A puncture-resistant and abrasion-resistant nitrile glove and a method of making the same

Abstract

The application discloses a wear-resistant and puncture-resistant nitrile glove and a preparation method thereof, and relates to the technical field of nitrile gloves.The nitrile glove is prepared from a composite latex solution.The composite latex solution comprises the following raw materials in mass parts: 80-90 parts of carboxyl nitrile latex, 13-18 parts of mixed dispersion liquid, 0.5-1.1 parts of anti-aging agent RD, 6-12 parts of accelerator solution and 6-8 parts of synergistic fiber.The basalt fiber after etching is subjected to ion plasma treatment, and then is wrapped by a spinning solution containing carboxylated single-walled carbon nanotubes, nanodiamonds and nitrile latex through electrostatic spinning, and then is coated by a solution containing water-based polyurethane, chitosan quaternary ammonium salt and graphene nanosheet, and finally, the synergistic fiber prepared by spraying a coating containing nanometer aluminum oxide, carboxyl nitrile rubber and silane coupling agent is obtained, so that the wear resistance, puncture resistance, anti-static property and antibacterial property of the nitrile glove are effectively improved.Therefore, the application has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of nitrile gloves, in particular to a wear-resistant and puncture-resistant nitrile glove and a preparation method thereof. BACKGROUND

[0002] The nitrile latex prepared by emulsion polymerization of butadiene and acrylonitrile has good oil resistance and chemical resistance, and is widely used in the automotive, aviation, petroleum and medical industries. Nitrile gloves are a kind of synthetic rubber protective gloves made of nitrile rubber as the main raw material through dipping molding process. As a synthetic material product, nitrile gloves do not contain allergenic proteins in natural latex, which can effectively avoid latex allergy problems; at the same time, due to the acrylonitrile segment in the molecular structure of nitrile rubber, it has excellent oil resistance, chemical corrosion resistance, and the butadiene segment provides good elasticity and flexibility, so it has both tensile strength and fit. Therefore, nitrile gloves are widely used in medical care, food processing, industrial operation, laboratory research and other scenes, mainly for hand protection, to isolate the hands from direct contact with pollutants, chemicals and microorganisms, and to ensure safe and sanitary operation.

[0003] However, nitrile gloves still have the problems of poor antistatic performance, excessive static accumulation which can damage electronic components or cause sparks, and poor wear resistance and puncture resistance, which limits their application. Therefore, the antistatic property, wear resistance and puncture resistance of the existing nitrile gloves still need to be further improved. SUMMARY

[0004] The purpose of the present application is to provide a wear-resistant and puncture-resistant nitrile glove and a preparation method thereof, which solves the following technical problems:

[0005] The existing nitrile gloves still have the problems of poor antistatic performance, wear resistance and puncture resistance.

[0006] The purpose of the present application can be achieved by the following technical solutions:

[0007] A wear-resistant and puncture-resistant nitrile glove, the nitrile glove is prepared from a composite latex emulsion;

[0008] The composite latex emulsion comprises the following raw materials by mass: carboxyl nitrile latex 80-90 parts, mixed dispersion liquid 13-18 parts, antioxidant RD 0.5-1.1 parts, accelerator solution 6-12 parts, and synergistic fiber 6-8 parts;

[0009] The mixed dispersion liquid is prepared from deionized water, sulfur, pigment and polycarboxylic acid sodium salt;

[0010] The synergistic fiber is prepared by electrospinning of basalt fiber etched with a spinning solution, and then coating graphene nanosheet doped polyurethane and nanometer alumina doped carboxyl nitrile rubber in sequence, wherein the spinning solution comprises carboxylated single-walled carbon nanotubes, sodium dodecyl benzene sulfonate, nanometer zinc oxide, nanometer diamond, gamma-cyanopropyl trimethoxysilane, nitrile rubber latex and polyvinylpyrrolidone.

[0011] Preferably, the preparation method of the composite latex is as follows:

[0012] The carboxyl nitrile rubber latex is stirred at 25-30 DEG C for 8-10 h at 50-70 r / min, then the mixed dispersion, antioxidant RD, accelerator solution and synergistic fiber are added in sequence while stirring, and the pH is adjusted to 8.5-9.5, and after stirring for 2-4 h, aging is carried out at 25-30 DEG C for 8-10 h to obtain the composite latex.

[0013] Preferably, the preparation method of the mixed dispersion is as follows:

[0014] Sulfur, pigment and polycarboxylic acid sodium salt are added in deionized water and ball milled to D90 of 0.5-2 microns to obtain the mixed dispersion;

[0015] The mass ratio of the deionized water, sulfur, pigment, polycarboxylic acid sodium salt is 5-7:3-4:5-7:0.2-0.4;

[0016] The pigment is a combination of titanium dioxide and zinc oxide, phthalocyanine blue and pearlescent pigment.

[0017] Preferably, the preparation method of the accelerator solution is as follows:

[0018] Accelerator ZDBC and accelerator ZDEC are added in deionized water at 45-50 DEG C and stirred for 20-40 min to obtain the accelerator solution;

[0019] The mass ratio of the deionized water, accelerator ZDBC and accelerator ZDEC is 5.4-10.8:0.4-0.8:0.2-0.4.

