Breathable rubber material for protecting harmful chemical reagents as well as preparation method and application of breathable rubber material

Abstract

The invention relates to an air-permeable rubber material for protecting harmful chemical reagents as well as a preparation method and application thereof, and belongs to the technical field of harmful chemical reagent protection materials. The breathable rubber material for protecting the harmful chemical reagents comprises a protective layer, an adsorption layer and a close-fitting layer which are sequentially connected, and every two adjacent layers are bonded through a hot melt adhesive; the adsorption layer comprises the following components in parts by weight: 45-75 parts of rubber latex, 30-50 parts of adsorption particles, 0.5-2.5 parts of an anti-aging agent, 0.5-3 parts of sulfur, 0.5-5 parts of zinc oxide, 0.1-3 parts of a vulcanization accelerator, 0.1-1 part of an alkaline pH regulator and 0.01-0.1 part of a stabilizer. According to the breathable rubber material, the adsorption layer with the rubber aerogel loaded adsorption particles is adopted, the combination of the protective layer and the base layer is matched, the prepared material is better in breathability, good in adsorption performance and resistant to rubbing and machine washing, the breathability, the chemical reagent protection performance and practicability of the rubber protective material are effectively improved, and the breathable rubber material can be widely applied to the field of protective clothing.

Description

Technical Field

[0001] The present application relates to a breathable rubber material for protecting against harmful chemical agents, a preparation method thereof and an application thereof, and belongs to the technical field of protective materials against harmful chemical agents. Background Art

[0002] The main purpose of chemical protective clothing is to protect the human body from external hazards such as chemical, thermal, mechanical, biological and radiation, while maintaining a safe and comfortable microclimate around the skin. However, comfort and protection are two contradictory directions. Maximizing comfort while maintaining protection is the main challenge facing chemical protective clothing.

[0003] Chemical protective clothing is mainly divided into isolation protective clothing and breathable protective clothing. Among them, isolation protective clothing is mainly made of airtight anti-toxic film materials, which has excellent isolation performance but poor air permeability and moisture permeability. When used in hot conditions, workers are prone to heatstroke. Breathable protective clothing blocks the intrusion of external toxic droplets and toxic vapors while allowing internal water vapor to pass outward. It has both protection and comfort, and therefore has a wider range of applications.

[0004] However, the protective effect of breathable protective clothing in the current prior art is not ideal, mainly because the adsorption efficiency of the internal adsorption particles on harmful molecules is low. For example, Chinese patent CN202110585676 discloses a composite fabric for anti-toxic clothing and a preparation method thereof, wherein the activated carbon is directly adhered to the rubber-coated base fabric. Since the contact area between the activated carbon and the rubber is too large, its breathability is greatly weakened; Chinese patent CN201821040739 discloses a composite structure including a fabric layer and a spherical activated carbon layer, wherein a depression extending from the surface to the inside of the fabric layer is provided on the surface of the fabric layer facing the spherical activated carbon, and at least a portion of the outer surface of the spherical activated carbon is bonded to at least a portion of the inner surface of the depression, thereby avoiding the use of too much adhesive. However, the bonding force between the activated carbon and the base fabric in this scheme is weak, and the activated carbon is prone to fall off after multiple uses, especially after washing in a washing machine, thereby affecting the protective effect.

[0005] Based on the problems existing in the breathable protective clothing in the prior art, there is an urgent need to develop a breathable chemical protective material with high adsorption efficiency and resistance to washing. Summary of the invention

[0006] In order to solve the above problems, a breathable rubber material for protecting against harmful chemical agents, a preparation method and application thereof are provided. The breathable rubber material provided in the present application adopts an adsorption layer of rubber aerogel loaded with adsorption particles, combined with a protective layer and a close-fitting layer. The prepared material has better air permeability, good adsorption performance and resistance to rubbing and machine washing, which effectively improves the air permeability, chemical agent protection performance and practicality of the rubber protective material, and can be widely used in the field of protective clothing.

[0007] The present application provides a breathable rubber material for protecting against harmful chemical agents, the breathable rubber material comprising a protective layer, an adsorption layer and a body-fitting layer connected in sequence, and two adjacent layers are bonded by hot melt adhesive; In parts by weight, the adsorption layer includes: 45-75 parts of rubber latex, 30-50 parts of adsorption particles, 0.5-2.5 parts of antioxidant, 0.5-3 parts of sulfur, 0.5-5 parts of zinc oxide, 0.1-3 parts of vulcanization accelerator, 0.1-1 parts of alkaline pH regulator, and 0.01-0.1 parts of stabilizer.

