A magnetically detectable nitrile glove and its preparation method

Abstract

This invention discloses a magnetically detectable nitrile glove and its preparation method, relating to the field of nitrile glove manufacturing technology. The raw materials include: carboxylated nitrile latex, modified magnetite magnetic particles, modified porous zein breathable microspheres, modified core-shell polysiloxane colored microspheres, sulfur, vulcanization accelerator, potassium hydroxide, and tributyl acetylacetate. In this invention, modified porous zein breathable microspheres are added, which can form stable breathable channels in the glove film, improving the glove's water vapor permeability and air permeability, solving the problems of stuffiness and poor breathability of ordinary nitrile gloves. Simultaneously, the modified microspheres form a hydrophobic protective and ionic bond anchoring layer on their surface, preventing clogging of their own pores and agglomeration with magnetic particles, and firmly bonding with the nitrile latex without detachment or exudation. While significantly improving breathability, this method maximizes the preservation of the glove's tensile strength, tear resistance, and other mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of nitrile glove manufacturing technology, and in particular to a magnetically detectable nitrile glove and its manufacturing method. Background Technology

[0002] Magnetic detectable nitrile gloves are specially designed protective gloves made of nitrile rubber with embedded magnetic particles, giving them magnetic properties. These gloves are primarily used in industries with high hygiene and safety requirements, such as food processing and pharmaceuticals. When the gloves are accidentally damaged or break into fragments during use, contaminants can be quickly identified and removed using magnetic detection equipment (such as metal detectors), effectively preventing cross-contamination during production and ensuring product quality and safety, while retaining the chemical resistance, elasticity, and protective properties of nitrile gloves.

[0003] Traditional magnetically detectable nitrile gloves suffer from magnetic particles that tend to agglomerate and accumulate, resulting in low metal detection sensitivity, slow response, and compromised mechanical strength. Ordinary breathable microspheres are prone to latex blockage, leading to poor dispersion and causing the gloves to feel stuffy and unbreathable. Furthermore, the microspheres are easily detached, affecting the glove's structural stability. Conventional coloring materials lack sufficient covering power to conceal the underlying color of the magnetic particles, resulting in dull colors, significant color differences, and issues such as color fading and migration. Therefore, this invention provides a magnetically detectable nitrile glove and its preparation method. Summary of the Invention

[0004] The main objective of this invention is to provide a magnetically detectable nitrile glove with high magnetic sensitivity and low color difference, and a method for preparing the same, which is applied in the preparation of a magnetically detectable nitrile glove.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] This invention provides a magnetically detectable nitrile glove, comprising the following raw materials in parts by weight: 95-105 parts carboxylated nitrile latex, 3.5-3.7 parts modified magnetite magnetic particles, 0.8-1.2 parts modified porous zein breathable microspheres, 0.8-1.2 parts modified core-shell polysiloxane colored microspheres, 0.7-0.8 parts sulfur, 0.2-0.3 parts vulcanization accelerator, 0.15-0.25 parts potassium hydroxide, and 1-1.4 parts tributyl acetylacetate.

[0007] The solid content of carboxylated nitrile rubber latex is 45%.

[0008] All materials must meet the GB4806.11-2016 food contact standard.

[0009] Sulfur, as a rubber vulcanizing agent, can undergo a cross-linking reaction with carboxylated nitrile latex to form a three-dimensional network structure, which greatly improves the tensile strength, tear resistance and structural stability of gloves, avoids the problems of gloves becoming sticky and easily damaged, and ensures that gloves have qualified mechanical properties and durability. It is the core vulcanizing component that ensures the performance of nitrile gloves after molding.

[0010] Acetyl tributyl citrate, as an environmentally friendly and non-toxic food and pharmaceutical grade plasticizer, can effectively improve the softness, flexibility, and fit of nitrile gloves, improve the feel of the gloves, and is not easy to migrate or leach out, so it will not contaminate the contact items. At the same time, it has good compatibility with latex and functional microspheres, does not interfere with the vulcanization reaction and the effect of various functional components, and takes into account both the comfort and safety of the gloves.

[0011] The vulcanization accelerator is one of zinc diethyldithiocarbamate, zinc dibenzyldithiocarbamate, and zinc dibutyldithiocarbamate.

[0012] Furthermore, the preparation of the modified iron oxide magnetic particles includes the following steps:

[0013] A1. Add nano-ferric oxide to a citric acid aqueous solution for ultrasonic cleaning. Set the power to 1000W and the frequency to 40kHz, and clean for 10 minutes. Wash the cleaned nano-ferric oxide with deionized water 3-4 times. Vacuum dry the washed nano-ferric oxide at a temperature of 60℃ and a vacuum degree of -0.095MPa for 2 hours to obtain dried powder.

