Hypoallergenic butyronitrile gloves and preparation method thereof

Abstract

The invention discloses a low-sensitization butyronitrile glove and a preparation method thereof, and relates to the technical field of rubber glove production. The low-sensitization butyronitrile glove is prepared from the following raw materials in parts by weight: 86 to 90 parts of butyronitrile latex, 3 to 4 parts of sulfur, 3 to 4 parts of zinc oxide, 1 to 2 parts of accelerant, 0.5 part of anti-aging agent, 3 to 4 parts of titanium dioxide, 2 parts of blue pigment and 2 to 5 parts of antibacterial nano silicon dioxide. The low-sensitization butyronitrile glove prepared by the invention has the advantages of low sensitization, high antibacterial property, high durability and comfort in wearing.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber glove production, and in particular to a low-allergenic nitrile glove and a preparation method thereof. Background Art

[0002] Natural latex has excellent elasticity and durability, making it suitable for making disposable gloves. With the surge in demand for gloves in the medical industry, latex gloves have begun to be widely used in surgery and nursing work. Its natural material comes from rubber trees. After extracting the latex liquid, it is made into gloves with good elasticity and identifiable properties through processes such as sulfurization, extrusion, and vulcanization. Although latex gloves have many advantages, their defects have gradually been exposed and attracted attention. First, latex gloves are prone to allergic reactions. The protein in natural latex is highly sensitive, causing some users, especially medical staff and allergy patients, to develop allergic contact dermatitis, asthma, and even anaphylactic shock. In response to this, manufacturers have tried to remove latex proteins or add anti-allergic agents in subsequent research and development, but the effect is limited.

[0003] As understanding of the shortcomings of latex gloves deepened, researchers began seeking safer, higher-performing alternatives, leading to the gradual entry of nitrile gloves into the market. Nitrile is a synthetic rubber material with excellent puncture and chemical resistance and good elasticity. Compared to latex, nitrile gloves are completely protein-free, thus avoiding allergic reactions and becoming the preferred choice in the medical field, especially for allergy sufferers. Furthermore, nitrile gloves offer superior puncture resistance, providing more reliable protection even in high-risk environments. Their strong chemical resistance makes them suitable for a variety of industrial and laboratory environments.

[0004] While existing nitrile gloves are less allergenic than latex gloves, allergies can still occur due to raw material residues in the nitrile rubber production process and the choice of vulcanizing agents during the vulcanization process. Therefore, for safety reasons, it is necessary to develop hypoallergenic nitrile gloves. At the same time, to meet evolving application requirements, nitrile gloves need to integrate high-performance features, such as antimicrobial properties and wear comfort. Summary of the Invention

[0005] The purpose of the present invention is to provide a hypoallergenic nitrile glove and a preparation method thereof to solve the following technical problems: Allergies may occur due to raw material residues in the nitrile rubber production process and the selection of vulcanizing agents in the vulcanization process. High-functionality integration meets ever-changing application needs.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A hypoallergenic nitrile glove, the preparation method of which comprises the following steps: S1. Pretreatment, compounding and ripening of latex: adjusting the pH of nitrile latex to 3.0, introducing ozone with an ozone generator for 1 hour, and then stirring at a low speed for 24 hours, sulfur, zinc oxide, titanium dioxide, and blue pigment are mixed with a dispersant and water, respectively, and prepared into a dispersion with a particle size of less than or equal to 5 μm by a ball mill, and the accelerator is directly dissolved in water to obtain an accelerator solution; zinc oxide dispersion, titanium dioxide dispersion, antioxidant, accelerator solution, and sulfur dispersion are added to the nitrile latex in sequence, adjusting the pH to 9.5-10.5, and stirring for 2-4 hours; adding antibacterial nano-silica, stirring for 1-2 hours, and keeping warm for 12 hours; S2. Pretreatment and dipping of the hand model: clean the hand model with a sodium hydroxide aqueous solution, rinse with pure water, and then dry; immerse the hand model in a mixed solution of calcium nitrate and methanol and then dry; S3, leaching, crimping and vulcanization: Soak the hand form in a hot water tank for 5-10 minutes, dry it, use a crimping machine to crimp the opening of the latex glove by 2-3 mm, vulcanize it in a tunnel vulcanization oven, and cool it to below 40°C after completion; S4. Demolding and subsequent processing: Use a pneumatic demoulding machine to blow off the semi-finished gloves with compressed air, place the semi-finished gloves in a chlorine washing tank and soak them in chlorine water for 1 minute, neutralize them with NaHSO3, and wash them with water to obtain low-allergenic nitrile gloves.

[0007] As a further embodiment of the present invention, the raw materials include the following parts by weight: 86-90 parts by weight of nitrile latex, 3-4 parts by weight of sulfur, 3-4 parts by weight of zinc oxide, 1-2 parts by weight of accelerator, 0.5 parts by weight of antioxidant, 3-4 parts by weight of titanium dioxide, 2 parts by weight of blue pigment, and 2-5 parts by weight of antibacterial nano-silica.