[0008] Compared with the low chemical adsorption of traditional breathable protective clothing, the present application can effectively improve the adsorption efficiency of the adsorption particles by evenly dispersing the adsorption particles in the aerogel, and this type of aerogel can also ensure that the protective clothing has good air permeability, so that it has both air permeability and high-efficiency adsorption, effectively ensuring the wearing comfort and personal safety of the wearer.

[0009] Optionally, the rubber latex is selected from one or more of natural rubber latex, nitrile rubber latex, styrene-butadiene rubber latex, chloroprene rubber latex, butyl rubber latex, butadiene-pentadiene rubber latex. Latex is a general term for a colloidal emulsion formed by polymer particles dispersed in water, and the water dispersion system of rubber particles is usually called rubber latex. The preparation of rubber latex is a routine skill of those skilled in the art and does not require much explanation.

[0010] It should be noted that the present application does not limit the specific type of rubber latex. In addition to the common rubber latex listed above, those skilled in the art can select other rubber latexes or improve or even modify the components of the rubber latex based on the inventive concept of the present application.

[0011] In addition, the present application is not limited to rubber latex. Other elastomers that can be used as protective materials can also achieve the same technical effects based on the inventive concept of the present application, such as ethylene-styrene random copolymers, chlorosulfonated polyethylene, chlorinated polyethylene, butadiene homopolymers, isoprene homopolymers, butadiene-isoprene random or block copolymers, and random or block copolymers of ethylene and monomer A, wherein monomer A is selected from one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene.

[0012] Optionally, the adsorption particles are selected from one or more of activated carbon, biochar, diatomaceous earth, organic bentonite, zeolite, and silica aerogel powder.

[0013] Optionally, the average particle size of the adsorption particles is not greater than 100 μm.

[0014] When the average particle size of the adsorption particles is too large, the surface area of ​​the adsorption particles becomes smaller, and at the same time the gaps between the particles become larger. Although the air permeability will improve, the adsorption performance of the adsorption particles will decrease, and harmful substances cannot be adsorbed in time.

[0015] Optionally, the alkaline pH regulator is selected from one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, potassium carbonate, trisodium phosphate, sodium citrate, potassium citrate, sodium lactate; and / or, The stabilizer is selected from one or more of casein, gelatin, sodium lauryl sulfate, potassium laurate, and peregal O.

[0016] After adding reinforcing fillers, the pH value of latex may change. By adding pH regulators, the pH of latex can be adjusted to a reasonable range to avoid latex flocculation, which affects the dispersion effect of reinforcing fillers. Adding stabilizers can improve the uniform dispersion of reinforcing fillers in aqueous mixed materials, keep the rubber latex system in good fluidity, and ensure that the performance of the resulting rubber aerogel is not affected. The synergy of the two can effectively ensure that the adsorbed particles are evenly dispersed in the aerogel cavity, ensuring a high chemical adsorption capacity.

[0017] Optionally, the protective layer is selected from one or more of a polytetrafluoroethylene microporous membrane, a nylon microporous membrane, a polyvinylidene fluoride microporous membrane, an aramid fiber microporous membrane, and a polyurethane microporous fiber membrane; and / or, The body-contacting layer is selected from one or more of cotton fiber fabrics, linen fiber fabrics, wool fiber fabrics, polyester fiber fabrics, nylon fiber fabrics, acetate fiber fabrics, polypropylene fiber fabrics, and spandex fiber fabrics.

[0018] It should be noted that the present application does not limit the specific selection of the above-mentioned protective layer and the close-fitting layer. In addition to the selections listed above, those skilled in the art may also select other commonly used materials, and based on the inventive concept of the present application, the same technical effect may also be achieved.

[0019] Optionally, the antioxidant is selected from one or more of antioxidant DNP, antioxidant AW, antioxidant TMQ, antioxidant 6PPD, antioxidant 4020 and antioxidant BLE; and / or, The vulcanization accelerator is selected from one or more of dithiocarbamate vulcanization accelerators, aldehyde amine vulcanization accelerators, thiuram vulcanization accelerators, thiazole vulcanization accelerators and sulfenamide vulcanization accelerators.