[0014] A2. Place the dried powder in anhydrous ethanol and stir at 2000 rpm for 30 minutes. Add γ-aminopropyltriethoxysilane and stir at 2000 rpm for 30 minutes. Reflux at 80°C for 2 hours to obtain a mixture. Centrifuge the mixture at 10000 rpm for 12 minutes. Collect the solid and add it to deionized water. Stir at 1500 rpm for 15 minutes. Use ultrasonic dispersion at 1200W power and 40kHz frequency for 1 minute. Add gelatin-fructooligosaccharide complex and stir at 60°C and 800 rpm for 40 minutes. Add cocamidopropyl betaine and stir at 2500 rpm for 15 minutes. Use ultrasonic dispersion at 1500W and 40kHz for 10 minutes. Add potassium hydroxide and stir at 800 rpm for 10 minutes to obtain material A. Spray dry material A at 120°C and 60°C to obtain modified magnetite magnetic particles.

[0015] The particle size of nano-ferric oxide is 30-60 nm.

[0016] Furthermore, the mass ratio of nano-ferric oxide and citric acid aqueous solution in A1 is 1:10.

[0017] The concentration of the citric acid aqueous solution is 0.1 mol / L.

[0018] The mass ratio of the dried powder, anhydrous ethanol, γ-aminopropyltriethoxysilane, gelatin-fructooligosaccharide complex, cocamidopropyl betaine, and deionized water in A2 is 100:400:6:12:10:300.

[0019] The pH is adjusted to 8.5-9 by adding potassium hydroxide.

[0020] Furthermore, the mass ratio of gelatin to fructooligosaccharides in the gelatin-fructooligosaccharide complex is 1:2.

[0021] Further, the preparation of the modified porous zein breathable microspheres includes the following steps: adding porous zein microspheres to a mixture and stirring, setting the temperature to 45℃ and the rotation speed to 600 rpm, stirring for 20 minutes; adding octenyl succinic acid starch ester and stirring, setting the temperature to 45℃ and the rotation speed to 600 rpm, stirring for 60 minutes; adding a pH adjuster and stirring, setting the rotation speed to 600 rpm, stirring for 5 minutes; adding ε-polylysine hydrochloride and stirring, setting the temperature to 50℃ and the rotation speed to 800 rpm, stirring for 40 minutes; lowering the temperature to 35℃; adding decaglycerol monostearate for shearing, setting the rotation speed to 2500 rpm, shearing for 10 minutes; using ultrasonic dispersion, setting the power to 1200W and the frequency to 40kHz, dispersing for 5 minutes to obtain material B; spray drying material B, setting the inlet air temperature to 85℃ and the outlet air temperature to 55℃, to obtain modified porous zein breathable microspheres.

[0022] The porous zein microspheres have a particle size of 1-3 μm.

[0023] Furthermore, the mixture is composed of ethanol and deionized water in a volume ratio of 7:3.

[0024] The mass ratio of the porous zein microspheres, the mixture, octenyl succinate starch ester, ε-polylysine hydrochloride and decaglycerol monostearate is 100:500:4:1.6:1.2.

[0025] The pH adjuster is either citric acid or potassium hydroxide.

[0026] The pH is adjusted to 7-7.5 by adding a pH adjuster.

[0027] Further, the preparation of the modified core-shell polysiloxane colored microspheres includes the following steps: adding the core-shell polysiloxane colored microspheres to deionized water and stirring, setting the temperature to 40℃ and the rotation speed to 600 rpm, stirring for 15 minutes; adding polydimethylsiloxane oligomer and stirring, setting the temperature to 40℃ and the rotation speed to 600 rpm, stirring for 30 minutes; adding triethyl citrate and stirring, setting the temperature to 40℃ and the rotation speed to 600 rpm, stirring for 30 minutes; adding sodium lauroyl sarcosinate and shearing, setting the rotation speed to 2500 rpm, shearing for 10 minutes; filtering with a 3μm filter membrane to remove impurities, obtaining material C; spray drying material C, setting the inlet air temperature to 115℃, the outlet air temperature to 60℃, and the atomization pressure to 0.25 MPa, to obtain the modified core-shell polysiloxane colored microspheres.

[0028] The particle size of the core-shell polysiloxane colored microspheres is 0.8-2 μm.

[0029] Furthermore, the mass ratio of the core-shell polysiloxane colored microspheres, deionized water, polydimethylsiloxane oligomer, triethyl citrate, and sodium lauroyl sarcosinate is 100:300:2.5:2:0.8.