[0020] Preferably, the preparation method of the synergistic fiber is as follows:

[0021] A1: Ammonium hydrogen fluoride and citric acid are added in deionized water and stirred for 10-20 min, then basalt fiber is added and ultrasonically dispersed at 45-50 DEG C for 30-50 min, then centrifuged and washed with deionized water for 5-7 times, and then dried at 55-60 DEG C to obtain etched fiber;

[0022] A2: adding deionized water, anhydrous ethanol, carboxylated single-walled carbon nanotubes, sodium dodecyl benzene sulfonate into the deionized water and performing ultrasonic dispersion for 30-50 min, then adding nano zinc oxide, nano diamond and performing ultrasonic dispersion for 30-50 min, then adding γ-cyanopropyl trimethoxysilane and stirring at 55-60℃ for 2-3h, finally adding butyl nitrile latex, polyvinylpyrrolidone and stirring for 10-20 min to obtain a spinning solution;

[0023] A3: performing plasma treatment on the etched fiber, then electrospinning with the spinning solution, and then vacuum drying at 75-80℃ for 1-2h to obtain a composite fiber;

[0024] A4: adding water-based polyurethane, chitosan quaternary ammonium salt, dioctyl terephthalate, graphene nanosheet into the deionized water and adjusting pH to 6.5-7.5, then treating for 30-40 min at 2500-3000r / min, then immersing in the composite fiber, taking out after soaking for 8-10 min and performing irradiation treatment, and finally air drying at 55-60℃ for 1-2h to obtain a coated fiber;

[0025] A5: adding silane coupling agent KH-560, glacial acetic acid into the deionized water and stirring for 10-20 min, then adding nano-alumina, carboxylated butyl nitrile rubber and stirring at 2000-2200r / min for 20-30 min, after grinding, spraying on the surface of the coated fiber, forming a coating with a thickness of 3-5μm, then performing infrared irradiation, then incubating at 60-80℃ for 1-2h, and finally immersing in the silane coupling agent KH-570 ethanol solution for 10-15 min, draining and then drying at 75-80℃ for 30-50 min to obtain a synergistic fiber.

[0026] Preferably, the mass ratio of the deionized water, ammonium hydrogen fluoride, citric acid and basalt fiber in A1 is 100-120:5-6:3-3.5:20-25;

[0027] The mass ratio of the deionized water, anhydrous ethanol, carboxylated single-walled carbon nanotubes, sodium dodecyl benzene sulfonate, nano zinc oxide, nano diamond, γ-cyanopropyl trimethoxysilane, butyl nitrile latex, polyvinylpyrrolidone in A2 is 30-45:30-45:1-1.5:0.05-0.07:3-4.5:2-3:0.18-0.28:5-7.5:0.2-0.3;

[0028] The power of the plasma treatment in A3 is 70-80W, the time is 50-60s, and the treatment atmosphere is argon-oxygen mixed gas (argon gas flow rate is 15L / h, oxygen gas flow rate is 5L / h);

[0029] The temperature during electrospinning in A3 is 25-30℃, the relative humidity is 40%-50%, the voltage is 15kV, the needle distance from the receiving plate is 15cm, the flow rate of the spinning solution is 0.7-0.9mL / h, and the etching fiber moving speed is 4-5cm / s;

[0030] The mass ratio of deionized water, aqueous polyurethane, chitosan quaternary ammonium salt, dioctyl terephthalate, graphene nanosheet, and composite fiber in A4 is 130-186: 140-200: 14-20: 22.5-32: 1-2: 14-20;

[0031] The temperature during irradiation in A4 is 45-55℃, the power is 100-150W, and the time length is 3-5min.

[0032] Preferably, the mass ratio of deionized water, silane coupling agent KH-560, glacial acetic acid, nano-aluminum oxide, carboxyl nitrile rubber, and silane coupling agent KH-570 ethanol solution in A5 is 9-10: 2-2.2: 0.5-0.6: 15-17: 75-83: 100-110;

[0033] D90 after grinding in A5 is 0.5-2μm;

[0034] The mass fraction of silane coupling agent KH-570 ethanol solution in A5 is 0.5%;

[0035] The wavelength during infrared irradiation in A5 is 3-5μm, the temperature is 100℃, and the time length is 3-5min.

[0036] A preparation method of a wear-resistant and puncture-resistant nitrile glove, comprising the following steps:

[0037] S1: immerse the ceramic hand mold in a sodium hydroxide solution for 2-5min, then rinse with deionized water for 3-5 times, dry at 75-80℃ for 10-30min, then immerse in an ethanol-containing calcium nitrate aqueous solution for 3-5s, and then dry at 65-70℃ for 2-5min to obtain a pretreated hand mold;

[0038] S2: immerse the pretreated hand mold in a composite latex emulsion for 5-8s, then take it out, dry at 45-50℃ for 1-3min after forming a film, then perform secondary immersion for 2-3s on the 2-3cm part of the fingertips, then immerse in deionized water at 55-60℃ for 5-10min, and finally dry at 75-80℃ with air blowing for 5-7min to obtain a crude nitrile glove;

[0039] S3: roll up the opening of the crude nitrile glove by 2-3mm with a crimping machine, then sequentially perform vulcanization treatment, chlorine washing, neutralization, water washing, and drying to demold to obtain a wear-resistant and puncture-resistant nitrile glove.

[0040] Preferably, the mass fraction of the sodium hydroxide solution in S1 is 5%, and the temperature is 55-60 DEG C.

[0041] The mass fraction of the calcium nitrate aqueous solution in S1 is 10%-15%, and the content of ethanol is 3%.

[0042] The speed of the drawing in S2 is 8-10 cm / min.

[0043] The thickness of the adhesive film in S2 is 0.08-0.12 mm.

[0044] Preferably, the vulcanization treatment in S3 is: first vulcanization at 110-120 DEG C for 15-20 min, then vulcanization at 98-100 DEG C for 20-30 min, and then water cooling to 20-40 DEG C.

[0045] The chlorine washing in S3 is: dipping in an active chlorine aqueous solution with a concentration of 300-500 mg / L for 30-40 s.

[0046] The neutralization in S3 is: neutralization to pH 6-7 with a sodium bisulfate aqueous solution.

[0047] The beneficial effects of the present application are:

[0048] The present application provides a wear-resistant and puncture-resistant nitrile glove and a preparation method thereof.

