A kind of preparation method of breathable latex gloves

Abstract

The present invention relates to the field of latex technology, and in particular to a method for preparing breathable latex gloves. The method for preparing breathable latex gloves of the present invention comprises modifying carbon nanotubes to obtain a rubber compound containing modified carbon nanotubes, then impregnating a glove blank with the rubber compound containing modified carbon nanotubes, and finally vulcanizing the gloves. The method for preparing breathable latex gloves of the present invention ensures that the gloves have good air permeability and good mechanical properties. During use, the gloves provide users with a comfortable experience and can be widely used in life and production.

Description

Technical Field

[0001] The invention relates to the technical field of latex, and in particular to a method for preparing breathable latex gloves. Background Art

[0002] Nitrile rubber gloves are a common type of protective gloves. Their main purpose is to provide hand protection and protection. They have good resistance to grease, solvents and other chemicals, good wear resistance and elasticity, a long service life, and good waterproof properties. They are commonly used in industrial, medical and laboratory fields.

[0003] Patent technical document CN202010249821.4 discloses a method for preparing nitrile microporous breathable foam gloves. The invention can obtain nitrile foam gloves with a number of tiny breathable holes on the surface by designing a special foaming surface treatment agent and a process flow, thereby reducing the damp and hot feeling when wearing the gloves. Compared with the prior art, the present invention is simpler, more water-saving, and reduces the waste of rubber materials. However, while it improves the breathability, it ignores the reduction in its mechanical properties.

[0004] Patent technical document CN202110299517.5 discloses a modified nitrile latex for gloves and a preparation method thereof, which mainly solves the problem of poor mechanical properties of existing nitrile latex; the gloves made of modified nitrile latex of the invention have excellent tensile strength and elongation, especially through the joint use of modified polyethylene glycol and modified attapulgite clay, the synergistic effect is further improved, and the mechanical properties of nitrile latex are further improved, and it has broad market prospects, but the air permeability of the gloves is poor, which affects the comfort of use. Summary of the invention

[0005] In view of this, the object of the present invention is to provide a method for preparing breathable latex gloves so that the nitrile latex gloves have both good mechanical properties and breathability.

[0006] Based on the above purpose, the present invention provides a method for preparing breathable latex gloves, comprising the following steps:

[0007] (1) adding silane coupling agent KH560 and N,N'-vinylbisacrylamide to N-methylpyrrolidone, stirring at 140-150°C for 3-4 hours, and rotary evaporating to obtain a modifier;

[0008] (2) adding the activated carboxylated carbon nanotubes and the modifier into anhydrous ethanol, stirring at 80-90° C. for 6-8 hours, centrifuging, washing, and drying to obtain modified carbon nanotubes;

[0009] (3) mixing 100 parts of nitrile latex, 1-5 parts of surfactant, 0.5-2 parts of vulcanizing agent, 1-5 parts of accelerator, 1-6 parts of thickener and 3-5 parts of modified carbon nanotubes by weight, heating to 60-80° C., and pre-curing for 15-45 minutes to obtain a rubber compound containing modified carbon nanotubes;

[0010] (5) putting the glove blank on the hand former and performing an immersion treatment with a coagulant to obtain a pretreated glove blank cover;

[0011] (6) The pretreated glove blank is impregnated with a rubber compound containing modified carbon nanotubes, and then vulcanized and dried to obtain a breathable latex glove.

[0012] Preferably, the weight ratio of the silane coupling agent KH560 to N,N'-vinylbisacrylamide is 4.5-5:1.5-1.8.

[0013] Preferably, the specific steps of activating the carboxylated carbon nanotubes in step (2) are: adding the carboxylated carbon nanotube powder to anhydrous ethanol, ultrasonically dispersing for 1-2 hours, then adjusting the pH to 3-4 with oxalic acid, stirring at 60-65° C. for 6 hours, washing, centrifuging, and drying to obtain activated carboxylated carbon nanotubes.

[0014] Preferably, the weight ratio of the carboxylated carbon nanotubes to anhydrous ethanol is 1-3:200.