[0030] Secondly, the present invention provides a method for preparing a magnetically detectable nitrile glove, the method comprising the following steps:

[0031] S1. Add carboxylated nitrile butadiene latex to a dispersion tank and stir at 500 rpm for 10 minutes. Add modified magnetite magnetic particles and shear at 2000 rpm for 10 minutes. Add modified core-shell polysiloxane colored microspheres and ultrasonically disperse at 1500W and 40kHz for 10 minutes. Add modified porous zein breathable microspheres and shear at 2200 rpm for 10 minutes. Add sulfur, vulcanization accelerator, potassium hydroxide, and tributyl acetyl citrate sequentially and stir at 500 rpm for 5 minutes. Add deionized water and stir at 500 rpm for 5 minutes. Adjust the dispersion tank temperature to 35℃ and stir at 600 rpm for 90 minutes. Stop heating and stirring, let stand for 12-24 hours, and pass through a 150-mesh sieve to obtain the latex.

[0032] S2. Immerse the hand mold in the coagulant solution, remove it, and dry it at 70-90℃ for 2.5 minutes. Then immerse the dried hand mold in latex at 35-40℃ and 6-8 cm / s for 40-50 seconds. Remove the hand mold and dry it at 95-115℃ for 60-90 seconds. Next, immerse the hand mold in latex again for 20-30 seconds, remove it, and dry it at 95-115℃ for 60 seconds. After drying, immerse the hand mold in deionized water at 40-50℃ for 1-2 minutes. Then, vulcanize the hand mold in a vulcanizing furnace at 125-135℃ for 6-8 minutes. After vulcanization, air-cool the hand mold to 20-25℃. Then, immerse the cooled hand mold in sodium hypochlorite solution for 10-15 seconds. Remove the hand mold, disassemble it, and obtain the glove. Dry the glove at 60-70℃ for 5-8 minutes to obtain a magnetically detectable nitrile glove.

[0033] Furthermore, deionized water is added to S1 to adjust the solid content to 40%.

[0034] The preparation of the coagulant solution in S1 includes the following steps: adding deionized water to a reaction vessel and stirring at 300 rpm for 2 minutes; adding calcium nitrate and calcium chloride sequentially and stirring for 15 minutes; adding γ-polyglutamic acid oligomer and stirring at 300 rpm for 10 minutes; stopping stirring and letting it stand for 5 minutes to obtain the coagulant solution.

[0035] The mass ratio of deionized water, calcium nitrate, calcium chloride, and γ-polyglutamic acid oligomer in the coagulant solution is 87.75:6:6:0.25.

[0036] The concentration of sodium hypochlorite solution in S2 is 0.5-0.8%.

[0037] The present invention has the following beneficial effects:

[0038] 1. In this invention, modified magnetite magnetic particles are added. γ-aminopropyltriethoxysilane acts as a coupling agent, grafting amino active sites onto the magnetite surface to enhance the interfacial bonding between the particles and nitrile latex and improve dispersibility. A gelatin-fructooligosaccharide complex forms a flexible coating layer on the outer layer of the particles, reducing their agglomeration tendency and enhancing their compatibility and stability in the latex system. Cocamidopropyl betaine, as a zwitterionic dispersant, further optimizes the surface charge state of the particles, improving their dispersion uniformity in the aqueous latex. These three components synergistically prevent the magnetic particles from agglomerating. The modified magnetite particles exhibit strong aggregation, firm bonding, and uniform magnetic distribution. They are evenly distributed within the nitrile latex system without agglomeration, ensuring consistent magnetism across all parts of the glove. This allows for rapid detection by metal detectors, effectively preventing glove fragment contamination during food and pharmaceutical production. The modified magnetic particles are firmly bonded to the nitrile latex matrix, without migration or detachment. This ensures that the glove's mechanical properties are not interfered with, while still meeting food contact safety standards. It balances magnetic detection functionality with the glove's safety and stability, addressing the pain points of unmodified magnetic particles' tendency to agglomerate, weak bonding, and negative impact on glove performance.

[0039] 2. In this invention, modified porous zein-based breathable microspheres are added. Octenyl succinate starch ester forms a hydrophobic modified layer on the pore walls and surface of the microspheres, preventing latex from seeping in and clogging the pores, while protecting the porous structure. ε-polylysine hydrochloride provides chemical anchoring sites for the microspheres with carboxylated nitrile latex through ionic bonding, improving the bonding strength of the microspheres in the film and reducing shedding. Deca-polyglycerol monostearate provides a steric hindrance effect, improving the dispersibility of the microspheres in the latex and preventing them from agglomerating with magnetic particles. These three components work synergistically to ensure the high breathability of the microspheres while achieving [the desired effect]. The modified porous zein microspheres have good matrix compatibility, stable structure, and do not clog pores. They can form stable air-permeable channels in the glove film, improving the water vapor permeability and air permeability of the gloves, thus solving the problem of stuffiness and lack of breathability of ordinary nitrile gloves. The modified microspheres form a hydrophobic protective layer and ionic bond anchoring layer on their surface, which does not clog their own pores or agglomerate with magnetic particles. They are also firmly bonded to nitrile latex, without falling off or precipitating. While significantly improving breathability, they can maximize the preservation of the gloves' tensile strength, tear resistance, and other mechanical properties, making them suitable for long-term wear.

