CN112480501B - Production process for improving cross-linking density of nitrile glove under condition of not increasing energy consumption - Google Patents
Production process for improving cross-linking density of nitrile glove under condition of not increasing energy consumption Download PDFInfo
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- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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Abstract
The invention relates to a preparation process of a disposable butyronitrile glove capable of improving the crosslinking density of the butyronitrile glove under the condition of not increasing energy consumption.
Description
Technical Field
The invention relates to a production process of disposable nitrile gloves, in particular to a production process for improving the crosslinking density of nitrile gloves under the condition of not increasing energy consumption, and belongs to the technical field of nitrile gloves.
Background
In recent years, along with the increasing importance of people on health, the demand of disposable gloves is rapidly increased, and particularly, the butyronitrile gloves with convenient use and stronger functionality are provided. In 2020, as the covd-19 rapidly spreads worldwide, the demand of the nitrile glove is increased, the capacity of the nitrile glove cannot meet the global supply, and the hot tide of the nitrile glove building and production line is raised worldwide. Compared with latex gloves, the nitrile glove does not contain protein which is easy to cause allergic reaction of human body in latex, is not easy to cause allergy and has low price; compared with PVC gloves, the PVC glove has good oil resistance, solvent resistance, puncture resistance, tearing resistance, higher tensile strength, excellent wear resistance, wearing comfort and the like. Nitrile gloves have been widely used in various fields of medical treatment, food, chemical industry, steam repair, agriculture, etc.
At present, the variety of the butyronitrile glove is more, most butyronitrile glove adopts sulfur as a vulcanizing agent, zinc dibutyl dithiocarbamate (BZ) as an accelerator, and zinc oxide as an active agent, and the butyronitrile glove is prepared by the processes of presulfiding, dipping butyronitrile latex, forming, leaching, vulcanizing, surface treatment, drying and the like. Because the demand of the nitrile glove is continuously increased, the nitrile glove production line is fully produced, so that the quality of the nitrile glove on the market is uneven, the problems of the nitrile glove are mainly concentrated on the defects of frosting, insufficient tensile strength, insufficient elongation, short wearing time and the like, and most of the defects are caused by low crosslinking density due to insufficient vulcanization degree of the nitrile glove, and the nitrile mixture formula and the vulcanization process are main factors influencing the crosslinking density of the nitrile glove. In the existing nitrile glove production formula, in order to improve the production efficiency, the nitrile glove produced by a factory is not vulcanized completely, but is vulcanized after being stored and transported, so that the vulcanization degree of the nitrile glove is influenced by the time of post vulcanization. In order to improve shipment efficiency, the problem of production energy consumption is increased by increasing the vulcanization degree on the nitrile glove line, and the production capacity is reduced by prolonging the vulcanization time, so that the problem is finally solved.
The invention comprises the following steps:
the invention aims to provide a preparation process of disposable butyronitrile gloves capable of improving the crosslinking density of the butyronitrile gloves under the condition of not increasing energy consumption, which comprises the steps of using double accelerators, optimally adjusting the dosage proportion of sulfur, zinc oxide and the accelerators, and carrying out dipping and vulcanization molding under the control of proper vulcanization conditions; the invention utilizes the synergistic effect between the accelerators, greatly improves the efficiency of the accelerators, further improves the vulcanization speed, increases the vulcanization degree, and can prepare the butyronitrile glove with high crosslinking density under the conditions of not increasing the production energy consumption and reducing the production efficiency.