[0015] Preferably, the carboxylated carbon nanotubes are carboxylated multi-walled carbon nanotubes with an inner diameter of 5-15 nm and a length of 10-20 μm.

[0016] Preferably, in step (2), the weight ratio of activated carboxylated carbon nanotubes, modifier and anhydrous ethanol is 10:1-2:50-70.

[0017] Preferably, the surfactant in step (3) is one of dioctyl sodium succinate sulfonate, sodium olefin sulfonate, sodium hexadecyl sulfate, sodium octadecyl sulfate, and sodium dodecyl sulfate.

[0018] Preferably, the accelerator in step (3) is one of sodium dibutyl dithiocarbamate, zinc diethyl dithiocarbamate and zinc dimethyl dithiocarbamate.

[0019] Preferably, the thickener in step (3) is one of sodium carboxymethyl cellulose and sodium hydroxyethyl cellulose.

[0020] Preferably, the vulcanizing agent in step (3) is sulfur.

[0021] Preferably, the coagulant in step (4) is a calcium chloride aqueous solution with a mass concentration of 5-10%.

[0022] Preferably, the glove blank in step (5) is a knitted glove blank.

[0023] Preferably, in the step (6), the vulcanization and drying is first performed at low temperature and then at high temperature; the temperature of the low temperature vulcanization is 60-85°C, and the drying time is 25-40 minutes; the temperature of the high temperature vulcanization is 100-120°C, and the drying time is 50-90 minutes.

[0024] Beneficial effects of the present invention:

[0025] (1) The present invention modifies carbon nanotubes and uniformly disperses and grafts them onto a cross-linked network. On the one hand, the air permeability of the gloves can be improved; on the other hand, the carbon nanotubes can be prevented from agglomerating, thereby further improving the air permeability and mechanical properties of the gloves.

[0026] (2) The present invention uses N,N'-vinylbisacrylamide to prepare the modifier. On the one hand, more carbon nanotubes can be introduced to improve the air permeability of the gloves; on the other hand, the density of the cross-linked network after vulcanization can be maintained, so that its mechanical properties are improved.

[0027] (3) The present invention adopts N,N'-vinylbisacrylamide to prepare the modifier, which not only introduces double bonds to increase the cross-linking density, but also introduces more reaction sites, so that more carbon nanotubes can be attached to the cross-linking network, further improving the air permeability and mechanical properties of the gloves. DETAILED DESCRIPTION

[0028] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0029] The inner diameter of the carboxylated multi-walled carbon nanotubes used in the examples and comparative examples of the present invention is 10 nm, and the length is 15 μm.

[0030] Example 1: A method for preparing breathable latex gloves, the specific preparation steps are as follows:

[0031] (1) 4.5 g of silane coupling agent KH560 and 1.5 g of N,N'-vinylbisacrylamide were added to 80 g of N-methylpyrrolidone, stirred at 140° C. for 3 h, and rotary evaporated to obtain a modifier;

[0032] (2) adding 10 g of carboxylated multi-walled carbon nanotubes to 2000 g of anhydrous ethanol, ultrasonically dispersing for 1 h, then adjusting the pH to 3 with oxalic acid, stirring at 60° C. for 6 h, washing, centrifuging, and drying to obtain activated carboxylated carbon nanotubes;

[0033] (3) adding 10 g of activated carboxylated carbon nanotubes and 1 g of a modifier into 50 g of anhydrous ethanol, stirring at 80° C. for 6 h, centrifuging, washing, and drying to obtain modified carbon nanotubes;

[0034] (4) 100 g of nitrile latex, 1 g of sodium dioctyl succinate sulfonate, 0.5 g of sulfur, 1 g of zinc dimethyldithiocarbamate, 1 g of sodium carboxymethyl cellulose and 3 g of modified carbon nanotubes were mixed uniformly, heated to 60° C., and pre-cured for 15 min to obtain a rubber compound containing modified carbon nanotubes;

[0035] (5) putting a knitted glove blank on a hand mold and immersing it in a calcium chloride aqueous solution with a mass concentration of 5% to obtain a pretreated glove blank;

[0036] (6) The pretreated glove blank is impregnated with a rubber compound containing modified carbon nanotubes, first dried at 60° C. for 25 min, and then dried at 100° C. for 50 min to obtain a breathable latex glove.