[0040] 3. In this invention, modified core-shell polysiloxane colored microspheres are added, wherein polydimethylsiloxane oligomers form a soft-light hydrophobic layer on the surface of the colored microspheres, improving the appearance and reducing interparticle adhesion; triethyl citrate, as a flexible coupling and color-fixing component, enhances the compatibility between the colored microspheres and nitrile latex, while locking in the internal colorant to prevent migration and fading; sodium lauroyl sarcosinate improves the surface wettability and dispersibility of the microspheres, allowing them to be evenly distributed in the latex and avoiding color difference and spots. The three components work synergistically to achieve high hiding power, uniform color, excellent color fastness, and without interfering with magnetic and breathable functions. Modified core-shell polysiloxane colored microspheres require only a small amount to completely cover the black background of iron oxide, and can be formulated with a variety of colors such as pure white and light colors, with uniform color and no color difference. The modified colored microspheres have excellent color fastness, strong light and heat resistance, and do not fade or migrate during use. They do not clog the pores of the breathable microspheres, do not interfere with the detection performance of magnetic particles, and have good compatibility with nitrile latex systems. They meet the color marking requirements of gloves without affecting the core functions and safety performance of gloves. Detailed Implementation

[0041] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0042] It should be noted that all raw materials used in the following experiments are commercially available.

[0043] The preparation methods of the modified magnetite magnetic particles, modified porous zein breathable microspheres, and modified core-shell polysiloxane colored microspheres in the following embodiments and comparative examples of the present invention are as follows:

[0044] I. Preparation of Modified Ferric Oxide Magnetic Particles

[0045] A1. Add 1 part of nano-Fe3O4 to 10 parts of 0.1mol / L citric acid aqueous solution for ultrasonic cleaning. Set the power to 1000W and the frequency to 40kHz, and clean for 10 minutes. Wash the cleaned nano-Fe3O4 with deionized water 3-4 times. Vacuum dry the washed nano-Fe3O4 at a temperature of 60℃ and a vacuum degree of -0.095MPa for 2 hours to obtain dried powder.

[0046] A2. Add 100 parts of dry powder to 400 parts of anhydrous ethanol and stir at 2000 rpm for 30 minutes. Add 6 parts of γ-aminopropyltriethoxysilane and stir at 2000 rpm for 30 minutes. Reflux at 80°C for 2 hours to obtain a mixture. Centrifuge the mixture at 10000 rpm for 12 minutes and collect the solid. Add the solid to 300 parts of deionized water and stir at 1500 rpm for 15 minutes. Use ultrasonic dispersion at 1200W power and 40kHz frequency for 1 minute. 0 minutes, add 12 parts of gelatin-fructooligosaccharide complex and stir, set the temperature to 60℃ and the speed to 800 rpm, stir for 40 minutes, add 10 parts of cocamidopropyl betaine and stir, set the speed to 2500 rpm, stir for 15 minutes, use ultrasonic dispersion, set the power to 1500W and the frequency to 40kHz, disperse for 10 minutes, add potassium hydroxide to adjust the pH to 8.7 and stir, set the speed to 800 rpm, stir for 10 minutes to obtain material A, spray dry material A, set the inlet air temperature to 120℃ and the outlet air temperature to 60℃ to obtain modified iron oxide magnetic particles.

[0047] The mass ratio of gelatin to fructooligosaccharides in the gelatin-fructooligosaccharide complex is 1:2.

[0048] II. Preparation of Modified Porous Zein Glycerin Breathable Microspheres

[0049] 100 parts of porous zein microspheres were added to 500 parts of a mixture and stirred at 45°C and 600 rpm for 20 minutes. 4 parts of octenyl succinate starch ester were added and stirred at 45°C and 600 rpm for 60 minutes. A pH adjuster was added to adjust the pH to 7.3 and stirred at 600 rpm for 5 minutes. 1.6 parts of ε-polylysine hydrochloride were added and stirred at 50°C and 800 rpm for 40 minutes. The temperature was lowered to 35°C, and 1.2 parts of decaglycerol monostearate were added and sheared at 2500 rpm for 10 minutes. Ultrasonic dispersion was performed at 1200W and 40kHz for 5 minutes to obtain material B. Material B was spray-dried at an inlet air temperature of 85°C and an outlet air temperature of 55°C to obtain modified porous zein breathable microspheres.

[0050] The mixture is a mixture of ethanol and deionized water in a volume ratio of 7:3.

[0051] The pH adjuster is either citric acid or potassium hydroxide.

