Coating composition for decontamination of chemical warfare agents and method for decontamination using the same

Abstract

The present invention relates to a film decontamination composition for chemical agents and a decontamination method using the same. A film decontamination composition for chemical agents according to one embodiment of the present invention comprises: a first solution containing polyvinyl alcohol (PVA) and a solvent; and a second solution containing borax (Na2B4O7ㆍ10H2O, Borax) and a solvent; wherein the polyvinyl alcohol may include low molecular weight polyvinyl alcohol with a degree of polymerization (PDI) of 300 to 800 and high molecular weight polyvinyl alcohol with a degree of polymerization of 1000 to 2000. The film decontamination composition for chemical agents and the decontamination method using the same according to the present invention have excellent decontamination effects against (similar) chemical agents, and can exhibit a decontamination performance of 90% or more. In addition, the film formed from the film detoxification agent composition for chemical agents of the present invention exhibits suitable viscoelastic properties, so that surface diffusion is easy initially due to low viscosity, but it hardens subsequently to facilitate easy detachment.

Description

Technology Field

[0001] The present invention relates to a coating composition for detoxifying chemical agents and a detoxification method using the same. Background Technology

[0002] Chemical warfare agents refer to toxic chemical substances used for military purposes that can cause fatalities or serious injuries. Many types of chemical agents have been reported, including Soman (GD), Tabun (GA), Sarin (GB), Chlorosarin (GF), and O-ethyl S-(2-diisopropylamino)ethylmethylphosphonothioate (VX) and their derivatives. The aforementioned chemical agents vaporize easily and can cause severe damage even in minute quantities indoors. For example, VX is classified as a powerful nerve agent; by inhibiting enzymes that break down neurotransmitters, it causes continuous muscle contraction signals to be transmitted to the human body, leading to muscle spasms and respiratory paralysis. Therefore, chemical agents must be decontaminated with high efficiency.

[0003] Currently, commonly used decontamination agents include STB (primarily composed of calcium oxide (CaO)), diethyltriamine, 2-ethoxyethylamine, DS-2 (primarily composed of sodium hydroxide (NaOH)), and German C-8 emulsion (primarily composed of calcium hypochlorite (Ca(OCl)2)). Although the aforementioned decontamination agents have excellent decontamination efficacy, their application is currently limited due to their high flammability, as well as the fact that they increase soil acidity or cause surface corrosion. Furthermore, if the decontamination agent is in liquid or powder form, complete removal after decontamination is difficult, which can result in residues remaining at the site and causing secondary contamination. Recently, the possibility of removing contaminants using a gel-type film has been reported; this method offers the advantage of being able to simultaneously remove both the chemical agent and the decontamination agent after application to the surface to decontaminate the agent.

[0004] In the case of the aforementioned chemical agent decontamination film, it must possess a certain degree of fluidity or flowability initially upon application to the surface, allowing for wide diffusion and uniform coating according to the surface shape; after a certain period, it must harden to enable easy detachment. Therefore, if the film can be adjusted to possess optimal viscoelastic properties and decontaminate chemical agents with high efficiency, the application of the film decontamination agent will become easier. Meanwhile, a hydrogel may be formed when polyvinyl alcohol (PVA) and borax (sodium tetraborate) come into contact in an aqueous solution. In an aqueous solution, borax produces borate ions (BO3 2- or BO4 3-It is known that the borate ions release the borate and crosslink the PVA to form a network structure. In the present invention, the viscoelastic properties of the above-mentioned PVA-Borax-based hydrogel were optimized to improve the detoxification efficiency of chemical agents and to realize a chemical agent detoxification coating that is easy to apply and detach from various surfaces. Through this, an eco-friendly alternative to detoxifiers and a potential for future conversion were presented. Prior art literature

[0005] Republic of Korea Registered Patent No. 10-1206360 The problem to be solved

[0006] The present invention can provide a film composition having excellent chemical agent detoxification efficiency. Additionally, it can provide a film detoxification agent for chemical agents formed from the film composition. The chemical agent detoxification film exhibits suitable viscoelastic properties, allowing for uniform diffusion on the surface, and hardens quickly, making it easy to detach along with contaminants. Furthermore, it can provide a method for detoxifying chemical agents using the chemical agent film detoxification agent composition. means of solving the problem

[0007] A film decontamination composition for chemical agents according to one embodiment of the present invention may be composed of: a first solution comprising polyvinyl alcohol (PVA) and a solvent; and a second solution comprising borax (Na2B4O7ㆍ10H2O, Borax) and a solvent.

[0008] In one embodiment, the polyvinyl alcohol may include a low molecular weight polyvinyl alcohol with a degree of polymerization (DP) of 300 to 800 and a high molecular weight polyvinyl alcohol with a degree of polymerization of 1000 to 2000.

[0009] In one embodiment, the high molecular weight polyvinyl alcohol may comprise 25 to 75 weight percent with respect to the total weight of the polyvinyl alcohol.