[0037] Example 2: A method for preparing breathable latex gloves, the specific preparation steps are as follows:

[0038] (1) 4.75 g of silane coupling agent KH560 and 1.65 g of N,N'-vinylbisacrylamide were added to 90 g of N-methylpyrrolidone, stirred at 145° C. for 3 h, and rotary evaporated to obtain a modifier;

[0039] (2) adding 20 g of carboxylated multi-walled carbon nanotubes to 2000 g of anhydrous ethanol, ultrasonically dispersing for 1 h, then adjusting the pH to 3.6 with oxalic acid, stirring at 63 ° C for 6 h, washing, centrifuging, and drying to obtain activated carboxylated carbon nanotubes;

[0040] (3) adding 10 g of activated carboxylated carbon nanotubes and 1.5 g of a modifier to 60 g of anhydrous ethanol, stirring at 85° C. for 7 min, centrifuging, washing, and drying to obtain modified carbon nanotubes;

[0041] (4) 100 g of nitrile latex, 3 g of sodium dioctyl succinate sulfonate, 1.5 g of sulfur, 3 g of zinc dimethyldithiocarbamate, 3 g of sodium carboxymethyl cellulose and 4 g of modified carbon nanotubes were mixed uniformly, heated to 70° C., and pre-cured for 30 min to obtain a rubber compound containing modified carbon nanotubes;

[0042] (5) putting a knitted glove blank on a hand mold and immersing it in an aqueous solution of calcium chloride with a mass concentration of 8% to obtain a pretreated glove blank;

[0043] (6) The pretreated glove blank is impregnated with a rubber compound containing modified carbon nanotubes, firstly dried at 75° C. for 30 min, and then dried at 110° C. for 70 min, to obtain a breathable latex glove.

[0044] Example 3: A method for preparing breathable latex gloves, the specific preparation steps are as follows:

[0045] (1) 4.8 g of silane coupling agent KH560 and 1.7 g of N,N'-vinylbisacrylamide were added to 95 g of N-methylpyrrolidone, stirred at 148° C. for 4 h, and rotary evaporated to obtain a modifier;

[0046] (2) adding 25 g of carboxylated multi-walled carbon nanotubes to 2000 g of anhydrous ethanol, ultrasonically dispersing for 2 h, then adjusting the pH to 3.3 with oxalic acid, stirring at 65 ° C for 6 h, washing, centrifuging, and drying to obtain activated carboxylated carbon nanotubes;

[0047] (3) adding 10 g of activated carboxylated carbon nanotubes and 2 g of a modifier into 70 g of anhydrous ethanol, stirring at 80° C. for 8 h, centrifuging, washing, and drying to obtain modified carbon nanotubes;

[0048] (4) 100 g of nitrile latex, 4 g of sodium dioctyl succinate sulfonate, 2 g of sulfur, 4 g of zinc dimethyldithiocarbamate, 4 g of sodium carboxymethyl cellulose and 4 g of modified carbon nanotubes were mixed uniformly, heated to 80° C., and pre-cured for 40 min to obtain a rubber compound containing modified carbon nanotubes;

[0049] (5) putting a knitted glove blank on a hand mold and immersing it in a calcium chloride aqueous solution with a mass concentration of 9% to obtain a pretreated glove blank;

[0050] (6) The pretreated glove blank is impregnated with a rubber compound containing modified carbon nanotubes, first dried at 80° C. for 35 min, and then dried at 110° C. for 80 min to obtain a breathable latex glove.

