Composition

Abstract

This specification discloses compositions, fire extinguishing devices, and their uses. The compositions and fire extinguishing devices may be applied to products that are likely to generate abnormal heat, ignition, and / or explosion during operation, storage, and / or maintenance, and may effectively respond to said heat, ignition, and explosion. The compositions and fire extinguishing devices may be applied, for example, to articles containing multiple said products to respond to abnormal heat, explosion, and / or ignition occurring in any one of the products and to prevent the propagation of such heat, explosion, and / or ignition to adjacent other products. The compositions and fire extinguishing devices also possess excellent handling and storage stability. This specification also discloses the uses of said compositions and fire extinguishing devices.

Description

Technology Field

[0001] This application claims the benefit of priority based on Korean Patent Applications No. 10-2023-0041413 and No. 10-2023-0041416 filed on March 29, 2023, and all contents disclosed in the documents of said patent applications are incorporated herein as part of this specification.

[0002] This specification discloses a composition, a fire extinguishing device, and uses thereof. Background Technology

[0003] Technology is required to ensure safety for products that pose a risk of abnormal heat generation, ignition, or explosion (hereinafter referred to as "hazardous products"). In particular, when multiple such hazardous products are included, a major problem may arise in terms of safety if abnormal heat generation, ignition, and / or explosion occurring in one product causes a chain reaction affecting adjacent products. A typical example of this phenomenon is the so-called TR (Thermal Runaway) or TP (Thermal Propagation) phenomenon occurring in battery modules or battery packs.

[0004] A battery module or battery pack includes multiple battery cells or multiple battery modules arranged adjacent to each other. In such a structure, if abnormal heat generation, ignition, and / or explosion occurs in any one of the battery cells and / or battery modules, the phenomenon in which such heat generation, ignition, and / or explosion propagates sequentially to other adjacent battery cells is called the TR or TP phenomenon.

[0005] With the development of products that require a lot of energy for operation, such as electric vehicles, the energy capacity of the battery module or battery pack is increasing significantly, and accordingly, the risk of the TR or TP phenomenon has also increased significantly.

[0006] In particular, in cases where user safety is directly affected by TR or TP phenomena, such as electric vehicles, sequential heat generation, ignition, and explosion such as TR or TP must be managed. The problem to be solved

[0007] This specification discloses compositions, fire extinguishing devices, and their uses.

[0008] The present specification aims to disclose a composition, a fire extinguishing device, and uses thereof that can be applied to products that have the potential for abnormal heat generation, ignition, and / or explosion during operation, storage, and / or maintenance, and can effectively respond to said heat generation, ignition, and explosion.

[0009] For example, the composition and fire extinguishing device disclosed herein may be applied to an article comprising a plurality of said products to respond to abnormal heat generation, explosion and / or ignition occurring in any one of the products and to prevent the propagation of such heat generation, explosion and / or ignition to adjacent other products.

[0010] One objective of this specification is also to disclose the above composition and fire extinguishing device having excellent handling and storage stability. This specification is also to disclose the use of the above composition and fire extinguishing device. means of solving the problem

[0011] Among the physical properties mentioned in this specification, those affected by temperature are properties measured at room temperature unless specifically otherwise defined.

[0012] The term room temperature refers to a natural temperature that has not been artificially heated or cooled, for example, any temperature within the range of about 10°C to 30°C or about 23°C or about 25°C.

[0013] Unless otherwise specifically defined in this specification, the unit of temperature is ℃.

[0014] Among the physical properties mentioned in this specification, those affected by pressure are properties measured at atmospheric pressure unless specifically otherwise defined.

[0015] The term atmospheric pressure refers to natural pressure that is not artificially pressurized or depressurized, typically ranging from about 700 mmHg to 800 mmHg.

[0016] Among the physical properties mentioned in this specification, those affected by humidity are properties measured at standard humidity, unless otherwise specifically defined.

[0017] Humidity in standard conditions means about 40%, 50%, 60%, or 65% in relative humidity.

[0018] This specification discloses a composition.

[0019] The term "composition" refers to an object containing two or more components. Such a composition may be a fire extinguishing composition. A fire extinguishing composition is a composition capable of responding to abnormal heat generation, flames, explosions, etc., that need to be suppressed.

[0020] This composition can exhibit excellent effects, particularly when combined with the structure of the fire extinguishing device described below.

[0021] Accordingly, the present specification also discloses a fire extinguishing device.

[0022] First, I will explain the fire extinguishing system.

[0023] The above-mentioned fire extinguishing device comprises a case having a sealed space inside and a vaporizable substance or composition present in the sealed space.

[0024] The above composition may be the aforementioned fire extinguishing composition, and the above vaporizable substance may be one component of the above composition.

[0025] The above case is a container for holding the above vaporizable substance or composition. The above case has the above-mentioned sealed space inside, or is prepared to form the above-mentioned sealed space. In this case, being prepared to form the above-mentioned sealed space inside means that the above-mentioned sealed space is formed inside the case, or that the case exists such that a certain space exists inside the case and, although that space is not sealed, the case is capable of forming a sealed space by sealing the open portion.

[0026] The sealed space of such a case may have a vent area. The term vent area may refer to an area that is sealed in a first state to maintain the sealed state of the space, but is open in a second state to allow the discharge of material inside the space. The second state may refer to a state in which abnormal ignition, heat generation, and / or explosion occurs in an environment where, for example, the composition or fire extinguishing device is applied, and the first state may refer to a state in which abnormal ignition, abnormal heat generation, and abnormal explosion do not occur.