[0010] In one embodiment, the film made of the polyvinyl alcohol may have a stiffness (NM) of 250 N / mm or more and an elastic recovery rate (nIT) of 35% or more.

[0011] In one embodiment, the film made of the polyvinyl alcohol may have a hardness (HIT) of 500 MPa or more.

[0012] In one embodiment, the polyvinyl alcohol may be included in an amount of 5 to 20 weight percent relative to the total weight of the first solution.

[0013] In one embodiment, the borax may be included in an amount of 1 to 15 weight percent relative to the total weight of the second solution.

[0014] In one embodiment, the first solution or the second solution further comprises a detoxifying agent, and the solution not comprising the detoxifying agent may further comprise a detoxifying agent.

[0015] In one embodiment, the detoxifier may be selected from one or more of the group consisting of hydrogen peroxide (H2O2), calcium oxide (CaO), calcium peroxide (CaO2), sodium perborate (NaBO3), sodium carbonate (Na2CO3), and potassium permanganate (K2FeO4).

[0016] In one embodiment, the detoxification agent may be selected from one or more of the group consisting of N-triethylamine, peracetic acid, tetraacetylethylenediamine, ethylenediaminetetraacetic acid, and peracetylpyrrolidine.

[0017] In one embodiment, the solvent may be selected from one or more of the group consisting of water, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, and glycerol.

[0018] In one embodiment, the first solution or the second solution may further include a surfactant.

[0019] In one embodiment, the surfactant may be selected from one or more of the group consisting of sodium lauryl sulfate, sodium lauryl ether sulfate, sodium dodecylbenzene sulfonate, cetyltrimethylammonium bromide, polyoxyethylene sorbitan monolate, Triton X-100, polyethylene glycol-400, sodium stearate, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, decyl glucoside, sodium oleate, and lecithin.

[0020] In one embodiment, the second liquid further comprises a pH adjuster, wherein the pH adjuster may be selected from one or more of the group consisting of acetic acid, citric acid, lactic acid, fumaric acid, tartaric acid, phosphoric acid, and acetohydroxyammonic acid.

[0021] In one embodiment, the pH adjuster may comprise 0.1 to 5 weight percent based on the total weight of the borax.

[0022] A chemical agent detoxification film according to one embodiment of the present invention can be prepared by mixing the first solution and the second solution in equal volume ratios.

[0023] In one embodiment, the weight ratio of polyvinyl alcohol to borax of the chemical agent detoxification film may be 4:1 to 1:1.

[0024] A chemical agent detoxification method according to one embodiment of the present invention may include the steps of: spraying the first solution and the second solution in equal volume ratios onto a surface coated with a chemical agent or a similar chemical agent; forming a film; and removing the film.

[0025] In one embodiment, the chemical agent comprises VX, GD, HD, and GB, and the pseudo-chemical agent may comprise paraoxon-methyl, diisopropyl chlorophosphite (DICP), 2-chloroethyl ethyl sulfide (CEES), dichlorophenol (DP), diphenyl chlorophosphite (DPCP), diisopropyl fluorophosphate (DFP), and O,S-diethyl methylphosphonothioate (OSDEMP). Effects of the invention

[0026] The film decontamination agent composition for chemical agents and the decontamination method using the same according to the present invention have excellent decontamination effects against (similar) chemical agents, and can exhibit a decontamination performance of 90% or more. In addition, the film formed from the film decontamination agent composition for chemical agents according to the present invention exhibits viscoelastic properties suitable for this purpose, so that surface diffusion is easy because the viscosity is low initially, but it hardens hard thereafter, making it easy to detach along with contaminants. Brief explanation of the drawing

[0027] Figure 1 shows the results of surface adhesion evaluation when a container containing a film detoxifier according to an embodiment of the present invention is inverted. Figure 2 shows the pencil hardness evaluation results according to one embodiment of the present invention. Figure 3 is a graph illustrating the nanoindentation evaluation results according to one embodiment of the present invention. Figure 4 evaluates the ease of removal of a film detoxification agent according to one embodiment of the present invention. Figure 5 shows the physical removal rate of indigo dye by a film detoxification agent according to one embodiment of the present invention. Figure 6 illustrates the detoxification effect of the chemical agent-based film detoxification composition of Example 3 of the present invention against the pseudo-chemical agent 2-CEES. Figure 7 illustrates the detoxification effect of the chemical agent film detoxification composition of Example 3 of the present invention against the pseudo-chemical agent OSDEMP. FIG. 8 is a schematic illustration of the detoxification effect of the chemical agent film detoxification composition of Example 3 of the present invention on the pseudo-chemical agent DCP. FIG. 9 is a schematic illustration of the detoxification effect of the film detoxification composition for chemical agents of Example 10 of the present invention against the pseudo-chemical agent 2-CEES. FIG. 10 is a schematic illustration of the detoxification effect of the chemical agent film detoxification agent composition of Example 3 of the present invention against the pseudo-chemical agent OSDEMP. Figure 11 illustrates the detoxification effect of the chemical agent film detoxification composition of Example 3 of the present invention on the pseudo-chemical agent DCP. Specific details for implementing the invention

[0028] Unless otherwise defined in this specification, all technical and scientific terms have the same meaning as generally understood by those skilled in the art to which the present invention pertains. The terms used in the description herein are merely for the purpose of effectively describing specific embodiments and are not intended to limit the present invention.

