Simulated frosted impregnated glove and preparation method thereof

Abstract

The invention belongs to the technical field of labor protection articles, and particularly relates to a simulated frosted gum dipping glove and a preparation method thereof.The simulated frosted gum dipping glove comprises a glove core, and a simulated frosted layer is fixed to the outer surface of the glove core in a gum dipping mode; the simulated frosted layer is prepared from the following components in parts by weight: 95 to 120 parts of nitrile rubber, 5 to 15 parts of vulcanizing agent, 8 to 18 parts of accelerant, 1.5 to 5 parts of active agent, 0.8 to 1.5 parts of coupling agent and 0.9 to 1.8 parts of acrylonitrile polymer, and the weight of the acrylonitrile polymer accounts for 1 to 1.5 percent of that of the nitrile rubber. The rubber surface of the simulated frosted impregnated glove not only has a frosted characteristic, but also has a heat insulation effect, and can be applied to the fields of fire fighting and the like with relatively high heat resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of labor protection products, and particularly relates to a simulated frosted rubber-dipped glove and a preparation method thereof. Background Art

[0002] Labor protection products are designed to prevent occupational injuries, reduce the occurrence of occupational diseases, and improve work safety. Dipped gloves are widely used labor protection products. They can be used in household, industrial, medical, beauty and other industries, and are essential hand protection products. At present, in order to increase the friction of dipped gloves, the rubber surface of the gloves is treated by salt spraying and water washing to prepare frosted gloves. However, the workshop environment is easily polluted during the salt spraying process, and water bodies contaminated by sodium sulfate will be produced after water washing, which will cause pollution and serious waste of materials.

[0003] There are studies on the problems of frosted gloves made by salt spraying and water washing in the prior art, such as patent application CN117796593A-A frosted glove and its preparation method, CN108456342A-A frosted glove manufacturing method, which uses glue to wrap microcapsule foaming agent and attach it to the outside of the glove embryo, so that it forms uneven textures on the surface of the glove embryo, or adjusts the rubber material and surface treatment oil to make the frosted glove surface have a frosted effect, which solves the problems of pollution and serious material waste in the frosted gloves currently made by salt spraying and water washing. However, the existing frosted gloves can only ensure the gripping force, wear resistance and anti-slip performance of the gloves, but it is difficult to effectively control the heat resistance of the gloves, thereby narrowing the scope of use of the frosted gloves. Therefore, a new technical solution is needed to solve the above technical problems. Summary of the invention

[0004] The object of the present invention is to provide a simulated frosted rubber-dipped glove and a preparation method thereof, so as to solve the problem mentioned in the above background technology that it is difficult to effectively control the heat resistance of the simulated frosted gloves at the current stage, thereby narrowing the use scope of the simulated frosted gloves.

[0005] To achieve the above-mentioned object, the present invention provides the following technical solution: a simulated frosted dipped glove, comprising a glove core, wherein a simulated frosted layer is fixed to the outer surface of the glove core by dipping, wherein the simulated frosted layer comprises, according to the weight proportions of the components: 95 to 120 parts of nitrile rubber, 5 to 15 parts of a vulcanizing agent, 8 to 18 parts of an accelerator, 1.5 to 5 parts of an activator, 0.8 to 1.5 parts of a coupling agent and 0.9 to 1.8 parts of an acrylonitrile polymer, wherein the weight of the acrylonitrile polymer accounts for 1 to 1.5% of the nitrile rubber.

[0006] The method for preparing the above-mentioned simulated frosted dipped gloves comprises the following specific steps: S1. Prepare the rubber material of the simulated frosted layer: stir and mix nitrile rubber with a vulcanizing agent, an accelerator, an activator, a coupling agent and an acrylonitrile polymer according to a set ratio to prepare the rubber material of the simulated frosted layer, wherein the vulcanizing agent is one of sulfur and zinc dithiocarbamate; the accelerator is one of cyclohexyl-2-benzothiazolylsulfonamide and zinc diethyldithiocarbamate; the activator is one of zinc oxide and stearic acid; the coupling agent is one of dodecyltrimethoxysilane and tetrabutyl zirconate; the acrylonitrile polymer is one of acrylonitrile-acrylate copolymer, acrylonitrile-vinyl acetate copolymer and acrylonitrile-butyl acrylate copolymer; S2. Mold-covering: The mold-covering process is to first cover the glove core on the hand mold, and then preheat the glove core on the hand mold, and the preheating temperature is controlled at 50-60℃; S3, dipping: before dipping, the coagulant must be dipped in the glue, let it stand for 50 to 70 seconds, and then dipped into the glue of the simulated frosted layer obtained in S1, and then dripped and spread the glue, wherein the coagulant is calculated according to the weight percentage of the components: 96 to 98% methanol, 1 to 2% calcium chloride and 1 to 2% penetrant, the penetrant is triethoxysilane, trimethoxysilane, and the viscosity of the glue of the simulated frosted layer is 1000 to 2000 mpa.s; S4, surface treatment: immerse the gloves obtained by dipping in S3 into a xylene surface treatment liquid for surface treatment and then dry naturally, wherein the xylene surface treatment liquid is a mixture of 60-90% methanol and 10-40% xylene; S5, preheating and drying: drying the gloves dried in S4 at 75-95°C for 20-40 minutes; S6. Soaking: put the gloves dried in S5 into normal temperature water and rinse for 20 to 40 minutes; S7, vulcanization and drying: drying the gloves rinsed in S6 at 90-120° C. for 60-90 minutes to obtain simulated frosted rubber-dipped gloves.