[0052] III. Preparation of Modified Core-Shell Polysiloxane Colored Microspheres

[0053] 100 parts of core-shell polysiloxane colored microspheres were added to 300 parts of deionized water and stirred at 40℃ and 600 rpm for 15 minutes. 2.5 parts of polydimethylsiloxane oligomer were added and stirred at 40℃ and 600 rpm for 30 minutes. 2 parts of triethyl citrate were added and stirred at 40℃ and 600 rpm for 30 minutes. 0.8 parts of sodium lauroyl sarcosinate were added and sheared at 2500 rpm for 10 minutes. The mixture was filtered through a 3 μm filter membrane to remove impurities, yielding material C. Material C was then spray-dried at an inlet air temperature of 115℃, an outlet air temperature of 60℃, and an atomization pressure of 0.25 MPa to obtain modified core-shell polysiloxane colored microspheres.

[0054] Example 1: A magnetically detectable nitrile glove, comprising the following raw materials in parts by weight: 95 parts carboxylated nitrile latex, 3.5 parts modified magnetite magnetic particles, 0.8 parts modified porous zein breathable microspheres, 0.8 parts modified core-shell polysiloxane colored microspheres, 0.7 parts sulfur, 0.2 parts vulcanization accelerator, 0.15 parts potassium hydroxide, and 1 part tributyl acetylacetate.

[0055] The vulcanization accelerator is zinc diethyldithiocarbamate.

[0056] A method for preparing magnetically detectable nitrile gloves, the method comprising the following steps:

[0057] S1. Add carboxylated nitrile butadiene latex to a dispersion tank and stir at 500 rpm for 10 minutes. Add modified magnetite magnetic particles and shear at 2000 rpm for 10 minutes. Add modified core-shell polysiloxane colored microspheres and ultrasonically disperse at 1500W and 40kHz for 10 minutes. Add modified porous zein breathable microspheres and shear at 2200 rpm for 10 minutes. Add sulfur, vulcanization accelerator, potassium hydroxide, and tributyl acetyl citrate sequentially and stir at 500 rpm for 5 minutes. Add deionized water and stir at 500 rpm for 5 minutes. Adjust the dispersion tank temperature to 35℃ and stir at 600 rpm for 90 minutes. Stop heating and stirring, let stand for 12 hours, and pass through a 150-mesh sieve to obtain the latex.

[0058] S2. Immerse the hand mold in the coagulant solution, lift it out and dry it. Set the drying temperature to 70℃ and dry for 2.5 minutes. Immerse the dried hand mold in latex. Set the latex temperature to 35℃ and the immersion speed to 6cm / s and immerse for 40 seconds. Lift the hand mold and dry it. Set the temperature to 95℃ and dry for 60 seconds. Immerse the hand mold in latex again for 20 seconds. Lift the hand mold and dry it. Set the temperature to 95℃ and dry for 60 seconds. Immerse the dried hand mold in deionized water at 40℃ for 1 minute. Put the soaked hand mold into a vulcanizing furnace for vulcanization. Set the temperature to 125℃ and vulcanize for 6 minutes. After vulcanization, air cool the hand mold to 20℃. After cooling, immerse the hand mold in sodium hypochlorite solution for 10 seconds. Lift the hand mold, remove the mold, and obtain the glove. Dry the glove at 60℃ for 5 minutes to obtain a magnetically detectable nitrile glove.

[0059] Add deionized water to S1 to adjust the solid content to 40%.

[0060] The preparation of the coagulant solution in S1 includes the following steps: adding deionized water to the reactor and stirring at 300 rpm for 2 minutes; adding calcium nitrate and calcium chloride in sequence and stirring for 15 minutes; adding γ-polyglutamic acid oligomer and stirring at 300 rpm for 10 minutes; stopping stirring and letting it stand for 5 minutes to obtain the coagulant solution.

[0061] The mass ratio of deionized water, calcium nitrate, calcium chloride, and γ-polyglutamic acid oligomer in the coagulant solution is 87.75:6:6:0.25.

[0062] The concentration of sodium hypochlorite solution in S2 is 0.5%.

[0063] Example 2: A magnetically detectable nitrile glove, comprising the following raw materials in parts by weight: 100 parts carboxylated nitrile latex, 3.6 parts modified iron oxide magnetic particles, 1 part modified porous zein breathable microspheres, 1 part modified core-shell polysiloxane colored microspheres, 0.75 parts sulfur, 0.25 parts vulcanization accelerator, 0.2 parts potassium hydroxide, and 1.2 parts tributyl acetylacetonate.

[0064] The vulcanization accelerator is zinc dibenzyl dithiocarbamate.