[0029] The singular form used in this specification is intended to include the plural form unless specifically indicated otherwise in the context.

[0030] Throughout this specification, the terms “comprising,” “having,” “containing,” or “having” any component mean that, unless specifically stated otherwise, other components are not excluded but may be included, and do not exclude elements, materials, or processes not additionally listed.

[0031] The numerical ranges used herein include lower and upper limits and all values ​​within the range, increments logically derived from the form and width of the defined range, all of which are limited, and all possible combinations of upper and lower limits of the numerical range defined in different forms. Unless otherwise specifically defined in this specification, values ​​outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range.

[0032] Unless otherwise specifically defined in this specification, “about” may be considered to be a value within 30%, 25%, 20%, 15%, 10%, or 5% of the specified value.

[0033] The present invention will be described in detail below. However, this is merely illustrative and the present invention is not limited to the specific embodiments described illustratively.

[0034] A film decontamination composition for chemical agents according to one embodiment of the present invention may comprise: a first solution containing polyvinyl alcohol (PVA) and a solvent; and a second solution containing borax (Na2B4O7ㆍ10H2O) and a solvent. The first solution containing polyvinyl alcohol and the second solution containing borax may be mixed at the time of use, wherein the hydroxyl groups (-OH) of the PVA chains and the borate ions (BO3) of borax 2- or BO4 3-) can combine to form a cross-linked network between PVA chains. Thus, a hydrogel can be formed within seconds or minutes, and the hydrogel can absorb a specific substance and then be easily detached.

[0035] In one embodiment, the polyvinyl alcohol may comprise a low molecular weight polyvinyl alcohol with a degree of polymerization (DP) of 300 to 800 and a high molecular weight polyvinyl alcohol with a degree of polymerization of 1,000 to 2,000. The degree of polymerization (DP) may refer to the number of repeating units constituting a polymer chain. The higher the degree of polymerization, the larger the molecular weight of the polymer, and the more significantly the physical properties of the polymer may differ. The degree of polymerization of the low molecular weight PVA may preferably be 400 to 700, and the degree of polymerization of the high molecular weight PVA may preferably be 1,200 to 1,700. For example, in the present invention, a mixture of low molecular weight PVA with a degree of polymerization of 500 and high molecular weight PVA with a degree of polymerization of 1,500 may be used, but is not limited thereto. Although the exact cause has not been determined, the inventors found that when PVAs having different molecular weights—relatively low molecular weight and relatively high molecular weight—are mixed and used, the viscoelastic behavior of the desired hydrogel is more suitable for use as a film decontamination agent. The viscoelastic behavior of the hydrogel being suitable as a film decontamination agent means that it has fluidity upon initial application so that the hydrogel diffuses regardless of the shape of the surface, and then hardens quickly and can be easily detached after sufficient decontamination is achieved.

[0036] In one embodiment, the high molecular weight polyvinyl alcohol may comprise 25 to 75 weight% with respect to the total weight of the polyvinyl alcohol. For example, the high molecular weight polyvinyl alcohol may be 25 weight% or more, 30 weight% or more, 35 weight% or more, 40 weight%, 45 weight% or more, 75 weight% or less, 65 weight% or less, 55 weight% or less, or a value between these.

[0037] In one embodiment, the film made of the polyvinyl alcohol may have a stiffness (NM) of 250 N / mm or more and an elastic recovery ratio (nIT) of 35% or more. Additionally, the film made of the polyvinyl alcohol may have a hardness (HIT) of 500 MPa or more. The stiffness (NM, Normalized Modulus) may refer to the resistance to deformation when deformation is applied to the surface of the film, and the greater the stiffness, the greater the resistance to deformation. The elastic recovery ratio (nIT, Elastic Recovery Ratio) is a quantitative representation of the restoring force to the original shape after the load is removed (after the deformation is removed). The greater the elastic recovery ratio, the greater the speed of recovery to the original shape and the greater the restoring force. The hardness (HIT, Indentation Hardness) may indicate how hard the material is when the surface is pressed with an indenter. The above stiffness (NM), elastic recovery rate (nIT), and hardness (HIT) can all be measured using a nanoindentation method with a nanoindentator, and may be values ​​obtained when a maximum load of 1 mN is applied. Nanoindentation involves embedding fine indenters into the surface of a specimen by applying a load, and various physical properties of the material can be derived from the load-strain curve.

[0038] The film prepared using the above polyvinyl alcohol may specifically be prepared by uniformly applying 3 mL of the first solution of the present invention to a 60 mm Petri dish and then drying it sufficiently. Accordingly, the polyvinyl alcohol used in the present invention is a mixture of low molecular weight and high molecular weight polyvinyl alcohol, which may have strong resistance to deformation, excellent elastic recovery rate, and hardness. Therefore, the chemical agent coating of the present invention prepared therefrom can diffuse uniformly to form a hard coating in a short period of time, and after the detoxification of the contaminant is completed, the contaminant and the coating can be easily detached simultaneously.