[0051] Example 4: A method for preparing breathable latex gloves, the specific preparation steps are as follows:

[0052] (1) Add 5 g of silane coupling agent KH560 and 1.8 g of N,N'-vinylbisacrylamide to 100 g of N-methylpyrrolidone, stir at 150° C. for 4 h, and perform rotary evaporation to obtain a modifier;

[0053] (2) adding 30 g of carboxylated multi-walled carbon nanotubes to 2000 g of anhydrous ethanol, ultrasonically dispersing for 2 h, then adjusting the pH to 4 with oxalic acid, stirring at 65 ° C for 6 h, washing, centrifuging, and drying to obtain activated carboxylated carbon nanotubes;

[0054] (3) adding 10 g of activated carboxylated carbon nanotubes and 2 g of a modifier into 70 g of anhydrous ethanol, stirring at 90° C. for 8 h, centrifuging, washing, and drying to obtain modified carbon nanotubes;

[0055] (4) 100 g of nitrile latex, 5 g of sodium dioctyl succinate sulfonate, 2 g of sulfur, 5 g of zinc dimethyldithiocarbamate, 6 g of sodium carboxymethyl cellulose and 5 g of modified carbon nanotubes were mixed uniformly, heated to 80° C., and pre-cured for 45 min to obtain a rubber compound containing modified carbon nanotubes;

[0056] (5) putting a knitted glove blank on a hand mold and immersing it in a calcium chloride aqueous solution with a mass concentration of 10% to obtain a pretreated glove blank;

[0057] (6) The pretreated glove blank is impregnated with a rubber compound containing modified carbon nanotubes, first dried at 85° C. for 40 min, and then dried at 120° C. for 90 min to obtain a breathable latex glove.

[0058] Comparative Example 1: A method for preparing latex gloves, the specific preparation steps are as follows:

[0059] (1) 4.75 g of silane coupling agent KH560 and 1.65 g of N,N'-vinylbisacrylamide were added to 90 g of N-methylpyrrolidone, stirred at 145° C. for 3 h, and rotary evaporated to obtain a modifier;

[0060] (2) 100 g of nitrile latex, 3 g of sodium dioctyl succinate sulfonate, 1.5 g of sulfur, 3 g of zinc dimethyldithiocarbamate, 3 g of sodium carboxymethyl cellulose, 3.47 g of carbon nanotubes and 0.53 g of a modifier were mixed uniformly, heated to 70° C., and pre-cured for 30 min to obtain a rubber compound containing modified carbon nanotubes;

[0061] (3) putting a knitted glove blank on a hand mold and immersing it in an aqueous solution of calcium chloride with a mass concentration of 8% to obtain a pretreated glove blank;

[0062] (4) The pretreated glove blank is impregnated with a rubber compound containing modified carbon nanotubes, firstly dried at 75° C. for 30 min, and then dried at 110° C. for 70 min, to obtain a breathable latex glove.

[0063] Comparative Example 2: A method for preparing latex gloves, the specific preparation steps are as follows:

[0064] The difference from Example 2 is that 1.65 g of N,N'-vinylbisacrylamide is replaced by 1.14 g of N-(2-aminoethyl)acrylamide, and the remaining steps are the same as Example 2.

[0065] Comparative Example 3: A method for preparing latex gloves, the specific preparation steps are as follows:

[0066] The difference from Example 2 is that 1.65 g of N,N'-vinylbisacrylamide is replaced by 1.83 g of N-octyl-2-propionamide, and the remaining steps are the same as Example 2.

[0067] Performance Testing

[0068] Air permeability: The samples obtained in the examples and comparative examples were tested according to the test method for artificial leather and synthetic leather of QB / T 5156-2017. The measuring method is as follows: the sample is fixed to form a pressure difference on both sides of the sample, and the air permeability is measured by observing whether bubbles are generated in the liquid in the device or the amount of bubbles. The test results are shown in Table 1.

[0069] Mechanical properties: According to GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber", the tensile speed is 500 mm / min, and the samples obtained in the embodiments and comparative examples are tested. The test results are shown in Table 1.

[0070]

[0071]

[0072] It can be seen from Examples 1-4 in Table 1 that the gloves obtained by the preparation method of the breathable latex gloves of the present invention have good air permeability and good mechanical properties; when used, they can give the wearer a comfortable experience and can be well applied in daily life.

[0073] It can be seen from Example 2 and Comparative Example 1 in Table 1 that the present invention can improve the air permeability of the gloves by modifying the carbon nanotubes and uniformly dispersing and grafting them onto the cross-linked network. At the same time, it can prevent the carbon nanotubes from agglomerating, thereby further improving the air permeability and mechanical properties of the gloves.

