a graphene-polylactic acid dispersion.

[0009] It can be understood that, in the embodiments of the present application, ethanol is used as a polar solvent to provide a dispersion medium for graphene and hexagonal boron nitride, ultrasonic treatment uses the mechanical vibration and local high temperature and high pressure generated by cavitation effect to break the agglomeration structure of graphene and hexagonal boron nitride, making them uniformly dispersed in ethanol, 60°C water bath heating increases the energy of the system, promotes the swelling of polylactic acid and enhances its interfacial affinity with nanoparticles, glycerol is used as a plasticizer to increase the flexibility and flowability of polylactic acid by reducing the intermolecular forces, which is beneficial to wrapping nanoparticles, and stirring further promotes the mixing of components by mechanical shear force, making polylactic acid molecules adsorbed on the surface of graphene and hexagonal boron nitride to form a stable graphene-polylactic acid dispersion, preventing the re-agglomeration of nanoparticles.

[0010] (3) Mix the low ammonia deproteinized latex 1000 parts with the graphene-polylactic acid dispersion at 60°C, add N-octyl-N-trimethyl chitosan 0.8-1.2 parts, stir at 200 r / min for 2 hours, add 2,6-di-tert-butyl-p-cresol 1 part, electron beam irradiation for 30 minutes to obtain a composite latex.

[0011] It can be understood that the embodiments of the present application improve the molecular thermal motion ability by heating at 60°C, promote the uniform mixing of low ammonia deproteinized latex and graphene-polylactic acid dispersion, enhance the interfacial compatibility, N-octyl-N-trimethyl chitosan as modified chitosan interacts with the components of latex and dispersion through its polar groups to improve the compatibility and stabilize the system, 200 r / min stirring promotes the full dispersion and fusion of each component through shear force to form a uniform mixed system, 2,6-di-tert-butyl-p-cresol as an antioxidant inhibits the oxidative degradation of latex components by capturing free radicals, electron beam irradiation uses high-energy particles to initiate intermolecular crosslinking reaction to form a stable three-dimensional network structure, enhance the mechanical properties and stability of the composite latex, and has sterilization effect at the same time.

[0012] (4) After the ceramic mold is cleaned by plasma, a coagulant is immersed and dried at 90°C. The mold is immersed in the composite latex with a content of 30% for 5 seconds at 25°C to form a 0.05mm base layer, dried, immersed in the composite latex with a content of 50% for 10 seconds at 30°C, dried, and then the edge is rolled to obtain a latex glove base.

[0013] It can be understood that the embodiments of the present application use high-energy plasma to remove impurities on the surface of the ceramic mold and activate the surface by plasma cleaning, thereby enhancing the adhesion of the subsequent substances. The immersion of the coagulant makes the rubber particles in the latex dehydrate and coagulate through the penetration effect, and the coagulant coating is fixed at 90°C to provide a basis for latex film formation. The latex is quickly coagulated to form a thin base layer under the action of the coagulant by immersing in the composite latex with a low concentration of 30% for a short time at 25°C. The structure is fixed by removing the water after drying. The latex fluidity is accelerated at a slightly higher temperature of 30°C, and the latex is further coagulated on the base layer by immersing in the composite latex with a high concentration of 50% for a longer time, thereby increasing the thickness and strength of the glove. The edge structure is shaped by mechanical action during rolling to facilitate wearing, and the latex film is fully cured and shaped by standing to ensure the stability of the structure of the latex glove base.

[0014] (5) Polyurethane emulsion 50-60 parts, titanium dioxide dispersion liquid 10-15 parts, glycerol 3 parts are mixed, and ammonia water 1.5 parts is added to adjust the pH to 7.0-7.5 to obtain a multifunctional coating liquid.

[0015] It can be understood that the embodiments of the present application use polyurethane emulsion as a film-forming substrate to provide basic film-forming properties and flexibility for the coating liquid. The titanium dioxide particles in the titanium dioxide dispersion liquid can impart functionality to the coating liquid through its photocatalytic and light-shielding properties. The dispersion liquid form ensures uniform distribution. Glycerol acts as a plasticizer to increase the flexibility of the coating layer by weakening intermolecular forces and reducing brittleness. Ammonia water is an alkaline adjusting agent that adjusts the pH to a neutral to slightly alkaline range of 7.0-7.5, which can maintain the colloidal stability of the polyurethane emulsion and titanium dioxide dispersion liquid, avoid demulsification and coagulation under acidic or strongly alkaline conditions, and ensure uniform mixing of all components to form a stable multifunctional coating liquid.

[0016] (6) Preheat the latex glove substrate to 50℃, electrostatically spray the multifunctional coating liquid 2 times, interval 5 minutes curing, 80℃ hot air circulation 15 minutes, ultraviolet lamp irradiation 10 minutes, to obtain a modified latex glove with a multifunctional coating.

[0017] It can be understood that the preheating of the latex glove substrate to 50℃ in the embodiment of the application enhances the wettability and adhesion of the multifunctional coating liquid by increasing the surface temperature, which is conducive to uniform spreading of the coating. Electrostatic spraying utilizes the electrostatic adsorption effect to make the charged coating liquid particles directionally adsorb to the grounded glove surface, realizing uniform and efficient adhesion of the coating. Interval 5 minutes curing allows the coating to be initially dried and shaped after the first spraying, avoiding coating mixing and sagging during the second spraying, ensuring the stability of the layered structure. 80℃ hot air circulation accelerates the volatilization of solvents in the coating liquid by heating, promotes the cross-linking of polyurethane molecules to form a film, and enhances the bonding strength between the coating and the substrate. Ultraviolet lamp irradiation activates the photocatalytic properties of titanium dioxide, strengthens its antibacterial and ultraviolet resistance functions, and at the same time promotes further curing of the coating, improving weather resistance and surface activity.

[0018] In the step (1), a 200-mesh sieve is used, and the vacuum distillation conditions are 60℃ and 0.1MPa.

[0019] It can be understood that the 200-mesh sieve is selected in the embodiment of the application because its 74μm mesh size can effectively trap bark chips, coarse fibers and other coarse impurities in the juice, while avoiding excessive interception of small rubber particles. This reduces the loss of effective ingredients while ensuring the purity of the raw materials. Vacuum distillation uses 60℃ and 0.1MPa. The 0.1MPa low-pressure environment reduces the boiling point of the system, allowing water to evaporate at 60℃. This avoids high temperatures that can cause rubber molecules to oxidize or enzyme activity to be abnormal, while accelerating dehydration to a dry rubber content of 60%. Under these conditions, ammonia is efficiently removed with the steam due to its volatile nature, reducing the impact of ammonia residues on subsequent reactions and the safety of the final product, while balancing dehydration, deamination efficiency and latex stability.

[0020] In the step (1), 0.3-0.5 parts of aminopeptidase and 0.5-0.8 parts of ficin are added.

[0021] It can be understood that the aminopeptidase acts on the amino terminus of the peptide chain to decompose small-molecule nitrogen-containing peptides, and the ficin breaks the peptide bonds of macromolecular proteins. The combination of the two can cover protein components of different molecular weights, improving the efficiency of deproteinization. The use amount of 0.3-0.5 parts of aminopeptidase and 0.5-0.8 parts of ficin is based on the matching of enzyme activity and protein content in the latex. Under the optimized conditions of 45℃ and pH 7.5-8.0, this amount can effectively remove proteins without damaging the structure of rubber molecules.

[0022] The centrifugal concentration speed of the step (1) is 12000 r / min.

[0023] The electron beam dosage of the step (3) is 35 kGy.

[0024] The coagulant of the step (4) is 10% calcium nitrate solution.

[0025] The drying process of the step (4) is hot air drying at 105 DEG C for 3 minutes.

[0026] It can be understood that, by the boiling point of water, the water in the latex can be quickly vaporized, and the curing of the glue film is accelerated. The temperature does not exceed the thermal stability range of the polymer in the composite latex, so that the molecular chain is not broken or the additive is not decomposed, and the structural integrity of the glue film is ensured. The time setting of 3 minutes can ensure that the free water in the base layer and the outer layer of the glue film is fully evaporated, and can prevent the glue film from being brittle due to excessive water loss, maintain its flexibility and mechanical properties, and the hot air circulation can also ensure that the surface temperature of the mold is uniform, so that the drying rate of each part of the glue film is consistent, and the cracks or bubbles caused by uneven local shrinkage are reduced, and a stable glue film foundation is provided for subsequent edge curling and standing.

[0027] The standing time after the step (4) is 1-3 min.

[0028] The wavelength of the ultraviolet lamp of the step (6) is 365 nm.