[0039] In one embodiment, the polyvinyl alcohol may be included in an amount of 5 to 20 weight% with respect to the total weight of the first solution. For example, the polyvinyl alcohol in the first solution may be 5 weight% or more, 6 weight% or more, 7 weight% or more, 8 weight% or more, 9 weight% or more, 10 weight% or more, 12 weight% or more, 14 weight% or more, 20 weight% or less, 18 weight% or less, 16 weight% or less, 15 weight% or less, 13 weight%, 11 weight% or less, and may be a value between these.

[0040] In one embodiment, the borax may be included in an amount of 1 to 15 weight% relative to the total weight of the second solution. For example, the borax in the second solution may be 1 weight% or more, 2 weight% or more, 3 weight% or more, 4 weight% or more, 5 weight% or more, 15 weight% or less, 13 weight% or less, 11 weight% or less, 8 weight% or less, or a value between these. When polyvinyl alcohol and borax are within the above ranges, they can be mixed in equal volume ratios thereafter to have the physical properties of a hydrogel suitable for use as a film decontamination agent.

[0041] In one embodiment, the first solution or the second solution further comprises a detoxifying agent, and the solution not comprising the detoxifying agent may further comprise a detoxifying agent. In one embodiment, the detoxifying agent may be selected from one or more of the group consisting of hydrogen peroxide (H2O2), calcium oxide (CaO), calcium peroxide (CaO2), sodium perborate (NaBO3), sodium carbonate (Na2CO3), and potassium permanganate (K2FeO4). In one embodiment, the detoxifying agent may be selected from one or more of the group consisting of N-triethylamine, peracetic acid, tetraacetylethylenediamine (TAED), ethylenediaminetetraacetetic acid (EDTA), and peracetylpyrrolidine. When the first solution and the second solution are mixed at the time of use, the detoxifying agent and the detoxifying agent may come into contact, thereby activating the detoxifying agent. For example, the oxidation reaction of hydrogen peroxide can be promoted by using hydrogen peroxide as the detoxifying agent and N-triethylamine as the detoxifying agent. Alternatively, by using sodium perborate as the detoxifying agent and tetraacetylethylenediamine as the detoxifying agent, the sodium perborate can be decomposed to produce hydrogen peroxide, allowing the detoxification reaction to occur efficiently.

[0042] In one embodiment, the solvent may be selected from one or more of the group consisting of water, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, and glycerol. The solvent may be adjusted according to the chemical agent to be detoxified. For example, to increase the solubility of chemical agent HD and to improve the detoxification effect, it may be preferable to mix water and ethylene glycol in a 1:1 volume ratio, and for chemical agent VX, it may be preferable to use water alone or to mix water and ethanol in a 3:1 volume ratio.

[0043] In one embodiment, the first solution or the second solution may further include a surfactant. In one embodiment, the surfactant is sodium lauryl sulfate (SLS), sodium laureth sulfate (SLES), sodium dodecylbenzenesulfonate (SDBS), cetyltrimethylammonium bromide (CTAB), polyoxyethylene sorbitan monolaurate, Triton X-100, polyethylene glycol 400 (PEG-400), sodium stearate, cocamidopropyl betaine (CAPB), cocamidopropyl hydroxysultaine (CAHS), decyl glucoside, It may be one or more selected from the group consisting of sodium oleate and lecithin (phosphatidylcholine). The above surfactant may be added in an appropriate amount to improve solubility depending on the type of chemical agent.

[0044] In one embodiment, the second liquid further comprises a pH adjuster, wherein the pH adjuster may be selected from one or more of the group consisting of acetic acid, citric acid, lactic acid, fumaric acid, tartaric acid, phosphoric acid, and acetohydroxyammonium acid. Favorable reaction conditions for the formation of the PVA-Borax hydrogel may be established when the pH is basic at 8 or higher, and the pH adjuster may lower the pH when the initial hydrogel is formed, thereby maintaining low viscosity within a few seconds.

[0045] In one embodiment, the pH adjuster may comprise 0.1 to 5 weight% based on the total weight of the borax. Preferably, it may comprise 0.1 to 3 weight%, and more preferably, 0.5 to 2 weight%.

[0046] A chemical agent decontamination film according to one embodiment of the present invention can be prepared by mixing the first solution and the second solution in equal volume ratios. The chemical agent film composition composed of the first solution and the second solution of the present invention can be applied to a surface coated with a chemical agent by spraying, spraying, or coating. In this case, the composition can be hydrogelated or film-formed and can act as a film decontamination agent. The chemical agent film decontamination composition of the present invention can be applied regardless of the shape of the surface, for example, whether the surface is smooth, uneven, horizontal, or vertical. Furthermore, if one surface of the film is detached after a certain period of time following decontamination, the entire film can be easily detached.