[0049] (1) The nano diamond and nano alumina in the synergistic fiber can resist external wear during friction and reduce the direct loss of the matrix material; after etching and plasma treatment, the surface roughness of the basalt fiber is increased, the bonding force with the spinning solution and the coating layer is enhanced, and the basalt fiber can bear the friction stress as a skeleton and reduce the wear caused by local stress concentration of the adhesive film; the structure of the carboxylated single-walled carbon nanotube and graphene can form a "lubrication-barrier" effect during friction, which not only reduces the friction coefficient, but also prevents the expansion of wear cracks; the silane coupling agent and plasma treatment optimize the interface bonding between the fiber and the carboxyl nitrile rubber latex matrix, avoid the separation of the fiber and the adhesive film to form abrasive dust, and further improve the wear resistance.

[0050] (2) The hard points such as nanometer diamond and nanometer aluminum oxide in the synergistic fiber can directly resist the penetration of the puncture object, and hinder the deformation and penetration caused by the sharp end of the puncture object through high hardness; the basalt fiber as a continuous phase reinforcing body disperses the local impact force during puncture, reduces the local damage of the puncture object to the rubber film; the high mechanical properties of the carboxylated single-walled carbon nanotube and graphene can form a "bridge" during the puncture process to prevent the crack from spreading from the puncture point to the surrounding, and delay the rupture of the rubber film; the butyronitrile latex of the electrospinning layer and the water-based polyurethane of the coating layer have a certain elasticity, which can absorb part of the puncture energy through deformation, and cooperate with the rigid component to form a "hard-tough" composite structure to improve the puncture resistance.

[0051] (3) The carboxylated single-walled carbon nanotube and graphene nanosheet in the synergistic fiber form a continuous conductive network during electrospinning and coating, so that the glove material has a certain conductivity; the plasma treatment introduces polar groups on the surface of the basalt fiber, enhances the bonding force with the carbon nanotube and graphene, reduces the interface resistance, and is beneficial to the rapid release of electric charge through the fiber network; the dispersion of the conductive component can reduce the surface resistance of the glove material, reduce the accumulation of static electricity on the surface, and thus improve the anti-static performance.

[0052] (4) The nanometer zinc oxide in the synergistic fiber can release zinc ions to damage the bacterial cell membrane and inhibit the enzyme activity of bacteria; the chitosan quaternary ammonium salt can adsorb negatively charged bacteria through electrostatic action, destroy the cell wall, and cooperate with the nanometer zinc oxide to improve the antibacterial efficiency; the nanometer zinc oxide and the chitosan quaternary ammonium salt are fixed in the synergistic fiber through coating and interfacial combination, which can slowly release or continuously exert the antibacterial effect through contact, prolonging the antibacterial time of the glove.

[0053] (5) The carboxylated butyronitrile rubber in the synergistic fiber has good compatibility with the chemical structure of the glove carboxylated butyronitrile latex matrix, and is not easy to cause mechanical property decline due to interface separation at low temperature; the elastic components such as butyronitrile latex and water-based polyurethane can reduce the low-temperature brittleness of the rubber film, cooperate with the reinforcing effect of the synergistic fiber, and maintain the tensile toughness at low temperature; the high toughness of the carbon nanotube and graphene can prevent crack propagation through "crack bridging" and "pull-out effect", reducing brittle fracture at low temperature; the silane coupling agent treatment enhances the interfacial bonding force between the synergistic fiber and the matrix, avoids the "debonding-fracture" problem caused by the decrease of the interfacial adhesion at low temperature, and maintains the mechanical stability at low temperature.

[0054] Therefore, the butyronitrile glove prepared by the application has excellent wear resistance, puncture resistance, anti-static property, antibacterial property and low-temperature resistance, and has a more extensive application prospect. DETAILED DESCRIPTION

[0055] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the protection scope of the present application.

[0056] Unless otherwise specified, the following information of some raw materials used in the examples and comparative examples of the present application is as follows:

[0057] Basalt fiber (diameter 5-7 μm, aspect ratio 5:1); nitrile latex (solid content 43.5%) was purchased from Xingtianwai Chemical (Shanghai) Co., Ltd.; polyvinylpyrrolidone was purchased from Shanghai Yuanye Biotechnology Co., Ltd., product code: S30268; water-based polyurethane was purchased from Shanghai Maier Biotechnology Co., Ltd., product code: M90109; graphene nanosheet was purchased from Xi'an Ruixi Biological Technology Co., Ltd., product code: 23801; carboxyl nitrile rubber was purchased from Dongguan Shenghao Plastic Raw Material Co., Ltd., product code: 5541254; polycarboxylic acid sodium salt was purchased from Nantong Deyi Chemical Co., Ltd., model number: DY-YL-330; carboxyl nitrile latex (solid content 44%) was purchased from Hubei Hongfuda Biological Technology Co., Ltd.

[0058] Example 1: A method for preparing a wear-resistant and puncture-resistant nitrile glove is as follows:

[0059] S1: 5 g of ammonium fluoride, 3 g of citric acid were added into 100 mL of deionized water and stirred for 10 min, then 20 g of basalt fiber was added and ultrasonically dispersed at 45°C for 30 min, then centrifuged and washed with deionized water for 5 times, and then dried at 55°C to obtain etched fibers;

[0060] S2: 30 g of anhydrous ethanol, 1 g of carboxylated single-walled carbon nanotubes, 0.05 g of sodium dodecylbenzenesulfonate were added into 30 g of deionized water and ultrasonically dispersed for 30 min, then 3 g of nano-zinc oxide, 2 g of nano-diamond were added and ultrasonically dispersed for 30 min, then 0.188 g of 3-cyanopropyltrimethoxysilane was added and stirred at 55°C for 2 h, finally 5 g of nitrile latex, 0.2 g of polyvinylpyrrolidone was added and stirred for 10 min to obtain a spinning solution;