[0029] Therefore, the present application has at least the following beneficial effects: 1. The present application uses a 200-mesh screen to intercept bark chips, coarse fibers and other mechanical impurities in the juice, blocks the residual protein allergen carried by the impurities, then adds potassium laurate and sodium dodecyl sulfate as an anionic surfactant, uniformly disperses the rubber particles through emulsification, creates a homogeneous environment for enzymatic reaction, and uses the synergistic effect of aminopeptidase and ficin for the deproteinization core link. The aminopeptidase targets the small peptide segment at the amino terminal of the peptide chain, and the ficin specifically breaks the hydrophobic peptide bond of macromolecular protein, specifically decomposes the soluble protein allergen in the latex, and the KOH solution adjusts the pH at the same time. OH -The hydrogen bond structure of the protein is destroyed to strengthen the enzymolysis, the addition of acetic acid makes the enzyme denature and inactivate in the acidic environment, the reaction is accurately terminated and the over-hydrolysis of the protective protein of the rubber particle is avoided, the vacuum distillation selectively removes the free ammonia and small molecule protein degradation products in the low pressure environment, avoids the thermal degradation of the rubber molecules, adds gingerol, the phenolic hydroxyl group of which is combined with the residual protein to close the sensitization site, and realizes physical sterilization through electron beam irradiation, replaces the traditional chemical sterilizing agent, avoids harmful chemical residues such as sulfides and accelerators, adopts the polyurethane-based multifunctional coating for surface packaging, forms a dense barrier layer, further blocks the migration of potential trace allergens, and titanium dioxide gives antibacterial performance, reduces the secondary pollution risk caused by the breeding of microorganisms, thereby significantly reduces the allergy risk of medical examination gloves and improves the biological safety; 2. The present application reduces the brittleness of the protein residue on the film structure by directed decomposition of the protein in the latex by aminopeptidase and ficin, and improves the dry rubber concentration by centrifugal concentration to form a more dense molecular network, which enhances the basic strength, and the stable nanocomposite formed by ultrasonic dispersion of graphene and hexagonal boron nitride has ultra-high specific surface area and breaking strength to construct a three-dimensional reinforced skeleton in the polylactic acid carrier, after mixing with low ammonia deproteinized latex, the deep crosslinking is induced by electron beam irradiation, which significantly improves the tensile strength, tear resistance and elastic modulus of the latex, the secondary gradient impregnation process combined with 105 DEG C hot air drying ensures the thickness uniformity through layered curing, avoids interface defects, optimizes the overall structural integrity, and the polyurethane-titanium dioxide coating forms a dense surface protective layer by electrostatic spraying, the titanium dioxide particles are dispersed in the polyurethane matrix, which not only provides antibacterial properties, but also further improves the surface hardness and wear resistance through the rigid particle reinforcement effect, and ultraviolet curing strengthens the bonding force between the coating and the substrate, reduces mechanical wear during use, thereby improving the tensile strength and anti-puncture tear strength of the medical examination gloves; 3. The present invention uses aminopeptidase and ficin to directionally decompose the allergenic protein in the latex, reducing the irritation of the residual protein to the skin while retaining the flexible network structure of the natural latex. The vacuum distillation deamination and the addition of gingerol to replace the traditional high-ammonia preservation system significantly reduce alkaline irritation and improve biocompatibility. Glycerol is added as a plasticizer to the polylactic acid dispersion to enhance the flexibility and hand comfort of the composite material. N-octyl-N-trimethyl chitosan is introduced to form a lubricating layer on the latex surface through its cationic properties, and electron beam irradiation is used to induce deep crosslinking of the molecular chains, thereby improving the biocompatibility. While improving strength, the elastic modulus is optimized, making the gloves fit the hand movements better and less prone to fatigue. A secondary gradient dipping process is combined with layered curing control of 105°C hot air drying for 3 minutes to ensure thickness uniformity and avoid local hardening, giving the gloves both overall strength and fingertip flexibility. The polyurethane-glycerin coating is formed into a micron-level thin film through electrostatic spraying. The high elasticity of polyurethane and the plasticizing effect of glycerin synergistically give the surface a silky touch, while UV curing strengthens the bonding between the coating and the substrate, avoiding the foreign body sensation caused by delamination, ultimately achieving a significant improvement in the wearing comfort of medical examination gloves. 4. The present invention removes water-soluble proteins from rubber latex by deproteinization, reduces the generation of free amino acids, slows down the aging rate of rubber molecules, and reduces the risk of biodegradation caused by protein residues, thereby prolonging the stability of the substrate. Gingerol is added, which has antioxidant properties and can capture free radicals generated during the oxidation process of rubber, inhibit the oxidative fracture of rubber molecular chains, and delay the aging of the substrate. At the same time, graphene and hexagonal boron nitride are used as nano-reinforced phases to improve the mechanical properties of the rubber substrate through the nano-filling effect, reducing the risk of tensile fracture during use. Polylactic acid is used as an interfacial compatibilizer to improve the interfacial bonding force between graphene and hexagonal boron nitride and the rubber matrix, avoiding local stress concentration caused by nanoparticle agglomeration, and preventing cracks caused by stress concentration during use. N-octyl-N-trimethyl chitosan has both antibacterial properties and compatibility, can inhibit the growth of microorganisms on the surface of the gloves, slow down the degradation rate of rubber, and strengthen the rubber. The interfacial interaction between molecules and nanofillers improves overall toughness. 2,6-di-tert-butyl-p-cresol is a phenolic antioxidant that blocks the auto-oxidation chain reaction of rubber by capturing free radicals. Under the friction-generated heat environment of repeated use, it delays the hardening and cracking of rubber due to oxidation. Electron beam irradiation can induce cross-linking of rubber molecular chains, increase the cross-linking density of latex, enhance the material's fatigue resistance and solvent resistance, and reduce the swelling damage of chemical reagents to rubber. Multi-layer coating reduces damage caused by excessive local force during use. Polyurethane has high wear resistance and elasticity. As a surface coating, it can directly withstand friction and reduce direct wear of the rubber substrate. At the same time, the chemical resistance of polyurethane can block the erosion of sweat, oil, etc. on rubber. Titanium dioxide has both photocatalytic and antibacterial properties. The photocatalytic effect can decompose organic pollutants attached to the surface and reduce the corrosion of pollutants on the coating, thereby increasing the service life of medical examination gloves. 5.The application decomposes the protein in natural latex by aminopeptidase and ficin, reduces the residual of refractory protein, replaces the traditional high-ammonia preservation system with gingerol to reduce the inhibition of nitrogen compounds on microbial degradation, introduces polylactic acid as a biodegradable carrier, the ester bond structure can be hydrolyzed to lactic acid by microbial lipase and further mineralized to carbon dioxide and water in the natural environment, significantly improving the biodegradation rate of the matrix material, adding N-octyl-N-trimethyl chitosan to enhance the hydrophilicity by quaternary ammonium salt modification, promoting microbial adhesion and secreting chitosanase to accelerate molecular chain rupture, titanium dioxide excites photocatalytic activity under ultraviolet irradiation to produce reactive oxygen to attack C-C and C-N bonds in the polyurethane coating, realizing the oxidative chain scission of the polymer chain, and forming a degradable network with polylactic acid, in addition, electron beam irradiation replaces the traditional sulfur vulcanization process to avoid the chemical stability of sulfur crosslinking bonds hindering degradation, making the crosslinking structure more susceptible to biological enzymatic hydrolysis, and finally realizing the controllable biodegradation and environmental compatibility of the glove after being discarded. BRIEF DESCRIPTION OF DRAWINGS

[0030] The above and / or additional aspects and advantages of the present application will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which: Figure 1 A process flow chart of a preparation method of a low-ammonia deproteinized latex medical examination glove according to an embodiment of the present application; Figure 2 A glove cross-sectional structure schematic diagram of a preparation method of a low-ammonia deproteinized latex medical examination glove according to an embodiment of the present application; Figure 3 A characteristic diagram of the influence of electron beam radiation dose on tensile strength of a preparation method of a low-ammonia deproteinized latex medical examination glove according to an embodiment of the present application; Figure 4 A characteristic diagram of the influence of N-octyl-N-trimethyl chitosan on compost degradation rate of a preparation method of a low-ammonia deproteinized latex medical examination glove according to an embodiment of the present application. DETAILED DESCRIPTION

[0031] The technical solutions of the present application are described below through specific specific examples. It should be understood that the one or more method steps mentioned in the present application do not exclude the existence of other method steps before and after the described combination steps or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are only used to illustrate the present application and not to limit the scope of the present application. Moreover, unless otherwise stated, the numbering of each method step is only a convenient tool to identify each method step, and is not a limitation on the arrangement order or a limitation on the scope of the present application that can be implemented. The change or adjustment of the relative relationship, without substantially changing the technical content, is also regarded as the scope of the present application that can be implemented.

[0032] For a better understanding of the above technical solutions, the exemplary embodiments of the present application are described in more detail below. Although the exemplary embodiments of the present application are shown, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided so that the present application can be more thoroughly and completely conveyed to those skilled in the art, and the scope of the present application can be fully conveyed to those skilled in the art.

[0033] The rubber tree juice used in the embodiments of the present application is from Hebei Derixin Material Technology Co., Ltd.; the potassium laurate used is from Shanghai Haohong Biological Medicine Technology Co., Ltd.; the sodium dodecyl sulfate used is from Qingdao Gangliwei Import and Export Co., Ltd.; the aminopeptidase used is from Beijing Bailingwei Technology Co., Ltd.; the ficin used is from Hebei Zhongfeng Technology Co., Ltd.; the acetic acid used is from Shanghai Aladdin Bio-Chem Technology Co., Ltd.; the gingerol used is from Chengdu Bishang Biological Technology Co., Ltd.; the graphene used is from Zhejiang Yame Nanometer Technology Co., Ltd.; the ethanol used is from Shanghai Aladdin Bio-Chem Technology Co., Ltd.; the polylactic acid used is from Beijing Thompson Biological Technology Co., Ltd.; the N-octyl-N-trimethyl chitosan used is from Shanghai Maclin Biochemical Technology Co., Ltd.; the polyurethane used is from Hubei Xinkang Pharmaceutical Chemical Co., Ltd.; the 2, 6-di-tert-butyl-p-cresol used is from Shandong Bosiwen New Material Co., Ltd.; the titanium dioxide used is from Jinan Ruiyao Mingzhi Medical Technology Co., Ltd.; the glycerol used is from Taishan Changshun Glycerin Products Co., Ltd.; and the ammonia water used is from Shanghai Maclin Biochemical Technology Co., Ltd.

[0034] A low-ammonia deproteinized latex medical examination glove and a preparation method thereof are described below with reference to the accompanying drawings. In view of the high allergenicity and poor wearing comfort of the low-ammonia deproteinized latex medical examination glove mentioned in the background art, the present application provides a preparation method of a low-ammonia deproteinized latex medical examination glove. The rubber tree sap is filtered through a 200-mesh screen to remove bark debris and allergenic protein carriers. Potassium laurate and sodium dodecyl sulfate are added to homogeneously disperse the rubber particles through emulsification, creating a stable environment for enzymatic hydrolysis. The N-terminal small peptide segment of the peptide chain is hydrolyzed by targeting the aminopeptidase. The protease breaks the hydrophobic peptide bond, efficiently decomposes the allergen, and adds acetic acid in the termination stage to inactivate the enzyme activity precisely, avoiding excessive hydrolysis of protective proteins. Centrifugal concentration is used to increase the dry rubber content, forming a dense molecular network. Vacuum distillation is used to remove free ammonia and degradation products, avoiding high-temperature damage to the rubber chain. Gingerol is added to replace the high-ammonia system, and its phenolic hydroxyl group blocks the residual protein allergenic site and inhibits oxidation and aging. Polylactic acid is added as a biodegradable carrier, and its ester bond can be hydrolyzed and mineralized by microbial lipase. Glycerol is added to improve flexibility. Graphene and hexagonal boron nitride are added to improve tear resistance. N-octyl-N-trimethyl chitosan is added to form a hydrophilic lubricating layer with its quaternary ammonium salt structure, promoting microbial adhesion and accelerating degradation. 2,6-Di-tert-butyl-p-cresol is added to capture free radicals, and electron beam irradiation is used to initiate C-C covalent crosslinking, increasing the crosslinking density and avoiding sulfur residues. Latex impregnation thickens the main body, and hot air drying is used to avoid interface defects. Polyurethane-glycerol forms a micron-sized high-elasticity film, and ultraviolet strengthening of the coating improves adhesion. Titanium dioxide photocatalysis produces active oxygen to break the polyurethane molecules, while also improving surface hardness and inhibiting bacteria. Thus, the problems of high allergenicity, poor mechanical strength, difficulty in degradation, and poor wearing comfort of the low-ammonia deproteinized latex medical examination glove are solved.