[0027] These vent areas can be formed in the manner described below.

[0028] In one example, the above case may have a Water Vapor Transmission Rate (WVTR) of a predetermined range or may include a portion having such a WVTR. For example, at least the portion of the case forming the sealed space may have a Water Vapor Transmission Rate (WVTR) of a predetermined range. For example, the upper limit of the WVTR in the above case may be approximately 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, 0.15, 0.1, 0.05, or 0.01, and the lower limit may be approximately 0, 0.1, 0.2, 0.3, 0.4, or 0.5. The WVTR is within a range less than or equal to any one of the upper limits described above; Alternatively, it may be within a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above. Within the range described above, superior effects can be secured as the WVTR approaches the range disclosed in the Examples section of this specification. The unit of the WVTR is g / m² 2· It is day, and this is measured in the manner described in "9. WVTR (Water Vapor Transmission Rate) Evaluation" of the Examples section of this specification.

[0029] In one example, when a sealed space is formed within at least the case, a certain level of the total area of ​​the case forming the sealed space may have a WVTR of the range described above.

[0030] For example, a WVTR of the range described above can be confirmed in an area of ​​at least a certain percentage of the total area of ​​the above case. For example, the lower limit of the ratio of the area of ​​the portion having a WVTR of the range described above to the total area of ​​the above case may be approximately 80%, 85%, 90%, 95%, 97%, or 99%, and the upper limit may be approximately 100%. The ratio may be within a range greater than or exceeding any of the lower limits described above; or within a range greater than or exceeding any of the lower limits described above while being less than or equal to the upper limit described above.

[0031] In another example, among the areas of the portion forming the sealed space in the above case, an area of ​​at least a certain level may have a Water Vapor Transmission Rate (WVTR) of the range described above. For example, the lower limit of the ratio of the area of ​​the portion of the case forming the sealed space that exhibits a WVTR of the range described above may be approximately 80%, 85%, 90%, 95%, 97%, or 99%, and the upper limit may be approximately 100%. The ratio may be within a range greater than or exceeding any of the lower limits described above; or within a range greater than or exceeding any of the lower limits described above while being less than or equal to the upper limit described above.

[0032] The above implies that the sealed space inside the case is substantially entirely surrounded by an area having a WVTR within the range described above. This configuration can effectively induce a momentary increase in internal pressure within the fire extinguishing device described later.

[0033] The above-described fire extinguishing device is configured to stably maintain an internal vaporizable substance or composition in a normal state, and to release all or part of the vaporizable substance or composition or the vaporized product to the outside in an abnormal state. The abnormal state may be, for example, the second state, and the normal state may be, for example, the first state.

[0034] The above explanation assumes that the fire extinguishing device is applied to a battery module.

[0035] FIG. 1 is a schematic diagram of the case where the fire extinguishing device (S) is applied to a battery module. As shown in FIG. 1, the battery module may be configured by arranging a plurality of battery cells (11, 12, 13, 14, 15, 16) adjacently, and the fire extinguishing device (S) may be placed between the battery cells (for example, between 12 and 13 in FIG. 1 and between 14 and 15 in FIG. 1) as shown in the drawing.

[0036] The above-mentioned fire extinguishing device (S) maintains a vaporizable substance, etc. inside in a normal state. In an abnormal state, the vaporizable substance, etc. of the fire extinguishing device (S) is ejected in a directional manner, for example, through the aforementioned vent area (dotted arrow in FIG. 1), thereby enabling response to high temperatures or flames resulting from abnormal heat generation, ignition, and / or explosion. FIG. 1 describes a case where the substance is ejected from both the top and bottom directions of the fire extinguishing device (S), but the ejection direction is not limited to FIG. 1. The ejection direction may be a single direction of the fire extinguishing device (S) or two or more directions. Such ejection directions can be controlled through the formation of a vent area.

[0037] In order for the fire extinguishing device to effectively perform the above function in an abnormal state, it is required that vaporizable substances, etc. present inside the case in a normal state be stably maintained, and that when an abnormal state occurs, said vaporizable substances, etc. be rapidly discharged to the outside in a vaporized state as much as possible to be consumed. The fire extinguishing device can satisfy the above requirements.

[0038] The principle by which the above-mentioned fire extinguishing device operates is explained.

[0039] FIG. 2 shows only the fire extinguishing device (S) of FIG. 1. In a configuration like FIG. 1, if abnormal heating, ignition, and / or explosion occurs in at least one of the battery cells, a high heat of a certain level or higher is instantaneously applied to the fire extinguishing device, as indicated by the solid arrow in FIG. 2. The vaporizable substance present inside the fire extinguishing device is vaporized by the applied heat. The vaporized substance then propagates randomly in all directions within the sealed space inside the case (1001) of the fire extinguishing device in FIG. 2, as indicated by the dotted arrow. At this time, if the sealed space of the case (1001) is substantially surrounded by the part having the aforementioned WVTR, the vaporized substance cannot be released to the outside, and thus the inside of the case (1001) becomes instantaneously under a very high pressure. When the vent area (1002) of the case is instantaneously opened at a high pressure of a certain level or higher, the gas inside is rapidly discharged to the outside through the opened vent area (1002).