[0061] S3: Put the etched fiber into an atmospheric pressure plasma treatment instrument, introduce argon / oxygen mixed gas (argon gas flow rate is 15 L / h, oxygen gas flow rate is 5 L / h) and perform plasma treatment with a power of 70 W for 50 s, then electrospun the etched fiber with a flow rate of 0.7 mL / h of the spinning solution at 25°C, a relative humidity of 40%, a voltage of 15 kV, a needle distance from the receiving plate of 15 cm and a moving speed of 4 cm / s, and then vacuum dried at 75°C for 1 h to obtain a composite fiber;

[0062] S4: Add 140 g of aqueous polyurethane, 14 g of chitosan quaternary ammonium salt, 22.5 g of dioctyl terephthalate, 1 g of graphene nanosheet to 130 g of deionized water, adjust the pH to 6.5 with 1% acetic acid aqueous solution, and treat for 30 min at 2500 r / min, then immerse in 14 g of composite fiber, soak for 8 min, take out and place in a microwave reactor for irradiation treatment at 45°C for 3 min with a power of 100 W, and finally air dry at 55°C for 1 h to obtain coated fiber;

[0063] S5: Add 2 g of silane coupling agent KH-560, 0.5 g of glacial acetic acid to 9 g of deionized water and stir for 10 min, then add 15 g of nano-alumina, 75 g of carboxyl nitrile rubber and stir at 2000 r / min for 20 min, grind to D90 of 0.5 μm, spray on the surface of the coated fiber, form a coating layer with a thickness of 3 μm, then place in an infrared curing oven for irradiation with a wavelength of 3 μm and a temperature of 100°C for 3 min, then incubate at 60°C for 1 h, finally immerse in 100 g of 0.5% silane coupling agent KH-570 ethanol solution for 10 min, drain and dry at 75°C for 30 min to obtain synergistic fiber;

[0064] S6: Add 3 g of sulfur, 4 g of titanium white, 1 g of zinc oxide, and 0.2 g of polycarboxylic acid sodium salt to 5 g of deionized water and ball mill to D90 of 0.5 μm to obtain a mixed dispersion liquid;

[0065] S7: Add 0.4 g of accelerator ZDBC and 0.2 g of accelerator ZDEC to 5.4 g of deionized water at 45°C and stir for 20 min to obtain an accelerator solution;

[0066] S8: Stir 80 g of carboxyl nitrile rubber latex at 25°C for 8 h, then add 13 g of mixed dispersion liquid, 0.5 g of antioxidant RD, 6 g of accelerator solution, and 6 g of synergistic fiber to the stirring solution in sequence, adjust the pH to 8.5, stir for 2 h, and then age at 25°C for 8 h to obtain a composite latex;

[0067] S9: The ceramic hand mold was cleaned by immersing in a 55℃ 5% by mass sodium hydroxide solution for 2 min, then rinsing with deionized water for 3 times, drying at 75℃ for 10 min, then immersing in a 10% by mass calcium nitrate aqueous solution containing 3% ethanol for 3 s, then drying at 65℃ for 2 min, to obtain a pretreated hand mold;

[0068] S10: The pretreated hand mold was immersed in a 25℃ composite latex emulsion for 5 s, then taken out at 8 cm / min, after forming a 0.08 mm thick glue film, air-dried at 45℃ for 1 min, then the 2 cm part at the fingertip was immersed for 2 s again, then immersed in 55℃ deionized water for 5 min, and finally air-dried at 75℃ for 5 min, to obtain a glove crude product;

[0069] S11: The glove crude product was rolled up by 2 mm at the opening with a rolling machine, then vulcanized at 110℃ for 15 min, then cooled to 98℃ at a rate of 5℃ / min and vulcanized at 98℃ for 20 min, then water-cooled to 20℃, then immersed in an active chlorine aqueous solution with a concentration of 300 mg / L for 30 s, then neutralized to pH 6 in a sodium bisulfate aqueous solution, then washed with water for 5 times, then coated with corn starch and demolded, to obtain a wear-resistant and puncture-resistant nitrile glove.

[0070] Example 2: A wear-resistant and puncture-resistant nitrile glove was prepared by the following method:

[0071] S1: 5.5 g of ammonium bifluoride, 3.3 g of citric acid were added into 110 mL of deionized water and stirred for 15 min, then 22.5 g of basalt fiber was added and ultrasonically dispersed at 48℃ for 40 min, then centrifuged and washed with deionized water for 6 times, then dried at 58℃, to obtain etched fibers;

[0072] S2: 37.5 g of anhydrous ethanol, 1.3 g of carboxylated single-walled carbon nanotubes, 0.06 g of sodium dodecylbenzenesulfonate were added into 37.5 g of deionized water and ultrasonically dispersed for 40 min, then 3.8 g of nano-zinc oxide, 2.5 g of nano-diamond were added and ultrasonically dispersed for 40 min, then 0.23 g of 3-cyanopropyltrimethoxysilane was added and stirred at 58℃ for 2.5 h, finally 6.3 g of nitrile latex, 0.25 g of polyvinylpyrrolidone were added and stirred for 15 min, to obtain a spinning solution;

[0073] S3: The etched fiber was placed in an atmospheric pressure plasma treatment instrument, argon / oxygen mixed gas was introduced (argon gas flow rate was 15 L / h, oxygen gas flow rate was 5 L / h) and plasma treatment was performed for 55 s at a power of 75 W, then electrospinning was performed on the etched fiber with a moving speed of 4.5 cm / s at 28℃, relative humidity of 45%, voltage of 15 kV, needle distance from the receiving plate of 15 cm, using a spinning solution with a flow rate of 0.8 mL / h, and then vacuum drying was performed at 78℃ for 1.5 h, to obtain a composite fiber;