[0047] In one embodiment, the loss modulus (G") of the chemical agent detoxification film is 20 to 150% of the storage modulus (G'), and the loss modulus (G") may decrease relative to the storage modulus (G') over time. Preferably, the loss modulus may be 30 to 80% of the storage modulus, and more preferably 40 to 60%. Storage modulus (G') and loss modulus (G") are useful methods for describing the viscoelastic behavior of a material; storage modulus (G') quantifies the degree to which a material returns to its original shape after deformation. On the other hand, the loss modulus (G") quantifies the degree to which a material deforms by absorbing energy. Generally, solids have a storage modulus that is very high compared to the loss modulus, liquids may have a loss modulus that is very high compared to the storage modulus, and viscoelastic materials may exhibit viscoelastic behavior depending on the ratio of the storage modulus to the loss modulus. The loss modulus (G") of the chemical agent detoxification film of the present invention can be classified as a viscoelastic material in the range of 20 to 150% of the storage modulus (G'), and as a cross-linked network is formed, the loss modulus decreases rapidly, allowing a relatively hard film to be formed.

[0048] In one embodiment, the function of the loss modulus (G) over time (t) may be derived from the following equation.

[0049] [Equation] G" (t)=G ∞ " + (G0" - G ∞ ")ㆍe -kㆍt

[0050] In the above equation, G(t) is the loss modulus (G") at time t (seconds), G0" is the loss modulus (G") at the initial time (i.e., t=0), and G Δ" is the loss modulus (G) at the equilibrium state that converges after a sufficient amount of time, and k is a rate constant, which can be from 0.01 to 0.5. The above k can be determined according to the components and composition ratio of the first solution and the second solution. For example, when the initial loss modulus is measured to be 100 Pa and k is 0.1, the time to substantially reach the equilibrium state according to the above equation may be within about 46 seconds.

[0051] In one embodiment, the weight ratio of polyvinyl alcohol to borax of the chemical agent detoxification film may be 4:1 to 1:1. The weight ratio may be the ratio that appears when the first solution and the second solution are mixed in equal volume ratios, and when polyvinyl alcohol and borax are in the above ratio, suitable viscoelastic behavior as a desired film detoxification agent can be secured.

[0052] A chemical agent detoxification method according to one embodiment of the present invention may include the steps of: spraying the first solution and the second solution in equal volume ratios onto a surface coated with a chemical agent or a similar chemical agent; forming a film; and removing the film.

[0053] In one embodiment, the chemical agent comprises VX, GD, HD, and GB, and the pseudo-chemical agent may comprise paraoxon-methyl, diisopropyl chlorophosphite (DICP), 2-chloroethyl ethyl sulfide (CEES), dichlorophenol (DCP), diphenyl chlorophosphite (DPCP), diisopropyl fluorophosphate (DFP), and O,S-diethyl methylphosphonothioate (OSDEMP). The CEES is a sulfide series compound mimicking chemical agent HD, the OSDEMP is a compound mimicking chemical agent VX, and the DCP may be a compound mimicking chemical agent sarin (GB).

[0054] The above-described embodiment will be explained in more detail below through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the claims.

[0055] [Preparation Example] Preparation of the first solution and the second solution

[0056] Water was added to a spherical flask and heated until it reached 65°C, at which point polyvinyl alcohol (PVA) and the detoxification agent TAED were added in the weight ratios according to Table 1 below and stirred for 3 hours to prepare a first solution that was 100% by total weight. Additionally, water was added to a spherical flask and heated until it reached 65°C, at which point the remaining components were added in the weight ratios according to Table 2 below and stirred for 3 hours to prepare a second solution that was 100% by total weight.

[0057] PVA(DP=500) PVA(DP=1500) TAED water Preparation Example 1-1 4 0 0.1 Remaining amount Preparation Example 1-2 6 0 0.1 Remaining amount Preparation Examples 1-3 10 0 0.1 Remaining amount Preparation Examples 1-4 15 0 0.1 Remaining amount Preparation Examples 1-5 3 7 0.1 Remaining amount Preparation Examples 1-6 5 5 0.1 Remaining amount Preparation Examples 1-7 7 3 0.1 Remaining amount

[0058] Borax Sodium perborate hydrogen peroxide SLS Citric acid water Preparation Example 2-1 4 2.5 0.5 0 Remaining amount Preparation Example 2-2 6 2.5 0.5 0 Remaining amount Preparation Example 2-3 10 2.5 0.5 0 Remaining amount Preparation Example 2-4 4 2.5 0.5 1 Remaining amount Preparation Example 2-5 4 2.5 0.5 0 Remaining amount

[0059] [Example] Preparation of a film by mixing the first solution and the second solution

[0060] As shown in Table 3 below, 4 mL each of the first solution selected from Preparation Examples 1-1 to 1-7 and the second solution selected from Preparation Examples 2-1 to 2-4 were injected into the bottom of the vial in equal volume ratios. After injecting the first and second solutions, the vials were left at room temperature for 30 minutes, then inverted to check the behavior of the hydrogel film, which is shown in Table 3 and Figure 1 below.