[0007] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention utilizes the thermal stability of acrylonitrile polymer to effectively control the heat resistance of the simulated frosted dipped gloves, which is more than 20% higher than that of existing frosted gloves, effectively expanding the use range of the simulated frosted dipped gloves; the weight of acrylonitrile polymer is set to 1-1.5% of nitrile rubber, so that the rubber material of the simulated frosted layer can expand violently at 75-120°C, so that the simulated frosted layer has a frosting effect, effectively reducing the risk of chipping; by adding a coupling agent, the simulated frosted layer with a frosting effect can eliminate the return phenomenon during the vulcanization process, effectively improving the wear resistance and durability of the simulated frosted dipped gloves, so that the simulated frosted dipped gloves have better fit to the hands, and have better grip and better durability than existing frosted gloves under the same liner; 2. The present invention adopts one of acrylonitrile-acrylate copolymer, acrylonitrile-vinyl acetate copolymer and acrylonitrile-butyl acrylate copolymer as the acrylonitrile polymer and mixes it with nitrile rubber, which not only enables the simulated frosted layer to have a frosted effect, effectively reducing the risk of chipping, but also enables the simulated frosted layer to have impact resistance, effectively improving the wear resistance and durability of the simulated frosted dipped gloves, and also enables the simulated frosted layer to have flexibility, ensuring the comfort of the simulated frosted dipped gloves when worn; 3. The present invention uses a mixture of methanol, calcium chloride and a penetrant as a coagulant, so that the rubber material of the simulated frosted layer can be more closely attached to the glove core, effectively avoiding the problem of environmental pollution caused by the frosted gloves falling off, and effectively improving the durability of the simulated frosted dipped gloves, thereby ensuring the service life of the simulated frosted dipped gloves; 4. The present invention adopts a mixture of methanol and xylene as the xylene-nano surface treatment liquid, which can not only effectively improve the dispersibility of the rubber material of the simulated frosted layer under the treatment of the nanoparticle surface treatment liquid and effectively avoid agglomeration, but also enable the rubber material of the simulated frosted layer to form a coating film under the coating of the xylene-nano surface treatment liquid, effectively reducing the risk of chipping and improving the comfort of the simulated frosted dipped gloves when worn, while also ensuring the stability and safety of the simulated frosted dipped gloves during preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 This is a finished product picture of the simulated frosted rubber-dipped gloves of the present invention; Figure 2 It is a partial enlarged view of the surface of the simulated frosted rubber-dipped gloves of the present invention; Figure 3 This is a detailed picture of the simulated frosted layer on the surface of the simulated frosted rubber-coated gloves of the present invention. DETAILED DESCRIPTION

[0009] The following examples are used to further illustrate the content of the present invention, but do not limit the application of the present invention. Embodiment 1:

[0010] The present embodiment provides a simulated frosted rubber-dipped glove. First, sulfur is selected as a vulcanizing agent, zinc diethyldithiocarbamate is selected as an accelerator, stearic acid is selected as an activator, dodecyltrimethoxysilane is selected as a coupling agent, acrylonitrile-butyl acrylate copolymer is selected as an acrylonitrile polymer, and triethoxysilane is selected as a penetrant. Secondly, 98 parts of nitrile rubber, 7 parts of sulfur, 8.6 parts of zinc diethyldithiocarbamate, 2.4 parts of stearic acid, 0.86 parts of dodecyltrimethoxysilane and 0.98 parts of acrylonitrile-butyl acrylate copolymer are stirred and mixed to prepare a rubber material for a simulated frosted layer for use, and the viscosity of the rubber material is controlled at 1000-2000mpa.s. Then, the rubber material for the simulated frosted layer is used to prepare the simulated frosted rubber-dipped glove. Specifically, the glove core is put on the hand mold, and the glove core on the hand mold is preheated. The preheating temperature is controlled at 50-60°C, and the preheated glove is immersed in 96.5% methanol, 1.5 % calcium chloride, 2% triethoxysilane mixed to form a coagulant for 8 to 10 seconds, take out the glove core and let it stand for 50 to 70 seconds, then immerse the glove core soaked in the coagulant into the rubber material of the above-mentioned standby simulated frosted layer for dipping (dipping can be once or multiple times), and then drip glue and spread glue (or spin glue), when the glue surface is not dry, immerse the dipped gloves in a xylene surface treatment liquid formed by a mixture of 60 to 90% methanol and 10 to 40% xylene for surface treatment, so that the rubber surface forms a coating film under the treatment of the xylene surface treatment liquid, reducing the risk of chipping, take out the surface treated gloves and dry them naturally, after drying, send the gloves to an oven, dry them at 75 to 95° C. for 20 to 40 minutes, take out the gloves and put them in room temperature water for 20 to 40 minutes, after rinsing, send the gloves to an oven again, dry them at 90 to 120° C. for 60 to 90 minutes to obtain simulated frosted dipped gloves (the finished product is as shown in Figure 1 As shown, the partial enlarged picture of its adhesive surface is as follows Figure 2 As shown, the fine picture of its adhesive surface is as follows Figure 3As shown in the figure), it is strictly forbidden to open the oven during the drying process, otherwise it will cause the polyacrylonitrile copolymer to react insufficiently and affect the texture of the rubber surface. The simulated frosted rubber-dipped gloves prepared by the rubber material of the simulated frosted layer, the coagulant formed by mixing 96.5% methanol, 1.5% calcium chloride, and 2% triethoxysilane, the xylene surface treatment liquid formed by mixing 60-90% methanol and 10-40% xylene, and the drying treatment process can not only make the rubber surface of the gloves have frosted characteristics, but also make the rubber surface of the gloves have heat insulation effect. Under the standard of GB 6245-2006 "Firefighter Protective Equipment", the thermal conductivity of the gloves can reach 0.028W / (m·K), and the time for the glove to contact the heat source of 260℃ without causing the internal temperature to exceed 45℃ is 40 seconds. When the glove is subjected to the heat radiation of 40kW / m² at a distance of 15cm from the heat source, the time for the internal temperature to not exceed 45℃ is 45 seconds. It meets the standards of fire protection equipment and can be used in fields with high heat resistance such as firefighting. Embodiment 2:

[0011] The present embodiment provides a simulated frosted dipped glove. First, zinc dithiocarbamate is used as a vulcanizing agent, cyclohexyl-2-benzothiazolyl sulfenamide is used as an accelerator, zinc oxide is used as an activator, tetrabutyl zirconate is used as a coupling agent, acrylonitrile-acrylate copolymer is used as an acrylonitrile polymer, and trimethoxysilane is used as a penetrant. Then, 109 parts by weight of nitrile rubber, 10 parts by weight of zinc dithiocarbamate, 12 parts by weight of cyclohexyl-2-benzothiazolyl sulfenamide, 3.1 parts by weight of zinc oxide, and 0.96 parts by weight of trimethoxysilane are added. Tetrabutyl zirconate and 1.36 parts of acrylonitrile-acrylate copolymer are stirred and mixed to prepare a rubber material for a simulated frosted layer, and the viscosity of the rubber material is controlled at 1000-2000 mPa.s. Then, the rubber material for the simulated frosted layer is used to prepare simulated frosted dipped gloves, specifically: a glove core is put on a hand mold, and then the glove core on the hand mold is preheated, and the preheating temperature is controlled at 50-60° C., and then the preheated gloves are immersed in 97.4% methanol, 1.3% calcium chloride, and 1.3% triethoxysilane by weight. The glove core is immersed in the coagulant for 8 to 10 seconds, and then the glove core is taken out and allowed to stand for 50 to 70 seconds, and then the glove core immersed in the coagulant is immersed in the rubber material of the above-mentioned reserved simulated frosted layer for dipping (dipping can be done once or multiple times), and then the glue is dripped and spread (spinning can also be done), and when the glue surface is not dry, the dipped gloves are immersed in a xylene surface treatment liquid formed by a mixture of 60 to 90% methanol and 10 to 40% xylene for surface treatment, so that the rubber surface is treated with the xylene surface treatment liquid to form a coating film, reducing There is less risk of chipping. After taking out the surface-treated gloves, air dry them naturally. After drying, put them into an oven and dry them at 75-95°C for 20-40 minutes. After taking them out, put them into room temperature water for 20-40 minutes to rinse. After rinsing, put them into an oven again and dry them at 90-120°C for 60-90 minutes to obtain simulated frosted dipped gloves. It is strictly forbidden to open the oven during the drying process, otherwise it will cause insufficient reaction of the polyacrylonitrile copolymer and affect the texture of the rubber surface. The simulated frosted rubber-dipped gloves prepared by the rubber material of the simulated frosted layer, the coagulant mixed with 97.4% methanol, 1.3% calcium chloride and 1.3% triethoxysilane, the xylene surface treatment liquid mixed with 60-90% methanol and 10-40% xylene, and the drying treatment process can not only make the rubber surface of the gloves have frosted characteristics, but also make the rubber surface of the gloves have heat insulation effect. Under the standard of GB 6245-2006 "Firefighter Protective Equipment", the thermal conductivity of the gloves can reach 0.0215W / (m·K), and the time for the glove to not exceed 45℃ when it contacts a heat source of 260℃ is 46 seconds. When the glove is subjected to a heat radiation of 40kW / m² at a distance of 15cm from the heat source, the time for not causing the internal temperature to exceed 45℃ is 51 seconds. It meets the standards of fire protection equipment and can be used in fields with high heat resistance such as firefighting. Embodiment 3:

