High-antibacterial latex gloves and preparation method thereof

Abstract

The invention discloses a high-antibacterial latex glove and a preparation method thereof, and belongs to the technical field of latex gloves. Comprising the following raw materials in parts by weight: 40-60 parts of butyronitrile latex, 50-70 parts of deionized water, 8-16 parts of nano zinc oxide, 5-15 parts of an antibacterial agent, 2-4 parts of sulfur, 4-6 parts of an anti-aging agent, 3-5 parts of a dispersing agent and 0.5-1 part of a vulcanization accelerator. According to the latex gloves prepared by the invention, butyronitrile latex is taken as a matrix, so that the gloves are endowed with excellent oil resistance and chemical resistance; wherein the nano zinc oxide can improve the antibacterial property of the latex gloves to a certain extent; wherein the antibacterial agent can enhance the moisture absorption and mechanical properties of the latex gloves, and also can play a synergistic effect with the nano zinc oxide, so that the antibacterial property of the latex gloves is remarkably enhanced, and the performance is stable; therefore, the prepared latex gloves are excellent in oil resistance, chemical resistance and mechanical property, have stable and efficient antibacterial property and hygroscopicity, and have important application value in the technical field of latex gloves.

Description

Technical Field

[0001] The invention belongs to the technical field of latex gloves, and in particular relates to a highly antibacterial latex glove and a preparation method thereof. Background Art

[0002] Latex gloves are a common personal protective equipment, mainly used to protect hands from injury and pollution. They are different from ordinary gloves and are made of natural latex. They can be used in household, industrial, medical, beauty and other industries, and are essential hand protection products.

[0003] Commonly used rubber latex gloves are made of natural rubber. Natural rubber has excellent resilience, insulation, water-proof and plasticity, but the annual output of natural rubber is limited, and its price is relatively expensive among rubber raw materials. Therefore, nitrile latex gloves are now receiving more and more attention. Nitrile latex gloves have good sealing properties, but when wearing latex gloves for a long time, it is inevitable to produce a certain amount of sweat, which cannot be absorbed in time, so it will cause the nitrile latex gloves to not fit the hands of people completely, affecting normal work. Since the raw material of nitrile latex gloves is nitrile rubber, nitrile rubber does not have antibacterial properties, sweat is not absorbed, and it is easier to breed bacteria in a humid environment, increasing the risk of infection. Therefore, it is necessary to add a certain amount of antibacterial agent to the latex gloves to achieve the antibacterial effect in the latex gloves.

[0004] There are many types of antimicrobial agents, among which natural antimicrobial agents are less toxic and more safe, but have a short service life and poor heat resistance. Organic antimicrobial agents have the characteristics of fast effect and strong bactericidal ability, but they are prone to microbial resistance and have defects such as easy migration and poor resistance. Therefore, the above problems need to be solved to meet the higher demands in the field of latex glove technology. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects of the prior art and provide a highly antibacterial latex glove and a preparation method thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A method for preparing highly antibacterial latex gloves comprises the following steps:

[0008] A1. Add nitrile latex, deionized water, nano zinc oxide, antibacterial agent, sulfur, antioxidant, dispersant and vulcanization accelerator into a batching barrel, and stir evenly to prepare nitrile latex liquid;

[0009] A2, the hand mold is cleaned, and then immersed in the coagulant, after 1 minute, dripped, dried, and then the glove lining is put on the hand mold, and then immersed in the nitrile latex solution prepared in step A1 for 1 minute, dripped, and dried in a rotating state. After drying, it is placed in a vulcanization box at 120-150°C, heated and vulcanized in a rotating state, and the vulcanization is completed to obtain a highly antibacterial latex glove.

[0010] Furthermore, the raw materials are calculated in parts by weight as follows: 40-60 parts of nitrile latex, 50-70 parts of deionized water, 8-16 parts of nano zinc oxide, 5-15 parts of antibacterial agent, 2-4 parts of sulfur, 4-6 parts of antioxidant, 3-5 parts of dispersant, and 0.5-1 part of vulcanization accelerator.

[0011] Furthermore, the antioxidant is one of 2-6-di-tert-butyl-p-cresol and 2-thiol benzoimidazole.

[0012] Furthermore, the dispersant is one of sodium methylene bis-naphthalene sulfonate and sodium dibutyl naphthalene sulfonate.

[0013] Furthermore, the vulcanization accelerator is one of 2-mercaptobenzothiazole and dibenzothiazole disulfide.