[0061] Solution 1 Solution 2 Surface adhesion Example 1 Preparation Example 1-2 Preparation Example 2-2 X Example 2 Preparation Example 1-1 Preparation Example 2-2 X Example 3 Preparation Examples 1-3 Preparation Example 2-1 △ Example 4 Preparation Examples 1-3 Preparation Example 2-2 △ Example 5 Preparation Examples 1-3 Preparation Example 2-3 △ Example 6 Preparation Examples 1-4 Preparation Example 2-1 △ Example 7 Preparation Examples 1-4 Preparation Example 2-2 ○ Example 8 Preparation Examples 1-4 Preparation Example 2-3 ○ Example 9 Preparation Examples 1-5 Preparation Example 2-1 ○ Example 10 Preparation Examples 1-6 Preparation Example 2-1 ○ Example 11 Preparation Examples 1-7 Preparation Example 2-1 ○ Example 12 Preparation Examples 1-5 Preparation Example 2-4 ○ Example 13 Preparation Examples 1-6 Preparation Example 2-5 ○

[0062] [Evaluation Example 1] Evaluation of Inversion Surface Adhesion

[0063] The behavior of the film of the present invention is considered suitable if it has fluidity upon initial application so that the hydrogel diffuses regardless of the shape of the surface, and then hardens quickly and can be easily detached after sufficient detoxification. Therefore, flowability after a certain period of time must be controlled or suppressed, and it must be sufficiently hardened to allow for easy detachment. In Examples 1 and 2, it was observed that the hydrogel did not form properly and flowed down even after 30 minutes. In Examples 3 to 6, some degree of flowability was observed, and in the case of the films in Examples 7 to 12, it was observed that the hydrogel hardened firmly and adhered firmly to the bottom surface or the surface.

[0064] [Evaluation Example 2] Pencil Hardness Evaluation

[0065] Figure 2 illustrates the results of the pencil hardness evaluation of the coatings of Example 3 and Example 10. The first solution and the second solution were uniformly applied to a slide glass, and after 3 hours, the hardened coating was measured by scratching the surface with a pencil hardness tester. The highest hardness was recorded when no scratches remained on the surface when a pencil was pushed in a certain direction under a 1 kg load condition; Example 3 showed no scratches up to 3H, and Example 10 showed no scratches up to 4H. Therefore, it was found that the surface hardness and scratch resistance of the coating were improved when high molecular weight PVA was blended.

[0066] [Evaluation Example 3] Evaluation of Nanoindentation (Nanoindentation Method)

[0067] Films (hereinafter referred to as Preparation Examples 1-6 and 1-3) were prepared by uniformly spreading 3 mL of the solutions of Preparation Examples 1-3 and 1-6 onto a 60 mm Petri dish and then completely drying them in a 50 ℃ oven for 6 hours. That is, the film of Preparation Example 1-3 may be a film containing only low molecular weight PVA, and the film of Preparation Example 1-6 may be a film in which low molecular weight and high molecular weight PVA are very uniformly mixed. The prepared films were subjected to nanoindentation evaluation (Bruker, Hysitron TI 950), and the results are shown in Table 4 and Figure 3 below. For the nanoindentation measurement, conditions were set so that when a load was applied to the film surface with an indenter, a maximum load of 1 mN was reached over 10 seconds.

[0068] Figure 3 shows the load-depth curve of the material. In the case of Manufacturing Examples 1-6, it was observed that the material exhibited a smaller displacement under the same load, indicating that it is harder and has a higher elastic modulus. Additionally, a steep slope in the loading section indicates that the material strongly resists indentation and may imply high stiffness. A steep slope in the unloading section indicates excellent resilience after deformation and may imply a high elastic modulus (EIT).

[0069] In Table 4 below, NM (Normalized Modulus, N / mm) represents the mechanical resistance of the film surface; a higher value indicates greater resistance to deformation (stiffness). It was observed that Preparation Example 1-6 exhibited superior stiffness or mechanical resistance compared to Preparation Example 1-3. HIT (Indentation Hardness, MPa) is a quantitative numerical representation of hardness, indicating how rigid the material is when pressed onto the surface with an indenter. It was observed that the hardness value of Preparation Example 1-6 was higher than that of Preparation Example 1-3. nIT (Elastic Recovery Ratio, %) is a quantitative numerical representation of the restoring force to the original shape after the load is removed. It was observed that Preparation Example 1-6 exhibited superior elastic recovery compared to Preparation Example 1-3. EIT / (1-vs 2The value represents the effective indentation modulus and is an indicator reflecting the overall elasticity / strength balance of the film. The indentation modulus of Preparation Example 1-6 did not increase significantly compared to Preparation Example 1-3, which appears to be the result of the simultaneous increase in stiffness and elasticity. Therefore, the nanoindentation results showed that Preparation Example 1-6, which blended or mixed high molecular weight PVA, exhibited superior overall stiffness, hardness, and elastic recovery compared to Preparation Example 1-3, which used low molecular weight PVA alone. It was estimated that this improvement was achieved by limiting molecular movement and enhancing crystallinity due to the increase in chain length and entanglement density. Thus, the properties of the material could be improved by increasing the molecular weight or blending PVA with different molecular weights.