[0065] A method for preparing magnetically detectable nitrile gloves, the method comprising the following steps:

[0066] S1. Add carboxylated nitrile butadiene latex to a dispersion tank and stir at 500 rpm for 10 minutes. Add modified magnetite magnetic particles and shear at 2000 rpm for 10 minutes. Add modified core-shell polysiloxane colored microspheres and ultrasonically disperse at 1500W and 40kHz for 10 minutes. Add modified porous zein breathable microspheres and shear at 2200 rpm for 10 minutes. Add sulfur, vulcanization accelerator, potassium hydroxide, and tributyl acetyl citrate sequentially and stir at 500 rpm for 5 minutes. Add deionized water and stir at 500 rpm for 5 minutes. Adjust the dispersion tank temperature to 35℃ and stir at 600 rpm for 90 minutes. Stop heating and stirring, let stand for 18 hours, and pass through a 150-mesh sieve to obtain the latex.

[0067] S2. Immerse the hand mold in the coagulant solution, remove the hand mold and dry it. Set the drying temperature to 80℃ and dry for 2.5 minutes. Immerse the dried hand mold in latex. Set the latex temperature to 37℃ and the immersion speed to 7cm / s and immerse for 45 seconds. Remove the hand mold and dry it. Set the temperature to 105℃ and dry for 75 seconds. Immerse the hand mold in latex again and immerse for 25 seconds. Remove the hand mold and dry it. Set the temperature to 105℃ and dry for 60 seconds. Immerse the dried hand mold in deionized water at 45℃ for 1.5 minutes. Put the soaked hand mold into a vulcanizing furnace for vulcanization. Set the temperature to 130℃ and vulcanize for 7 minutes. After vulcanization, air cool the hand mold to 22℃. After cooling, immerse the hand mold in sodium hypochlorite solution for 13 seconds. Remove the hand mold, remove the mold, and obtain the glove. Dry the glove at 65℃ for 6.5 minutes to obtain a magnetically detectable nitrile glove.

[0068] Add deionized water to S1 to adjust the solid content to 40%.

[0069] The preparation of the coagulant solution in S1 includes the following steps: adding deionized water to the reactor and stirring at 300 rpm for 2 minutes; adding calcium nitrate and calcium chloride in sequence and stirring for 15 minutes; adding γ-polyglutamic acid oligomer and stirring at 300 rpm for 10 minutes; stopping stirring and letting it stand for 5 minutes to obtain the coagulant solution.

[0070] The mass ratio of deionized water, calcium nitrate, calcium chloride, and γ-polyglutamic acid oligomer in the coagulant solution is 87.75:6:6:0.25.

[0071] The concentration of sodium hypochlorite solution in S2 is 0.65%.

[0072] Example 3: A magnetically detectable nitrile glove, comprising the following raw materials in parts by weight: 105 parts carboxylated nitrile latex, 3.7 parts modified magnetite magnetic particles, 1.2 parts modified porous zein breathable microspheres, 1.2 parts modified core-shell polysiloxane colored microspheres, 0.8 parts sulfur, 0.3 parts vulcanization accelerator, 0.25 parts potassium hydroxide, and 1.4 parts tributyl acetylacetate.

[0073] The vulcanization accelerator is zinc dibutyldithiocarbamate.

[0074] A method for preparing magnetically detectable nitrile gloves, the method comprising the following steps:

[0075] S1. Add carboxylated nitrile butadiene latex to a dispersion tank and stir at 500 rpm for 10 minutes. Add modified magnetite magnetic particles and shear at 2000 rpm for 10 minutes. Add modified core-shell polysiloxane colored microspheres and ultrasonically disperse at 1500W and 40kHz for 10 minutes. Add modified porous zein breathable microspheres and shear at 2200 rpm for 10 minutes. Add sulfur, vulcanization accelerator, potassium hydroxide, and tributyl acetyl citrate sequentially and stir at 500 rpm for 5 minutes. Add deionized water and stir at 500 rpm for 5 minutes. Adjust the dispersion tank temperature to 35℃ and stir at 600 rpm for 90 minutes. Stop heating and stirring, let stand for 24 hours, and pass through a 150-mesh sieve to obtain the latex.

[0076] S2. Immerse the hand mold in the coagulant solution, lift it out and dry it. Set the drying temperature to 90℃ and dry for 2.5 minutes. Immerse the dried hand mold in latex. Set the latex temperature to 40℃ and the immersion speed to 8cm / s. Immerse for 50 seconds. Lift the hand mold and dry it. Set the temperature to 115℃ and dry for 90 seconds. Immerse the hand mold in latex again for 30 seconds. Lift the hand mold and dry it. Set the temperature to 115℃ and dry for 60 seconds. Immerse the dried hand mold in 50℃ deionized water for 2 minutes. Put the soaked hand mold into a vulcanizing furnace for vulcanization. Set the temperature to 135℃ and vulcanize for 8 minutes. After vulcanization, air cool the hand mold to 25℃. After cooling, immerse the hand mold in sodium hypochlorite solution for 15 seconds. Lift the hand mold, remove the mold, and obtain the glove. Dry the glove at 70℃ for 8 minutes to obtain a magnetically detectable nitrile glove.