[0035] A low-ammonia deproteinized latex medical examination glove and a preparation method thereof are described below with reference to the accompanying drawings.

[0036] Specifically, Figure 1 A flowchart of the preparation method of the low-ammonia deproteinized latex medical examination glove provided in the present application is shown.

[0037] As Figure 1 shown, the preparation method of the low-ammonia deproteinized latex medical examination glove includes the following steps: In step S101, 1800-1900 parts of rubber tree sap are sieved, 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate are added, stirred for 30 minutes, aminopeptidase and ficin are added, 6-7 parts of 10% KOH solution is added, stirred at 50 r / min at 45°C for 6h, the pH is adjusted to 7.5-8.0, 1% acetic acid 19-20 parts is added to terminate the enzymatic hydrolysis, centrifugal concentration is used to increase the dry rubber content to 60%, vacuum distillation is used to remove free ammonia and degradation products, and gingerol is added to replace the high-ammonia system, and its phenolic hydroxyl group blocks the residual protein allergenic site and inhibits oxidation and aging. Polylactic acid is added as a biodegradable carrier, and its ester bond can be hydrolyzed and mineralized by microbial lipase. Glycerol is added to improve flexibility. Graphene and hexagonal boron nitride are added to improve tear resistance. N-octyl-N-trimethyl chitosan is added to form a hydrophilic lubricating layer with its quaternary ammonium salt structure, promoting microbial adhesion and accelerating degradation. 2,6-Di-tert-butyl-p-cresol is added to capture free radicals, and electron beam irradiation is used to initiate C-C covalent crosslinking, increasing the crosslinking density and avoiding sulfur residues. Latex impregnation thickens the main body, and hot air drying is used to avoid interface defects. Polyurethane-glycerol forms a micron-sized high-elasticity film, and ultraviolet strengthening of the coating improves adhesion. Titanium dioxide photocatalysis produces active oxygen to break the polyurethane molecules, while also improving surface hardness and inhibiting bacteria. Thus, the problems of high allergenicity, poor mechanical strength, difficulty in degradation, and poor wearing comfort of the low-ammonia deproteinized latex medical examination glove are solved.

[0038] The screen mesh is 200 mesh, the vacuum distillation conditions are 60°C and 0.1 MPa, the amount of added aminopeptidase is 0.3-0.5 parts, the amount of added ficin is 0.5-0.8 parts, and the centrifugal concentration rotation speed is 12000 r / min.

[0039] It can be understood that, in the present application, the impurities in the rubber tree latex are removed by screening to purify the raw material, potassium laurate and sodium dodecyl sulfate are used as surfactants to stabilize the latex particles through emulsification and dispersion, prevent coagulation, and aminopeptidase and ficin are used to hydrolyze the proteins in the latex to achieve deproteinization under the conditions of a suitable temperature of 45°C, a basic pH of 7.5-8.0, and stirring to promote contact, 10% KOH solution is used to adjust the pH to provide an alkaline environment for enzymolysis, 1% acetic acid is used to change the pH to inactivate the enzyme to terminate the reaction, centrifugation is used to separate and concentrate by centrifugal force, vacuum distillation is used to remove water under low pressure to make the dry rubber content reach 60%, and gingerol is used as a stabilizer to improve the stability of the low-ammonia deproteinized latex.

[0040] Specifically, the mechanical impurities such as bark chips are removed by filtering through a screen, then 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate are added as anionic surfactants, and the rubber particles are uniformly emulsified by stirring for 30 minutes, then aminopeptidase and ficin are added for synergistic enzymolysis, the aminopeptidase targets small peptide segments at the N-terminal of the peptide chain, and the ficin breaks the hydrophobic peptide bond to jointly decompose the soluble allergen proteins in the latex, 10% KOH solution is added at 45°C and 50 r / min for 6 hours, OH - The hydrogen bond structure of the protein is destroyed to strengthen the enzymolysis efficiency, the pH is adjusted to 7.5-8.0 to maintain the reaction environment, 1% acetic acid is added to precisely inactivate the enzyme activity in an acidic environment to avoid excessive hydrolysis of the protective protein layer; then the dry rubber content is increased to 60% by centrifugal concentration to form a dense molecular network, and the free ammonia and small molecule degradation products are selectively removed by vacuum distillation to avoid damage to the rubber molecular chain at high temperature, finally 0.5 parts of gingerol is added, the phenolic hydroxyl group of which closes the residual protein allergen sites and inhibits oxidation and aging, and a low-ammonia deproteinized latex is obtained.

[0041] In step S102, graphene 0.05-0.1 parts and hexagonal boron nitride 0.05-0.1 parts are ultrasonically treated in an ethanol solution, polylactic acid 15-20 parts and glycerol 3 parts are added, and stirring is performed in a 60°C water bath for 2 hours to form a graphene-polylactic acid dispersion.

[0042] It can be understood that, in the embodiment of the application, ethanol is used as a polar solvent to provide a dispersion medium for graphene and hexagonal boron nitride, ultrasonic treatment uses mechanical vibration and local high temperature and high pressure generated by cavitation effect to break the agglomeration structure of graphene and hexagonal boron nitride, so that the graphene and hexagonal boron nitride are uniformly dispersed in ethanol, heating in a 60℃ water bath improves the energy of the system, promotes swelling of polylactic acid, and enhances the interfacial affinity of polylactic acid and nanoparticles, glycerol is used as a plasticizer to increase the flexibility and flowability of polylactic acid by reducing the intermolecular force of polylactic acid, which is beneficial to wrapping nanoparticles, and stirring further promotes mixing of the components by mechanical shear force, so that polylactic acid molecules are adsorbed on the surface of graphene and hexagonal boron nitride to form a stable graphene-polylactic acid dispersion, and the nanoparticles are prevented from re-agglomerating.

[0043] Specifically, graphene and hexagonal boron nitride are dispersed in an ethanol solution together, the nanomaterials are fully exfoliated and uniformly dispersed by ultrasonic treatment to form a stable suspension, then polylactic acid is added as a matrix material, the molecular chains of which are initially unfolded by ethanol swelling, and glycerol is added as a plasticizer to improve interfacial compatibility, the mixed system is placed in a 60℃ water bath environment, and the reaction is continuously carried out at a mechanical stirring speed of 200-400 r / min for 2 hours. In this process, the polylactic acid molecular chains are combined with graphene / h-BN nanosheets through hydrogen bonds and van der Waals forces to form a three-dimensional network structure, and the glycerol is inserted between the polylactic acid molecular chains to reduce the crystallinity and enhance the flexibility. Finally, a graphene-polylactic acid dispersion is obtained.

[0044] In step S103, the low ammonia deproteinized latex 1000 parts is mixed with the graphene-polylactic acid dispersion at 60℃, N-octyl-N-trimethyl chitosan 0.8-1.2 parts is added, and stirring is carried out at 200 r / min for 2 hours, 2,6-di-tert-butyl-p-cresol 1 part is added, and electron beam irradiation is carried out for 30 minutes to obtain a composite latex.

[0045] The electron beam dose is 35 kGy.

[0046] It can be understood that, in the embodiment of the application, heating at 60℃ improves the molecular thermal motion ability, promotes uniform mixing of the low ammonia deproteinized latex and the graphene-polylactic acid dispersion, and enhances the interfacial compatibility, N-octyl-N-trimethyl chitosan is used as a modified chitosan to interact with the components of the latex and the dispersion through its polar groups, improve the compatibility, and stabilize the system, 200 r / min stirring promotes full dispersion and fusion of the components through shear force to form a uniform mixed system, 2,6-di-tert-butyl-p-cresol is used as an antioxidant to inhibit oxidative degradation of the latex components by capturing free radicals, electron beam irradiation uses high-energy particles to initiate intermolecular crosslinking reaction to form a stable three-dimensional network structure, enhance the mechanical properties and stability of the composite latex, and at the same time has a sterilization effect.

[0047] Specifically, the low-ammonia deproteinized latex is mixed with the graphene-polylactic acid dispersion prepared by ultrasonic dispersion and water bath stirring at 60°C, and then N-octyl-N-trimethyl chitosan is added as an amphiphilic modifier. The quaternary ammonium salt structure forms a hydrophilic lubricating layer on the surface of the latex through cationic properties, and promotes the interfacial compatibility of the nanofiller and the rubber matrix. The mixing system is continuously reacted for 2 hours at a mechanical stirring speed of 200 r / min, so that the components are fully and uniformly dispersed and a stable three-dimensional network structure is formed. Then 2,6-di-tert-butyl-p-cresol is added as a phenolic antioxidant to inhibit the oxidative degradation of the rubber molecular chain by capturing free radicals. Finally, electron beam irradiation is used to initiate C-C covalent crosslinking between the rubber molecular chain and the nanofiller, replacing the traditional sulfur vulcanization process, which improves the crosslinking density of the material while avoiding the residue of sulfides, and makes the crosslinking structure more easily biodegraded. Finally, a composite latex with high strength, high elasticity and environmental compatibility is obtained.

[0048] In step S104, after the ceramic mold is plasma cleaned, a coagulant is immersed, dried at 90°C, and the mold is immersed in 30% content composite latex at 25°C for 5 seconds to form a 0.05mm base layer, dried, immersed in 50% content composite latex at 30°C for 10 seconds, dried, and after edge rolling, the latex glove base is obtained.

[0049] Wherein, the coagulant is 10% calcium nitrate solution, the drying process is hot air drying at 105°C for 3 minutes, and the standing time after edge rolling is 1-3min.

[0050] It can be understood that the embodiments of the present application use high-energy plasma to remove impurities from the surface of the ceramic mold and activate the surface through plasma cleaning, thereby enhancing the adhesion of the subsequent substances. The coagulant is immersed to make the rubber particles in the latex dehydrate and coagulate through penetration, and the coagulant coating is fixed by drying at 90°C to provide a basis for latex film formation. The latex is quickly coagulated to form a thin base layer under the action of the coagulant by immersing in 30% composite latex at 25°C for a short time and at low concentration. The structure is fixed by removing water during drying, the latex fluidity is accelerated at a slightly higher temperature of 30°C, and the latex is further coagulated on the base layer to form a thicker outer layer by immersing in 50% high-concentration latex for a longer time, thereby improving the thickness and strength of the glove. The edge structure is shaped by mechanical action during edge rolling to facilitate wearing, and the latex film is fully cured and shaped by standing to ensure the stability of the structure of the latex glove base.