[0070] item Preparation Examples 1-3 Preparation Examples 1-6 NM (N / mm) 284.2 322.36 HIT (MPa) 499.14 604.22 nIT (%) 38.86 43.65 EIT / (1-vs 2 ) 6607.05 6815.71

[0071] [Evaluation Example 4] Evaluation of Viscoelastic Properties

[0072] Storage modulus (G) of the film after 60 seconds using a dynamic mechanical analyzer (TA Instruments, Q800 dynamic Mechanical Analyzer) 60 '), initial loss modulus (G0") and loss modulus after 60 seconds (G 60 The initial loss modulus is better when higher, and the loss modulus is better when lower after a certain period of time. Over time, the loss modulus (G) may decrease relative to the storage modulus (G'), and preferably, the loss modulus may be 20 to 150% of the storage modulus, and more preferably 40 to 60%.

[0073] G 60 '(Pa) G0(Pa) G 60 "(Pa) G 60 " / G 60 '(%) Example 1 86 135 95 110 Example 3 105 126 72 69 Example 10 122 113 61 50 Example 12 116 128 54 47

[0074] [Evaluation Example 5] Evaluation of film removal ease

[0075] Figures 4 and 5 show the evaluation of the ease of physical removal of a film according to one embodiment of the present invention. To evaluate this, Example 3, which is a film using low molecular weight PVA alone, and Examples 10 and 13, which are films in which low molecular weight and high molecular weight PVA are mixed in a 5:5 ratio, were compared. Specifically, Example 10 contains sodium perborate, a solid decontamination agent, and Example 13 contains hydrogen peroxide, a liquid decontamination agent. The first solution and the second solution were uniformly applied to a 90 mm glass petri dish in equal volume ratios of 4 mL each, and the ease of removal of the film was evaluated after leaving it at room temperature for 1 hour.

[0076] Figure 4 shows the qualitative evaluation of ease of removal when the experimenter directly lifted the film. In the case of Example 3, removal was not easy because it was not sufficiently cured. In the case of Example 13, it was removed as a single film, but a part remained on the bottom of the glass petri dish, while in the case of Example 10, it was easy to remove in one go. In the case of Example 3, it was not sufficiently cured within one hour, but in the case of Examples 10 and 13, it was observed that curing occurred within a short period of time. It is expected that if it cures within a short period of time, the detoxification efficiency as a film detoxifier will be superior.

[0077] Figure 5 evaluates the physical removal rate of indigo dye by the film decontamination agent. First, 0.025 g of indigo, an insoluble dye, was applied to the center of a 90 mm glass petri dish. The first and second solutions were applied over the indigo, and after curing at room temperature for 1 hour, the film was removed. The remaining amount of indigo was converted to 8-bit using the Image J program, and the removal rate relative to the initial applied amount was measured. In the case of Example 3, the indigo dye removal rate was 69.15%, meaning that 30.85% of the weight of the initially applied indigo still remained at the bottom of the glass petri dish even after the film was removed. It was confirmed that 98.95% removal was possible in Example 13, and 99.94% removal was achieved in Example 10. Therefore, it was confirmed that the film decontamination agent of the present invention not only has excellent adsorption properties with the target to be removed but also enables easy removal of the film. As previously evaluated regarding the characteristics of the material, the film remover of the present invention facilitates surface diffusion and hardens quickly, possessing high rigidity and elastic modulus, thereby facilitating the removal of films along with contaminants.

[0078] [Evaluation Example 6] Evaluation of Detoxification of Pseudo-Chemical Agents

[0079] 10 μL each of the pseudo-chemical agents 2-CEES (2-Chloroethyl Ethyl Sulfide), OSEDMP (O-ethyl-S-(2-diisopropylamino)ethyl methylphosphonothioate), and DCP (Diisopropylchlorophosphate) were injected into the bottom of a 75 mL vial, followed by the injection of 2 mL of the first solution and 2 mL of the second solution. After 3 hours had passed for each vial, the film was removed, 20 mL of ethyl acetate (EA) was added to the vial, the vial lid was closed, and the mixture was thoroughly mixed using a vortex mixer. Subsequently, the remaining amount of decontamination agent was measured using GC-MS for 1 mL of the EA solution, and the decontamination rate was calculated by setting the area of ​​the control group, which did not receive any of the film decontamination agent of the present invention, to 100%. The results are illustrated in Table 5 and Figures 2 to 7 below.

[0080] 2-CEES(%) OSDEMP(%) DCP(%) Example 3 92.46 91.09 99.97 Example 10 82.56 97.27 99.99

[0081] As can be seen from the above results, the film decontamination agent of the present invention exhibits a very excellent decontamination rate for pseudo-chemical agents and the film could also be easily removed. Therefore, the film decontamination agent of the present invention possesses both practicality and efficiency and is expected to demonstrate decontamination performance in a wider variety of environments.