[0020] It should be noted that the present application does not limit the specific selection of the above-mentioned antioxidants and vulcanization accelerators. In addition to the above-mentioned options, those skilled in the art may also select other commonly used materials, and based on the inventive concept of the present application, the same technical effects may also be achieved.

[0021] The present application provides a method for preparing the above-mentioned breathable rubber material for protecting against harmful chemical agents, the preparation method comprising the following steps: 1) Preparing adsorption layer latex: adding rubber latex, adsorption particles, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a mixer, adding water and stirring evenly, and adjusting the pH value to 7.8-10 to obtain adsorption layer latex; 2) Preparing the adsorption layer: After the adsorption layer latex is cast and formed, it is frozen, and then the frozen latex ice cubes are freeze-dried to obtain a porous rubber aerogel layer, and then the porous rubber aerogel layer is vulcanized to obtain the adsorption layer; 3) Preparation of breathable rubber material: heating and melting the protective layer and the laminating layer on one side, then adding the adsorption layer, stacking them in sequence and calendering them to obtain the breathable rubber material for protecting against harmful chemical agents.

[0022] The rubber aerogel preparation system using rubber latex in the present application can obtain a more uniform system and better fluidity than ordinary rubber materials; in addition, the added pH regulator can also ensure that the entire latex system will not flocculate due to changes in pH value, resulting in uneven morphology of the obtained aerogel or loss of good morphological characteristics, so as to avoid affecting the air permeability; after freezing, it can further ensure that the aerogel will not change in morphology during the cooling process, ensure the uniform dispersion of the adsorbed particles therein, and ultimately facilitate the acquisition of a highly adsorbent and highly permeable aerogel product.

[0023] Optionally, in step 1), sulfur and zinc oxide are ground into a suspension by adding water before being added to the rubber latex; and / or, In the step 1), before the vulcanization accelerator is added to the rubber latex, water is first added to prepare a water emulsion.

[0024] Formulating sulfur and zinc oxide into suspensions and vulcanization accelerators into water emulsions can ensure the uniformity and effective dispersion of these three substances in the latex system, ensure that the latex can be efficiently vulcanized, and improve the overall performance of the product.

[0025] Optionally, the thickness of the adsorption layer in step 2) is 4-8 mm; and / or, Vulcanization temperature is 140~180℃, time is 10~30min.

[0026] It should be noted that the thickness of the adsorption layer in the present application can be flexibly adjusted according to specific protection and breathability requirements.

[0027] Optionally, the protective layer and the bonding layer are heated and melted on one side using a glue dispensing process. This can reduce the amount of glue used to prevent clogging of holes and increase the bonding strength between layers to prevent peeling between layers.

[0028] The present application provides the use of the above-mentioned air-permeable rubber material for protecting against harmful chemical agents in the preparation of protective products for protecting against harmful chemical agents.

[0029] Optionally, the product is protective clothing, a protective mask or a protective blanket.

[0030] The beneficial effects of this application include but are not limited to: 1. According to the breathable rubber material for protecting against harmful chemical agents and its preparation method and application, the breathable rubber material adopts an adsorption layer structure of rubber aerogel loaded with adsorption particles, wherein the rubber aerogel serves as a skeleton to support the adsorption particles, giving the adsorption layer a certain flexibility and bending resistance, and the aerogel cavity increases the contact area between the adsorption particles and the harmful gas molecules, which can improve the adsorption efficiency. In addition, the adsorption particles can be loaded by the aerogel, so that the bonding force between the two is stronger, thereby preventing the adsorption particles from falling off, and thus the performance of rubbing and machine washing resistance is also good.

[0031] 2. According to the breathable rubber material for protecting against harmful chemical agents and its preparation method and application of the present application, the protective layer, the adsorption layer and the body-contacting layer cooperate with each other, wherein the protective layer has selective permeability, can prevent harmful agent droplets from penetrating while allowing water molecules to penetrate, can provide preliminary protection, the contacting layer has perspiration and moisture absorption properties, can improve the wearing comfort of the human body, and the adsorption layer can have the advantages of good breathability, adsorption performance and resistance to rubbing and machine washing.