To achieve the purpose, the invention adopts the following technical scheme:
the production process for improving the cross-linking density of the nitrile glove under the condition of not increasing energy consumption comprises the following steps:
1. raw materials
The raw materials mainly comprise the following components:
nitrile latex: a series of acrylonitrile-butadiene latex with 25-35 percent of acrylonitrile mass percent
Stabilizing agent: one or more of sodium dodecyl benzene sulfonate, sodium diisooctyl succinate, sodium dibutyl naphthalene sulfonate and sodium tetrapolypropylene benzene sulfonate
Potassium hydroxide: purity is more than or equal to 90 percent
Titanium white powder: the purity is more than or equal to 92 percent
Zinc oxide: the purity is more than or equal to 99.5 percent
Sulfur: purity is more than or equal to 99 percent
Accelerator a: one of zinc di-n-butyl dithiocarbamate (BZ) and zinc diethyl dithiocarbamate (EZ)
Accelerator B: one of zinc dimethyldithiocarbamate (PZ) and zinc ethylphenyl dithiocarbamate (PX)
Dispersing agent: anionic surfactants
2. The formula of the butyronitrile mixture prepreg comprises the following components:
1) Formula of butyronitrile latex
100 parts of nitrile latex
0.1 to 0.3 part of stabilizer
1.5 to 2 parts of potassium hydroxide
100 to 200 parts of pure water
2) Auxiliary material formula for ball grinding material
0.8 to 1.5 portions of zinc oxide
0.5 to 1.2 portions of sulfur
0.3 to 0.6 part of accelerator A, 0.3 to 0.6 part of accelerator B, and the ratio of the accelerator B to the accelerator A is 0.8 to 1.2
Titanium dioxide 1.0-2 parts
0.2 to 0.5 part of dispersing agent
10 to 20 parts of pure water
3. Preparation process of butyronitrile mixture prepreg
The nitrile latex, the stabilizer, the potassium hydroxide, the ball mill auxiliary materials and the pure water with the amounts shown in the formulation of the nitrile mixture are added into a stirring tank. Adding the nitrile latex according to the sequence, diluting with pure water according to a certain proportion, and adding a stabilizing agent diluted by 50-100 times; diluting potassium hydroxide to 1% -5% by using water in another stirring tank, and then adding the diluted potassium hydroxide into a stirring kettle; the ball grinding material auxiliary materials are added into a stirring kettle after being ground for 4-8 hours by a grinder according to the amount shown in the formula of the butyronitrile mixture, and the required pure water amount is supplemented. After the preparation of the butyronitrile mixture is finished, continuously stirring for 24-48 hours at the rotating speed of 80-120 r/min for standby.
4. Production process of butyronitrile glove
The nitrile glove molding process is shown in figure 1
1) Adding the butyronitrile mixture prepared in the stirring tank into a glue tank 1 and a glue tank 2, wherein the number of filter meshes is not less than 400;
2) Washing the hand mould with acid, washing with water for the first time, washing with alkali, washing with water for the second time, washing with cleaning agent, washing with water for the third time, and drying;
3) Immersing the hand mould cleaned in the step 2) in a coagulant solution;
4) Drying the hand mould dipped with the coagulant solution in the step 3), and then placing the hand mould into the nitrile latex mixture prepared in the step 1) for gum dipping;
5) Drying the hand mould dipped in the step 4), and then placing the hand mould into the nitrile latex mixture prepared in the step 1) again for dipping;
6) Leaching and curling the adhesive film dipped in the step 5) with clear water, and then placing the adhesive film in a vulcanizing tank for vulcanization and drying;
7) Cooling the adhesive film subjected to vulcanization drying in the step 6), placing the adhesive film in chlorine water for chlorine washing, neutralizing with alkaline water, cleaning with clear water, drying in an oven, and demolding to obtain the butyronitrile glove.
In the step 2), the surfaces of the hand molds are cleaner through acid washing, first water washing, alkali washing, second water washing, cleaning agent washing and third water washing, so that the subsequent operations of dipping the coagulants, gum dipping, demolding and the like are facilitated. Wherein the pH of the pickling solution used in pickling is 2-3, and the pH of the alkaline solution used in alkaline washing is 10-11. The cleaning agent is a hand mold cleaning agent, and is mainly used for removing metal ions such as calcium and zinc and the like remained in the hand mold, the surface of the hand mold after cleaning is smooth, no flow mark is generated uniformly when the hand mold is immersed in a coagulating agent, and the surface of the prepared butyronitrile glove is clean and the adhesive film is uniform.
In the step 3), the calcium content of the coagulant solution is controlled to be 8-15%, and the surface tension is controlled to be 20-40 mN/m.
The solid content of the mixture in the step 4) and the step 5) is controlled to be 10% -20%, the dipping time is 12+ -5 seconds (adjusted according to the thickness of the final glove film), the temperature of the oven is 60 ℃ -110 ℃, and the baking time is 2-5 minutes.
The temperature of the leaching water in the step 6) is controlled between 30 ℃ and 70 ℃, the hardness is 500ppm to 2000ppm, the vulcanization temperature is 110+/-10 ℃, and the vulcanization time is 20+/-10 min.
In the step 7), the chlorine ion concentration of the chlorine water is 300 ppm-800 ppm, and the pH value of the neutralized water is controlled to be 12+/-2.
The film thickness of the butyronitrile glove prepared by the invention is 0.05-0.12 mm, the tensile strength of the glove film is more than 28MPa, the elongation is more than 620%, and the swelling index is less than 8.
Drawings
FIG. 1 is a flow chart of one embodiment of the dip forming process of the disposable nitrile glove of the present invention.