[0008] As a further embodiment of the present invention: the solid content of the nitrile latex is 40%; The accelerator comprises the following raw materials in parts by weight: 2 parts by weight of DTDC-80, 2 parts by weight of ZDBC, and 1 part by weight of ZDEC; The antioxidant is antioxidant RD; The dispersant is polyethylene glycol 200; The solid content of each dispersion is 60%; The concentration of the accelerator solution is 10wt%; The temperature for heat preservation and aging is 25℃.

[0009] As a further solution of the present invention: the ozone concentration in S1 is 70% (v / v), and the air intake volume of the ozone generator is 0.3 L / min.

[0010] As a further embodiment of the present invention, the preparation method of the antibacterial nano-silica comprises the following steps: A1: Place N,N-dimethylethanolamine and octyl bromide in a reaction flask, reflux under condensation for 3-4 hours, cool, add a mixed solvent, control the temperature at 70-80°C to react for 10-14 hours, rotary evaporate, wash, purify, filter, and dry to obtain a quaternary ammonium salt intermediate. Blend the quaternary ammonium salt intermediate, tetrahydrofuran, isophorone diisocyanate, and dibutyltin dilaurate, control the temperature at 30-40°C to react for 8-12 hours, rotary evaporate, wash, purify, and dry to obtain a quaternary ammonium salt monomer. A2: Chitosan powder and acetic acid solution were added to a reactor and dispersed evenly. Quaternary ammonium salt monomer and N,N-dimethylformamide were mixed and added to the reactor. The temperature was controlled at 30-40°C and stirred for 10-14 hours. The mixture was dialyzed and dried to obtain chitosan quaternary ammonium salt powder. A3: Add nano-silica and 30wt% hydrogen peroxide into a reaction flask, control the temperature to 40-50℃ for reflux, and dry to obtain surface-activated nano-silica; blend chitosan quaternary ammonium salt powder, 2vt% glacial acetic acid solution, and surface-activated nano-silica, react for 22-26h, and dry to obtain antibacterial nano-silica.

[0011] As a further embodiment of the present invention: in A1, the addition ratio of N,N-dimethylethanolamine and bromooctane is 1.25-1.45 g:3.1-3.3 g, the mixed solvent is composed of propanol and methanol in a volume ratio of 1:3, and the addition ratio of the quaternary ammonium salt intermediate, isophorone diisocyanate, tetrahydrofuran, and dibutyltin dilaurate is 2.2 g:2.3-2.7 g:40-50 mL:0.4-0.6 mL; The acetic acid solution in A2 is a 1-4 wt% acetic acid solution; The addition ratio of chitosan powder, acetic acid solution, quaternary ammonium salt monomer, and N,N-dimethylformamide is 1.6 g: 25-100 mL: 10.8-13.5 g: 40-80 mL; The addition ratio of nano-silica, 30wt% hydrogen peroxide, chitosan quaternary ammonium salt powder, and 2vt% glacial acetic acid in A3 is 2.0-2.4g:25-35mL:0.8g:25-35mL.

[0012] As a further solution of the present invention: the hand model material in S2 is ceramic; The concentration of the sodium hydroxide aqueous solution is 5wt%, and the alkali washing temperature is 60°C; The mass ratio of calcium nitrate to methanol in the mixed solution is 10-15:5; During the hand mold dipping process, the latex temperature is controlled at 25-30° C., the dipping time is 5-8 seconds, the pulling speed is 10 cm / min, and the film thickness is 0.08-0.12 mm.

[0013] As a further solution of the present invention: the temperature of the hot water tank in S3 is 60°C; The vulcanization process is divided into two stages: One-stage vulcanization: vulcanize at 110-120℃ for 15-20min; Second stage vulcanization: vulcanize at 100℃ for 30min.

[0014] As a further solution of the present invention: During the demoulding process described in S4, the pneumatic demoulding machine compresses the air to 0.3-0.5 MPa.

[0015] Beneficial effects of the present invention: (1) The present invention first uses ozone to remove the residual raw material acrylonitrile in the nitrile latex. This method has the characteristics of good treatment effect, fast reaction, and no secondary pollution. Then, the more low-toxic and low-odor DTDC-80 is used as the vulcanizing agent. At the same time, the hand mold after immersion is placed in a hot water tank to soak to remove water-soluble substances and reduce allergenicity.