[0032] 3. The breathable rubber material for protecting against harmful chemical agents and its preparation method and application according to the present application only comprises a protective layer, an adsorption layer and a close-fitting layer, so the preparation process is simple, and it can also have excellent chemical protection and breathability, and still maintain excellent protection effects after multiple machine washings, making the present application scheme suitable for industrial application and having important industrial application economic value, especially for the preparation of breathable chemical protective clothing and breathable chemical protective masks, which has obvious technical advantages over the existing technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings: Figure 1 This is a schematic structural diagram of a breathable rubber material for protecting against harmful chemical agents according to an embodiment of the present application. DETAILED DESCRIPTION

[0034] The present application is described in detail below in conjunction with examples, but the present application is not limited to these examples. Unless otherwise specified, the raw materials and reagents in the examples of the present application are purchased through commercial channels.

[0035] like Figure 1 As shown, the present application provides a breathable rubber material for protecting against harmful chemical agents, wherein the outer layer is a protective layer, the inner layer is a body-contacting layer, and the rubber aerogel with adsorption particles in the middle is the adsorption layer. The present application scheme is described below through specific embodiments.

[0036] Example 1 A breathable rubber material for protecting against harmful chemical agents, comprising: The protective layer is a tetrafluoroethylene microporous membrane with a pore size of 200nm and a thickness of 0.05mm; The adsorption layer comprises the following components in parts by weight: 55 parts of natural rubber latex, 40 parts of activated carbon, 0.8 parts of antioxidant 6PPD, 0.7 parts of sulfur, 1 part of zinc oxide, 1 part of thiuram vulcanization accelerator TMTD, 0.2 parts of ammonia water, and 0.04 parts of gelatin; wherein the average particle size of the activated carbon is 30µm; The base layer is made of cotton fiber fabric.

[0037] The preparation method of the air permeable rubber material comprises the following steps: 1) preparing an adsorption layer latex: adding rubber latex, adsorption particles, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a mixer according to the weight ratio, stirring and dispersing them uniformly with water as solvent, and adjusting the pH value to 8.5, wherein sulfur and zinc oxide are ground into a suspension by adding water before being added into the rubber latex, and the vulcanization accelerator is added into a water emulsion by adding water before being added into the rubber latex; 2) Preparation of adsorption layer: pour the prepared latex into a metal copper mold with a groove, the thickness of the metal copper mold is 6mm, put it in a refrigerator and freeze it into ice, put the frozen latex ice cubes into a freeze dryer until all the water is sublimated, set the freeze dryer condensation temperature to -50°C, the vacuum degree to -0.05Mpa, and the drying time to 36h to obtain a porous rubber aerogel layer, and the adsorption particles are evenly loaded in the internal cavity of the aerogel, and the material is further placed in an oven for vulcanization at 150°C for 20min; 3) Glue the protective layer and the laminating layer on one side at a certain interval, then add the adsorption layer, stack them in sequence and calender them with a calendering roller. Set the calendering pressure to 0.5 MPa, the temperature to 120°C, and the fabric forward speed to 1.5 m / min to obtain a breathable rubber material that protects against harmful chemical agents.

[0038] Example 2 A breathable rubber material for protecting against harmful chemical agents, comprising: The protective layer is a nylon microporous membrane with a pore size of 200nm and a thickness of 0.05mm; The adsorption layer includes the following materials in parts by weight: 45 parts of nitrile rubber latex, 30 parts of activated carbon, 0.5 parts of antioxidant 4020, 0.5 parts of sulfur, 0.5 parts of zinc oxide, 0.1 parts of sulfonamide vulcanization accelerator NOBS, 0.1 parts of sodium hydroxide, and 0.01 parts of casein; wherein the average particle size of the activated carbon is 30 µm; The next-to-skin layer is made of linen fiber fabric.

[0039] The preparation method of the air permeable rubber material comprises the following steps: 1) preparing an adsorption layer latex: adding rubber latex, adsorption particles, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a mixer according to the weight ratio, stirring and dispersing them uniformly with water as solvent, and adjusting the pH value to 7.8, wherein sulfur and zinc oxide are ground into a suspension before being added into the rubber latex, and the vulcanization accelerator is added into a water emulsion before being added into the rubber latex; 2) Preparation of adsorption layer: pour the prepared latex into a metal copper mold with a groove, the thickness of the metal copper mold is 4mm, put it in a refrigerator and freeze it into ice, put the frozen latex ice cubes into a freeze dryer until all the water is sublimated, set the freeze dryer condensation temperature to -40°C, the vacuum degree to -0.001Mpa, and the drying time to 24h to obtain a porous rubber aerogel layer, and the adsorption particles are evenly loaded in the internal cavity of the aerogel, and the material is further placed in an oven for vulcanization at 140°C for 10min; 3) Preparation of breathable rubber material: glue the protective layer and the laminating layer on one side at a certain interval, then add the adsorption layer, stack them in sequence and calender them with a calendering roller, set the calendering pressure to 0.3 MPa, the temperature to 100°C, and the fabric forward speed to 1.2 m / min, to obtain a breathable rubber material that protects against harmful chemical agents.