Detailed Description
The present invention is described in detail below in connection with example gloves and comparative conventional nitrile gloves, but the examples should not be construed as limiting the scope of the invention.
Example 1
A production process for improving the cross-linking density of nitrile gloves without increasing energy consumption comprises the following steps:
(1) Adding 100 parts of nitrile latex into a stirring tank, adding pure water to dilute for 2 times, and then adding 0.3 part of stabilizer (sodium dodecyl benzene sulfonate) and 1.5 parts of potassium hydroxide (3% aqueous solution) which are diluted with the pure water for 50 times; 1.5 parts of ball grinding auxiliary materials zinc oxide, 1.2 parts of sulfur, 0.5 part of accelerator A zinc di-n-butyl dithiocarbamic acid (BZ), 0.4 part of accelerator B zinc dimethyl dithiocarbamic acid (PZ), 1.5 parts of titanium dioxide, 0.4 part of dispersing agent polycarboxylic acid sodium salt anionic surfactant and 20 parts of pure water, grinding for 6 hours, adding into a stirring tank, and continuously stirring for 36 hours at the rotating speed of 100-120r/min for later use.
(2) The ceramic hand mould is cleaned, enters a coagulator tank, is dried by an oven, is immersed in a rubber tank 1 and a rubber tank 2 in sequence, is vulcanized by a vulcanizing tank at 110 ℃ for 20min after being dried, leached and curled, is subjected to surface treatment by chlorine water after being cooled, and is finally cleaned and dried to obtain the butyronitrile glove. The glove film has a thickness of 0.065 mm, a tensile strength of 29.5MPa, an elongation of 635%, a swelling index of 7.5, and a crosslinking density of 2.46 x 10 -4 mol/cm 3 。
Example 2
A production process for improving the cross-linking density of nitrile gloves without increasing energy consumption comprises the following steps:
1) Adding 100 parts of nitrile latex into a stirring tank, adding pure water to dilute for 2 times, and then adding 0.3 part of stabilizer (sodium dodecyl benzene sulfonate) and 1.5 parts of potassium hydroxide (3% aqueous solution) which are diluted with the pure water for 50 times; 1.2 parts of ball grinding auxiliary materials zinc oxide, 1.1 parts of sulfur, 0.4 part of accelerator A zinc di-n-butyl dithiocarbamic acid (EZ), 0.4 part of accelerator B zinc ethyl phenyl dithiocarbamic acid (PX), 1.5 parts of titanium dioxide, 0.4 part of dispersing agent polycarboxylic acid sodium salt anionic surfactant and 20 parts of pure water, grinding for 6 hours, adding into a stirring tank, and continuously stirring for 36 hours at the rotating speed of 100-120r/min for later use.
(2) The ceramic hand mould is cleaned, enters a coagulator tank, is dried by an oven, is immersed in a rubber tank 1 and a rubber tank 2 in sequence, is vulcanized by a vulcanizing tank at 110 ℃ for 20min after being dried, leached and curled, is subjected to surface treatment by chlorine water after being cooled, and is finally cleaned and dried to obtain the butyronitrile glove. The glove film has a thickness of 0.065 mm, a tensile strength of 28.9MPa, an elongation of 628%, a swelling index of 7.7 and a crosslinking density of 2.44×10 -4 mol/cm 3 。
Comparative example 1
Only 0.9 part of accelerator A zinc di-n-Butyldithiocarbamate (BZ) was added, and the remaining components and the method were the same as in example 1.
Comparative example 2
Only 0.9 part of accelerator B zinc dimethyldithiocarbamate (PZ) was added, and the remaining components and the method were the same as in example 1.
Comparative example 3
1.6 parts of zinc oxide, 1.3 parts of sulfur, 0.4 part of accelerator A zinc di-n-butyl dithiocarbamate (BZ) and 0.5 part of accelerator B zinc dimethyl dithiocarbamate (PZ) are added, and the rest of components and the method are the same as in example 1.
Comparative example 4
1.6 parts of zinc oxide, 1.3 parts of sulfur, 0.2 part of accelerator A zinc di-n-butyl dithiocarbamate (EZ), 0.7 part of accelerator B zinc ethylphenyl dithiocarbamate (PX) and the rest of components and the method are the same as in example 1.
Table 1 nitrile glove film Performance test
TABLE 2 Total migration of nitrile glove membranes in different solvents
As can be seen from the table, the disposable nitrile glove prepared by the invention exceeds the performance of the glove produced by the traditional process (the tensile strength of the traditional nitrile glove is more than or equal to 20MPa, the elongation is more than or equal to 500 percent and the swelling index is 9-12), and the migration resistance of the nitrile glove is improved.