[0012] The present embodiment provides a simulated frosted dipped glove. First, sulfur is selected as a vulcanizing agent, zinc diethyldithiocarbamate is used as an accelerator, stearic acid is used as an activator, dodecyltrimethoxysilane is used as a coupling agent, acrylonitrile-vinyl acetate copolymer is used as an acrylonitrile polymer, and triethoxysilane is used as a penetrant. Then, 119 parts by weight of nitrile rubber, 14 parts by weight of sulfur, 17 parts by weight of zinc diethyldithiocarbamate, 4.8 parts by weight of stearic acid, and 1.46 parts by weight of dodecyltrimethoxysilane are added. and 1.79 parts of acrylonitrile-vinyl acetate are stirred and mixed to prepare a rubber material for a simulated frosted layer for use, and the viscosity of the rubber material is controlled at 1000-2000 mpa.s; then the rubber material for the simulated frosted layer is used to prepare a simulated frosted dipped glove, specifically: a glove core is put on a hand mold, and then the glove core on the hand mold is preheated, and the preheating temperature is controlled at 50-60° C., and then the preheated glove is immersed in a coagulant formed by mixing 98% by weight of methanol, 1% by weight of calcium chloride, and 1% by weight of triethoxysilane. 8 to 10 seconds, take out the glove core and let it stand for 50 to 70 seconds, then immerse the glove core soaked with coagulant into the rubber material of the above-mentioned reserved simulated frosted layer for dipping (dipping can be done once or multiple times), and then drip glue and spread glue (or spin glue), and when the glue surface is not dry, immerse the dipped gloves in a xylene surface treatment liquid formed by mixing 60 to 90% methanol and 10 to 40% xylene for surface treatment, so that the rubber surface is treated with the xylene surface treatment liquid to form a coating film, thereby reducing chip shedding. In order to avoid the risk of damage to the surface of the gloves, take out the surface treated gloves and dry them naturally. After drying, put the gloves into an oven and dry them at 75-95°C for 20-40 minutes. After taking them out, put the gloves into room temperature water for 20-40 minutes to rinse them. After rinsing, put the gloves into an oven again and dry them at 90-120°C for 60-90 minutes to obtain simulated frosted dipped gloves. It is strictly forbidden to open the oven during the drying process, otherwise it will cause insufficient reaction of the polyacrylonitrile copolymer and affect the texture of the rubber surface. The simulated frosted rubber-dipped gloves prepared by the rubber material of the simulated frosted layer, the coagulant mixed with 98% methanol, 1% calcium chloride and 1% triethoxysilane, the xylene surface treatment liquid mixed with 60-90% methanol and 10-40% xylene, and the drying treatment process can not only make the rubber surface of the gloves have frosted characteristics, but also make the rubber surface of the gloves have heat insulation effect. Under the standard of GB 6245-2006 "Firefighter Protective Equipment", the thermal conductivity of the gloves can reach 0.018W / (m·K), and the time for the glove to not exceed 45℃ when it contacts a heat source of 260℃ is 54 seconds. When the glove is subjected to a heat radiation of 40kW / m² at a distance of 15cm from the heat source, the time for not causing the internal temperature to exceed 45℃ is 62 seconds. It meets the standards of fire protection equipment and can be used in fields with high heat resistance such as firefighting.