[0040] Example 3 A breathable rubber material for protecting against harmful chemical agents, comprising: The protective layer is a polyvinylidene fluoride microporous membrane with a pore size of 200nm and a thickness of 0.05mm; The adsorption layer includes the following materials in parts by weight: 75 parts of styrene-butadiene rubber latex, 50 parts of activated carbon, 2.5 parts of antioxidant DNP, 3 parts of sulfur, 5 parts of zinc oxide, 3 parts of thiazole vulcanization accelerator DM, 1 part of potassium hydroxide, and 0.1 part of sodium dodecyl sulfate; wherein the average particle size of the activated carbon is 30 µm; The base layer is made of cotton fiber fabric.

[0041] The preparation method of the air permeable rubber material comprises the following steps: 1) preparing an adsorption layer latex: adding rubber latex, adsorption particles, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a mixer according to the weight ratio, stirring and dispersing them uniformly with water as solvent, and adjusting the pH value to 10, wherein sulfur and zinc oxide are ground into a suspension before being added into the rubber latex, and the vulcanization accelerator is added into a water emulsion before being added into the rubber latex; 2) Preparation of adsorption layer: pouring the prepared latex into a metal copper mold with a groove, the thickness of the metal copper mold is 8mm, placing it in a refrigerator to freeze it into ice, placing the frozen latex ice cubes in a freeze dryer until all the water is sublimated, setting the freeze dryer condensation temperature to -60°C, the vacuum degree to -0.01Mpa, and the drying time to 72h, to obtain a porous rubber aerogel layer, the internal cavity of the aerogel is evenly loaded with adsorption particles, and further placing the material in an oven at 180°C for vulcanization for 30min; 3) Preparation of breathable rubber material: glue the protective layer and the laminating layer on one side at a certain interval, then add the adsorption layer, stack them in order and calender them with a calendering roller. Set the calendering pressure to 0.8MPa, the temperature to 130℃, and the fabric forward speed to 1.7m / min. Get a breathable rubber material that protects against harmful chemical agents.

[0042] Example 4 This embodiment is basically the same as Embodiment 1, except that the protective layer is a polyurethane microporous fiber membrane, the rubber latex is chloroprene rubber latex, the adsorption particles in the adsorption layer are diatomaceous earth, and the average particle size of the diatomaceous earth is 50 μm.

[0043] Example 5 This embodiment is basically the same as Embodiment 1, except that the protective layer is an aramid fiber microporous membrane, the rubber latex is butadiene-vinyl rubber latex, and the adsorbent particles in the adsorption layer are silica aerogel powder, and the average particle size of the silica aerogel powder is 100 µm.

[0044] Example 6 This embodiment is basically the same as Embodiment 1, except that the adsorption layer includes the following materials in parts by weight: 55 parts of nitrile rubber latex, 20 parts of adsorption particles, 0.2 parts of antioxidant 4020, 0.2 parts of sulfur, 0.2 parts of zinc oxide, 0.05 parts of sulfonamide vulcanization accelerator NOBS, 0.05 parts of sodium hydroxide, and 0.01 parts of sodium dodecyl sulfate.

[0045] Example 7 This embodiment is basically the same as Embodiment 1, except that the adsorption layer includes the following materials in parts by weight: 55 parts of styrene-butadiene rubber latex, 60 parts of adsorption particles, 5 parts of antioxidant DNP, 4 parts of sulfur, 7 parts of zinc oxide, 5 parts of thiazole vulcanization accelerator DM, 3 parts of potassium hydroxide, and 3 parts of sodium dodecyl sulfate.

[0046] Example 8 This embodiment is basically the same as Embodiment 1, except that the thickness of the metal copper template is 2 mm.

[0047] Example 9 This embodiment is basically the same as Embodiment 1, except that the thickness of the metal copper template is 10 mm.

[0048] Example 10 This embodiment is basically the same as Embodiment 1, except that the average particle size of the activated carbon in the adsorption layer is 200 μm.