[0082] As described above, the present invention has been explained by specific details and limited embodiments; however, this is provided merely to aid in a more comprehensive understanding of the invention, and the invention is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

[0083] Accordingly, the present invention is not limited to the embodiments described above, and all things equivalent to or having equivalent variations to the claims set forth below, as well as the claims set forth below, shall be considered to be within the scope of the present invention.

Claims

Claim 1 A film decontamination composition for chemical agents comprising: a first solution containing polyvinyl alcohol (PVA) and a solvent; and a second solution containing borax (Na2B4O7ㆍ10H2O, Borax) and a solvent; wherein the polyvinyl alcohol comprises low molecular weight polyvinyl alcohol with a degree of polymerization (DP) of 300 to 800 and high molecular weight polyvinyl alcohol with a degree of polymerization of 1200 to 1700, and wherein the high molecular weight polyvinyl alcohol with a degree of polymerization of 1200 to 1700 comprises 25 to 75 weight% with respect to the total weight of the polyvinyl alcohol. Claim 2 delete Claim 3 delete Claim 4 A film detoxification composition for chemical agents according to claim 1, wherein the film made of the polyvinyl alcohol has a stiffness (NM) of 250 N / mm or more and an elastic recovery rate (nIT) of 35% or more. Claim 5 A film detoxification composition for chemical agents according to claim 1, wherein the film made of the polyvinyl alcohol has a hardness (HIT) of 500 MPa or higher. Claim 6 A film detoxifying agent composition for chemical agents according to claim 1, comprising 5 to 20 weight percent of the polyvinyl alcohol based on the total weight of the first solution. Claim 7 A film detoxifying agent composition for chemical agents according to claim 1, comprising 1 to 15 weight percent of the borax based on the total weight of the second solution. Claim 8 A film detoxification agent composition for chemical agents according to claim 1, wherein the first solution or the second solution further comprises a detoxification agent, and the solution not comprising the detoxification agent further comprises a detoxification activator. Claim 9 A film decontamination composition for chemical agents according to claim 8, wherein the decontamination agent is selected from one or more of the group consisting of hydrogen peroxide (H2O2), calcium oxide (CaO), calcium peroxide (CaO2), sodium perborate (NaBO3), sodium carbonate (Na2CO3), and potassium permanganate (K2FeO4). Claim 10 A film detoxification agent composition for chemical agents according to claim 8, wherein the detoxification agent is selected from one or more of the group consisting of N-triethylamine, peracetic acid, tetraacetylethylenediamine, ethylenediaminetetraacetic acid, and peracetylpyrrolidine. Claim 11 A film detoxification composition for chemical agents according to claim 1, wherein the solvent is selected from one or more of the group consisting of water, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, and glycerol. Claim 12 A film detoxification agent composition for chemical agents according to claim 1, wherein the first solution or the second solution further comprises a surfactant. Claim 13 A film detoxification composition for chemical agents according to claim 12, wherein the surfactant is selected from one or more of the group consisting of sodium lauryl sulfate, sodium lauryl ether sulfate, sodium dodecylbenzene sulfonate, cetyltrimethylammonium bromide, polyoxyethylene sorbitan monolate, polyethylene glycol-400, sodium stearate, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, decyl glucoside, sodium oleate, and lecithin. Claim 14 A film detoxification composition for chemical agents according to claim 1, wherein the second solution further comprises a pH adjuster, wherein the pH adjuster is selected from one or more of the group consisting of acetic acid, citric acid, lactic acid, fumaric acid, tartaric acid, phosphoric acid, and acetohydroxyammonic acid. Claim 15 A film detoxifying agent composition for chemical agents according to claim 14, wherein the pH adjuster comprises 0.1 to 5 weight percent based on the total weight of borax. Claim 16 A film decontamination agent for chemical agents, prepared by mixing the first solution and the second solution of any one of claims 1, 4 to 15 in equal volume ratios. Claim 17 A film decontamination agent for chemical agents according to claim 16, wherein the weight ratio of polyvinyl alcohol to borax of the film decontamination agent is 4:1 to 1:

1. Claim 18 A method for detoxifying a chemical agent, comprising: a step of spraying a first solution and a second solution selected from any one of claims 1, 4 to 15 in equal volume ratios onto a surface coated with a chemical agent or a similar chemical agent; a step of forming a film; and a step of removing the film. Claim 19 A method for detoxifying chemical agents according to claim 18, wherein the chemical agent comprises VX, GD, HD, and GB, and the pseudo-chemical agent comprises paraoxon-methyl, diisopropyl chlorophosphite (DICP), 2-chloroethyl ethyl sulfide (CEES), dichlorophenol (DP), diphenyl chlorophosphite (DPCP), diisopropyl fluorophosphate (DFP), and O,S-diethyl methylphosphonothioate (OSDEMP).

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