[0040] If the WVTR of the case surrounding the sealed space is not high, the internal pressure of the case (1001) in the above state may not increase effectively, or the rate of increase may be slow, so the vent area (1002) may not open effectively, or even if the vent area (1002) is opened, the internal pressure may not be sufficient, so some of the vaporized material may remain without being discharged to the outside or the discharge rate may be excessively slow.

[0041] Maintaining a low WVTR of the case also has the additional effect of ensuring the storage stability of the internal material under normal conditions.

[0042] The method of forming the above-mentioned vent region is not particularly limited. The vent region can be formed by designing it so that it opens when the internal pressure of the case forming the sealed space reaches a certain level. For example, if some areas of the case forming the sealed space are configured to have lower strength compared to other areas, the parts having lower strength may open due to increased internal pressure. In addition, methods such as forming the sealed space through sealing using a hot-melt material, thereby causing opening by melting at a predetermined temperature, may also be used. Alternatively, the vent region can be formed by making only a certain part of the case forming the sealed space thinner than other areas. Such methods of forming the vent region can be easily adopted by those skilled in the art.

[0043] For example, when the above-mentioned fire extinguishing device is applied to a battery module or pack, for convenience of application, the case may be a prismatic case, a pouch-type case, and / or a cylindrical case that is shaped like a battery cell. In such cases, a vent area may also be formed by controlling the bonding strength of a cover that forms a sealed space in a prismatic or cylindrical case.

[0044] The above case can be constructed using a known material that can satisfy the aforementioned WVTR, and the material may have a single layer or a single-layer structure of two or more layers.

[0045] For example, the above case can be formed using a material capable of exhibiting a WVTR of the above range among a suitable organic layer and / or inorganic layer.

[0046] For example, known polymer films or sheets may be used as the above organic layer. Examples of organic films include cellulose-based polymer films; COP (cyclo olefin copolymer) films; acrylic polymer films; polyolefin films; PVA (polyvinyl alcohol) films; PVC (poly(vinyl chloride)) films; PES (poly ether sulfone) films; PEEK (polyetherether ketone) films; PPS (polyphenylsulfone) films; PEI (polyetherimide) films; PEN (polyethylenemaphthatlate) films; PET (poly(ethylene terephthalate)) films, polyester films; PI (polyimide) films; PSF (polysulfone) films and / or PAR (polyarylate) films, etc.

[0047] For example, the inorganic layer may be a metal layer, a metal oxide layer, a metal nitride layer, or a metal oxynitride layer. For example, the inorganic layer may be a metal layer, a metal oxide layer, a metal nitride layer, or a metal oxynitride layer comprising one or more selected from the group consisting of In, Sn, Pb, Au, Cu, Ag, Zr, Hf, Zn, Al, Si, La, Ti, and Ni. For example, a foil, sheet, or film of the above material may be applied, or a layer formed by depositing the metal layer, metal oxide layer, metal nitride layer, or metal oxynitride layer on a suitable substrate may be used.

[0048] The material forming the case may be a single layer selected from the inorganic layer and the organic layer, or a multilayer structure in which two or more of the layers are stacked.

[0049] The thickness of the above inorganic layer and / or organic layer is selected considering the desired physical properties, such as WVTR, and is not particularly limited. For example, the lower limit of the thickness may be approximately 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, and the upper limit may be approximately 5,000 μm, 4,000 μm, 3,000 μm, 2,000 μm, 1,000 μm, 500 μm, 200 μm, 150 μm, 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, or 30 μm. The thickness is within a range less than or equal to any one of the upper limits described above; Or within a range greater than or equal to any of the lower limits described above; or within a range greater than or equal to any of the lower limits described above and less than or equal to any of the upper limits described above.

[0050] The above-mentioned extinguishing device may include additional configurations to perform the above action more effectively.

[0051] For example, the fire extinguishing device may additionally include a heat-conducting layer. Such a heat-conducting layer may be present at an appropriate location within the fire extinguishing device. For example, the heat-conducting layer may be present between the case and the vaporizable material or composition in the fire extinguishing device, or the heat-conducting layer may be present adjacent to the case.

[0052] FIG. 3 is an example of a case in which the heat conductive layer (2001) is added to the fire extinguishing device of FIG. 2. The heat conductive layer may be located at different locations inside the case, and the number thereof may be one or more than two.

[0053] The term "thermal conductive layer" refers to a layer whose thermal conductivity (at 20°C) is within the range described below. The lower limit of the thermal conductivity (at 20°C) of the thermal conductive layer may be approximately 15, 18, 20, 50, 100, 150, 200, 250, 300, 350, or 400, and the upper limit may be approximately 2,000, 1,500, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, or 50. The thermal conductivity may be within a range greater than or exceeding any of the lower limits described above; or within a range greater than or exceeding any of the lower limits described above, while being less than or equal to any of the upper limits described above. The unit of the above thermal conductivity is W / mK, and it can be evaluated in the manner described in "15. Evaluation of Thermal Conductivity" of the Examples section of this specification.

[0054] The type of thermal conductive layer is not particularly limited as long as it has the above thermal conductivity. Typically, metal materials can be used as thermal conductive layers because they have excellent thermal conductivity characteristics. For example, a layer made of metal materials such as aluminum, gold, pure silver, tungsten, copper, nickel, or platinum may be applied.