[0016] (2) This application utilizes N,N-dimethylethanolamine and octyl bromide in a mixed solvent of propanol and methanol at a volume ratio of 1:3 to obtain a quaternary ammonium salt intermediate, and then blends the quaternary ammonium salt intermediate, tetrahydrofuran, isophorone diisocyanate, and dibutyltin dilaurate to obtain a quaternary ammonium salt monomer. Chitosan powder is dissolved in an acetic acid solution and blended with the quaternary ammonium salt monomer and N,N-dimethylformamide to obtain chitosan quaternary ammonium salt powder. The chitosan quaternary ammonium salt powder is grafted onto surface-activated nano-silica to prepare antibacterial nano-silica. Due to the strong positive charge of the quaternary nitrogen atom in the quaternary ammonium salt, when it comes into contact with the negatively charged bacterial cell membrane, the bacterial charge balance is broken, and the bacteria rupture and die under the action of their own osmotic pressure. Therefore, the quaternary ammonium salt exhibits excellent antibacterial, antifungal, antiviral and antiparasitic activity. The introduction of quaternary ammonium salt into the chitosan skeleton can weaken the hydrogen bonds between and within the chitosan molecules, reduce its crystallinity, and thus improve its solubility and antibacterial properties in a wider pH range.

[0017] (3) The vulcanization process of this scheme adopts a two-stage vulcanization process, which can fully eliminate the internal stress of the material and improve durability; after demolding, the surface is chlorinated to increase the slipperiness of the gloves and improve wearing comfort. DETAILED DESCRIPTION

[0018] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0019] Example 1 The preparation method of antibacterial nano-silica comprises the following steps: A1: 1.25 g of N,N-dimethylethanolamine and 3.1 g of bromooctane were placed in a reaction flask and refluxed under condensation for 3-4 h. After cooling, a mixed solvent was added and the reaction was controlled at 70°C for 10 h. The mixture was rotary evaporated, washed, purified, filtered, and dried to obtain a quaternary ammonium salt intermediate. 2.2 g of the quaternary ammonium salt intermediate, 40 mL of tetrahydrofuran, 2.3 g of isophorone diisocyanate, and 0.4 mL of dibutyltin dilaurate were mixed and the reaction was controlled at 30°C for 8 h. The mixture was rotary evaporated, washed, purified, and dried to obtain a quaternary ammonium salt monomer. A2: 1.6 g of chitosan powder and 100 mL of 1 wt% acetic acid solution were added to a reactor and dispersed evenly. 10.8 g of quaternary ammonium salt monomer and 40 mL of N,N-dimethylformamide were blended and added to the reactor. The temperature was controlled at 30°C and stirred for 10 h. The mixture was dialyzed and dried to obtain chitosan quaternary ammonium salt powder. A3: Add 2.0g of nano-silica and 25mL of 30wt% hydrogen peroxide to a reaction flask, control the temperature to reflux at 40℃, and dry to obtain surface-activated nano-silica; blend 0.8g of chitosan quaternary ammonium salt powder, 25mL of 2vt% glacial acetic acid solution, and surface-activated nano-silica, react for 22h, and dry to obtain antibacterial nano-silica.

[0020] Example 2 The preparation method of antibacterial nano-silica comprises the following steps: A1: 1.35 g of N,N-dimethylethanolamine and 3.2 g of bromooctane were placed in a reaction flask and reacted under condensation reflux for 3.5 h. After cooling, a mixed solvent was added and the reaction was controlled at 75°C for 12 h. The mixture was rotary evaporated, washed, purified, filtered, and dried to obtain a quaternary ammonium salt intermediate. 2.2 g of the quaternary ammonium salt intermediate, 45 mL of tetrahydrofuran, 2.5 g of isophorone diisocyanate, and 0.5 mL of dibutyltin dilaurate were mixed and the reaction was controlled at 35°C for 10 h. The mixture was rotary evaporated, washed, purified, and dried to obtain a quaternary ammonium salt monomer. A2: 1.6 g of chitosan powder and 50 mL of 2 wt% acetic acid solution were added to a reactor and dispersed evenly. 12.2 g of quaternary ammonium salt monomer and 60 mL of N,N-dimethylformamide were blended and added to the reactor. The temperature was controlled at 35°C and stirred for 12 h. The mixture was dialyzed and dried to obtain chitosan quaternary ammonium salt powder. A3: Add 2.2g of nano-silica and 30mL of 30wt% hydrogen peroxide into a reaction flask, control the temperature to reflux at 45℃, and dry to obtain surface-activated nano-silica; blend 0.8g of chitosan quaternary ammonium salt powder, 30mL of 2vt% glacial acetic acid solution, and surface-activated nano-silica, react for 24h, and dry to obtain antibacterial nano-silica.