[0049] Embodiment 11 This embodiment is basically the same as the embodiment 1, except that, before sulfur and zinc oxide are added to the rubber latex, they are not ground into a suspension by adding water, and before the vulcanization accelerator is added to the rubber latex, it is not prepared into a water emulsion by adding water.

[0050] Example 12 This embodiment is basically the same as embodiment 1, except that the pH value is adjusted to 6 in preparing the adsorption layer latex.

[0051] Embodiment 13 This embodiment is basically the same as embodiment 1, except that the pH value is adjusted to 11 in preparing the adsorption layer latex.

[0052] Embodiment 14 This embodiment is basically the same as embodiment 1, except that the adsorption layer is prepared by sulfurization at 120° C. for 5 minutes.

[0053] Embodiment 15 This embodiment is basically the same as embodiment 1, except that the adsorption layer is prepared by sulfurization at 200° C. for 40 minutes.

[0054] Comparative Example 1 This comparative example is basically the same as Example 1, except that it does not contain the step of preparing the porous rubber aerogel layer, but directly obtains the rubber material by calendering film forming. Specifically, on the basis of step (1) of Example 1, 5 g of the adsorption layer latex is evenly scraped on the tetrafluoroethylene microporous membrane and the cotton fiber fabric, dried at room temperature for 5 h, and sent to the extrusion calender for calendering film forming. The calendering pressure is set to 0.25 MPa, the temperature is set to 125°C, and the fabric forward speed is set to 2.2 m / min. After cooling, the protective material is obtained by hot pressing and vulcanization. The vulcanization pressure is 1.5 MPa, the vulcanization temperature is 150°C, and the vulcanization time is 15 min.

[0055] Comparative Example 2 This comparative example is substantially the same as Example 1, except that no adsorption particles are added to the adsorption layer.

[0056] Comparative Example 3 This comparative example is substantially the same as Example 1, except that no stabilizer is added to the adsorption layer.

[0057] Comparative Example 4 This comparative example is the product disclosed in Chinese patent CN202110585676.

[0058] Comparative Example 5 This comparative example is the product disclosed in Chinese patent CN201821040739.

[0059] Comparative Example 6 This comparative example is the product disclosed in Chinese patent CN2023113590152.

[0060] Test Example 1 Water penetration: GB / T 24218.17 "Textile nonwovens test methods Part 17: Determination of water penetration resistance (spray impact method)" is used to simulate the limited liquid splash protection performance of ready-made clothing in EN13034+A1.

[0061] Particle protection filtration performance: The test method for fabric filtration efficiency in Chapter 5.7 of GB19082-2009 "Technical Requirements for Medical Disposable Protective Clothing" is adopted, that is, sodium chloride aerosol (particle median diameter is 0.075μm±0.02μm) is used for testing in an environment with a relative humidity of 30%±10% and a temperature of 25℃±5℃, and an air flow rate of 15L / min±2L / min.

[0062] Fabric air permeability test: GB / T 24218.15-2018 "Textile nonwoven fabric test methods Part 15: Determination of air permeability" is adopted.

[0063] Fabric moisture permeability test: The fabric adopts GB / T 12704.1-2009 "Test method for moisture permeability of textile fabrics Part 1: Moisture absorption method", the test environment is 38℃, relative humidity is 90%.

[0064] Mustard gas protection performance: According to GJB 6629-2008 standard, the time for mustard gas to penetrate the fabric is tested using standard testing instruments to evaluate the mustard gas protection performance of protective fabrics.

[0065] Toluene resistance: According to GB / T 23462-2009 standard, the time for toluene to penetrate the fabric is tested using standard testing instruments to evaluate the toluene resistance of protective fabrics.

[0066] Acid and alkali resistance: According to GB 24540-2009 "Protective clothing for acid and alkali chemicals", the time for acid and alkali test solutions to penetrate the fabric is used as a representation of its acid and alkali resistance.

[0067] Machine wash resistance: Cut a sample and put it into a 40℃ oven to dry until the mass no longer changes or changes very little. Put the sample into a washing machine and wash it for 15 minutes. Dry the washed sample again and measure its mass. The ratio of the mass of the shed material to the original total mass is the machine wash shedding rate.

[0068] The test results are shown in Table 1 below.