[0055] There are no special limitations on the thickness of the heat-conducting layer, and an appropriate thickness may be set considering the specifications of the fire extinguishing device, etc. For example, the lower limit of the thickness of the heat-conducting layer may be approximately 1 μm, 5 μm, 10 μm, 15 μm, 50 μm, 75 μm, or 90 μm, and the upper limit may be approximately 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, 50 μm, 40 μm, or 30 μm. The thickness may be within a range lower than or less than any of the upper limits described above; or within a range greater than or greater than any of the lower limits described above; or within a range greater than or greater than any of the lower limits described above and lower than or less than any of the upper limits described above.

[0056] As shown in FIG. 3, in some cases, the heat generated in the abnormal state may not be applied uniformly to the fire extinguishing device but may be applied locally to only a certain area. However, in order for the vaporizable material inside the fire extinguishing device to rapidly vaporize and achieve a high-pressure state, the heat from the abnormal state must be applied uniformly to the fire extinguishing device. When a heat conductive layer is present, even if the heat from the abnormal state is applied locally, the heat can be rapidly transferred to the entire fire extinguishing device, and accordingly, the fire extinguishing action of the aforementioned fire extinguishing device can occur rapidly and efficiently.

[0057] In order for the fire extinguishing device to more efficiently secure the above effect, the amount of the vaporizable substance or the composition described below containing the vaporizable substance present in the internal space or sealed space of the case in the fire extinguishing device may be adjusted. For example, the lower limit of the ratio of the volume occupied by the vaporizable substance or the composition within the total volume of the internal space or sealed space of the case may be approximately 70%, 75%, 80%, 85%, 90%, or 95%, and the upper limit may be approximately 100%. The ratio may be within a range greater than or exceeding any of the lower limits described above; or within a range greater than or exceeding any of the lower limits described above and less than or equal to any of the upper limits described above. Under such ratios, a rapid rise in the aforementioned internal pressure can be induced more effectively.

[0058] The above-mentioned fire extinguishing composition is described below.

[0059] The above fire extinguishing composition may be contained in a sealed space inside the fire extinguishing device, and in particular, may be composed so that the action described in FIGS. 2 and 3 may be exhibited more effectively.

[0060] The above composition can be non-flammable and be formulated to be friendly to the environment and the human body.

[0061] For example, the above composition may have a flammability rating of 0 or 1 according to the NFPA (National Fire Protection Association) 704 standard. The NFPA 704 standard is a standard published by the National Fire Protection Association (NFPA) and is a standard represented by the so-called fire diamond, designed to enable a rapid response to hazardous materials in emergency situations; the flammability rating is indicated by a red zone. The standard is classified into grades 0, 1, 2, 3, and 4, among which grade 0 means non-flammable, and grade 1 means igniting when sufficiently heated, which is approximately a flash point of 93°C or higher. The method of evaluating such flammability ratings follows the NFPA (National Fire Protection Association) 704 standard.

[0062] The above composition may exhibit non-flammability with a flammability rating of 0 or 1 according to the NFPA (National Fire Protection Association) 704 standard. For example, the above composition may have a health hazard rating of 0, 1, or 2 according to the NFPA (National Fire Protection Association) 704 standard. The health hazard rating is indicated by the blue area on the fire diamond of the NFPA 704 standard. The standard is classified into 0, 1, 2, 3, and 4 grades, of which 0 grade is a case where there is no health threat and no special precautions are required, 1 grade is a case where there is a possibility of causing minor injury upon exposure, and 2 grade is a case where there is a possibility of causing temporary impairment or injury through continuous / general contact rather than chronic contact.

[0063] In order for the above composition to exhibit the above grade, each component constituting the above composition may also be a substance exhibiting the above flammability and / or health hazard grade.

[0064] The above composition comprises at least the above-mentioned vaporizable substance. This vaporizable substance vaporizes under certain temperature and / or pressure conditions and serves to increase internal pressure as described above. Additionally, this vaporizable substance can be ejected to the outside in a vaporized state to perform extinguishing and / or cooling functions.

[0065] A suitable type of vaporizable substance may be selected and used. For example, the vaporizable substance may be a substance known as a so-called vaporizable substance. For example, the vaporizable substance may exist in a liquid state at least at room temperature (about 25°C). Such a vaporizable substance may be used to increase the internal pressure of the enclosed space by instantaneous vaporization in response to abnormal heat generation, flames, and explosions occurring in adjacent objects, to reduce heat through heat exchange, or to eliminate flames.

[0066] As for such volatile substances, any non-flammable substance may be used without special restrictions. For example, as the volatile substance, a substance having a freezing point and / or boiling point within a predetermined range may be used.

[0067] For example, the lower limit of the freezing point of the above-mentioned vaporizable substance may be approximately -5°C, -4°C, -3°C, -2°C, -1°C, or 0°C, and the upper limit may be approximately 10°C, 9°C, 8°C, 7°C, 6°C, 5°C, 4°C, 3°C, or 2°C. The above-mentioned freezing point may be within a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above. The above-mentioned freezing point is the freezing point under 1 atmosphere.