[0074] S4: 170 g of aqueous polyurethane, 17 g of chitosan quaternary ammonium salt, 27.2 g of dioctyl terephthalate, 1.5 g of graphene nanosheet were added in 158 g of deionized water, and then 1% acetic acid aqueous solution was used to adjust the pH to 7, and then treated at 2800 r / min for 35 min, then immersed in 17 g of composite fiber, soaked for 9 min, taken out and placed in a microwave reactor for irradiation treatment at 50℃ for 4 min at a power of 130 W, and finally air dried at 58℃ for 1.5 h to obtain coated fiber;

[0075] S5: 2.1 g of silane coupling agent KH-560, 0.55 g of glacial acetic acid were added in 9.5 g of deionized water and stirred for 15 min, then 16 g of nano-alumina, 79 g of carboxyl nitrile rubber were added and stirred at 2100 r / min for 25 min, after grinding to D90 of 1 μm, sprayed on the surface of the coated fiber, formed a coating layer with a thickness of 4 μm, then placed in an infrared curing oven for irradiation at a wavelength of 4 μm and a temperature of 100℃ for 4 min, then incubated at 70℃ for 1.5 h, finally immersed in 105 g of 0.5% silane coupling agent KH-570 ethanol solution for 13 min, drained and dried at 78℃ for 40 min to obtain synergistic fiber;

[0076] S6: 3.5 g of sulfur, 3 g of titanium white, 3 g of phthalocyanine blue, 0.3 g of polycarboxylic acid sodium salt were added in 6 g of deionized water and ball milled to D90 of 0.1 μm to obtain a mixed dispersion liquid;

[0077] S7: 0.6 g of accelerator ZDBC, 0.3 g of accelerator ZDEC were added in 8.1 g of deionized water at 48℃ and stirred for 30 min to obtain an accelerator solution;

[0078] S8: 85 g of carboxyl nitrile rubber latex was stirred at 28℃ for 9 h at 60 r / min, then 15.5 g of mixed dispersion liquid, 0.8 g of antioxidant RD, 9 g of accelerator solution, 7 g of synergistic fiber were added in sequence while stirring, and the pH was adjusted to 9, stirred for 3 h, then aged at 28℃ for 9 h to obtain a composite latex;

[0079] S9: immerse the ceramic hand mold into a 58℃ 5% by mass sodium hydroxide solution for 3 min, rinse with deionized water 4 times, dry at 78℃ for 20 min, immerse into a 13% by mass calcium nitrate aqueous solution containing 3% ethanol for 4 s, then dry at 68℃ for 4 min, to obtain a pretreated hand mold;

[0080] S10: immerse the pretreated hand mold into a 27℃ composite latex emulsion for 7 s, then pull out at 9 cm / min, after forming a 0.1 mm thick glue film, air dry at 48℃ for 2 min, then perform secondary immersion for 2.5 s on a 2.5 cm portion at the fingertip, then immerse in 58℃ deionized water for 8 min, and finally air dry at 78℃ for 6 min, to obtain a glove crude product;

[0081] S11: roll up the glove crude product at the opening by 2.5 mm using a crimping machine, then vulcanize at 115℃ for 18 min, cool down to 99℃ at a rate of 5℃ / min, vulcanize at 99℃ for 25 min, then water cool to 30℃, immerse in an active chlorine aqueous solution with a concentration of 400 mg / L for 35 s, then neutralize in a sodium bisulfate aqueous solution to a pH of 6.5, wash with water 8 times, then apply corn starch and demold, to obtain a wear-resistant puncture-resistant nitrile glove.

[0082] Example 3: a wear-resistant puncture-resistant nitrile glove is prepared according to the following method:

[0083] S1: add 6 g of ammonium bifluoride, 3.5 g of citric acid into 120 mL of deionized water, and stir for 20 min, then add 25 g of basalt fibers and ultrasonically disperse at 50℃ for 50 min, then centrifugalize and wash with deionized water 7 times, and then dry at 60℃, to obtain etched fibers;

[0084] S2: add 45 g of anhydrous ethanol, 1.5 g of carboxylated single-walled carbon nanotubes, and 0.07 g of sodium dodecyl benzene sulfonate into 45 g of deionized water, and ultrasonically disperse for 50 min, then add 4.5 g of nano zinc oxide, 3 g of nano diamond, and ultrasonically disperse for 50 min, then add 0.28 g of 3-cyanopropyl trimethoxysilane, and stir at 60℃ for 3 h, finally add 7.5 g of nitrile latex, and 0.3 g of polyvinylpyrrolidone, and stir for 20 min, to obtain a spinning solution;

[0085] S3: place the etched fibers into an atmospheric pressure plasma treatment instrument, introduce argon / oxygen mixed gas (argon gas flow rate is 15 L / h, oxygen gas flow rate is 5 L / h), and perform plasma treatment at a power of 80 W for 60 s, then use a spinning solution with a flow rate of 0.9 mL / h to electrospun the etched fibers moving at a speed of 5 cm / s under the conditions of 30℃, relative humidity 50%, voltage 15 kV, and needle distance from the receiving plate 15 cm, then vacuum dry at 80℃ for 2 h, to obtain composite fibers.