[0069] Table 1 Test results of chemical protection performance of rubber materials for protection against chemical agents

[0070] Table 1 Continued Table 1

[0071] Table 1 Continuation Table 2

[0072] According to the test results in Table 1, the present application scheme can effectively improve the protective filtration performance, air permeability and moisture permeability of the rubber protective material, and reduce the amount of water seepage, which greatly improves the wearing comfort of the protective clothing, and has a good ability to protect against organic reagents, which can effectively prevent the wearer from being harmed by organic reagents.

[0073] Specific analysis of the experimental results shows that: According to the experimental results of Examples 1 and 6-7, it can be seen that the rubber protective material of the present application needs to follow certain ratios and preparation parameters during preparation. If the ratios or preparation parameters are inappropriate, the air permeability, chemical agent protection performance and washing fastness of the rubber protective material will be affected.

[0074] According to the experimental results of Examples 1 and 8-9, the thickness of the metal copper template used in the casting process determines the thickness of the adsorption layer, and the thickness of the adsorption layer will affect the air permeability and barrier properties of the protective material. When the template thickness decreases, the adsorption layer thickness decreases, so that the air permeability increases, but the barrier properties and chemical absorption capacity of the protective material decrease; when the template thickness increases, the adsorption layer thickness increases, so that the air permeability decreases, but the barrier properties and chemical absorption capacity of the material increase. It should be noted that those skilled in the art can design and select the thickness of the adsorption layer according to actual needs.

[0075] According to the experimental results of Example 1 and Example 10, the particle size of the adsorbed particles in the adsorption layer will affect the adsorption and protective properties of the rubber material. The reason is that the smaller the average particle size of the adsorbed particles, the larger the surface area of ​​the material, which is more conducive to improving the protective properties of the rubber protective material against organic chemical reagents. If the average particle size of the adsorbed particles is too large, its protective performance is poor.

[0076] According to the experimental results of Examples 1 and 12 and 13, the addition of the pH regulator plays an important role in the uniform fluidity of the entire aerogel preparation system. When the pH value of the system is too high or too low, the latex may settle or flocculate, thereby affecting the air permeability and barrier properties of the rubber protective material.

[0077] According to the experimental results of Example 1 and Comparative Example 1, the rubber protective material obtained by the traditional calendering method has higher density and therefore higher barrier properties, but too high density will have a greater impact on air permeability; it will also reduce the washing fastness and the protective material will be less durable.

[0078] According to the experimental results of Example 1 and Comparative Example 2, compared with Example 1, when no adsorption particles are added, the adsorption performance and protective performance of the rubber protective material are significantly reduced, indicating that the addition of adsorption particles plays an important role in the performance of the rubber protective material of the present application.

[0079] According to the experimental results of the embodiment and comparative example 3, when no stabilizer is added, the comprehensive performance of the rubber protective material decreases. The reason is that the addition of the stabilizer can ensure the uniformity of the fluidity of the system and promote the stable synthesis of the rubber aerogel. The more uniform the aerogel morphology, the better the air permeability of the rubber protective material; at the same time, it also ensures that the rubber protective material has good washing fastness.

[0080] Comparing the present application with comparative example 4, patent CN202110585676 adopts a method of evenly arranging spherical activated carbon on the rubber-coated base fabric. According to the data in the embodiment, this method will have a great impact on the air permeability, and the final air permeability is 669mm / s. The present application adopts an adsorption layer structure of rubber aerogel-loaded adsorption particles, in which the rubber aerogel serves as a skeleton to support the adsorption particles, giving the adsorption layer a certain flexibility and bending resistance, and the aerogel cavity increases the contact area between the adsorption particles and the harmful gas molecules, which can improve the adsorption efficiency, enhance the adsorption capacity of the protective material, achieve effective barrier to chemical substances, improve the protective performance of the protective material, and maintain good air permeability.

[0081] Comparing the present application with comparative example 5, patent CN201821040739 uses a composite structure of a fabric layer and a spherical activated carbon layer to obtain a rubber protective material with high comfort and high water washing fastness. According to the results of the embodiment, its water washing fastness is optimally 0.49%, and there is still room for further optimization. However, the present application uses aerogel to load adsorbent particles, making the bonding force between the two stronger and thus preventing the adsorbent particles from falling off, so that the rubber protective material not only has high air permeability and protective performance, but also has good resistance to rubbing and machine washing.