[0014] Furthermore, the coagulant comprises the following components in parts by weight: 60-80 parts of deionized water, 8-15 parts of calcium nitrate, and 0.1-0.2 parts of propylene glycol alginate.

[0015] Furthermore, the glove lining is a knitted lining with 7, 10, 13, 15 and 18 needles; the yarn used is nylon.

[0016] With nitrile rubber as the matrix, latex gloves are endowed with excellent oil resistance and chemical resistance; the added nano zinc oxide is an inorganic antibacterial agent with good photocatalytic activity. It can produce active oxygen under light. These active oxygen free radicals have extremely strong oxidizing properties and can react with organic matter in bacteria, thereby killing the bacteria, improving the antibacterial properties of latex gloves to a certain extent; finally, the introduced vulcanization accelerator is a thiazole vulcanization accelerator, which can effectively shorten the vulcanization time, lower the vulcanization temperature, and reduce the amount of vulcanizing agent used.

[0017] Furthermore, the antibacterial agent is prepared by the following steps:

[0018] S1. Polyethylene glycol (molecular weight 4000) was dried at 80°C for 12 hours and then transferred to a three-necked flask. Nitrogen was introduced as a protective gas and the temperature was raised to 70°C. After 10 minutes, succinic anhydride and N,N-dimethylformamide (DMF) were added. The temperature was maintained constant and the reaction was carried out for 5 hours. After the reaction was completed, the mixture was washed with anhydrous ethanol for 3-4 times and dried in vacuo to obtain intermediate 1. The ratio of polyethylene glycol, succinic anhydride and N,N-dimethylformamide was 20 g:5.4 g:100 mL.

[0019] Polyethylene glycol reacts with succinic anhydride to obtain intermediate 1. The specific reaction process is as follows:

[0020]

[0021] S2. In a three-necked flask equipped with a stirring device, 5-chloro-2-methyl-4-isothiazoline-3-one (CMIT) and N,N-dimethylformamide were mixed and the stirrer was turned on. Dibutyltin oxide (catalyst), potassium carbonate and 4,4'-azodiphenylamine were added in sequence, and the temperature was slowly raised to 65°C. The reaction was kept warm for 4 hours. After the reaction was completed, deionized water was added, and the mixture was stirred evenly and filtered. The residue was taken and washed with anhydrous ethanol for 3-4 times, and vacuum dried to obtain intermediate 2. The ratio of 5-chloro-2-methyl-4-isothiazoline-3-one, N,N-dimethylformamide, dibutyltin oxide, potassium carbonate, 4,4'-azodiphenylamine and deionized water was 14.8 g:100 mL:0.3 g:5.3 g:23.3 g:50 mL.

[0022] Under the catalysis of dibutyltin oxide, 5-chloro-2-methyl-4-isothiazoline-3-one and 4,4'-azodiphenylamine undergo nucleophilic substitution. By controlling the molar ratio of the two to be close to 1:1 and a slight excess of 4,4'-azodiphenylamine, only one amino group on 4,4'-azodiphenylamine participates in the reaction. Potassium carbonate removes the hydrogen chloride generated by the reaction to obtain intermediate 2. The specific reaction is shown below:

[0023]

[0024] S3. Add intermediate 1, intermediate 2, dicyclohexylcarbodiimide (DCC, dehydrating agent) and N,N-dimethylformamide to a three-necked flask equipped with a stirring device, stir and mix well, place in a water bath at 50°C, heat in a water bath for 8 hours, and complete the reaction. Filter, remove the solvent by vacuum distillation, and purify by column chromatography (the eluent is a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two is 3:2), remove the eluent by rotary evaporation to obtain an antibacterial agent; the ratio of intermediate 1, intermediate 2, dicyclohexylcarbodiimide and N,N-dimethylformamide is 28.4g:6.6g:4.1g:150mL;

[0025] Under the action of DCC, intermediate 1 and intermediate 2 undergo amidation reaction, and an excess of intermediate 2 is added so that two carboxyl groups on intermediate 1 participate in the reaction to obtain an antibacterial agent; the specific reaction process is as follows:

[0026]