[0068] The above-mentioned vaporizable substance may have a boiling point within a certain range to exhibit appropriate vaporization. For example, the lower limit of the boiling point of the above-mentioned vaporizable substance may be approximately 80°C, 85°C, 90°C, or 95°C, and the upper limit may be approximately 120°C, 115°C, 110°C, or 105°C. The above-mentioned boiling point may be within a range that is greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above. The above-mentioned boiling point is the boiling point under 1 atmosphere.

[0069] As long as the volatile substance has a freezing point and / or boiling point within the above range and is non-flammable, any suitable type may be selected and used without special restrictions. A representative example of a non-flammable volatile substance having a freezing point and / or boiling point within the above range is water, and accordingly, water may be used as the volatile substance, but the types of applicable volatile substances are not limited to the above.

[0070] In order for the above composition to be applied to the sealed space of the fire extinguishing device to increase the internal pressure at an appropriate rate at the necessary time, it is necessary to control the content of the vaporizable substance within the sealed space or within the composition.

[0071] For example, the lower limit of the proportion of the vaporizable substance within the composition or within the sealed space of the fire extinguishing device may be approximately 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, or 80 wt%, and the upper limit may be approximately 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt%, 65 wt%, or 60 wt%. The proportion may be within a range greater than or exceeding any of the lower limits described above; or within a range greater than or exceeding any of the lower limits described above and less than or equal to any of the upper limits described above. The effect may be improved as the content of the vaporizable substance approaches the range disclosed in the examples within the range described above. The proportion is a percentage based on the total weight of all components present in the composition or all components present within the sealed space.

[0072] The above composition or sealed space may contain only a vaporizable substance, or may additionally contain other components.

[0073] For example, the above composition or sealed space may additionally include a freezing point regulator. The term freezing point regulator is a component that controls the freezing point and / or boiling point of the above composition through the so-called freezing point depression phenomenon. In order for the fire extinguishing device to effectively exhibit the operation described with reference to FIGS. 2 and 3, instantaneous vaporization of the above volatile substance must occur at the necessary time, and for this purpose, a freezing point regulator may be applied. Furthermore, since it is advantageous for the above volatile substance, etc., to exist in a liquid state at the time the above abnormal state occurs, this state can also be secured by the freezing point regulator. In addition, when the above composition is applied to a high-density product such as a battery module or battery cell, if a phase transition occurs due to cooling of the above composition in a low-temperature environment, it may adversely affect adjacent products due to changes in volume and hardness of the above composition, and this problem can also be solved by adding a freezing point regulator.

[0074] The form in which the above-described freezing point control agent is applied can be controlled in order to secure the effect described above, particularly the instantaneous, complete, and rapid vaporization of a vaporizable substance at a time when it is required.

[0075] For example, the above freezing point regulator is △T of Formula 1 below. f It may exist to be within a predetermined range.

[0076] [Equation 1]

[0077] △T f = K f × M × I

[0078] K in Equation 1 f is the freezing point depression constant of the above volatile substance.

[0079] The above K f The unit is °C / m, and for example, if the vaporizable substance is water, the above K f It is about 1.86.

[0080] M in Equation 1 is the molal concentration of the freezing point regulator, which is the molal concentration of the volatile substance. Accordingly, M is the number of moles of the freezing point regulator present per 1 kg of the volatile substance in the composition or a sealed space.

[0081] I in Equation 1 is the number of ions (moles) formed by 1 mole of the freezing point regulator when the above freezing point regulator is dissociated, where dissociation means a state in which the above freezing point regulator is completely dissociated. Therefore, for example, if the above freezing point regulator is not an ionic compound, I is 1.

[0082] In cases where two or more types of freezing point regulators or ionic compounds are present in the above composition, for each compound, the above △T f Calculate and sum the values ​​as △T for the composition f It is set as a value.

[0083] △T in Equation 1 f The lower limit of may be, for example, around 5, 10, 15, 20, 22, or 24, and the upper limit may be around 50, 45, 40, 35, 30, 25, 20, or 15. The above △T f The unit of is ℃. The above △T f It may be a range that is greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above.

[0084] By applying a freezing point regulator within the above range, the vaporizable substance can rapidly and substantially completely vaporize at the necessary time to quickly increase the internal pressure of the sealed space, and at the necessary time, the vaporizable substance can exist in a liquid state, thereby preventing changes in the volume and hardness of the composition or fire extinguishing device that could affect the operation of the product under normal conditions. The above △T fThe closer the range of the example is to the above range, the more excellent the effect can be.

[0085] For example, alcohols or ionic compounds may be used as the above freezing point regulators. The category of the above ionic compounds includes substances that are ionic themselves or capable of generating ions, for example, salts.

[0086] For example, the above alcohol may be an alcohol having a boiling point within a predetermined range. For example, the lower limit of the boiling point of the above alcohol may be approximately 150°C, 170°C, or 190°C, and the upper limit may be approximately 300°C, 280°C, 260°C, 240°C, 220°C, or 200°C. The above boiling point may be within a range that is greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above.

[0087] For example, the above alcohol may be an alcohol having a molar weight within a predetermined range. For example, the lower limit of the molar weight of the above alcohol may be approximately 20 g / mol, 30 g / mol, 40 g / mol, 50 g / mol, 60 g / mol, 70 g / mol, 80 g / mol, or 90 g / mol, and the upper limit may be approximately 300 g / mol, 280 g / mol, 260 g / mol, 240 g / mol, 220 g / mol, 200 g / mol, 180 g / mol, 160 g / mol, 140 g / mol, 120 g / mol, 100 g / mol, 90 g / mol, 80 g / mol, or 70 g / mol. The molar mass may be within a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above.