[0021] Example 3 The preparation method of antibacterial nano-silica comprises the following steps: A1: 1.45 g of N,N-dimethylethanolamine and 3.3 g of bromooctane were placed in a reaction flask and refluxed under condensation for 4 h. After cooling, a mixed solvent was added and the reaction was controlled at 80°C for 14 h. The mixture was rotary evaporated, washed, purified, filtered, and dried to obtain a quaternary ammonium salt intermediate. 2.2 g of the quaternary ammonium salt intermediate, 50 mL of tetrahydrofuran, 2.7 g of isophorone diisocyanate, and 0.6 mL of dibutyltin dilaurate were mixed and the reaction was controlled at 40°C for 12 h. The mixture was rotary evaporated, washed, purified, and dried to obtain a quaternary ammonium salt monomer. A2: 1.6 g of chitosan powder and 25 mL of 4 wt% acetic acid solution were added to a reactor and dispersed evenly. 13.5 g of quaternary ammonium salt monomer and 80 mL of N,N-dimethylformamide were blended and added to the reactor. The temperature was controlled at 40°C and stirred for 14 h. The mixture was dialyzed and dried to obtain chitosan quaternary ammonium salt powder. A3: Add 2.4g of nano-silica and 35mL of 30wt% hydrogen peroxide to a reaction flask, control the temperature to reflux at 50℃, and dry to obtain surface-activated nano-silica; blend 0.8g of chitosan quaternary ammonium salt powder, 35mL of 2vt% glacial acetic acid solution, and surface-activated nano-silica, react for 26h, and dry to obtain antibacterial nano-silica.

[0022] Example 4 A hypoallergenic nitrile glove, the preparation method of which comprises the following steps: S1, take 88g of nitrile latex and adjust the pH to 3.0, after passing 70% (v / v) ozone for 1h with an ozone generator at 0.3L / min, stir at low speed and ripen for 24h, 4g sulfur, 4g zinc oxide, 4g titanium dioxide, 2g blue pigment are mixed with polyethylene glycol 200 and water, respectively, and prepared into a dispersion with a particle size of less than or equal to 5μm and a solid content of 60% by a ball mill, 0.6g DTDC-80, 0.6g ZDBC, and 0.3g ZDEC are dissolved in water to obtain a accelerator solution with a concentration of 10wt%; zinc oxide dispersion, titanium dioxide dispersion, 0.5g antioxidant RD, accelerator solution, and sulfur dispersion are added to the nitrile latex in sequence, the pH is adjusted to 9.5-10.5, and stirred for 4h; 4g of the antibacterial nano-silica of Example 1 is added, stirred for 2h, and kept warm at 25°C for 12h; S2. Clean the ceramic hand model with a 5 wt% sodium hydroxide aqueous solution at 60°C, rinse with pure water, and then dry. Immerse the ceramic hand model in a mixed solution of calcium nitrate and methanol with a mass ratio of 13:5. During the immersion process, the latex temperature is controlled at 25°C, the immersion time is 8 seconds, the pulling speed is 10 cm / min, the film thickness is 0.1 mm, and then dry. S3. Soak the ceramic hand model in a 60°C hot water tank for 10 minutes and dry it. Roll up the opening of the latex glove by 3mm using a crimping machine. Vulcanize the latex glove in a tunnel vulcanization oven, with the first stage vulcanization at 120°C for 20 minutes and the second stage vulcanization at 100°C for 30 minutes. Cool the glove to below 40°C. S4. Use a pneumatic demoulding machine to compress air to 0.4 MPa to blow off the semi-finished gloves, place the semi-finished gloves in a chlorine washing tank and soak them in chlorine water for 1 minute, neutralize them with NaHSO3, and wash them with water to obtain low-allergenic nitrile gloves.

[0023] Example 5 A hypoallergenic nitrile glove, the preparation method of which comprises the following steps: S1, take 88g of nitrile latex and adjust the pH to 3.0, introduce 70% (v / v) ozone with an ozone generator at 0.3L / min for 1h, and then stir at a low speed for 24h, 4g of sulfur, 4g of zinc oxide, 4g of titanium dioxide, and 2g of blue pigment are mixed with polyethylene glycol 200 and water respectively, and prepared by ball mill into a dispersion with a particle size of less than or equal to 5μm and a solid content of 60%, 0.6g of DTDC-80, 0.6g of ZDBC, and 0.3g of ZDEC are dissolved in water to obtain a concentration of 10w t% accelerator solution; zinc oxide dispersion, titanium dioxide dispersion, 0.5g antioxidant RD, accelerator solution, sulfur dispersion were added to the nitrile latex in sequence, the pH was adjusted to 9.5-10.5, and stirred for 4h; 4g of the antibacterial nano-silica of Example 1 was added, stirred for 2h, and kept warm at 25°C for 12h; sulfur dispersion, pH was adjusted to 9.5-10.5, and stirred for 4h; 4g of the antibacterial nano-silica of Example 2 was added, stirred for 2h, and kept warm at 25°C for 12h; S2. Clean the ceramic hand model with a 5 wt% sodium hydroxide aqueous solution at 60°C, rinse with pure water, and then dry. Immerse the ceramic hand model in a mixed solution of calcium nitrate and methanol with a mass ratio of 13:5. During the immersion process, the latex temperature is controlled at 25°C, the immersion time is 8 seconds, the pulling speed is 10 cm / min, the film thickness is 0.1 mm, and then dry. S3. Soak the ceramic hand model in a 60°C hot water tank for 10 minutes and dry it. Roll up the opening of the latex glove by 3mm using a crimping machine. Vulcanize the latex glove in a tunnel vulcanization oven, with the first stage vulcanization at 120°C for 20 minutes and the second stage vulcanization at 100°C for 30 minutes. Cool the glove to below 40°C. S4. Use a pneumatic demoulding machine to compress air to 0.4 MPa to blow off the semi-finished gloves, place the semi-finished gloves in a chlorine washing tank and soak them in chlorine water for 1 minute, neutralize them with NaHSO3, and wash them with water to obtain low-allergenic nitrile gloves.