[0027] The prepared antibacterial agent molecule is mainly composed of polyethylene glycol, connected with azobenzene and isothiazolinone groups, wherein the hydrophilic chain polyethylene glycol can effectively improve the hydrophilicity of the matrix and the hygroscopicity of the gloves. In addition, polyethylene glycol, as a flexible chain segment, can also improve the mechanical properties of the matrix to a certain extent; not only that, the antibacterial agent with polyethylene glycol as the main body is a large molecule, which is not easy to migrate and seep out compared with the antibacterial properties of small molecules, and has long-term stable performance; the introduced azobenzene, as an excellent antibacterial structure, can combine with the chitin of bacteria, destroy the bacterial structure, have a bactericidal effect, and improve the antibacterial properties of the matrix; the introduced isothiazolinone has excellent properties such as strong antibacterial ability, environmental safety and a broad antibacterial spectrum. It forms a disulfide bond with the thiol group on the cysteine ​​in the pathogen protein through the bond active site on the heterocycle, thereby inactivating the protein to achieve the purpose of sterilization, and can synergize with azobenzene and nano zinc oxide to greatly enhance the antibacterial properties of the matrix.

[0028] Beneficial effects of the present invention:

[0029] 1. The latex gloves prepared by the present invention use nitrile rubber as a matrix, which gives the latex gloves excellent oil resistance and chemical resistance;

[0030] 2. Adding nano zinc oxide can improve the antibacterial properties of latex gloves to a certain extent;

[0031] 3. The prepared antibacterial agent can enhance the moisture absorption and mechanical properties of latex gloves, and can also work synergistically with nano zinc oxide to significantly enhance the antibacterial properties of latex gloves, and has stable performance and is not easy to fall off;

[0032] Therefore, the latex gloves prepared by the present invention have excellent oil resistance, chemical resistance and mechanical properties, stable and efficient antibacterial and hygroscopic properties, and have important application value in the technical field of latex gloves. DETAILED DESCRIPTION

[0033] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Embodiment 1

[0035] Preparation of antimicrobial agent:

[0036] S1. Dry 20 g of polyethylene glycol (molecular weight 4000) at 80 ° C for 12 h and transfer it to a three-necked flask. Pass nitrogen as a protective gas and heat to 70 ° C. After 10 min, add 5.4 g of succinic anhydride and 100 mL of N, N-dimethylformamide. Maintain the temperature and react for 5 h. After the reaction is completed, wash with anhydrous ethanol for 3 times and dry in vacuo to obtain intermediate 1.

[0037] S2. In a three-necked flask equipped with a stirring device, 14.8 g of 5-chloro-2-methyl-4-isothiazoline-3-one and 100 mL of N,N-dimethylformamide were mixed and the stirrer was turned on. 0.3 g of dibutyltin oxide, 5.3 g of potassium carbonate and 23.3 g of 4,4'-azodiphenylamine were added in sequence. The temperature was slowly raised to 65°C and the reaction was kept at this temperature for 4 hours. After the reaction was completed, 50 mL of deionized water was added, the mixture was stirred evenly and filtered. The filter residue was washed with anhydrous ethanol for 4 times and dried under vacuum to obtain intermediate 2.

[0038] S3. Add 28.4 g of intermediate 1, 6.6 g of intermediate 2, 4.1 g of dicyclohexylcarbodiimide and 150 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirring device, stir and mix evenly, place in a 50°C water bath, heat in a water bath for 8 hours, and when the reaction is completed, filter, remove the solvent by vacuum distillation, and purify by column chromatography (the eluent is a mixed solvent of benzene / ethyl acetate in a volume ratio of 3:2), remove the eluent by rotary evaporation, and obtain an antibacterial agent.

[0039] Embodiment 2

[0040] Preparation of antimicrobial agent:

[0041] S1. 40 g of polyethylene glycol (molecular weight 4000) was dried at 80 ° C for 12 h and then transferred to a three-necked flask. Nitrogen was introduced as a protective gas and the temperature was raised to 70 ° C. After 10 min, 10.8 g of succinic anhydride and 200 mL of N, N-dimethylformamide were added. The temperature was maintained constant and the reaction was kept warm for 5 h. After the reaction was completed, the mixture was washed with anhydrous ethanol for 3 times and dried in vacuo to obtain intermediate 1.

[0042] S2. In a three-necked flask equipped with a stirring device, 29.6 g of 5-chloro-2-methyl-4-isothiazoline-3-one and 200 mL of N,N-dimethylformamide were mixed and the stirrer was turned on. 0.6 g of dibutyltin oxide, 10.6 g of potassium carbonate and 46.6 g of 4,4'-azodiphenylamine were added in sequence. The temperature was slowly raised to 65°C and the reaction was kept at this temperature for 4 hours. After the reaction was completed, 100 mL of deionized water was added, the mixture was stirred evenly and filtered, the filter residue was taken, washed with anhydrous ethanol 4 times, and vacuum dried to obtain intermediate 2;

[0043] S3. Add 56.8 g of intermediate 1, 13.2 g of intermediate 2, 8.2 g of dicyclohexylcarbodiimide and 300 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirring device, stir and mix evenly, place in a 50°C water bath, heat in a water bath for 8 hours, and when the reaction is completed, filter, remove the solvent by vacuum distillation, and purify by column chromatography (the eluent is a mixed solvent of benzene / ethyl acetate in a volume ratio of 3:2), remove the eluent by rotary evaporation, and obtain an antibacterial agent.