[0051] Specifically, the ceramic mold is subjected to plasma cleaning to remove surface contaminants and improve surface activity, then the mold is immersed in a coagulant to form an ion cross-linking layer, and is dried at 90°C to fix the coagulant coating, then the mold is immersed in a 30% content of composite latex at 25°C ambient temperature for 5 seconds to form a uniform base layer with a thickness of 0.05mm, the thin layer provides good fit and fingertip flexibility after drying and curing, then secondary dipping is carried out at 30°C, the mold is immersed in a 50% content of composite latex for 10 seconds to thicken the main structure, after drying, the layered curing ensures close interlayer bonding and no interface defects, finally, the formed glove is subjected to edge rolling treatment to enhance the edge strength, and is left to stand for 1-3 minutes to release internal stress, finally, a latex glove substrate with complete structure and optimized mechanical properties is obtained.

[0052] In step S105, polyurethane emulsion 50-60 parts, titanium dioxide dispersion liquid 10-15 parts, glycerol 3 parts are mixed, and ammonia water 1.5 parts is added to adjust the pH to 7.0-7.5 to obtain a multifunctional coating liquid.

[0053] It can be understood that the polyurethane emulsion is used as a film-forming base material in the embodiments of the present application to provide the coating liquid with basic film-forming property and flexibility, the titanium dioxide particles in the titanium dioxide dispersion liquid can endow the coating liquid with functionality through photocatalytic property and light shielding property, the dispersion liquid form ensures uniform distribution, glycerol is used as a plasticizer to increase the flexibility of the coating layer by weakening the intermolecular force and reduce brittleness, and ammonia water is used as an alkaline adjusting agent to adjust the pH to the neutral to slightly alkaline range of 7.0-7.5, which can maintain the colloidal stability of the polyurethane emulsion and the titanium dioxide dispersion liquid, avoid demulsification and coagulation under acidic or strong alkaline conditions, ensure uniform mixing of the components, form a stable multifunctional coating liquid, and facilitate subsequent coating operation.

[0054] Specifically, the polyurethane emulsion is used as a basic film-forming material, mixed with the titanium dioxide dispersion liquid, and the titanium dioxide is uniformly dispersed in the polyurethane matrix through mechanical stirring to form a preliminary composite system, then glycerol is added as a plasticizer to improve the flexibility and adhesion of the coating layer, and finally ammonia water is added to adjust the pH to the weak alkaline range of 7.0-7.5, neutralize the acidic groups in the polyurethane emulsion, ensure the stability of the system and avoid side reactions in the subsequent curing process, the photocatalytic activity of titanium dioxide can endow the coating layer with antibacterial property and ultraviolet shielding function, and the interface bonding between polyurethane and titanium dioxide is optimized through the pH environment adjusted by ammonia water, finally a coating liquid with uniform dispersibility, suitable viscosity and functionality is formed, which is suitable for subsequent electrostatic spraying process.

[0055] In step S106, the latex glove substrate is preheated to 50°C, electrostatically sprayed with the multifunctional coating liquid twice with an interval of 5 minutes for curing, and subjected to 80°C hot air circulation for 15 minutes and ultraviolet lamp irradiation for 10 minutes to obtain a modified latex glove with a multifunctional coating layer.

[0056] The wavelength of the ultraviolet lamp is 365 nm.

[0057] It can be understood that the latex glove substrate is preheated to 50°C in the embodiment of the application, the wettability and adhesion with the multifunctional coating liquid are enhanced by increasing the surface temperature, which is beneficial to uniform spreading of the coating layer. The electrostatic spraying utilizes the electrostatic adsorption effect to make the charged coating liquid particles directional adsorption on the grounded glove surface, realizing uniform and efficient adhesion of the coating layer. The interval of 5 minutes solidification allows the coating layer to be preliminarily dried and shaped after the first spraying, avoiding coating mixing and flowing during secondary spraying, ensuring the stability of the layered structure, and the 80°C hot air circulation accelerates the evaporation of solvents in the coating liquid by heating, promotes the crosslinking of polyurethane molecules to form a film, enhances the bonding strength of the coating layer and the substrate, the ultraviolet lamp irradiation activates the photocatalytic performance of titanium dioxide, strengthens its antibacterial, anti-ultraviolet and other functions, and at the same time promotes the further curing of the coating layer, and improves the weather resistance and surface activity.

[0058] Specifically, the latex glove substrate is preheated to 50°C to enhance the adhesion of the coating layer, and then the multifunctional coating liquid prepared by mixing polyurethane emulsion 60 parts, titanium dioxide dispersion liquid 10-15 parts, glycerol 3 parts and ammonia water 1.5 parts to adjust the pH to 7.0-7.5 is applied twice by electrostatic spraying process, the spraying parameters include electrostatic voltage 60-90 kV, distance between spray gun and workpiece 150-300 mm, atomization pressure 0.30-0.45 MPa, the negatively charged coating particles are uniformly adsorbed to the surface of the substrate by high-voltage electrostatic field, the coating layer is leveled and partially crosslinked after each spraying interval of 5 minutes, then the coating layer is deeply solidified and the residual solvent is evaporated by 80°C hot air circulation for 15 minutes, finally, a multifunctional coating layer with antibacterial, wear-resistant and comfortable properties is formed by irradiating a 365 nm wavelength ultraviolet lamp for 10 minutes to excite the photocatalytic activity of titanium dioxide and further solidify the polyurethane molecular chain.

[0059] The application provides a preparation method of a low-ammonia deproteinized latex medical examination glove, wherein rubber tree sap is filtered through a 200-mesh screen to remove bark debris and allergen protein carriers, potassium laurate and sodium dodecyl sulfate are added, rubber particles are uniformly dispersed through emulsification to create a stable environment for enzymolysis, aminopeptidase targets and hydrolyzes small peptide segments at the N-terminal of a peptide chain, ficin breaks hydrophobic peptide bonds to efficiently decompose allergens, acetic acid is added in the termination stage to accurately inactivate enzyme activity, to avoid excessive hydrolysis of protective proteins, centrifugal concentration is performed to increase the dry rubber content, to form a dense molecular network, vacuum distillation is performed to remove free ammonia and degradation products, to avoid damage to rubber chains caused by high temperature, gingerol is added to replace a high-ammonia system, the phenolic hydroxyl groups of the gingerol close residual protein allergen sites and inhibit oxidation and aging, polylactic acid is added as a biodegradable carrier, the ester bonds of the polylactic acid can be hydrolyzed and mineralized by microbial lipase, glycerol is added to improve flexibility, graphene and hexagonal boron nitride are added to improve tear resistance, N-octyl-N-trimethyl chitosan is added, the quaternary ammonium salt structure of the N-octyl-N-trimethyl chitosan forms a hydrophilic lubricating layer, to promote microbial adhesion and accelerate degradation, 2,6-di-tert-butyl-p-cresol is added to capture free radicals, electron beam irradiation is performed to initiate C-C covalent crosslinking, to improve crosslinking density and avoid sulfur residues, the latex is impregnated to thicken the main body, hot air drying is combined to avoid interface defects, polyurethane-glycerol forms a micron-sized high-elasticity film, ultraviolet strengthening is used to improve the adhesion of the coating, titanium dioxide is used for photocatalysis to produce active oxygen to break the polyurethane molecules, and the surface hardness is improved and bacteria are inhibited. Therefore, the problems of high allergenicity, poor mechanical strength, poor degradation, poor wearing comfort and the like of the low-ammonia deproteinized latex medical examination glove are solved.

[0060] A preparation method of a low-ammonia deproteinized latex medical examination glove according to the application will be described below through specific examples, including the following steps:

[0061] Example 1 The application provides a low-ammonia deproteinized latex medical examination glove, which is composed of modified low-ammonia deproteinized latex, graphene-polylactic acid reinforced dispersion, functional additives and a surface functional coating.

[0062] The application also provides a preparation method of a low-ammonia deproteinized latex medical examination glove, including the following steps: (1) 1800 parts of rubber tree sap are sieved, 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate are added, stirring is performed for 30 minutes, aminopeptidase and ficin are added, 6 parts of 10% KOH solution is added, stirring is performed at 50 r / min at 45°C for 6 hours, the pH is adjusted to 7.5, 19 parts of 1% acetic acid is added to terminate the enzymolysis, centrifugal concentration is performed to a dry rubber content of 60%, vacuum distillation is performed, and 0.5 parts of gingerol is added to obtain low-ammonia deproteinized latex; (2) graphene 0.05 parts and hexagonal boron nitride 0.05 parts are ultrasonically treated in an ethanol solution, polylactic acid 15 parts and glycerol 3 parts are added, and stirring is performed in a 60°C water bath for 2 hours to form a graphene-polylactic acid dispersion; (3) low ammonia deproteinized latex 1000 parts and the graphene-polylactic acid dispersion are mixed at 60°C, N-octyl-N-trimethyl chitosan 0.8 parts is added, stirring is performed at 200 r / min for 2 hours, 2,6-di-tert-butyl-p-cresol 1 part is added, and electron beam irradiation is performed for 30 minutes to obtain a composite latex; (4) after the ceramic mold is plasma cleaned, a coagulant is immersed, and drying is performed at 90°C; the mold is immersed in the composite latex with a content of 30% for 5 seconds at 25°C to form a 0.05mm base layer, drying is performed, the mold is immersed in the composite latex with a content of 50% for 10 seconds at 30°C, drying is performed, and a modified latex glove with a multifunctional coating is obtained after edge rolling and standing, as shown in (5) polyurethane emulsion 50 parts, titanium dioxide dispersion liquid 10 parts, and glycerol 3 parts are mixed, ammonia water 1.5 parts is added to adjust the pH to 7.0 to obtain a multifunctional coating liquid; (6) the latex glove base is preheated to 50°C, and the multifunctional coating liquid is electrostatically sprayed twice with an interval of 5 minutes for curing, hot air circulation is performed at 80°C for 15 minutes, and ultraviolet lamp irradiation is performed for 10 minutes to obtain a modified latex glove with a multifunctional coating, as shown in Figure 2 .

[0063] In the step (1), a 200-mesh sieve is used for screening, and the vacuum distillation conditions are 60°C and 0.1MPa.

[0064] In the step (1), 0.3 parts of aminopeptidase and 0.5 parts of ficin are added.

[0065] In the step (1), the centrifugal concentration speed is 12000r / min.

[0066] In the step (3), the electron beam dose is 35kGy.