[0082] Comparing the present application with Comparative Example 6, Patent 2023113590152 uses a dual-effect finishing agent and a non-woven fabric to prepare a dual-effect absorption fixing layer material, which is combined with a skin-contacting layer material and an outer barrier protective layer material. Its air permeability is optimally 118.52 mm / s, its anti-mustard gas time is optimally >120 min, its toluene resistance time is optimally 60 min, its acid resistance time is optimally >60 min, and its alkali resistance time is optimally >60 min, all of which have further room for optimization. The rubber material provided in the present application is combined with a protective layer, an adsorption layer and a skin-contacting layer, especially through the structural improvement of the adsorption layer, so as to have better air permeability and protective performance.

[0083] The above is only the embodiment of the present application, and the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application can have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the technical ideas and principles of the present application should be included in the protection scope of the present application.

Claims

1. A breathable rubber material for protecting against harmful chemical agents, characterized in that: The air-permeable rubber material comprises a protective layer, an adsorption layer and a body-fitting layer which are connected in sequence, and two adjacent layers are bonded by hot-melt adhesive; In parts by weight, the adsorption layer includes: 45-75 parts of rubber latex, 30-50 parts of adsorption particles, 0.5-2.5 parts of antioxidant, 0.5-3 parts of sulfur, 0.5-5 parts of zinc oxide, 0.1-3 parts of vulcanization accelerator, 0.1-1 parts of alkaline pH regulator, and 0.01-0.1 parts of stabilizer.

2. The breathable rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The rubber latex is selected from one or more of natural rubber latex, nitrile rubber latex, styrene-butadiene rubber latex, chloroprene rubber latex, butyl rubber latex, and butadiene-pentadiene rubber latex.

3. The breathable rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The adsorption particles are selected from one or more of activated carbon, biochar, diatomaceous earth, organic bentonite, zeolite, and silica aerogel powder.

4. The breathable rubber material for protecting against harmful chemical agents according to claim 3, characterized in that: The average particle size of the adsorption particles is no greater than 100 μm.

5. The breathable rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The alkaline pH regulator is selected from one or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia water, sodium bicarbonate, potassium carbonate, trisodium phosphate, sodium citrate, potassium citrate, sodium lactate; and / or, The stabilizer is selected from one or more of casein, gelatin, sodium lauryl sulfate, potassium laurate, and peregal O.

6. The breathable rubber material for protecting against harmful chemical agents according to claim 1, characterized in that: The protective layer is selected from one or more of polytetrafluoroethylene microporous membrane, nylon microporous membrane, polyvinylidene fluoride microporous membrane, aramid fiber microporous membrane, polyurethane microporous fiber membrane; and / or, The body-contacting layer is selected from one or more of cotton fiber fabrics, linen fiber fabrics, wool fiber fabrics, polyester fiber fabrics, nylon fiber fabrics, acetate fiber fabrics, polypropylene fiber fabrics, and spandex fiber fabrics.

7. A method for preparing a breathable rubber material for protecting against harmful chemical agents according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: 1) Preparing adsorption layer latex: adding rubber latex, adsorption particles, antioxidant, vulcanization accelerator, alkaline pH regulator, stabilizer, sulfur and zinc oxide into a mixer, adding water and stirring evenly, and adjusting the pH value to 7.8-10 to obtain adsorption layer latex; 2) Preparing the adsorption layer: After the adsorption layer latex is cast and formed, it is frozen, and then the frozen latex ice cubes are freeze-dried to obtain a porous rubber aerogel layer, and then the porous rubber aerogel layer is vulcanized to obtain the adsorption layer; 3) Preparation of breathable rubber material: heating and melting the protective layer and the laminating layer on one side, then adding the adsorption layer, stacking them in sequence and calendering them to obtain the breathable rubber material for protecting against harmful chemical agents.

8. The method for preparing a breathable rubber material for protecting against harmful chemical agents according to claim 7, characterized in that: In the step 1), before adding sulfur and zinc oxide to rubber latex, they are first ground into a suspension with water; and / or, In the step 1), before the vulcanization accelerator is added to the rubber latex, water is first added to prepare a water emulsion.

9. The method for preparing a breathable rubber material for protecting against harmful chemical agents according to claim 7, characterized in that: In step 2), the thickness of the adsorption layer is 4-8 mm; and / or, Vulcanization temperature is 140~180℃, time is 10~30min.

10. Use of the breathable rubber material for protecting against harmful chemical agents according to any one of claims 1 to 6 in preparing protective products for protecting against harmful chemical agents.

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