[0077] Add deionized water to S1 to adjust the solid content to 40%.

[0078] The preparation of the coagulant solution in S1 includes the following steps: adding deionized water to the reactor and stirring at 300 rpm for 2 minutes; adding calcium nitrate and calcium chloride in sequence and stirring for 15 minutes; adding γ-polyglutamic acid oligomer and stirring at 300 rpm for 10 minutes; stopping stirring and letting it stand for 5 minutes to obtain the coagulant solution.

[0079] The mass ratio of deionized water, calcium nitrate, calcium chloride, and γ-polyglutamic acid oligomer in the coagulant solution is 87.75:6:6:0.25.

[0080] The concentration of sodium hypochlorite solution in S2 is 0.8%.

[0081] Comparative Example 1: The difference between this comparative example and Example 1 is that:

[0082] Unmodified magnetite particles were used in this comparative example.

[0083] Comparative Example 2: The difference between this comparative example and Example 1 is that:

[0084] This comparative example uses unmodified porous zein-permeable microspheres.

[0085] Comparative Example 3 differs from Example 1 in that:

[0086] Unmodified core-shell polysiloxane-colored microspheres were used in this comparative example.

[0087] Performance testing: The magnetically detectable nitrile gloves prepared in Examples 1, 2, 3, Comparative Examples 1, 2, and 3, and their preparation methods were tested.

[0088] Performance testing: The relevant properties of the magnetically detectable nitrile gloves and their preparation methods provided in Examples 1-3 and Comparative Examples 1-3 were tested respectively, and the test data are recorded in Table 1 below:

[0089] Table 1 - Performance Testing of Magnetic-Detectable Nitrile Gloves

[0090]

[0091] Based on the above data, the following conclusions can be drawn:

[0092] Among them, the magnetic sensitivity metal detector response time of magnetically detectable nitrile gloves prepared using the test methods in GB / T15822.1-2024 in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 was tested.

[0093] Water vapor transmission rate test of magnetically detectable nitrile gloves prepared according to the test methods in GB / T1037-2021, Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3.

[0094] Color difference test of magnetically detectable nitrile gloves prepared according to the test methods in GB / T22899-2008 (Examples 1, 2, 3, Comparative Examples 1, 2, and 3).

[0095] Modified magnetite particles can achieve uniform dispersion in nitrile latex without agglomeration or sedimentation, resulting in a uniform and stable magnetic distribution throughout the glove. This avoids localized excessive or absent magnetic signals caused by particle aggregation, ensuring that the metal detector can stably receive clear and consistent magnetic response signals. This effectively improves the magnetic detection sensitivity of tiny glove fragments and eliminates recognition delays caused by magnetic signal disturbances, significantly shortening the metal detector's response time and enabling rapid and accurate detection of glove fragments. Modified porous zein breathable microspheres prevent nitrile latex from penetrating and clogging micropores. The modification treatment also improves the uniformity of microsphere dispersion in the latex system, creating a continuous and unobstructed water vapor transport path within the glove film. This allows water vapor to efficiently penetrate the film and diffuse outwards, significantly improving the glove's water vapor permeability compared to the poor dispersion and clogging issues of unmodified microspheres, thus enhancing breathability and moisture wicking performance during wear. Modified core-shell polysiloxane colored microspheres can be uniformly distributed in nitrile latex without agglomeration or stratification. They can cover the dark brown base color of iron oxide in a comprehensive and uniform manner, avoiding problems such as color spots, color patterns, or uneven shades due to uneven distribution of colorants. At the same time, the modified layer ensures that the coloring components are stable and do not migrate, so that the overall color of the glove remains uniform and consistent, effectively reducing the color difference between samples and different parts of the sample, and improving the uniformity and stability of the appearance color.

[0096] Based on the above demonstrations, the present invention is significantly superior to the comparative group in terms of response time, water vapor transmittance, and color difference of the magnetic sensitivity metal detector.

[0097] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0098] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A magnetically detectable nitrile glove, characterized in that, The magnetically detectable nitrile glove comprises the following raw materials in parts by weight: 95-105 parts carboxylated nitrile latex, 3.5-3.7 parts modified magnetite magnetic particles, 0.8-1.2 parts modified porous zein breathable microspheres, 0.8-1.2 parts modified core-shell polysiloxane colored microspheres, 0.7-0.8 parts sulfur, 0.2-0.3 parts vulcanization accelerator, 0.15-0.25 parts potassium hydroxide, and 1-1.4 parts tributyl acetylacetate; The vulcanization accelerator is one of zinc diethyldithiocarbamate, zinc dibenzyldithiocarbamate, and zinc dibutyldithiocarbamate.