[0024] Example 6 A method for preparing a hypoallergenic nitrile glove comprises the following steps: S1, take 88g of nitrile latex and adjust the pH to 3.0, after passing 70% (v / v) ozone for 1h with an ozone generator at 0.3L / min, stir at low speed and ripen for 24h, 4g sulfur, 4g zinc oxide, 4g titanium dioxide, 2g blue pigment are mixed with polyethylene glycol 200 and water, and prepared into a dispersion with a particle size of less than or equal to 5μm and a solid content of 60% by a ball mill, 0.6g DTDC-80, 0.6g ZDBC, and 0.3g ZDEC are dissolved in water to obtain a accelerator solution with a concentration of 10wt%; zinc oxide dispersion, titanium dioxide dispersion, 0.5g antioxidant RD, accelerator solution, and sulfur dispersion are added to the nitrile latex in sequence, the pH is adjusted to 9.5-10.5, and stirred for 4h; 4g of the antibacterial nano-silica of Example 3 is added, stirred for 2h, and kept warm at 25°C for 12h; S2. Clean the ceramic hand model with a 5 wt% sodium hydroxide aqueous solution at 60°C, rinse with pure water, and then dry. Immerse the ceramic hand model in a mixed solution of calcium nitrate and methanol with a mass ratio of 13:5. During the immersion process, the latex temperature is controlled at 25°C, the immersion time is 8 seconds, the pulling speed is 10 cm / min, the film thickness is 0.1 mm, and then dry. S3. Soak the ceramic hand model in a 60°C hot water tank for 10 minutes and dry it. Roll up the opening of the latex glove by 3mm using a crimping machine. Vulcanize the latex glove in a tunnel vulcanization oven, with the first stage vulcanization at 120°C for 20 minutes and the second stage vulcanization at 100°C for 30 minutes. Cool the glove to below 40°C. S4. Use a pneumatic demoulding machine to compress air to 0.4 MPa to blow off the semi-finished gloves, place the semi-finished gloves in a chlorine washing tank and soak them in chlorine water for 1 minute, neutralize them with NaHSO3, and wash them with water to obtain low-allergenic nitrile gloves.

[0025] Example 7 A hypoallergenic nitrile glove, the preparation method of which comprises the following steps: S1, take 86g of nitrile latex and adjust the pH to 3.0, after passing 70% (v / v) ozone for 1h with an ozone generator at 0.3L / min, stir at low speed and ripen for 24h, 3g of sulfur, 3g of zinc oxide, 3g of titanium dioxide, and 2g of blue pigment are mixed with polyethylene glycol 200 and water, respectively, and prepared into a dispersion with a particle size of less than or equal to 5μm and a solid content of 60% by a ball mill, 0.4g of DTDC-80, 0.4g of ZDBC, and 0.2g of ZDEC are dissolved in water to obtain a accelerator solution with a concentration of 10wt%; zinc oxide dispersion, titanium dioxide dispersion, 0.5g of antioxidant RD, accelerator solution, and sulfur dispersion are added to the nitrile latex in sequence, the pH is adjusted to 9.5-10.5, and stirred for 2h; 2g of the antibacterial nano-silica of Example 2 is added, stirred for 1h, and kept warm at 25°C for 12h; S2. Clean the ceramic hand model with a 5 wt% sodium hydroxide aqueous solution at 60°C, rinse with pure water, and then dry. Immerse the ceramic hand model in a mixed solution of calcium nitrate and methanol with a mass ratio of 10:5. During the immersion process, the latex temperature is controlled at 25°C, the immersion time is 5 seconds, the pulling speed is 10 cm / min, the film thickness is 0.08 mm, and then dry. S3. Soak the ceramic hand model in a 60°C hot water tank for 5-10 minutes and dry it. Roll up the opening of the latex glove by 3mm using a crimping machine. Vulcanize the latex glove in a tunnel vulcanization oven, with the first stage vulcanization at 110°C for 15 minutes and the second stage vulcanization at 100°C for 30 minutes. Cool the glove to below 40°C. S4. Use a pneumatic demoulding machine to compress air to 0.3 MPa to blow off the semi-finished gloves, place the semi-finished gloves in a chlorine washing tank and soak them in chlorine water for 1 minute, neutralize them with NaHSO3, and wash them with water to obtain low-allergenic nitrile gloves.