[0067] In the step (4), the coagulant is a 10% calcium nitrate solution.

[0068] In the step (4), the drying process is hot air drying at 105°C for 3 minutes.

[0069] In the step (4), the standing time after edge rolling is 3 minutes.

[0070] In the step (6), the wavelength of the ultraviolet lamp is 365nm.

[0071] The low-ammonia deproteinized latex medical examination gloves of Example 1 are tested for puncture resistance and tensile / tear properties by an intelligent electronic tensile tester, evaluated for antibacterial rate of titanium dioxide coating against E. coli and S. aureus according to ISO22196, determined for service life extension effect by laboratory simulation and accelerated aging test, measured for 4-month degradation rate by CO2 release amount at 58±2°C by composting method, quantified for surface wear resistance by a standard friction tester, and specifically detected for allergen protein residual amount by inhibition ELISA, to obtain specific performance parameters of the medical examination gloves of Example 1, the values of which are compared with those of ordinary medical examination gloves, as shown in Table 1:

[0072] Example 1 greatly removes allergens and ammonia in the latex by adding aminopeptidase and ficin, improves the tensile strength and puncture resistance of the gloves by adding graphene and hexagonal boron nitride, and improves the compost degradation rate of the gloves and reduces the aging rate of the gloves by adding polylactic acid and N-octyl-N-trimethyl chitosan.

[0073] Example 2 The application provides a low-ammonia deproteinized latex medical examination glove.

[0074] The application also provides a preparation method of the low-ammonia deproteinized latex medical examination glove, which comprises the following steps: (1) 1800 parts of rubber tree juice are sieved, 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate are added, stirring is performed for 30 minutes, aminopeptidase and ficin are added, 6 parts of 10% KOH solution are added, stirring is performed at 50 r / min at 45°C for 6 hours, the pH value is adjusted to 7.5, 19 parts of 1% acetic acid are added to terminate enzyme hydrolysis, and the low-ammonia deproteinized latex is obtained by centrifugal concentration to a dry rubber content of 60% and vacuum distillation with the addition of 0.5 parts of gingerol; (2) graphene 0.06 parts and hexagonal boron nitride 0.06 parts are ultrasonically treated in an ethanol solution, polylactic acid 16 parts and glycerol 3 parts are added, and stirring is performed in a 60°C water bath for 2 hours to form a graphene-polylactic acid dispersion; (3) the low-ammonia deproteinized latex 1000 parts and the graphene-polylactic acid dispersion are mixed at 60°C, N-octyl-N-trimethyl chitosan 0.9 parts is added, stirring is performed at 200 r / min for 2 hours, 2,6-di-tert-butyl-p-cresol 1 part is added, and electron beam irradiation is performed for 30 minutes to obtain a composite latex; (4) After the ceramic mold is cleaned by plasma, dip coagulant, dry at 90℃, dip the mold into 5 seconds of 30% content of composite latex at 25℃, form 0.05mm base layer, dry, dip into 10 seconds of 50% content of composite latex at 30℃, dry, after edge rolling, get the modified latex glove with multifunctional coating. (5) Mix 52 parts of polyurethane emulsion, 12 parts of titanium dioxide dispersion, 3 parts of glycerol, add 1.5 parts of ammonia to adjust the pH to 7.0, and get multifunctional coating liquid. (6) Preheat the latex glove base to 50℃, use the multifunctional coating liquid to electrostatically spray twice, interval 5 minutes for curing, 80℃ hot air circulation for 15 minutes, ultraviolet lamp irradiation for 10 minutes, get the modified latex glove with multifunctional coating.

[0075] In step (1), the screening is selected by 200 mesh screen, and the vacuum distillation conditions are 60℃ and 0.1MPa.

[0076] In step (1), 0.3 parts of aminopeptidase and 0.5 parts of ficin are added.

[0077] In step (1), the centrifugal concentration speed is 12000r / min.

[0078] In step (3), the electron beam dose is 35kGy, as shown in Figure 3 .

[0079] In step (4), the coagulant is 10% calcium nitrate solution.

[0080] In step (4), the drying process is 105℃ hot air drying for 3 minutes.

[0081] In step (4), the standing time after edge rolling is 3 minutes.

[0082] In step (6), the wavelength of the ultraviolet lamp is 365nm.

[0083] The low ammonia deproteinized latex medical examination glove of Example 2 is tested for puncture resistance and tensile / tear resistance by an intelligent electronic tensile testing machine, the antibacterial rate of the titanium dioxide coating on Escherichia coli and Staphylococcus aureus is evaluated according to ISO22196, the service life extension effect is determined by laboratory simulation and accelerated aging test, the degradation rate is determined by CO2 release amount for 4 months at 58±2℃ by composting method, the surface wear resistance is quantified by using a standard friction tester, and the specific performance parameters of the medical examination glove of Example 2 are obtained by specific detection of allergen protein residual amount by inhibition ELISA method, and the values are compared with those of ordinary medical examination gloves, as shown in Table 2:

[0084] Example 2 improves the addition amount of graphene, hexagonal boron nitride and titanium dioxide, improves the tensile strength and puncture resistance of the glove, increases the sandpaper friction durability, increases the addition amount of N-octyl-N-trimethyl chitosan, polyurethane emulsion and polylactic acid, improves the compost degradation rate of the glove as shown in Figure 4 , and reduces the aging rate of the glove.

[0085] Example 3 The present application provides a low ammonia deproteinized latex medical examination glove, which is composed of modified low ammonia deproteinized latex, graphene-polylactic acid reinforced dispersion, functional additives and surface functional coating.

[0086] The present application also provides a preparation method of a low ammonia deproteinized latex medical examination glove, which comprises the following steps: (1) Sieve 1800 parts of rubber tree juice, add 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate, stir for 30 minutes, add aminopeptidase and ficin, add 7 parts of 10% KOH solution, stir at 50 r / min at 45°C for 6h, adjust the pH to 8.0, add 20 parts of 1% acetic acid to terminate the enzyme hydrolysis, centrifugal concentration to dry rubber content of 60%, vacuum distillation, add 0.5 parts of gingerol, and obtain low ammonia deproteinized latex; (2) Ultrasonic treatment of graphene 0.06 parts and hexagonal boron nitride 0.06 parts in ethanol solution, add polylactic acid 16 parts and glycerol 3 parts, 60°C water bath stirring for 2 hours, form graphene-polylactic acid dispersion; (3) Mix low ammonia deproteinized latex 1000 parts with graphene-polylactic acid dispersion at 60°C, add N-octyl-N-trimethyl chitosan 0.9 parts, stir at 200 r / min for 2 hours, add 2,6-di-tert-butyl-p-cresol 1 part, electron beam irradiation for 30 minutes, and obtain composite latex; (4) After plasma cleaning of the ceramic mold, immerse the coagulant, dry at 90°C, immerse the mold in the composite latex with a content of 30% for 5 seconds at 25°C, form a 0.05mm base layer, dry, immerse in the composite latex with a content of 50% for 10 seconds at 30°C, dry, and get the latex glove base after edge rolling and standing; (5) Mix polyurethane emulsion 52 parts, titanium dioxide dispersion liquid 12 parts and glycerol 3 parts, add ammonia water 1.5 parts to adjust the pH to 7.5, and obtain multifunctional coating liquid; (6) Preheat the latex glove base to 50°C, electrostatically spray the multifunctional coating liquid twice with an interval of 5 minutes for curing, circulate hot air at 80°C for 15 minutes, and irradiate under ultraviolet lamp for 10 minutes, and obtain modified latex glove with multifunctional coating.

[0087] The step (1) is screened by using a 200-mesh sieve, and the vacuum distillation condition is 60 DEG C and 0.1 MPa.

[0088] The step (1) adds 0.3 parts of aminopeptidase and 0.5 parts of ficin.

[0089] The step (1) is centrifuged at a speed of 12000 r / min.

[0090] The step (3) is performed at an electron beam dose of 35 kGy.

[0091] The step (4) uses 10% calcium nitrate solution as a coagulant.

[0092] The step (4) is dried at 105 DEG C for 3 minutes.

[0093] The step (4) is placed for 3 minutes after the edge is rolled.

[0094] The step (6) uses a UV lamp with a wavelength of 365 nm.

[0095] The low-ammonia deproteinized latex medical examination glove of Example 3 is tested for puncture resistance and tensile / tear properties by an intelligent electronic tensile testing machine, the antibacterial rate of the titanium dioxide coating on E. coli and S. aureus is evaluated according to ISO22196, the service life extension effect is determined by laboratory simulation and accelerated aging test, the degradation rate is determined by the amount of CO2 released at 58±2 DEG C for 4 months by the composting method, the surface wear resistance is quantified by using a standard friction tester, and the specific amount of allergenic protein residues is specifically detected by the inhibition ELISA method, so as to obtain the specific performance parameters of the medical examination glove of Example 3, and the values are compared with those of the ordinary medical examination glove, as shown in Table 3:

[0096] Compared with Example 2, the amount of 10% KOH solution is increased, the pH is adjusted to 8.0, the amount of acetic acid is increased, the allergic risk of the glove is reduced, the sandpaper friction durability is improved, the amount of ammonia is increased, the antibacterial durability and composting degradation rate are improved, and the aging rate is reduced.

[0097] Example 4 The application provides a low-ammonia deproteinized latex medical examination glove.

[0098] The application also provides a preparation method of the low-ammonia deproteinized latex medical examination glove, which comprises the following steps: (1) Rubber tree juice 1800 parts, sieve, add 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate, stir for 30 minutes, add aminopeptidase and ficin, add 7 parts of 10% KOH solution, stir at 45℃ for 6h at 50r / min, adjust pH to 8.0, add 20 parts of 1% acetic acid to terminate the enzymatic hydrolysis, centrifugal concentration to dry rubber content 60%, vacuum distillation, add 0.5 parts of gingerol, get low ammonia deproteinized latex; (2) Ultrasonic treatment of graphene 0.1 parts and hexagonal boron nitride 0.1 parts in ethanol solution, add polylactic acid 20 parts and glycerol 3 parts, 60℃ water bath stirring for 2 hours, form graphene-polylactic acid dispersion; (3) Mix low ammonia deproteinized latex 1000 parts with graphene-polylactic acid dispersion at 60℃, add N-octyl-N-trimethyl chitosan 1.2 parts, stir at 200r / min for 2 hours, add 2,6-di-tert-butyl-p-cresol 1 part, electron beam irradiation for 30 minutes, get composite latex; (4) After plasma cleaning of ceramic mold, immerse in coagulant, dry at 90℃, immerse the mold in 5 seconds in 30% content composite latex at 25℃, form 0.05mm base layer, dry, immerse in 10 seconds in 50% content composite latex at 30℃, dry, after edge rolling, get latex glove substrate; (5) Mix polyurethane emulsion 60 parts, titanium dioxide dispersion liquid 15 parts, glycerol 3 parts, add ammonia water 1.5 parts to adjust pH to 7.5, get multifunctional coating liquid; (6) Preheat the latex glove substrate to 50℃, use multifunctional coating liquid to electrostatically spray 2 times, interval 5 minutes for curing, 80℃ hot air circulation for 15 minutes, ultraviolet lamp irradiation for 10 minutes, get modified latex glove with multifunctional coating.