[0044] Embodiment 3

[0045] A1, 40g nitrile latex, 50g deionized water, 8g nano zinc oxide, 5g antibacterial agent prepared in Example 1, 2g sulfur, 4g 2-6-di-tert-butyl-p-cresol, 3g sodium methylenebisnaphthalenesulfonate and 0.5g 2-thiol benzothiazole were added to a batching barrel, and stirred to prepare a nitrile latex solution;

[0046] A2, the hand model is cleaned, and then immersed in a coagulant (mixed with 60g of deionized water, 8g of calcium nitrate and 0.1g of propylene glycol alginate), and after 1 minute, dripped and dried, and then the glove lining is put on the hand model, and then immersed in the nitrile latex solution prepared in step A1 for 1 minute, and then dripped and dried in a rotating state. After drying, it is placed in a vulcanization box at 120°C, heated and vulcanized in a rotating state, and the vulcanization is completed to obtain a highly antibacterial latex glove;

[0047] The number of needles of the glove lining is 7, and the yarn used is nylon.

[0048] Embodiment 4

[0049] A1, 50g of nitrile latex, 60g of deionized water, 12g of nano zinc oxide, 10g of the antibacterial agent prepared in Example 2, 3g of sulfur, 5g of 2-mercaptobenzoimidazole, 4g of sodium dibutylnaphthalenesulfonate and 1g of dibenzothiazole disulfide were added to a batching barrel, and stirred to prepare a nitrile latex solution;

[0050] A2, the hand model is cleaned, and then immersed in a coagulant (mixed with 70g of deionized water, 11g of calcium nitrate and 0.2g of propylene glycol alginate), and after 1 minute, dripped and dried, and then the glove lining is put on the hand model, and then immersed in the nitrile latex solution prepared in step A1 for 1 minute, and then dripped and dried in a rotating state. After drying, it is placed in a vulcanization box at 135°C, heated and vulcanized in a rotating state, and the vulcanization is completed to obtain a highly antibacterial latex glove;

[0051] The number of needles of the glove lining is 10, and the yarn used is nylon.

[0052] Embodiment 5

[0053] A1, 60g of nitrile latex, 70g of deionized water, 16g of nano zinc oxide, 15g of the antibacterial agent prepared in Example 2, 4g of sulfur, 6g of 2-mercaptobenzoimidazole, 5g of sodium dibutylnaphthalenesulfonate and 1g of dibenzothiazole disulfide were added to a batching barrel, and stirred to prepare a nitrile latex solution;

[0054] A2, the hand model is cleaned, and then immersed in a coagulant (mixed with 80g of deionized water, 15g of calcium nitrate and 0.2g of propylene glycol alginate), after 1 minute, dripped, dried, and then the glove lining is put on the hand model, and then immersed in the nitrile latex solution prepared in step A1 for 1 minute, dripped, and dried in a rotating state. After drying, it is placed in a vulcanization box at 150°C, heated and vulcanized in a rotating state, and the vulcanization is completed to obtain a highly antibacterial latex glove;

[0055] The number of needles of the glove lining is 15, and the yarn used is nylon.

[0056] Comparative Example 1

[0057] The antibacterial agent in Example 5 was replaced by a commercially available antibacterial agent of equal quality, and the remaining steps were the same as those in Example 5 to prepare latex gloves.

[0058] Comparative Example 2

[0059] Use commercially available nitrile gloves.