[0026] Comparative Example 1 A nitrile glove, the preparation method of which comprises the following steps: S1, take 88g of nitrile latex and adjust the pH to 3.0, stir and ripen at low speed for 24h, 4g of sulfur, 4g of zinc oxide, 4g of titanium dioxide, and 2g of blue pigment are mixed with polyethylene glycol 200 and water respectively, and prepared into a dispersion with a particle size of less than or equal to 5μm and a solid content of 60% by a ball mill, 1g of ZDBC and 0.5g of ZDEC are dissolved in water to obtain an accelerator solution with a concentration of 10wt%; zinc oxide dispersion, titanium dioxide dispersion, 0.5g of antioxidant RD, accelerator solution, and sulfur dispersion are added to the nitrile latex in sequence, the pH is adjusted to 9.5-10.5, and stirred for 4h; 4g of the antibacterial nano-silica of Example 2 is added, stirred for 2h, and kept warm at 25°C for 12h; S2. Clean the ceramic hand model with a 5 wt% sodium hydroxide aqueous solution at 60°C, rinse with pure water, and then dry. Immerse the ceramic hand model in a mixed solution of calcium nitrate and methanol with a mass ratio of 13:5. During the immersion process, the latex temperature is controlled at 25°C, the immersion time is 8 seconds, the pulling speed is 10 cm / min, the film thickness is 0.1 mm, and then dry. S3. Use a crimping machine to roll up the opening of the latex gloves by 3mm; vulcanize in a tunnel vulcanization oven, vulcanize at 120℃ for 20min in the first stage and 100℃ for 30min in the second stage, and cool to below 40℃; S4. Use a pneumatic demoulding machine to compress air to 0.4 MPa to blow off the semi-finished gloves, place the semi-finished gloves in a chlorine washing tank and soak them in chlorine water for 1 minute, neutralize them with NaHSO3, and wash them with water to obtain low-allergenic nitrile gloves.

[0027] Comparative Example 2 A nitrile glove, the preparation method of which comprises the following steps: S1, take 88g of nitrile latex and adjust the pH to 3.0, after introducing 70% (v / v) ozone for 1h with an ozone generator at 0.3L / min, stir at low speed and ripen for 24h, 4g of sulfur, 4g of zinc oxide, 4g of titanium dioxide, and 2g of blue pigment were mixed with polyethylene glycol 200 and water, and prepared into a dispersion with a particle size of less than or equal to 5μm and a solid content of 60% by a ball mill, 0.6g of DTDC-80, 0.6g of ZDBC, and 0.3g of ZDEC were dissolved in water to obtain an accelerator solution with a concentration of 10wt%; zinc oxide dispersion, titanium dioxide dispersion, 0.5g of antioxidant RD, accelerator solution, and sulfur dispersion were added to the nitrile latex in sequence, the pH was adjusted to 9.5-10.5, stirred for 4h until uniform, and kept warm at 25°C for 12h; S2. Clean the ceramic hand model with a 5 wt% sodium hydroxide aqueous solution at 60°C, rinse with pure water, and then dry. Immerse the ceramic hand model in a mixed solution of calcium nitrate and methanol with a mass ratio of 13:5. During the immersion process, the latex temperature is controlled at 25°C, the immersion time is 8 seconds, the pulling speed is 10 cm / min, the film thickness is 0.1 mm, and then dry. S3. Soak the ceramic hand model in a 60°C hot water tank for 10 minutes and dry it. Roll up the opening of the latex glove by 3mm using a crimping machine. Vulcanize the latex glove in a tunnel vulcanization oven, with the first stage vulcanization at 120°C for 20 minutes and the second stage vulcanization at 100°C for 30 minutes. Cool the glove to below 40°C. S4. Use a pneumatic demoulding machine to compress air to 0.4 MPa to blow off the semi-finished gloves, place the semi-finished gloves in a chlorine washing tank and soak them in chlorine water for 1 minute, neutralize them with NaHSO3, and wash them with water to obtain low-allergenic nitrile gloves.