[0099] Among them, step (1) uses 200 mesh sieve, vacuum distillation conditions are 60℃, 0.1MPa.

[0100] Among them, step (1) adds 0.3 parts of aminopeptidase and 0.5 parts of ficin.

[0101] Among them, step (1) centrifugal concentration speed is 12000r / min.

[0102] Among them, step (3) electron beam dose is 35kGy.

[0103] Among them, step (4) coagulant is 10% calcium nitrate solution.

[0104] Among them, step (4) drying process is 105℃ hot air drying for 3 minutes.

[0105] Among them, step (4) after edge rolling, standing time is 3min.

[0106] wherein, step (6) UV lamp wavelength is 365nm.

[0107] The low-ammonia deproteinized latex medical examination gloves of Example 4 were tested for puncture resistance and tensile / tear properties by an intelligent electronic tensile tester, the antibacterial rate of the titanium dioxide coating on Escherichia coli and Staphylococcus aureus was evaluated according to ISO22196, the service life extension effect was determined by laboratory simulation and accelerated aging test, the degradation rate after 4 months was determined by CO2 release at 58±2°C by the composting method, the surface wear resistance was quantified by using a standard friction tester, and the specific performance parameters of the medical examination gloves of Example 4 were obtained by specifically detecting the amount of allergenic protein residues by inhibition ELISA, and the values were compared with those of ordinary medical examination gloves, as shown in Table 4:

[0108] Compared with Example 3, Example 4 further increases the amount of graphene, hexagonal boron nitride and titanium dioxide, greatly improves the tensile strength and puncture resistance of the gloves, increases the sandpaper friction durability, increases the amount of N-octyl-N-trimethyl chitosan, polyurethane emulsion and polylactic acid, improves the compost degradation rate of the gloves, and reduces the aging rate of the gloves.

[0109] Example 5 The application provides a low-ammonia deproteinized latex medical examination glove, which is composed of modified low-ammonia deproteinized latex, graphene-polylactic acid reinforced dispersion, functional additives and a surface functional coating.

[0110] The application also provides a preparation method of the low-ammonia deproteinized latex medical examination glove, which comprises the following steps: (1) 1800 parts of rubber tree juice are sieved, 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate are added, stirring is performed for 30 minutes, an aminopeptidase and a ficin are added, 7 parts of a 10% KOH solution is added, stirring is performed at 50 r / min at 45°C for 6 hours, the pH value is adjusted to 8.0, 20 parts of 1% acetic acid is added to terminate the enzymolysis, and the low-ammonia deproteinized latex is obtained by centrifugal concentration to a dry rubber content of 60% and vacuum distillation. (2) graphene 0.1 parts and hexagonal boron nitride 0.1 parts are ultrasonically treated in an ethanol solution, polylactic acid 20 parts and glycerol 3 parts are added, and stirring is performed in a 60°C water bath for 2 hours to form a graphene-polylactic acid dispersion; (3) the low-ammonia deproteinized latex 1000 parts and the graphene-polylactic acid dispersion are mixed at 60°C, N-octyl-N-trimethyl chitosan 1.2 parts is added, stirring is performed at 200 r / min for 2 hours, 2,6-di-tert-butyl-p-cresol 1 part is added, and electron beam irradiation is performed for 30 minutes to obtain a composite latex. (4) After plasma cleaning of the ceramic mold, immerse the coagulant, dry at 90℃, immerse the mold into the 30% content of the composite latex for 5 seconds at 25℃ to form a 0.05mm base layer, dry, immerse into the 50% content of the composite latex for 10 seconds at 30℃, dry, and get the modified latex glove with multifunctional coating after edge rolling and standing; (5) Mix 60 parts of polyurethane emulsion, 15 parts of titanium dioxide dispersion, and 3 parts of glycerol, add 1.5 parts of ammonia water to adjust the pH to 7.5 to obtain a multifunctional coating liquid; (6) Preheat the latex glove base to 50℃, electrostatically spray the multifunctional coating liquid twice with an interval of 5 minutes for curing, circulate hot air at 80℃ for 15 minutes, and irradiate with ultraviolet lamp for 10 minutes to obtain a modified latex glove with multifunctional coating.

[0111] In step (1), a 200-mesh sieve is used for screening, and the vacuum distillation conditions are 60℃ and 0.1MPa.

[0112] In step (1), 0.5 parts of aminopeptidase and 0.8 parts of ficin are added.

[0113] In step (1), the centrifugal concentration speed is 12000r / min.

[0114] In step (3), the electron beam dose is 35kGy.

[0115] In step (4), the coagulant is 10% calcium nitrate solution.

[0116] In step (4), the drying process is hot air drying at 105℃ for 3 minutes.

[0117] In step (4), the standing time after edge rolling is 3 minutes.

[0118] In step (6), the wavelength of the ultraviolet lamp is 365nm.

[0119] The low-ammonia deproteinized latex medical examination glove of Example 5 is tested for puncture resistance and tensile / tear resistance by an intelligent electronic tensile testing machine, the antibacterial rate of the titanium dioxide coating on Escherichia coli and Staphylococcus aureus is evaluated according to ISO22196, the service life extension effect is determined by laboratory simulation and accelerated aging test, the degradation rate is determined by CO2 release amount at 58±2℃ for 4 months by composting method, the surface wear resistance is quantified by a standard friction tester, and the specific performance parameters of the medical examination glove of Example 5 are obtained by specific detection of allergen protein residual amount by inhibition ELISA method, and the values are compared with those of ordinary medical examination gloves, as shown in Table 5:

[0120] Example 5 The addition amount of aminopeptidase and ficin is increased compared with Example 4, the tensile strength and puncture resistance of the glove are increased, and the compost degradation rate of the glove is also improved.

[0121] Comparative Example 1 lacks aminopeptidase-assisted deamination compared with Example 1.

[0122] The application provides a low-ammonia deproteinized latex medical examination glove.

[0123] The application also provides a preparation method of the low-ammonia deproteinized latex medical examination glove. (1) 1800 parts of rubber tree juice are sieved, 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate are added, stirring is performed for 30 minutes, ficin is added, 6 parts of a 10% KOH solution is added, stirring is performed at 50 r / min at 45°C for 6 hours, the pH value is adjusted to 7.5, 19 parts of 1% acetic acid is added to terminate the enzymolysis, and the low-ammonia deproteinized latex is obtained through centrifugal concentration to a dry rubber content of 60%, vacuum distillation and addition of 0.5 parts of gingerol; (2) graphene 0.05 parts and hexagonal boron nitride 0.05 parts are ultrasonically treated in an ethanol solution, 15 parts of polylactic acid and 3 parts of glycerol are added, and stirring is performed in a 60°C water bath for 2 hours to form a graphene-polylactic acid dispersion; (3) 1000 parts of the low-ammonia deproteinized latex and the graphene-polylactic acid dispersion are mixed at 60°C, 0.8 parts of N-octyl-N-trimethyl chitosan is added, stirring is performed at 200 r / min for 2 hours, 1 part of 2,6-di-tert-butyl-p-cresol is added, and electron beam irradiation is performed for 30 minutes to obtain a composite latex; (4) after plasma cleaning, a ceramic mold is immersed in a coagulant, is dried at 90°C, and is immersed in 5 seconds of the composite latex with a content of 30% at 25°C to form a 0.05mm base layer, is dried, is immersed in 10 seconds of the composite latex with a content of 50% at 30°C, is dried, is rolled over and is left to stand to obtain a latex glove base; (5) 50 parts of a polyurethane emulsion, 10 parts of a titanium dioxide dispersion and 3 parts of glycerol are mixed, 1.5 parts of ammonia water is added to adjust the pH value to 7.0, and a multifunctional coating liquid is obtained; (6) the latex glove base is preheated to 50°C, is electrostatically sprayed with the multifunctional coating liquid twice with an interval of 5 minutes for solidification, is subjected to hot air circulation at 80°C for 15 minutes, and is irradiated with an ultraviolet lamp for 10 minutes to obtain a modified latex glove with a multifunctional coating.

[0124] In the step (1), a 200-mesh sieve is used for sieving, and the vacuum distillation conditions are 60°C and 0.1 MPa.

[0125] Wherein, step (1) ficin is added 0.5 parts.

[0126] Wherein, step (1) the centrifugal concentration rotation speed is 12000r / min.

[0127] Wherein, step (3) the electron beam dose is 35kGy.

[0128] Wherein, step (4) the coagulant is 10% calcium nitrate solution.

[0129] Wherein, step (4) the drying process is hot air drying at 105℃ for 3 minutes.

[0130] Wherein, step (4) the standing time after crimping is 3min.

[0131] Wherein, step (6) the wavelength of the ultraviolet lamp is 365nm.

[0132] The low-ammonia deproteinized latex medical examination glove of Comparative Example 1 is tested for puncture resistance and tensile / tear properties by an intelligent electronic tensile testing machine, the antibacterial rate of the titanium dioxide coating on Escherichia coli and Staphylococcus aureus is evaluated according to ISO22196, the service life extension effect is determined by laboratory simulation and accelerated aging test, the degradation rate is determined by CO2 release amount at 58±2℃ for 4 months by composting method, the surface wear resistance is quantified by using a standard friction tester, and the specific performance parameters of the medical examination glove of Comparative Example 1 are obtained by specifically detecting the amount of allergenic protein residues by inhibition ELISA, and the values are compared with those of the medical examination glove of Example 1, as shown in Table 6:

[0133] Compared with Example 1, Comparative Example 1 lacks aminopeptidase-assisted deamination, the protein residue of the glove increases, the risk of allergy increases, the tensile strength, puncture resistance and sandpaper friction durability decrease.

[0134] Comparative Example 2 lacks graphene in the material compared with Example 1.

[0135] The application provides a low-ammonia deproteinized latex medical examination glove.