[0013] The following is a data comparison table of relevant variables in Examples 1-3: ; It can be seen from the above table that the heat resistance of the simulated frosted dipped gloves is related to the type and amount of acrylonitrile polymer. Therefore, the present invention adopts one of acrylonitrile-acrylate copolymer, acrylonitrile-vinyl acetate copolymer, and acrylonitrile-butyl acrylate copolymer as the acrylonitrile polymer and mixes them with 1-1.5% by weight of nitrile rubber, so that the heat resistance of the simulated frosted layer is effectively controlled. The simulated frosted dipped gloves are prepared by a coagulant mixed with 98% methanol, 1% calcium chloride, and 1% triethoxysilane before and after the gloves are dipped in the late stage, and a xylene surface treatment liquid mixed with 60-90% methanol and 10-40% xylene, and a drying treatment method. Not only can the rubber surface of the gloves have frosted characteristics, but also the rubber surface of the gloves has a heat-insulating effect, and can be used in fields with high heat resistance such as firefighting.

Claims

1. A simulated frosted rubber-dipped glove, comprising a glove core, the outer surface of which is fixed with a simulated frosted layer by dipping, characterized in that: The simulated frosted layer comprises, by weight, 95 to 120 parts of nitrile rubber, 5 to 15 parts of vulcanizing agent, 8 to 18 parts of accelerator, 1.5 to 5 parts of activating agent, 0.8 to 1.5 parts of coupling agent and 0.9 to 1.8 parts of acrylonitrile polymer, wherein the weight of the acrylonitrile polymer accounts for 1 to 1.5% of the nitrile rubber.

2. The method for preparing the simulated frosted dipped gloves according to claim 1, characterized in that: The specific steps are as follows: S1. preparing a rubber material for a simulated frosted layer: mixing nitrile rubber, a vulcanizing agent, an accelerator, an activator, a coupling agent and an acrylonitrile polymer according to a set ratio to prepare a rubber material for a simulated frosted layer; S2, set mold; S3, dipping in glue: before dipping in glue, it is necessary to first dip in a coagulant, then dip in the glue material of the simulated frosted layer obtained in S1, and then drip and spread the glue; S4, surface treatment: immerse the gloves obtained by dipping in S3 into a xylene surface treatment solution for surface treatment and then dry naturally; S5, preheating and drying: drying the gloves dried in S4 at 75-95°C; S6. Soaking: Rinse the gloves dried in S5 in water at room temperature; S7, vulcanization and drying: drying the gloves rinsed in S6 at 90-120° C. to obtain simulated frosted and dipped gloves.

3. The method for preparing the simulated frosted dipped gloves according to claim 2, characterized in that: In S1, the vulcanizing agent is one of sulfur and zinc dithiocarbamate; the accelerator is one of cyclohexyl-2-benzothiazolylsulfonamide and zinc diethyldithiocarbamate; the activator is one of zinc oxide and stearic acid; and the coupling agent is one of dodecyltrimethoxysilane and tetrabutyl zirconate.

4. The method for preparing the simulated frosted dipped gloves according to claim 2, characterized in that: In S1, the acrylonitrile polymer is one of acrylonitrile-acrylate copolymer, acrylonitrile-vinyl acetate copolymer, and acrylonitrile-butyl acrylate copolymer.

5. The method for preparing the simulated frosted dipped gloves according to claim 2, characterized in that: In S2, the mold is put on by first putting the glove core on the hand mold, and then preheating the glove core on the hand mold, and the preheating temperature is controlled at 50-60°C.

6. The method for preparing the simulated frosted dipped gloves according to claim 2, characterized in that: In S3, the coagulant is composed of 96-98% methanol, 1-2% calcium chloride and 1-2% penetrant according to the weight percentage of the components, wherein the penetrant is triethoxysilane or trimethoxysilane.

7. The method for preparing the simulated frosted dipped gloves according to claim 2, characterized in that: In S3, the glove core needs to be kept still for 50 to 70 seconds after being dipped in the coagulant and before being dipped in the simulated frosted layer rubber.

8. The method for preparing the simulated frosted dipped gloves according to claim 2, characterized in that: In S3, the viscosity of the rubber material of the simulated frosted layer is 1000-2000 mpa·s.

9. The method for preparing the simulated frosted dipped gloves according to claim 2, characterized in that: In S4, the xylene surface treatment liquid is a mixture of 60-90% methanol and 10-40% xylene.

10. The method for preparing the simulated frosted dipped gloves according to claim 2, characterized in that: In S5 and S7, the drying time is 20 to 40 minutes and 60 to 90 minutes respectively, and in S6, the rinsing time is 20 to 40 minutes.

Images