[0060] The gloves of Examples 3, 4, 5 and Comparative Examples 1 and 2 were subjected to the following performance tests:

[0061] The national standard GB / T 7543-2020 "Single-use sterile rubber surgical gloves" is used to measure the tear force;

[0062] The national standard GB / T 31402-2015 "Test method for antibacterial performance of plastic surfaces" was used to determine the antibacterial properties and calculate the antibacterial efficiency;

[0063] The antibacterial efficiency test method is as follows: Staphylococcus aureus and Escherichia coli are used as test bacteria to inoculate the sample, and the inoculated sample is placed in an environment of 25°C and humidity greater than 85% for 24 hours, the number of live bacteria is tested, and the antibacterial efficiency is calculated; the same standard is used to determine the antibacterial rate of the sample after it is placed at room temperature for 30 days;

[0064] The test piece was immersed in water, taken out after 15 minutes, and the mass change of the sample before and after immersion was measured; the measured results are shown in the following table:

[0065]

[0066]

[0067] It can be seen from the above table that the mechanical properties, antibacterial properties and hygroscopic properties of the latex gloves prepared in the embodiment of the present invention are higher than those of the comparative example, and the properties are long-lasting and stable, which has important application value in the field of latex gloves technology.

[0068] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0069] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing highly antibacterial latex gloves, characterized in that: The following steps are involved: A1. Add nitrile latex, deionized water, nano zinc oxide, antibacterial agent, sulfur, antioxidant, dispersant and vulcanization accelerator into a batching barrel, and stir evenly to prepare nitrile latex liquid; A2, the hand mold is cleaned, and then immersed in the coagulant, after 1 minute, dripped, dried, and then the glove lining is put on the hand mold, and then immersed in the nitrile latex solution prepared in step A1 for 1 minute, dripped, and dried in a rotating state. After drying, it is placed in a vulcanization box at 120-150°C, heated and vulcanized in a rotating state, and the vulcanization is completed to obtain a highly antibacterial latex glove.

2. The method for preparing a highly antibacterial latex glove according to claim 1, characterized in that: The antibacterial agent is prepared by the following steps: S1. After drying polyethylene glycol at 80°C for 12 hours, transfer it to a three-necked flask, introduce nitrogen, raise the temperature to 70°C, add succinic anhydride and N,N-dimethylformamide after 10 minutes, maintain the temperature unchanged, and react for 5 hours. After the reaction is completed, wash and dry to obtain intermediate 1; S2, 5-chloro-2-methyl-4-isothiazoline-3-one and N,N-dimethylformamide were mixed and stirred, dibutyltin oxide, potassium carbonate and 4,4'-azodiphenylamine were added in sequence, the temperature was slowly raised to 65°C, and the reaction was kept at this temperature for 4 hours. After the reaction was completed, deionized water was added, the mixture was stirred evenly, and then filtered. The residue was collected, washed, and vacuum dried to obtain intermediate 2; S3. Stir and mix the intermediate 1, intermediate 2, dicyclohexylcarbodiimide and N,N-dimethylformamide, heat in a water bath at 50°C for 8 hours, and when the reaction is finished, filter, distill under reduced pressure, purify by column chromatography, and rotary evaporate to obtain an antibacterial agent.

3. The method for preparing a highly antibacterial latex glove according to claim 2, characterized in that: In step S1, the ratio of polyethylene glycol, succinic anhydride and N,N-dimethylformamide is 20 g:5.4 g:100 mL.

4. The method for preparing a highly antibacterial latex glove according to claim 2, characterized in that: In step S2, the ratio of 5-chloro-2-methyl-4-isothiazoline-3-one, N,N-dimethylformamide, dibutyltin oxide, potassium carbonate, 4,4'-azodiphenylamine, and deionized water is 14.8 g:100 mL:0.3 g:5.3 g:23.3 g:50 mL.

5. The method for preparing a highly antibacterial latex glove according to claim 2, characterized in that: In step S3, the ratio of the amount of intermediate 1, intermediate 2, dicyclohexylcarbodiimide, and N,N-dimethylformamide is 28.4 g: 6.6 g: 4.1 g: 150 mL.

6. The method for preparing a highly antibacterial latex glove according to claim 1, characterized in that: The raw materials are calculated in parts by weight as follows: 40-60 parts of nitrile latex, 50-70 parts of deionized water, 8-16 parts of nano zinc oxide, 5-15 parts of antibacterial agent, 2-4 parts of sulfur, 4-6 parts of antioxidant, 3-5 parts of dispersant, and 0.5-1 part of vulcanization accelerator.

7. The method for preparing a highly antibacterial latex glove according to claim 1, characterized in that: The antioxidant is one of 2-6-di-tert-butyl-p-cresol and 2-thiol benzoimidazole.

8. The method for preparing a highly antibacterial latex glove according to claim 1, characterized in that: The vulcanization accelerator is one of 2-mercaptobenzothiazole and dibenzothiazole disulfide.

9. A highly antibacterial latex glove, characterized in that: Prepared according to the method according to any one of claims 1 to 8.

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