[0028] Comparative Example 3 A nitrile glove, the preparation method of which comprises the following steps: S1, take 88g of nitrile latex and adjust the pH to 3.0, after passing 70% (v / v) ozone for 1h with an ozone generator at 0.3L / min, stir at low speed and ripen for 24h, 4g sulfur, 4g zinc oxide, 4g titanium dioxide, 2g blue pigment are mixed with polyethylene glycol 200 and water, respectively, and prepared into a dispersion with a particle size of less than or equal to 5μm and a solid content of 60% by a ball mill, 0.6g DTDC-80, 0.6g ZDBC, and 0.3g ZDEC are dissolved in water to obtain a accelerator solution with a concentration of 10wt%; zinc oxide dispersion, titanium dioxide dispersion, 0.5g antioxidant RD, accelerator solution, and sulfur dispersion are added to the nitrile latex in sequence, the pH is adjusted to 9.5-10.5, and stirred for 4h; 4g of the antibacterial nano-silica of Example 1 is added, stirred for 2h, and kept warm at 25°C for 12h; S2. Clean the ceramic hand model with a 5 wt% sodium hydroxide aqueous solution at 60°C, rinse with pure water, and then dry. Immerse the ceramic hand model in a mixed solution of calcium nitrate and methanol with a mass ratio of 13:5. During the immersion process, the latex temperature is controlled at 25°C, the immersion time is 8 seconds, the pulling speed is 10 cm / min, the film thickness is 0.1 mm, and then dry. S3. Soak the ceramic hand model in a 60°C hot water bath for 10 minutes and dry it; roll up the opening of the latex glove by 3mm using a crimping machine; vulcanize it in a tunnel-type vulcanization oven at 100°C for 50 minutes and cool it to below 40°C; S4. Use a pneumatic demoulding machine to compress air to 0.4 MPa to blow off the semi-finished gloves, and wash with water to obtain low-allergenic nitrile gloves.

[0029] Performance testing (1) Allergy: According to ISO 10993-12:2021 “Sample preparation and reference materials for the biological evaluation of medical devices”, the human reconstructed skin model was used to test whether the glove material causes an allergic reaction. The test results are shown in Table 1. (2) Antibacterial property: According to QB / T 2591-2003 “Antibacterial plastics, antibacterial performance test methods and antibacterial effects”, the sample size was selected as 50mm×50mm×5mm, and the test was carried out at 37℃ and relative humidity greater than 90%. Bacteria were inoculated on the surface of the sample and the antibacterial rate was obtained by recovering the bacteria within a certain period of time. The test results are shown in Table 1. (3) Durability: According to GB 10213-2006 “Disposable Medical Rubber Examination Gloves”, tensile tests were performed on samples cut from gloves to obtain the breaking force, breaking strength, and elongation of the gloves. The test results are shown in Table 1.

[0030] Table 1 Statistics of performance test data of Examples 4-7 and Comparative Examples 1-3

[0031] As can be seen from Table 1, in Comparative Example 1, ozone was not used to remove residual acrylonitrile in the nitrile latex raw material during the production process, the hand mold after dipping was not soaked in hot water to remove water-soluble allergens, and the selection of the vulcanizing agent was not optimized, resulting in the nitrile gloves being sensitized to the human reconstructed skin model; in Comparative Example 2, the nitrile gloves lacked antibacterial properties due to the lack of antibacterial nano-silica components; in Comparative Example 3, two-stage vulcanization was not adopted in the vulcanization process, and the gloves were not chlorinated in a chlorine water tank after demolding, resulting in the failure to completely eliminate the internal stress of the gloves, poor mechanical properties, and poor durability.

[0032] The above is a detailed description of an embodiment of the present invention. However, the content described is only a preferred embodiment of the present invention and should not be considered to limit the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing low-allergenic nitrile gloves, characterized in that: The steps include: S1. Pretreatment, compounding and ripening of latex: adjusting the pH of nitrile latex to 3.0, introducing ozone with an ozone generator for 1 hour, and then stirring at a low speed for 24 hours, sulfur, zinc oxide, titanium dioxide, and blue pigment are mixed with a dispersant and water, respectively, and prepared into a dispersion with a particle size of less than or equal to 5 μm by a ball mill, and the accelerator is directly dissolved in water to obtain an accelerator solution; zinc oxide dispersion, titanium dioxide dispersion, antioxidant, accelerator solution, and sulfur dispersion are added to the nitrile latex in sequence, adjusting the pH to 9.5-10.5, and stirring for 2-4 hours; adding antibacterial nano-silica, stirring for 1-2 hours, and keeping warm for 12 hours; S2. Pretreatment and dipping of the hand model: clean the hand model with a sodium hydroxide aqueous solution, rinse with pure water, and then dry; immerse the hand model in a mixed solution of calcium nitrate and methanol and then dry; S3, leaching, crimping and vulcanization: Soak the hand form in a hot water tank for 5-10 minutes, dry it, use a crimping machine to crimp the opening of the latex glove by 2-3 mm, vulcanize it in a tunnel vulcanization oven, and cool it to below 40°C after completion; S4. Demolding and subsequent processing: Use a pneumatic demoulding machine to blow off the semi-finished gloves with compressed air, place the semi-finished gloves in a chlorine washing tank and soak them in chlorine water for 1 minute, neutralize them with NaHSO3, and wash them with water to obtain low-allergenic nitrile gloves.