[0086] S4: 200 g of aqueous polyurethane, 20 g of chitosan quaternary ammonium salt, 32 g of dioctyl terephthalate, 2 g of graphene nanosheet were added in 186 g of deionized water, and the pH was adjusted to 7.5 with 1% acetic acid aqueous solution, and then treated at 3000 r / min for 40 min, then immersed in 20 g of composite fiber, soaked for 10 min, taken out and placed in a microwave reactor for irradiation treatment at 55℃ for 5 min with a power of 150 W, and finally dried at 60℃ with air blowing for 2 h to obtain coated fiber;

[0087] S5: 2.2 g of silane coupling agent KH-560, 0.6 g of glacial acetic acid were added in 10 g of deionized water and stirred for 20 min, then 17 g of nano-alumina, 83 g of carboxyl nitrile rubber were added and stirred at 2200 r / min for 30 min, ground to D90 of 2 μm, then sprayed on the surface of the coated fiber to form a coating with a thickness of 5 μm, then placed in an infrared curing furnace for irradiation at a wavelength of 5 μm and a temperature of 100℃ for 5 min, then incubated at 80℃ for 2 h, finally immersed in 110 g of 0.5% silane coupling agent KH-570 ethanol solution for 15 min, drained and dried at 80℃ for 50 min to obtain synergistic fiber;

[0088] S6: 4 g of sulfur, 5 g of titanium white, 2 g of pearl pigment, 0.4 g of sodium polycarboxylate were added in 7 g of deionized water and ball milled to D90 of 2 μm to obtain a mixed dispersion liquid;

[0089] S7: 0.8 g of accelerator ZDBC, 0.4 g of accelerator ZDEC were added in 10.8 g of deionized water at 50℃ and stirred for 40 min to obtain an accelerator solution;

[0090] S8: 90 g of carboxyl nitrile rubber latex was stirred at 30℃ for 10 h, then 18 g of mixed dispersion liquid, 1.1 g of antioxidant RD, 12 g of accelerator solution, 8 g of synergistic fiber were added in sequence while stirring, and the pH was adjusted to 9.5, stirred for 4 h, then aged at 30℃ for 10 h to obtain a composite latex;

[0091] S9: the ceramic hand mold was immersed in 60℃ 5% NaOH solution for 5 min, then washed with deionized water for 5 times, dried at 80℃ for 30 min, then immersed in 15% Ca(NO3)2 aqueous solution containing 3% ethanol for 5 s, then dried at 70℃ for 5 min to obtain a pretreated hand mold;

[0092] S10: The pre-processed hand mold was immersed in a 30℃ composite latex emulsion for 8s and then taken out at 10cm / min, forming a 0.12mm thick glue film, which was then air-dried at 50℃ for 3min, after which the 3cm part at the fingertip was secondarily immersed for 3s, then soaked in 60℃ deionized water for 10min, and finally air-dried at 80℃ for 7min, obtaining the glove crude product;

[0093] S11: The glove crude product was rolled up by 3mm at the opening with a rolling machine, then vulcanized at 120℃ for 20min, cooled to 100℃ at 5℃ / min and vulcanized at 100℃ for 30min, then water-cooled to 40℃, and finally immersed in an active chlorine water solution with a concentration of 500mg / L for 40s, neutralized to pH 7 in a sodium bisulfate aqueous solution, washed with water for 10 times, coated with corn starch, and demolded, obtaining the wear-resistant and puncture-resistant nitrile glove.

[0094] Comparative Example 1:

[0095] This comparative example is compared with Example 1 only without adding "carboxylated single-walled carbon nanotubes" in the preparation process of S1, and the rest of the steps and parameters are the same. This comparative example will not be repeated here. Finally, the wear-resistant and puncture-resistant nitrile glove is obtained.

[0096] Comparative Example 2:

[0097] This comparative example is compared with Example 1 only without adding "nano zinc oxide" in the preparation process of S2, and the rest of the steps and parameters are the same. This comparative example will not be repeated here. Finally, the wear-resistant and puncture-resistant nitrile glove is obtained.

[0098] Comparative Example 3:

[0099] This comparative example is compared with Example 1 only without adding "nano diamond" in the preparation process of S2, and the rest of the steps and parameters are the same. This comparative example will not be repeated here. Finally, the wear-resistant and puncture-resistant nitrile glove is obtained.

[0100] Comparative Example 4:

[0101] This comparative example is compared with Example 1 only by replacing the "etched fiber" added in the preparation process of S3 with "basalt fiber", and the rest of the steps and parameters are the same. This comparative example will not be repeated here. Finally, the wear-resistant and puncture-resistant nitrile glove is obtained.

[0102] Comparative Example 5:

[0103] This comparative example is compared with Example 1 only without adding "graphene nanosheet" in the preparation process of S4, and the rest of the steps and parameters are the same. This comparative example will not be repeated here. Finally, the wear-resistant and puncture-resistant nitrile glove is obtained.

[0104] Comparative Example 6:

[0105] The comparative example is compared with example 1 only by replacing the “coated fiber” added in the preparation process of S5 with “composite fiber”, and the rest of the steps and parameters are the same, and the comparative example will not be repeated, and finally the wear-resistant and puncture-resistant nitrile glove is obtained.

[0106] Comparative example 7:

[0107] The comparative example is compared with example 1 only by not adding “nano-alumina” in the preparation process of S5, and the rest of the steps and parameters are the same, and the comparative example will not be repeated, and finally the wear-resistant and puncture-resistant nitrile glove is obtained.

[0108] Comparative example 8:

[0109] The comparative example is compared with example 1 only by replacing the “coated fiber” added in the preparation process of S5 with “composite fiber”, and the rest of the steps and parameters are the same, and the comparative example will not be repeated, and finally the wear-resistant and puncture-resistant nitrile glove is obtained.

[0110] Comparative example 9:

[0111] The comparative example is compared with example 1 only by replacing the “synergistic fiber” added in the preparation process of S8 with “coated fiber”, and the rest of the steps and parameters are the same, and the comparative example will not be repeated, and finally the wear-resistant and puncture-resistant nitrile glove is obtained.

[0112] Comparative example 10:

[0113] The comparative example is compared with example 1 only by not adding “synergistic fiber” in the preparation process of S8, and the rest of the steps and parameters are the same, and the comparative example will not be repeated, and finally the wear-resistant and puncture-resistant nitrile glove is obtained.