[0074] It can be seen from Example 2 and Comparative Example 2 in Table 1 that the present invention uses N,N'-vinylbisacrylamide to prepare the modifier. On the one hand, more carbon nanotubes can be introduced to make the air permeability of the gloves better; on the other hand, the density of the cross-linked network after vulcanization can be maintained, so that the mechanical properties are improved.

[0075] It can be seen from Example 2 and Comparative Example 3 in Table 1 that the present invention uses N,N'-vinylbisacrylamide to prepare the modifier, which not only introduces double bonds and increases the cross-linking density, but also introduces more reaction sites, so that more carbon nanotubes can be attached to the cross-linking network, further improving the air permeability and mechanical properties of the gloves.

[0076] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

Claims

1. A method for preparing breathable latex gloves, characterized in that: The following steps are involved: (1) Add silane coupling agent KH560 and N,N'-vinylbisacrylamide to N-methylpyrrolidone, stir at 140-150°C for 3-4 hours, and perform rotary evaporation to obtain a modifier; (2) adding the activated carboxylated carbon nanotubes and the modifier into anhydrous ethanol, stirring at 80-90° C. for 6-8 hours, centrifuging, washing, and drying to obtain modified carbon nanotubes; (3) By weight, 100 parts of nitrile latex, 1-5 parts of surfactant, 0.5-2 parts of vulcanizing agent, 1-5 parts of accelerator, 1-6 parts of thickener and 3-5 parts of modified carbon nanotubes are mixed uniformly, heated to 60-80° C., and pre-cured for 15-45 minutes to obtain a rubber compound containing modified carbon nanotubes; (4) putting the glove blank on the hand mold and impregnating it with a coagulant to obtain a pretreated glove blank; (5) The pretreated glove blank is impregnated with a rubber compound containing modified carbon nanotubes, vulcanized and dried to obtain a breathable latex glove.

2. The method for preparing the breathable latex gloves according to claim 1, characterized in that: The weight ratio of the silane coupling agent KH560 to N,N'-vinylbisacrylamide is 4.5-5:1.5-1.

8.

3. The method for preparing the breathable latex gloves according to claim 1, characterized in that: The specific steps of activating the carboxylated carbon nanotubes in step (2) are as follows: adding the carboxylated carbon nanotube powder to anhydrous ethanol, ultrasonically dispersing for 1-2 hours, then adjusting the pH to 3-4 with oxalic acid, stirring at 60-65° C. for 6 hours, washing, centrifuging, and drying to obtain activated carboxylated carbon nanotubes.

4. The method for preparing the breathable latex gloves according to claim 2, characterized in that: The weight ratio of the carboxylated carbon nanotubes to anhydrous ethanol is 1-3:

200.

5. The method for preparing the breathable latex gloves according to claim 1, characterized in that: In the step (2), the weight ratio of activated carboxylated carbon nanotubes, modifier and anhydrous ethanol is 10:1-2:50-70.

6. The method for preparing the breathable latex gloves according to claim 1, characterized in that: The surfactant in step (3) is one of dioctyl sodium succinate sulfonate, sodium olefin sulfonate, sodium hexadecyl sulfate, sodium octadecyl sulfate, and sodium dodecyl sulfate.

7. The method for preparing the breathable latex gloves according to claim 1, characterized in that: In the step (3), the vulcanizing agent is sulfur.

8. The method for preparing the breathable latex gloves according to claim 1, characterized in that: In the step (4), the coagulant is a calcium chloride aqueous solution with a mass concentration of 5-10%.

9. The method for preparing the breathable latex gloves according to claim 1, characterized in that: The glove blank in step (4) is a knitted glove blank.

10. The method for preparing the breathable latex gloves according to claim 1, characterized in that: In the step (5), the vulcanization and drying is first performed at a low temperature and then at a high temperature; the temperature of the low temperature vulcanization is 60-85°C and the drying time is 25-40 minutes, and the temperature of the high temperature vulcanization is 100-120°C and the drying time is 50-90 minutes.

Images