[0088] There are no special restrictions on the type of alcohol mentioned above, and polyhydric alcohols such as ethylene glycol or glycerin may be used, for example.

[0089] The above ionic compound that can be applied as a freezing point regulator includes, for example, one or more salts selected from the group consisting of formates, acetates, carbonates, and sulfates, and specifically, one or more of the salts such as sodium acetate (CH3COONa), sodium formate (HCOONa), potassium acetate (CH3COOK), potassium formate (HCOOK), calcium formate ((HCOO)2Ca), magnesium formate ((HCOO)2Mg), potassium carbonate (K2CO3), and / or ammonium sulfate ((NH4)2SO4) may be used.

[0090] The above freezing point regulator may be present such that the concentration calculated based on the above volatile substance is within a predetermined range. The concentration is molal concentration, specifically, the number of moles of freezing point regulator present per 1 kg of the above volatile substance present in the composition. In one example, the lower limit of the molal concentration may be 1, 1.5, 2, 4, 6, 8, 10, 12, 14, or 16, and the upper limit may be approximately 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 15, 11, 9, 7, 5, or 3. The molal concentration may be in a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above. The above molal concentration is △T of Equation 1 above. f It can be adjusted by considering.

[0091] As a freezing point regulator, it may be appropriate to use a component that has a flammability rating of 0 or 1 according to the above NFPA (National Fire Protection Association) 704 standard and / or a health hazard rating of 0, 1, or 2 according to the above NFPA (National Fire Protection Association) 704 standard. Although various freezing point regulators capable of inducing freezing point depression are known, most of them are flammable and / or toxic; therefore, when it is necessary to achieve the above-mentioned NFPA ratings, it is necessary to consider the above NFPA ratings when selecting a freezing point regulator.

[0092] As for the above freezing point regulator, it may be appropriate to have a certain level of solubility with respect to the above volatile substance. In order to select a freezing point regulator with appropriate solubility, the degree of freedom in the amount of additive of the above freezing point regulator is increased, and an amount of additive that can secure the desired freezing point while improving the extinguishing function without impeding it can be selected.

[0093] For example, the lower limit of the solubility of the above freezing point regulator for 100 g of the above volatile substance or water at 0°C is 20 g, 25 g, 30 g, 35 g, 40 g, 45 g, 50 g, 55 g, 60 g, 65 g, 70 g, 75 g, 80 g, 85 g, 90 g, 95 g, 100 g, 110 g, 115 g, 120 g, 125 g, 130 g, 135 g, 140 g, 145 g, 150 g, 155 g, 160 g, 165 g, 170 g, 175 g, 180 g, 185 g, 190 g, 195 g, 200 g, 205 g, 210 g or It may be around 215 g, and the upper limit is 1000 g, 900 g, 800 g, 700 g, 600 g, 500 g, 400 g, 300 g, 250 g, 245 g, 240 g, 235 g, 230 g, 225 g, 220 g, 215 g, 210 g, 205 g, 200 g, 195 g, 190 g, 185 g, 180 g, 175 g, 170 g, 165 g, 160 g, 155 g, 150 g, 145 g, 140 g, 135 g, 130 g, 125 g, 120 g, 115 g, 110 g, 105 g, The solubility may be approximately 100 g, 95 g, 90 g, 85 g, 80 g, 75 g, 70 g, 65 g, 60 g, 55 g, 50 g, 45 g, 40 g, 35 g, or 30 g. The solubility may be within a range greater than or equal to any of the lower limits described above; or within a range greater than or equal to any of the lower limits described above and less than or equal to any of the upper limits described above. The solubility is the weight (g) of the freezing point regulator that can be maximally dissolved in 100 g of a vaporizable substance or water at 0°C. Such solubility may be evaluated in the manner described in “10. Evaluation of Solubility”.

[0094] The lower limit of the solubility of the above freezing point regulator for 100 g of the above volatile substance or water at 25°C is 70 g, 75 g, 80 g, 85 g, 90 g, 95 g, 100 g, 110 g, 115 g, 120 g, 125 g, 130 g, 135 g, 140 g, 145 g, 150 g, 155 g, 160 g, 165 g, 170 g, 175 g, 180 g, 185 g, 190 g, 195 g, 200 g, 205 g, 210 g, 215 g, 225 g, 230 g, 235 g, 240 g, 255 g, 260 g, 265 g, It may be approximately 270 g, 275 g, 280 g, 285 g, 290 g, 295 g, 300 g, 305 g, 310 g, 315 g, or 320 g, and the upper limit is 1000 g, 900 g, 800 g, 700 g, 600 g, 500 g, 400 g, 350 g, 345 g, 340 g, 335 g, 330 g, 325 g, 320 g, 315 g, 310 g, 305 g, 300 g, 295 g, 290 g, 280 g, 275 g, 270 g, 265 g, 260 g, 255 g, 250 g, 245 g, The solubility may be approximately 240 g, 235 g, 230 g, 225 g, 220 g, 215 g, 210 g, 205 g, 200 g, 195 g, 190 g, 185 g, 180 g, 175 g, 170 g, 165 g, 160 g, 155 g, 150 g, 145 g, 140 g, 135 g, 130 g, 125 g, 120 g, 115 g, 110 g, 105 g, or 100 g. The solubility may be within a range greater than or exceeding any of the lower limits described above; or within a range greater than or exceeding any of the lower limits described above, while being less than or equal to any of the upper limits described above. The above solubility is the weight (g) of the freezing point regulator that can be maximally dissolved in 100 g of a vaporizable substance or water at 25°C.This solubility can be evaluated in the manner described in "10. Evaluation of Solubility".