2. The method for preparing a hypoallergenic nitrile glove according to claim 1, characterized in that: The nitrile gloves include the following raw materials in parts by weight: 86-90 parts by weight of nitrile latex, 3-4 parts by weight of sulfur, 3-4 parts by weight of zinc oxide, 1-2 parts by weight of an accelerator, 0.5 parts by weight of an antioxidant, 3-4 parts by weight of titanium dioxide, 2 parts by weight of a blue pigment, and 2-5 parts by weight of antibacterial nano-silica.

3. The method for preparing a hypoallergenic nitrile glove according to claim 1, wherein: The solid content of the nitrile latex is 40%; The accelerator comprises the following raw materials in parts by weight: 2 parts by weight of DTDC-80, 2 parts by weight of ZDBC, and 1 part by weight of ZDEC; The antioxidant is antioxidant RD; The dispersant is polyethylene glycol 200; The solid content of each dispersion is 60%; The concentration of the accelerator solution is 10wt%; The temperature for heat preservation and aging is 25℃.

4. The method for preparing a hypoallergenic nitrile glove according to claim 1, wherein: The ozone concentration described in S1 is 70% (v / v), and the air intake volume of the ozone generator is 0.3 L / min.

5. The method for preparing a hypoallergenic nitrile glove according to claim 1, wherein: The preparation method of the antibacterial nano-silica comprises the following steps: A1: Place N,N-dimethylethanolamine and octyl bromide in a reaction flask, reflux under condensation for 3-4 hours, cool, add a mixed solvent, control the temperature at 70-80°C to react for 10-14 hours, rotary evaporate, wash, purify, filter, and dry to obtain a quaternary ammonium salt intermediate. Blend the quaternary ammonium salt intermediate, tetrahydrofuran, isophorone diisocyanate, and dibutyltin dilaurate, control the temperature at 30-40°C to react for 8-12 hours, rotary evaporate, wash, purify, and dry to obtain a quaternary ammonium salt monomer. A2: Chitosan powder and acetic acid solution were added to a reactor and dispersed evenly. Quaternary ammonium salt monomer and N,N-dimethylformamide were mixed and added to the reactor. The temperature was controlled at 30-40°C and stirred for 10-14 hours. The mixture was dialyzed and dried to obtain chitosan quaternary ammonium salt powder. A3: Add nano-silica and 30wt% hydrogen peroxide to a reaction flask, control the temperature to 40-50℃ for reflux, and dry to obtain surface-activated nano-silica; blend chitosan quaternary ammonium salt powder, 2vt% glacial acetic acid solution, and surface-activated nano-silica, react for 22-26h, and dry to obtain antibacterial nano-silica.

6. The method for preparing a hypoallergenic nitrile glove according to claim 5, characterized in that: In A1, the addition ratio of N,N-dimethylethanolamine and octyl bromide is 1.25-1.45 g:3.1-3.3 g, the mixed solvent is composed of propanol and methanol in a volume ratio of 1:3, and the addition ratio of quaternary ammonium salt intermediate, isophorone diisocyanate, tetrahydrofuran, and dibutyltin dilaurate is 2.2 g:2.3-2.7 g:40-50 mL:0.4-0.6 mL; The acetic acid solution in A2 is a 1-4 wt% acetic acid solution; The addition ratio of chitosan powder, acetic acid solution, quaternary ammonium salt monomer, and N,N-dimethylformamide is 1.6 g: 25-100 mL: 10.8-13.5 g: 40-80 mL; The addition ratio of nano-silica, 30wt% hydrogen peroxide, chitosan quaternary ammonium salt powder, and 2vt% glacial acetic acid in A3 is 2.0-2.4g:25-35mL:0.8g:25-35mL.

7. The method for preparing a hypoallergenic nitrile glove according to claim 1, wherein: The hand model material described in S2 is ceramic; The concentration of the sodium hydroxide aqueous solution is 5wt%, and the alkali washing temperature is 60°C; The mass ratio of calcium nitrate to methanol in the mixed solution is 10-15:5; During the hand mold dipping process, the latex temperature is controlled at 25-30° C., the dipping time is 5-8 seconds, the pulling speed is 10 cm / min, and the film thickness is 0.08-0.12 mm.

8. The method for preparing a hypoallergenic nitrile glove according to claim 1, wherein: The temperature of the hot water tank in S3 is 60°C; The vulcanization process is divided into two stages: One-stage vulcanization: vulcanize at 110-120℃ for 15-20min; Second stage vulcanization: vulcanize at 100℃ for 30min.

9. The method for preparing a hypoallergenic nitrile glove according to claim 1, wherein: During the demoulding process described in S4, the pneumatic demoulding machine compresses the air to 0.3-0.5 MPa.

10. A hypoallergenic nitrile glove, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.

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