[0114] Performance test:

[0115] Determination of wear resistance:

[0116] According to the standard of GB / T 1689-2014 “Determination of abrasion resistance of vulcanized rubber (using Akron abrasion tester)”, the abrasion amount (cm 3 ) of the wear-resistant and puncture-resistant nitrile glove prepared by example 1- example 3 and comparative example 1- comparative example 10 is determined after 1.61km of friction under the constant load of 26.5N, and the test results are shown in table 1;

[0117] Determination of puncture resistance:

[0118] According to the standard of GB / T 21867-2008 “Gloves-General technical conditions”, the puncture resistance (N) of the palm part of the wear-resistant and puncture-resistant nitrile glove prepared by example 1- example 3 and comparative example 1- comparative example 10 is determined at a puncture speed of 100mm / min, and the test results are shown in table 1;

[0119] Determination of antistatic property:

[0120] According to GB / T 1410-2006 "Test Method for Volume Resistivity and Surface Resistivity of Solid Insulating Materials", the surface resistivity (Ω) of the wear-resistant and puncture-resistant nitrile glove prepared by the application examples 1-3 and the comparative examples 1-10 was determined, and the test results are shown in Table 1.

[0121] Determination of antibacterial property:

[0122] According to GB 15979-2024 "Hygienic Requirements for Disposable Hygienic Products", the antibacterial rate (%) of the wear-resistant and puncture-resistant nitrile glove prepared by the application examples 1-3 and the comparative examples 1-10 was determined, and the test results are shown in Table 1.

[0123] Determination of low temperature resistance:

[0124] According to GB / T 528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber", the elongation at break (%) of the palm part of the wear-resistant and puncture-resistant nitrile glove prepared by the application examples 1-3 and the comparative examples 1-10 was determined at -40℃ (determined at -40℃ after being stored at -40℃ for 24h) with a tensile speed of 500mm / min, and the test results are shown in Table 1.

[0125] Table 1: Performance test results of the application examples 1-3 and the comparative examples 1-10

[0126] Item Wear resistance / cm 3 ]] Puncture resistance / N Antistatic property / Ω Antibacterial property / % Low temperature resistance / % Example 1 0.04 87.7 1.5 x 10 6 ]]> 99.9 349 Example 2 0.03 88.1 1.3 x 10 6 ]]> 99.9 355 Example 3 0.04 87.5 1.6 x 10 6 ]]> 99.9 347 Comparative Example 1 0.09 79.8 8.5 x 10 8 ]]> 99.8 301 Comparative Example 2 0.05 86.2 1.7 x 10 6 ]]> 87.4 342 Comparative Example 3 0.07 80.8 1.6 x 10 6 ]] 99.9 345 Comparative Example 4 0.10 73.9 1.9 x 10 7 ]] 99.7 338 Comparative Example 5 0.08 80.1 5.8 x 10 8 ]]> 99.9 306 Comparative Example 6 0.17 60.0 9.1 x 10 8 ]]> 85.6 283 Comparative Example 7 0.07 80.9 1.5 x 10 6 ]]> 99.8 346 Comparative Example 8 0.15 63.2 1.8 x 10 6 ]]> 67.8 172 Comparative Example 9 0.14 63.8 2.3 x 10 7 ]]> 99.5 169 Comparative Example 10 0.25 39.1 9.5 x 10 11 ]]> 45.2 66

[0127] Data analysis:

[0128] As can be seen from Table 1, the wear-resistant and puncture-resistant nitrile glove prepared by the application examples has excellent wear resistance, puncture resistance, antistatic property, antibacterial property and low temperature resistance.

[0129] The above describes one embodiment of the application in detail, but the content described is only the preferred embodiment of the application, and cannot be considered as limiting the scope of the application. Any equivalent changes and improvements made according to the scope of the application should still be within the scope of the patent coverage of the application.

Claims

1. A puncture and abrasion resistant nitrile glove characterized in that, The butyronitrile gloves are made of a composite latex solution; The composite latex solution comprises the following raw materials in mass parts: carboxyl butyronitrile latex 80-90 parts, mixed dispersion liquid 13-18 parts, antioxidant RD 0.5-1.1 parts, accelerator solution 6-12 parts, and synergistic fiber 6-8 parts; The mixed dispersion liquid is made of deionized water, sulfur, pigment, and polycarboxylic acid sodium salt; The synergistic fiber is made of basalt fiber etched and then combined with a spinning solution through electrospinning to obtain a composite fiber, and then coated with graphene nanosheet doped polyurethane and nano-aluminum oxide doped carboxyl butyronitrile rubber in sequence, wherein the spinning solution comprises carboxylated single-walled carbon nanotubes, sodium dodecyl benzene sulfonate, nano-zinc oxide, nano-diamond, gamma-cyanopropyl trimethoxysilane, butyronitrile latex, and polyvinylpyrrolidone.

2. The puncture and abrasion resistant nitrile glove of claim 1, wherein, The preparation method of the composite latex solution is as follows: The carboxyl butyronitrile latex is stirred for 8-10 hours, and then the mixed dispersion liquid, the antioxidant RD, the accelerator solution, and the synergistic fiber are added in sequence while stirring, and the pH is adjusted to 8.5-9.5; after stirring for 2-4 hours, aging is performed at 25-30°C for 8-10 hours to obtain the composite latex solution.

3. The puncture and abrasion resistant nitrile glove of claim 1, wherein, The preparation method of the mixed dispersion liquid is as follows: Sulfur, pigment, and polycarboxylic acid sodium salt are added to deionized water and ball milled to obtain the mixed dispersion liquid. The mass ratio of the deionized water, sulfur, pigment, and polycarboxylic acid sodium salt is 5-7:3-4:5-7:0.2-0.

4. The pigment is a combination of titanium white and any one of zinc oxide, phthalocyanine blue, and pearlescent pigment.