[0136] The application also provides a preparation method of the low-ammonia deproteinized latex medical examination glove, including the following steps: (1) Rubber tree juice 1800 parts, sieved, 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate were added, stirred for 30 minutes, and aminopeptidase and ficin were added, 6 parts of 10% KOH solution was added, stirred at 45°C at 50 r / min for 6h, the pH was adjusted to 7.5, 19 parts of 1% acetic acid was added to terminate the enzymatic hydrolysis, centrifugal concentration to dry rubber content of 60%, vacuum distillation, addition of 0.5 parts of gingerol, to obtain low ammonia deproteinized latex; (2) Hexagonal boron nitride 0.05 parts was ultrasonically treated in an ethanol solution, 15 parts of polylactic acid and 3 parts of glycerol were added, and stirred in a 60°C water bath for 2 hours to form a hexagonal boron nitride-polylactic acid dispersion; (3) The low ammonia deproteinized latex 1000 parts was mixed with the hexagonal boron nitride-polylactic acid dispersion at 60°C, 0.8 parts of N-octyl-N-trimethyl chitosan was added, and stirred at 200 r / min for 2 hours, 1 part of 2,6-di-tert-butyl-p-cresol was added, and electron beam irradiation was performed for 30 minutes to obtain a composite latex; (4) After the ceramic mold was plasma cleaned, it was immersed in a coagulant and dried at 90°C. The mold was immersed in a 30% content composite latex for 5 seconds at 25°C to form a 0.05mm base layer, dried, immersed in a 50% content composite latex for 10 seconds at 30°C, dried, and after edge rolling, a latex glove substrate was obtained; (5) Polyurethane emulsion 50 parts, titanium dioxide dispersion liquid 10 parts, glycerol 3 parts were mixed, and ammonia water 1.5 parts was added to adjust the pH to 7.0 to obtain a multifunctional coating liquid; (6) The latex glove substrate was preheated to 50°C, and the multifunctional coating liquid was electrostatically sprayed twice with an interval of 5 minutes for curing, 80°C hot air circulation for 15 minutes, and ultraviolet lamp irradiation for 10 minutes to obtain a modified latex glove with a multifunctional coating.

[0137] In step (1), a 200 mesh sieve was used for sieving, and the vacuum distillation conditions were 60°C and 0.1 MPa.

[0138] In step (1), 0.3 parts of aminopeptidase and 0.5 parts of ficin were added.

[0139] In step (1), the centrifugal concentration speed was 12000 r / min.

[0140] In step (3), the electron beam dose was 35 kGy.

[0141] In step (4), the coagulant was 10% calcium nitrate solution.

[0142] In step (4), the drying process was 105°C hot air drying for 3 minutes.

[0143] In step (4), the standing time after edge rolling was 3 minutes.

[0144] wherein, step (6) UV lamp wavelength is 365 nm.

[0145] The low ammonia deproteinized latex medical examination gloves of Comparative Example 2 were tested for puncture resistance and tensile / tear properties by an intelligent electronic tensile tester, evaluated for antibacterial rate of titanium dioxide coating against E. coli and S. aureus according to ISO22196, determined for service life extension effect by laboratory simulation and accelerated aging test, measured for 4-month degradation rate by CO2 release amount at 58±2℃ by composting method, quantified surface abrasion resistance by a standard abrasion tester, and specifically detected for allergenic protein residual amount by inhibition ELISA, to obtain specific performance parameters of the medical examination gloves of Comparative Example 2, the values of which were compared with those of the medical examination gloves of Example 1, as shown in Table 7:

[0146] Compared with Example 1, Comparative Example 2 lacks graphene in the material, and the tensile strength, puncture resistance, and sandpaper friction durability of the gloves are greatly reduced.

[0147] Comparative Example 3 lacks N-octyl-N-trimethyl chitosan in the composite latex compared with Example 1.

[0148] The present application provides a low ammonia deproteinized latex medical examination glove, which is composed of modified low ammonia deproteinized latex, graphene-polylactic acid reinforced dispersion, functional additives, and surface functional coating.

[0149] The present application also provides a preparation method of the low ammonia deproteinized latex medical examination glove, which comprises the following steps: (1) Sieve 1800 parts of rubber tree juice, add 0.1 parts of potassium laurate and 0.05 parts of sodium dodecyl sulfate, stir for 30 minutes, add aminopeptidase and ficin, add 6 parts of 10% KOH solution, stir at 50 r / min at 45℃ for 6 h, adjust the pH to 7.5, add 19 parts of 1% acetic acid to terminate the enzyme hydrolysis, centrifuge and concentrate to a dry rubber content of 60%, vacuum distill, and add 0.5 parts of gingerol to obtain a low ammonia deproteinized latex; (2) Ultrasonically treat 0.05 parts of graphene and 0.05 parts of hexagonal boron nitride in an ethanol solution, add 15 parts of polylactic acid and 3 parts of glycerol, and stir in a 60℃ water bath for 2 hours to form a graphene-polylactic acid dispersion; (3) Mix 1000 parts of the low ammonia deproteinized latex with the graphene-polylactic acid dispersion at 60℃, stir at 200 r / min for 2 hours, add 1 part of 2,6-di-tert-butyl-p-cresol, and perform electron beam irradiation for 30 minutes to obtain a composite latex; (4) After the ceramic mold is cleaned by plasma, it is immersed in a coagulant, dried at 90℃, and then immersed in a 30% content composite latex for 5 seconds at 25℃ to form a 0.05mm base layer, dried, immersed in a 50% content composite latex for 10 seconds at 30℃, dried, and then placed after edge curling to obtain a latex glove base; (5) A multifunctional coating liquid is obtained by mixing 50 parts of polyurethane emulsion, 10 parts of titanium dioxide dispersion liquid, 3 parts of glycerol, and 1.5 parts of ammonia water to adjust the pH to 7.0; (6) The latex glove base is preheated to 50℃, and then electrostatically sprayed with the multifunctional coating liquid twice with an interval of 5 minutes for curing, and then subjected to hot air circulation at 80℃ for 15 minutes and ultraviolet lamp irradiation for 10 minutes to obtain a modified latex glove with a multifunctional coating.

[0150] In step (1), a 200-mesh sieve is used for screening, and the vacuum distillation conditions are 60℃ and 0.1MPa.

[0151] In step (1), 0.3 parts of aminopeptidase and 0.5 parts of ficin are added.

[0152] In step (1), the centrifugal concentration speed is 12000r / min.

[0153] In step (3), the electron beam dose is 35kGy.

[0154] In step (4), the coagulant is a 10% calcium nitrate solution.

[0155] In step (4), the drying process is hot air drying at 105℃ for 3 minutes.

[0156] In step (4), the standing time after edge curling is 3 minutes.

[0157] In step (6), the wavelength of the ultraviolet lamp is 365nm.

[0158] The low-ammonia deproteinized latex medical examination glove of Comparative Example 3 is tested for puncture resistance and tensile / tear resistance by an intelligent electronic tensile testing machine, the antibacterial rate of the titanium dioxide coating against Escherichia coli and Staphylococcus aureus is evaluated according to ISO22196, the service life extension effect is determined by laboratory simulation and accelerated aging test, the degradation rate is determined by CO2 release amount at 58±2℃ for 4 months by composting method, the surface wear resistance is quantified by a standard friction tester, and the specific performance parameters of the medical examination glove of Comparative Example 3 are obtained by specific detection of allergenic protein residual amount by inhibition ELISA, so that the numerical values are compared with those of the medical examination glove of Example 1, as shown in Table 8:

[0159] Comparative Example 3 lacks N-octyl-N-trimethyl chitosan in the composite latex, and the tensile strength, puncture resistance, and sandpaper abrasion durability of the glove are reduced, the antibacterial durability and compost degradation rate are reduced, and the aging rate is greatly increased compared to Example 1.

[0160] Example 2 increases the amount of graphene and hexagonal boron nitride added compared to Example 1. The two-dimensional sheet structure of graphene forms a dense network in the latex matrix, improving mechanical strength, while the layered structure of hexagonal boron nitride has super fracture resistance. Its lattice asymmetry makes the crack bifurcation turn, consumes additional energy to hinder expansion, and titanium dioxide enhances the wear resistance of the material through ultraviolet shielding function and filling effect. The sandpaper abrasion durability is therefore improved. At the same time, increasing the amount of N-octyl-N-trimethyl chitosan, polyurethane emulsion and polylactic acid can significantly improve the compost degradation rate and delay the aging rate. The quaternary ammonium salt structure of N-octyl-N-trimethyl chitosan provides antibacterial properties while its biocompatible component and ester bond hydrolysis properties of polylactic acid synergistically promote microbial decomposition. The microphase separation structure of the polyurethane emulsion delays photothermal degradation through a crosslinked network, and 365 nm ultraviolet irradiation further cures the coating, forming a long-acting protective mechanism, which together inhibits material aging.

[0161] Example 3 increases the amount of 10% KOH solution and adjusts the pH to 8.0 to more effectively decompose the allergenic proteins in the latex. Through the synergistic action of aminopeptidase and ficin, macromolecular allergens are degraded into small peptide segments. At the same time, the alkaline environment can inhibit protein denaturation and aggregation, reducing the protein content of the final product and significantly reducing the risk of allergy. Increasing the amount of acetic acid not only can precisely terminate the enzymatic reaction, but also promotes the agglomeration of latex particles to form a more dense network structure, which synergistically enhances the crosslinking density of the material with the subsequent addition of polylactic acid, improving sandpaper abrasion durability. Increasing the amount of ammonia, the hypochlorous acid produced by its decomposition can damage the microbial enzyme system, forming a double antibacterial mechanism with the quaternary ammonium salt structure of N-octyl-N-trimethyl chitosan, improving antibacterial properties. The alkaline environment promoted by ammonia increases the compost degradation rate by delaying the hydrolysis of polylactic acid ester bonds, and reduces the aging rate by inhibiting free radical chain reactions.

[0162] Compared with Example 3, the addition of graphene, hexagonal boron nitride and titanium dioxide further improves the formation of a dense network of the two-dimensional sheet structure of graphene in the latex matrix, the tensile strength is improved, the super strong anti-fracture ability of the layered structure of hexagonal boron nitride, and the toughness, the lattice asymmetry of which makes the crack bifurcation turn, consumes additional energy to hinder expansion, titanium dioxide enhances the wear resistance of the material through the synergistic effect of ultraviolet shielding function and filling effect, and the sandpaper friction durability is thus improved. At the same time, increasing the amount of N-octyl-N-trimethyl chitosan, polyurethane emulsion and polylactic acid can significantly improve the compost degradation rate and delay the aging rate. The quaternary ammonium salt structure of N-octyl-N-trimethyl chitosan provides antibacterial properties, and its biocompatibility component and ester bond hydrolysis properties of polylactic acid synergistically promote microbial decomposition, while the microphase separation structure of polyurethane emulsion delays photothermal degradation through crosslinking network and inhibits material aging.