In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (1)
1. A method for improving the cross-linking density of nitrile gloves without increasing energy consumption comprises the following steps:
(1) Adding 100 parts of nitrile butadiene latex into a stirring tank, wherein the mass percent of acrylonitrile in the nitrile butadiene latex is 25% -35%, adding pure water to dilute for 2 times, and adding 0.3 part of stabilizer sodium dodecyl benzene sulfonate and 1.5 parts of potassium hydroxide which are diluted for 50 times, wherein the potassium hydroxide is a 3% aqueous solution; 1.5 parts of ball grinding auxiliary materials zinc oxide, 1.2 parts of sulfur, 0.5 part of accelerator A zinc di-n-butyl dithiocarbamic acid (BZ), 0.4 part of accelerator B zinc dimethyl dithiocarbamic acid (PZ), 1.5 parts of titanium dioxide, 0.4 part of dispersing agent polycarboxylic acid sodium salt anionic surfactant and 20 parts of pure water, grinding for 6 hours, adding into a stirring tank, and continuously stirring for 36 hours at the rotating speed of 100-120 r/min;
(2) Cleaning a ceramic hand mould, then, entering a coagulant tank, drying by a baking oven, immersing the ceramic hand mould in the glue tank 1 and the glue tank 2 in sequence, drying, leaching and curling, then, vulcanizing by a vulcanizing tank at 110 ℃ for 20min, cooling, performing surface treatment by chlorine water, and finally, cleaning and drying to obtain the butyronitrile gloves; the prepared butyronitrile glove has a film thickness of 0.065 mm, a tensile strength of 29.5MPa, an elongation of 635%, a swelling index of 7.5 and a crosslinking density of 2.46×10 -4 mol/cm 3 。
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| CN114031827A (en) * | 2021-12-17 | 2022-02-11 | 中红普林医疗用品股份有限公司 | Butyronitrile gloves with good wearability and no allergic component and preparation method thereof |
| CN114854057B (en) * | 2022-04-26 | 2024-06-07 | 濮阳林氏医疗制品有限公司 | Low-temperature vulcanizing bag set and preparation method and application thereof |
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|---|---|---|---|---|
| GB722107A (en) * | 1951-11-27 | 1955-01-19 | Dunlop Rubber Co | Manufacture of rubber products |
| WO2008017230A1 (en) * | 2006-08-03 | 2008-02-14 | Tianjin Greencoat Polymer Material Tech. Co., Ltd. | A method for making a functional acrylonitrile-butadiene rubber glove |
| WO2018129805A1 (en) * | 2017-01-13 | 2018-07-19 | 山东星宇手套有限公司 | Disposable butyronitrile gloves with diamond pattern and manufacturing process therefor |
| CN108384079A (en) * | 2018-02-27 | 2018-08-10 | 山东星宇手套有限公司 | A kind of preparation method of nitrile rubber corrugation gloves |
| CN108586856A (en) * | 2018-03-30 | 2018-09-28 | 山东星宇手套有限公司 | NBR latex composite mortar and preparation method thereof, butyronitrile gloves and preparation method thereof |
| CN111253639A (en) * | 2020-04-01 | 2020-06-09 | 山东星宇手套有限公司 | Preparation method of environment-friendly thermosensitive butyronitrile protective gloves |
-
2020
- 2020-10-09 CN CN202011072021.6A patent/CN112480501B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB722107A (en) * | 1951-11-27 | 1955-01-19 | Dunlop Rubber Co | Manufacture of rubber products |
| WO2008017230A1 (en) * | 2006-08-03 | 2008-02-14 | Tianjin Greencoat Polymer Material Tech. Co., Ltd. | A method for making a functional acrylonitrile-butadiene rubber glove |
| WO2018129805A1 (en) * | 2017-01-13 | 2018-07-19 | 山东星宇手套有限公司 | Disposable butyronitrile gloves with diamond pattern and manufacturing process therefor |
| CN108384079A (en) * | 2018-02-27 | 2018-08-10 | 山东星宇手套有限公司 | A kind of preparation method of nitrile rubber corrugation gloves |
| CN108586856A (en) * | 2018-03-30 | 2018-09-28 | 山东星宇手套有限公司 | NBR latex composite mortar and preparation method thereof, butyronitrile gloves and preparation method thereof |
| CN111253639A (en) * | 2020-04-01 | 2020-06-09 | 山东星宇手套有限公司 | Preparation method of environment-friendly thermosensitive butyronitrile protective gloves |
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