4. The puncture and abrasion resistant nitrile glove of claim 1, wherein, The preparation method of the accelerator solution is as follows: The accelerator ZDBC and the accelerator ZDEC are added to deionized water and stirred uniformly to obtain the accelerator solution. The mass ratio of the deionized water, accelerator ZDBC, and accelerator ZDEC is 5.4-10.8:0.4-0.8:0.2-0.

4.

5. The puncture and abrasion resistant nitrile glove of claim 1, wherein, The preparation method of the synergistic fiber is as follows: A1: Ammonium fluoride and citric acid are added to deionized water and stirred uniformly, and then basalt fiber is added and ultrasonicated, followed by centrifugation and drying to obtain etched fiber; A2: Anhydrous ethanol, carboxylated single-walled carbon nanotubes, and sodium dodecyl benzene sulfonate are added to deionized water and ultrasonicated, and then nano-zinc oxide and nano-diamond are added and ultrasonicated, followed by the addition of gamma-cyanopropyl trimethoxysilane and stirring for 2-3 hours, and finally butyronitrile latex and polyvinylpyrrolidone are added and stirred uniformly to obtain a spinning solution; A3: The etched fiber is subjected to plasma treatment and then electrospun with the spinning solution, and after drying, a composite fiber is obtained; A4: Water-based polyurethane, chitosan quaternary ammonium salt, dioctyl terephthalate, and graphene nanosheet are added to deionized water and stirred after adjusting the pH, and then the composite fiber is immersed, taken out, and irradiated, and after drying, a coated fiber is obtained; A5: Silane coupling agent KH-560 and glacial acetic acid are added to deionized water and stirred uniformly, and then nano-aluminum oxide and carboxyl butyronitrile rubber are added and stirred uniformly, and after grinding and spraying on the surface of the coated fiber, infrared irradiation is performed and the mixture is incubated at 60-80°C for 1-2 hours, and finally the mixture is immersed in a silane coupling agent KH-570 ethanol solution, drained, and dried to obtain the synergistic fiber.

6. The puncture and abrasion resistant nitrile glove of claim 5, wherein, The mass ratio of the deionized water, ammonium hydrogen fluoride, citric acid and basalt fiber in A1 is 100-120:5-6:3-3.5:20-25; The mass ratio of the deionized water, anhydrous ethanol, carboxylated single-walled carbon nanotubes, sodium dodecyl benzene sulfonate, nano zinc oxide, nano diamond, gamma-cyanopropyl trimethoxysilane, butyronitrile latex and polyvinylpyrrolidone in A2 is 30-45:30-45:1-1.5:0.05-0.07:3-4.5:2-3:0.18-0.28:5-7.5:0.2-0.3; The power of the plasma treatment in A3 is 70-80W, the time length is 50-60s, and the treatment atmosphere is argon and oxygen mixed gas; The temperature of the electrospinning in A3 is 25-30℃, the relative humidity is 40%-50%, the voltage is 15kV, the distance between the needle and the receiving plate is 15cm, the flow rate of the spinning solution is 0.7-0.9mL / h, and the moving speed of the etched fiber is 4-5cm / s; The mass ratio of the deionized water, aqueous polyurethane, chitosan quaternary ammonium salt, dioctyl terephthalate, graphene nanosheet and composite fiber in A4 is 130-186:140-200:14-20:22.5-32:1-2:14-20; The pH value after the pH adjustment in A4 is 6.5-7.5; The stirring treatment in A4 is stirring at 2500-3000r / min for 30-40min; The temperature of the irradiation in A4 is 45-55℃, the power is 100-150W, and the time length is 3-5min.

7. The puncture and abrasion resistant nitrile glove of claim 5, wherein, The mass ratio of the deionized water, silane coupling agent KH-560, glacial acetic acid, nano aluminum oxide, carboxylated butyronitrile rubber and silane coupling agent KH-570 ethanol solution in A5 is 9-10:2-2.2:0.5-0.6:15-17:75-83:100-110; The wavelength of the infrared irradiation in A5 is 3-5μm, the temperature is 100℃, and the time length is 3-5min.

8. A process for the production of the puncture resistant and abrasion resistant nitrile glove according to any one of claims 1 to 7, characterized in that, The method comprises the following steps: S1: washing the ceramic hand mold in a sodium hydroxide solution, then rinsing with deionized water, drying, then immersing in a calcium nitrate aqueous solution containing ethanol, taking out and drying to obtain a pretreated hand mold; S2: immersing the pretreated hand mold in a composite latex emulsion, then taking out, drying the formed film at 45-50℃ for 1-3min, then performing secondary immersion on the fingertip part, then immersing in deionized water at 55-60℃, finally taking out and drying to obtain a crude nitrile glove; S3: rolling up the crude nitrile glove by 2-3mm at the opening, then sequentially performing vulcanization treatment, chlorine washing, neutralization, water washing and drying to obtain a wear-resistant and puncture-resistant nitrile glove.

9. The method of making a puncture and abrasion resistant nitrile glove according to claim 8, wherein, The mass fraction of the sodium hydroxide solution in S1 is 5%, and the temperature is 55-60℃; The mass fraction of the calcium nitrate aqueous solution in S1 is 10%-15%, and the content of ethanol is 3%; The thickness of the film in S2 is 0.08-0.12mm.

10. The method of making a puncture and abrasion resistant nitrile glove according to claim 8, wherein, The vulcanization treatment in S3 is: first vulcanization at 110-120℃ for 15-20min, then vulcanization at 98-100℃ for 20-30min, and water cooling to 20-40℃; The chlorine washing in S3 is: dipping in an active chlorine water solution with a concentration of 300-500mg / L for 30-40s; The neutralization in S3 is: neutralization to pH 6-7 with a sodium bisulfate water solution.