[0163] Compared with Example 4, the amount of aminopeptidase and ficin is increased. Aminopeptidase specifically degrades allergenic proteins in the latex by hydrolyzing peptide bonds from the N-terminus of proteins, degrading them into small peptide segments, significantly reducing the protein content in the latex, thereby reducing material defects caused by protein aggregation, making the latex molecular chain arrangement more compact, and improving the tensile strength. Ficin, as a sulfhydryl protease, can efficiently cleave collagen fibers and connective tissue proteins through the cysteine in its active center, destroying the weak points of the crosslinking network in the latex, and re-forming a more uniform three-dimensional crosslinking structure, thereby improving the puncture resistance. In addition, its degradation products can act as plasticizers to alleviate material brittleness, and cooperate with electron beam irradiation to further strengthen the crosslinking density, thereby improving the sandpaper friction durability. In addition, the two enzyme degradation products are biodegradable, can promote microbial metabolic activity in the compost environment, accelerate the ester bond hydrolysis of components such as polylactic acid, and improve the degradation rate.

[0164] Compared with Example 1, the absence of aminopeptidase in Comparative Example 1 lacks the key role of aminopeptidase in specifically hydrolyzing the allergen protein in the latex, and the synergistic effect of aminopeptidase and ficin in Example 1 can reduce the final protein content to a certain extent. In Comparative Example 1, the amount of residual allergen protein increases significantly due to the lack of aminopeptidase, which increases the risk of allergic reactions. After aminopeptidase-assisted deamination, the arrangement of the latex molecular chain is more uniform, and the defects are reduced. The enzymatic product in Example 1 can be used as a natural plasticizer, and can be synergistically enhanced with the subsequent addition of N-octyl-N-trimethyl chitosan and polylactic acid to enhance the crosslinking density, thereby improving the tensile strength. In Comparative Example 1, the tensile strength is reduced due to the weak points formed by the aggregation of proteins, and the crack propagation resistance is weakened, resulting in a decrease in the puncture resistance. The latex treated by aminopeptidase is combined more closely with the graphene-poly lactic acid dispersion to form a nano-enhanced network. In Example 1, this structure improves the sandpaper friction durability, while in Comparative Example 1, the latex matrix has interface defects due to the presence of undegraded proteins, which exacerbates abrasive wear and causes the coating to peel off.

[0165] Compared with Example 1, Comparative Example 2 lacks the reinforcing effect of graphene in the material. The two-dimensional sheet structure of graphene can form a dense network structure in the latex matrix, significantly improving the mechanical properties of the material. The high elastic modulus and fracture strength of graphene can effectively hinder crack propagation, thereby improving the tensile strength. In addition, the interlayer slip mechanism of graphene can absorb impact energy, thereby enhancing the puncture resistance. Furthermore, the nanoscale surface roughness and high thermal conductivity of graphene can reduce the accumulation of friction heat, thereby improving the sandpaper friction durability. In Comparative Example 2, the absence of graphene prevents the latex matrix from forming a reinforcing network, resulting in a decrease in mechanical properties.

[0166] Compared with Example 1, Comparative Example 3 lacks N-octyl-N-trimethyl chitosan in the composite latex, and the quaternary ammonium salt structure of the modified chitosan can form an ionic bond crosslinking network with the carboxyl group in the latex, significantly enhancing the binding force between molecular chains. After the absence of this component in Comparative Example 3, the crosslinking density of the latex is reduced, resulting in a decrease in tensile strength and a decrease in puncture resistance. At the same time, the modified chitosan can promote the uniform dispersion of nanofillers by producing hydrophobic interaction with the graphene sheet layer through its long-chain alkyl group. After the absence of this component, the graphene is easy to agglomerate, the stress transfer efficiency is reduced, and the material toughness is further weakened. The dense crosslinking structure formed by the modified chitosan in the coating can resist abrasive cutting, and the absence of this component causes the surface hardness to decrease and the wear rate to increase. The quaternary ammonium salt group can destroy the bacterial cell membrane through electrostatic adsorption, and its slow-release characteristics can maintain long-term antibacterial properties. Due to the lack of this mechanism in Comparative Example 3, microorganisms are easy to colonize on the surface and secrete acidic metabolites, accelerating the degradation of the material. The antioxidant and ultraviolet shielding functions of the modified chitosan can delay photo-thermal aging, and after the absence of this component, the aging rate increases. The biodegradability of the modified chitosan and its characteristics of promoting microbial activity are the key to compost degradation. In Comparative Example 3, the hydrolysis of the ester bond of polylactic acid is slowed down due to the lack of microbial catalysis, and the composting rate is reduced.

[0167] The present application provides a preparation method of a low-ammonia deproteinized latex medical examination glove. The rubber tree sap is filtered through a 200-mesh screen to remove bark debris and allergen protein carriers. Potassium laurate and sodium dodecyl sulfate are added to homogeneously disperse rubber particles through emulsification, creating a stable environment for enzymatic hydrolysis. The aminopeptidase targets small peptide segments at the N-terminal of the peptide chain for hydrolysis. The ficin breaks the hydrophobic peptide bond, efficiently decomposing allergens. Acetic acid is added in the termination stage to precisely inactivate enzyme activity, avoiding excessive hydrolysis of protective proteins. Centrifugal concentration increases the dry rubber content, forming a dense molecular network. Vacuum distillation removes free ammonia and degradation products, avoiding high-temperature damage to rubber chains. Gingerol is added to replace the high-ammonia system, and its phenolic hydroxyl group closes the residual protein allergen sites and inhibits oxidative aging. Polylactic acid is added as a biodegradable carrier, and its ester bond can be hydrolyzed and mineralized by microbial lipase. Glycerol is added for plasticization to improve flexibility. Graphene and hexagonal boron nitride synergistically improve tear resistance. N-octyl-N-trimethyl chitosan is added, and its quaternary ammonium salt structure forms a hydrophilic lubricating layer, promoting microbial adhesion and accelerating degradation. 2,6-Di-tert-butyl-p-cresol is added to capture free radicals, and electron beam irradiation is used to initiate C-C covalent crosslinking, increasing crosslinking density and avoiding sulfur residues. Latex impregnation thickens the main body, and hot air drying avoids interface defects. Polyurethane-glycerol forms a micron-sized high-elasticity film, and ultraviolet reinforcement improves coating adhesion. Titanium dioxide photocatalysis produces reactive oxygen species to break the polyurethane molecule, while also improving surface hardness and inhibiting bacteria. Thus, the problems of high allergenicity, poor mechanical strength, difficulty in degradation, and discomfort in wearing of low-ammonia deproteinized latex medical examination gloves are solved.

[0168] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and that variations, modifications, substitutions and changes can be made by those skilled in the art without departing from the scope of the present application.

Claims

1. A low-ammonia deproteinized latex medical examination glove, characterized in that: The low-ammonia deproteinized latex medical examination gloves include: modified low-ammonia deproteinized latex, graphene-polylactic acid reinforced dispersion, functional additives and surface functional coating.

2. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 1, characterized in that: The preparation method of the low-ammonia deproteinized latex medical examination gloves comprises the following steps: (1) 1800-1900 parts of rubber tree sap were sieved, 0.1 parts of potassium laurate and 0.05 parts of sodium lauryl sulfate were added, and the mixture was stirred for 30 minutes. Aminopeptidase and ficin were added, and 6-7 parts of 10% KOH solution were added. The mixture was stirred at 50 r / min at 45°C for 6 hours, the pH was adjusted to 7.5-8.0, and 19-20 parts of 1% acetic acid were added to terminate the enzymatic hydrolysis. The mixture was concentrated by centrifugation to a dry rubber content of 60%, vacuum distilled, and 0.5 parts of gingerol were added to obtain low-amino deproteinized latex. (2) 0.05-0.1 parts of graphene and 0.05-0.1 parts of hexagonal boron nitride were ultrasonically treated in an ethanol solution, 15-20 parts of polylactic acid and 3 parts of glycerol were added, and the mixture was stirred in a water bath at 60°C for 2 hours to form a graphene-polylactic acid dispersion; (3) 1000 parts of the low-ammonia deproteinized latex and the graphene-polylactic acid dispersion were mixed at 60° C., 0.8-1.2 parts of N-octyl-N-trimethyl chitosan were added, and the mixture was stirred at 200 r / min for 2 hours. 1 part of 2,6-di-tert-butyl-p-cresol was added, and electron beam irradiation was performed for 30 minutes to obtain a composite latex; (4) After plasma cleaning, the ceramic mold is immersed in a coagulant and dried at 90°C. At 25°C, the mold is immersed in 30% of the composite latex for 5 seconds to form a 0.05 mm base layer. The mold is dried. At 30°C, the mold is immersed in 50% of the composite latex for 10 seconds. The mold is dried, crimped, and allowed to stand to obtain a latex glove base. (5) Mix 50-60 parts of polyurethane emulsion, 10-15 parts of titanium dioxide dispersion, and 3 parts of glycerin, add 1.5 parts of ammonia water and adjust the pH to 7.0-7.5 to obtain a multifunctional coating solution; (6) The latex glove substrate is preheated to 50°C, and the multifunctional coating liquid is electrostatically sprayed twice, cured at intervals of 5 minutes, circulated with hot air at 80°C for 15 minutes, and irradiated with a UV lamp for 10 minutes to obtain a modified latex glove with a multifunctional coating.

3. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 2, characterized in that: The step (1) is screened with a 200-mesh sieve, and the vacuum distillation conditions are 60° C. and 0.1 MPa.

4. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 2, characterized in that: In the step (1), 0.3-0.5 parts of aminopeptidase and 0.5-0.8 parts of ficin are added.

5. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 2, characterized in that: The centrifugal concentration speed in step (1) is 12000 r / min.

6. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 2, characterized in that: The electron beam dose in step (3) is 35 kGy.

7. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 2, characterized in that: The coagulant in step (4) is 10% calcium nitrate solution.

8. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 2, characterized in that: The drying process in step (4) is hot air drying at 105° C. for 3 minutes.

9. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 2, characterized in that: The standing time after curling in step (4) is 1-3 minutes.

10. The method for preparing a low-ammonia deproteinized latex medical examination gloves according to claim 2, characterized in that: The wavelength of the ultraviolet lamp in step (6) is 365nm.

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