[0095] As the above freezing point regulator, a component having a molar weight within a predetermined range may be used. When the molar weight of the freezing point regulator is maintained at an appropriate level, the function of other components of the composition (e.g., digestive function) can be maintained and improved. For example, the lower limit of the molar mass of the above freezing point regulator may be approximately 10 g / mol, 15 g / mol, 20 g / mol, 25 g / mol, 30 g / mol, 35 g / mol, 40 g / mol, 45 g / mol, 50 g / mol, 55 g / mol, 60 g / mol, 65 g / mol, 70 g / mol, 75 g / mol, 80 g / mol, 85 g / mol, 90 g / mol, or 95 g / mol, and the upper limit may be approximately 300 g / mol, 250 g / mol, 200 g / mol, 150 g / mol, 145 g / mol, 140 g / mol, 135 g / mol, 130 g / mol, 125 g / mol, 120 g / mol, 115 g / mol, 110 The molar mass may be approximately g / mol, 105 g / mol, 100 g / mol, 95 g / mol, 90 g / mol, 85 g / mol, 80 g / mol, 75 g / mol, 70 g / mol, or 65 g / mol. The molar mass may be within a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above.

[0096] In order for the freezing point regulator to exhibit the flammability and health hazard ratings of the NFPA 704 mentioned above, a component that does not contain specific functional groups may be used. For example, as the freezing point regulator, components that do not contain hydroxyl groups and / or chlorine may be used, and components that do not generate sulfur dioxide, ammonia, and ethylene oxide, or components that do not generate such components may be used. A freezing point regulator containing such components or functional groups may not exhibit the flammability rating (red category) and health hazard rating (blue category) of the NFPA 704 standard described above.

[0097] Examples of such freezing point regulators may include, for instance, one or more ionic compounds among the types described above, selected from the group consisting of formate, acetate, carbonate, and sulfate.

[0098] The specific content of the above freezing point regulator is △T of Formula 1 above. f It can be adjusted by taking into consideration. For example, the lower limit of the weight ratio of the freezing point regulator to 100 parts by weight of the volatile substance may be approximately 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, or 65 parts by weight, and the upper limit may be approximately 200 parts by weight, 180 parts by weight, 160 parts by weight, 140 parts by weight, 120 parts by weight, 100 parts by weight, 90 parts by weight, 85 parts by weight, 80 parts by weight, 75 parts by weight, 70 parts by weight, 65 parts by weight, 60 parts by weight, 55 parts by weight, 50 parts by weight, 45 parts by weight, or 40 parts by weight. The above ratio may be within a range that is greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above.

[0099] Additionally, where an ionic compound added for a purpose other than the freezing point regulator (e.g., an ionic compound as a carbonization catalyst) is present in the above composition or sealed space, all freezing point regulators and the other ionic compound present in the above composition or sealed space are △T of Formula 1. f α can exist in an amount within a predetermined range. In this case, △T f The specific method for calculating is the same as in the case of the above-mentioned freezing point regulator. In cases where two or more types of freezing point regulators and ionic compounds exist within the above composition or a sealed space, the above △T for each compound. f Calculate and sum the values ​​for the composition or enclosed space △T f It is set as a value.

[0100] △T of Formula 1 for all freezing point regulators and other ionic compounds present in the above composition or a sealed space f The lower limit of the sum of the values ​​of may be, for example, around 3, 5, 10, 15, or 20, and the upper limit may be around 50, 45, 40, 35, 30, 25, 20, 15, or 10. The above △T f may be within a range greater than or equal to any of the lower limits described above or greater than; or within a range less than or equal to any of the upper limits described above or less than; or within a range greater than or equal to any of the lower limits described above and simultaneously less than or equal to any of the upper limits described above or less than. △T of Equation 1 f The unit is °C. By adjusting the content of the freezing point regulator and the ionic compound within the above range, the vaporization rate of the above volatile substance can be appropriately controlled and the desired characteristics can be exhibited.

[0101] The sealed space of the above composition or fire extinguishing device may include, for example, a fire extinguishing agent as an additional component to ensure appropriate fire extinguishing function when necessary. When a fire extinguishing agent is included, the fire extinguishing agent may perform the function of promoting the carbonization of carbonizable organic matter described below and / or the function of promoting the generation of gas from gas-generating substances described below.

[0102] Since the above-mentioned extinguishing agent acts to promote the carbonization of the above-mentioned carbonizable organic matter, the above-mentioned extinguishing agent may also be called a carbonization catalyst.

[0103] As such a fire extinguishing agent, it may be appropriate to use one that has a solubility of a certain level or higher with respect to the above-mentioned volatile substance (e.g., a volatile substance such as water). By controlling the solubility, aggregation or phase separation phenomena within the composition are prevented, and the aforementioned carbonization or gas generation action can proceed more effectively.