2. The magnetically detectable nitrile glove according to claim 1, characterized in that, The preparation of the modified iron oxide magnetic particles includes the following steps: A1. Add nano-iron oxide to citric acid aqueous solution for ultrasonic cleaning, wash the cleaned nano-iron oxide with deionized water, and vacuum dry the washed nano-iron oxide to obtain dry powder. A2. Place the dried powder in anhydrous ethanol and stir. Add γ-aminopropyltriethoxysilane and stir to obtain a mixture. Centrifuge the mixture, collect the solid, add the solid to deionized water and stir. Disperse using ultrasound. Add gelatin-fructooligosaccharide complex and stir. Add cocamidopropyl betaine and stir. Disperse using ultrasound. Add potassium hydroxide and stir to obtain material A. Spray dry material A to obtain modified iron oxide magnetic particles.

3. The magnetically detectable nitrile glove according to claim 2, characterized in that, The mass ratio of nano-ferric oxide and citric acid aqueous solution in A1 is 1:10; The mass ratio of the dried powder, anhydrous ethanol, γ-aminopropyltriethoxysilane, gelatin-fructooligosaccharide complex, cocamidopropyl betaine, and deionized water in A2 is 100:400:6:12:10:

300.

4. The magnetically detectable nitrile glove according to claim 2, characterized in that, The mass ratio of gelatin to fructooligosaccharides in the gelatin-fructooligosaccharide complex is 1:

2.

5. The magnetically detectable nitrile glove according to claim 1, characterized in that, The preparation of the modified porous zein breathable microspheres includes the following steps: adding porous zein microspheres to a mixture and stirring, adding octenyl succinate starch ester and stirring, adding a pH adjuster and stirring, adding ε-polylysine hydrochloride and stirring, adding decaglycerol monostearate and shearing, and dispersing using ultrasound to obtain material B. Material B is then spray-dried to obtain the modified porous zein breathable microspheres.

6. The magnetically detectable nitrile glove according to claim 5, characterized in that, The mixture is composed of ethanol and deionized water in a volume ratio of 7:

3. The mass ratio of the porous zein microspheres, the mixture, octenyl succinate starch ester, ε-polylysine hydrochloride, and decaglycerol monostearate is 100:500:4:1.6:1.

2. The pH adjuster is either citric acid or potassium hydroxide.

7. The magnetically detectable nitrile glove according to claim 1, characterized in that, The preparation of the modified core-shell polysiloxane colored microspheres includes the following steps: adding the core-shell polysiloxane colored microspheres to deionized water and stirring, adding polydimethylsiloxane oligomer and stirring, adding triethyl citrate and stirring, adding sodium lauroyl sarcosinate and shearing, filtering with a filter membrane to remove impurities, obtaining material C, and spray drying material C to obtain the modified core-shell polysiloxane colored microspheres.

8. The magnetically detectable nitrile glove according to claim 7, characterized in that, The mass ratio of the core-shell polysiloxane colored microspheres, deionized water, polydimethylsiloxane oligomer, triethyl citrate, and sodium lauroyl sarcosinate is 100:300:2.5:2:0.

8.

9. A method for preparing a magnetically detectable nitrile glove according to any one of claims 1-8, characterized in that, The method for preparing the magnetically detectable nitrile glove includes the following steps: S1. Add carboxylated nitrile latex to a dispersion tank and stir. Add modified iron oxide magnetic particles for shearing. Add modified core-shell polysiloxane colored microspheres for ultrasonic dispersion. Add modified porous zein breathable microspheres for shearing. Add sulfur, vulcanization accelerator, potassium hydroxide and tributyl acetyl citrate in sequence and stir. Add deionized water and stir. Adjust the temperature of the dispersion tank and stir. Stop heating and stirring. Let stand and sieve to obtain latex. S2. Immerse the hand mold in the coagulant solution, lift it out and dry it. Immerse the dried hand mold in latex, lift it out and dry it. Immerse the hand mold in latex again, lift it out and dry it. Immerse the dried hand mold in deionized water. Put the soaked hand mold into a vulcanizing furnace for vulcanization. After vulcanization, the hand mold is cooled by air cooling. After cooling, the hand mold is immersed in sodium hypochlorite solution. Lift the hand mold, remove the mold, and obtain the glove. Dry the glove to obtain a magnetically detectable nitrile glove.

10. The method for preparing the magnetically detectable nitrile glove according to claim 9, characterized in that, The preparation of the coagulant solution in S1 includes the following steps: adding deionized water to a reaction vessel and stirring, adding calcium nitrate and calcium chloride in sequence and stirring, adding γ-polyglutamic acid oligomer and stirring, stopping stirring, and letting it stand to obtain the coagulant solution. The mass ratio of deionized water, calcium nitrate, calcium chloride, and γ-polyglutamic acid oligomer in the coagulant solution is 87.75:6:6:0.25; The concentration of sodium hypochlorite solution in S2 is 0.5-0.8%.

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