[0104] For example, the lower limit of the solubility of the above-described extinguishing agent may be approximately 5 g, 10 g, 15 g, 20 g, 25 g, 30 g, 35 g, or 40 g, and the upper limit may be approximately 1000 g, 900 g, 800 g, 700 g, 600 g, 500 g, 400 g, 300 g, 200 g, 100 g, 90 g, 80 g, 70 g, 60 g, 50 g, 40 g, or 30 g. The above-described solubility may be within a range greater than or exceeding any of the lower limits described above; or within a range greater than or exceeding any of the lower limits described above and less than or equal to any of the upper limits described above. The above solubility is the maximum weight (g) of a fire extinguishing agent that can be dissolved in 100 g of water at 25°C, and this can be measured in the manner described in "10. Evaluation of Solubility".

[0105] As a fire extinguishing agent, one having the above solubility may be appropriately selected and used, examples of which include phosphoric acid, phosphate, phosphonate compound or phosphate compound. The fire extinguishing agent may be, for example, first or second ammonium phosphate, urea phosphate, guanyle urea phosphate, or ammonium polyphosphate, and one or more of the above may be selected and used.

[0106] The above-mentioned fire extinguishing agent may be present in the composition at an appropriate content considering the intended effect. For example, the lower limit of the weight ratio of the fire extinguishing agent relative to 100 parts by weight of the above-mentioned vaporizable substance may be approximately 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, or 20 parts by weight, and the upper limit may be approximately 100 parts by weight, 95 parts by weight, 90 parts by weight, 85 parts by weight, 80 parts by weight, 75 parts by weight, 70 parts by weight, 65 parts by weight, 60 parts by weight, 55 parts by weight, 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 25 parts by weight, 20 parts by weight, or 15 parts by weight. The ratio may be within a range lower than or equal to any of the upper limits described above; or within a range greater than or equal to any of the lower limits described above. Or it may be a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above.

[0107] The sealed space of the above composition or fire extinguishing device may include carbonized organic material as an additional component.

[0108] The above-mentioned carbonizable organic material is an organic material that carbonizes to form a carbonized material when exposed to a flame or heat at a predetermined temperature. The carbonized material formed by such an organic material is often porous and, accordingly, can possess a thermal insulation function. Therefore, when the composition or fire extinguishing device is exposed to heat generation, ignition, or explosion, the organic material can form an appropriate carbonized material to exhibit a thermal insulation function. For example, when applied together with the above-mentioned gas-generating material, porous carbonized materials can be formed more effectively through the action of the gas generated by the gas-generating material during the process in which the organic material forms carbonized material when exposed to heat generation, ignition, or explosion.

[0109] The carbonization action of the above-mentioned carbonizable organic matter can be induced or promoted by the aforementioned extinguishing agent. That is, the extinguishing agent decomposes at high temperatures to produce acid, salt, or ionic components, and these acid, salt, or ionic components can promote the carbonization action of the above-mentioned carbonizable organic matter through catalytic action.

[0110] As for the above-mentioned carbonizable organic material, any material that forms carbons when exposed to heat or flame may be applied without special restrictions.

[0111] Examples of such organic substances include sugars such as sorbitol or mannitol; polysaccharides such as starch or dextrins (e.g., maleated cyclodexdrin (MC) or metal salts of said MC); polyhydric alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, or THEIC (tris(hydroxyethyl)isocyanurate); cellulose; BSPPO (bi(4-methoxy-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octan-1-sulfide)phenylphosphate); lignin (alkali lignin or urea-modified liginin, etc.); melamine compounds such as methylol melamine; and phenol-formaldehyde. Examples may include, but are not limited to, resins (phenol-formaldehyde resins) and / or char-forming polymers such as PA6T (Poly-hexamethylene terephthalamide).

[0112] A representative material applicable as the above-mentioned carbonizable organic material is starch. Starch is relatively easy to obtain and can form suitable carbonized products when exposed to heat or flame.

[0113] The type of starch can be controlled in order to efficiently form the above carbonized material and to ensure that the formed carbonized material effectively exerts the desired digestion or thermal insulation effect.

[0114] For example, the above starch may be a starch containing amylose and amylopectin, with their ratio adjusted to an appropriate level. As is known, amylopectin and amylose are types of polysaccharides found mainly in plants, and among polysaccharides, starch is composed of amylose and amylopectin. Amylose consists of glucose molecules linked by α (1→4) glycosidic bonds and has a linear chain structure, whereas amylopectin has relatively short and highly branched chains. Amylose crystallizes relatively easily compared to amylopectin, and amylopectin has relatively high solubility in water compared to amylose.

[0115] The desired composition can be provided more efficiently by using starch in which amylose and amylopectin having the above characteristics are present in an appropriate ratio.

[0116] For example, in a starch containing the above amylose and amylopectin, the lower limit of the weight ratio of amylopectin relative to 100 parts by weight of the above amylose may be approximately 150 parts by weight, 200 parts by weight, 250 parts by weight, or 300 parts by weight, and the upper limit may be approximately 900 parts by weight, 850 parts by weight, 800 parts by weight, 750 parts by weight, 700 parts by weight, 650 parts by weight, 600 parts by weight, 550 parts by weight, 500 parts by weight, 450 parts by weight, 400 parts by weight, 350 parts by weight, or 300 parts by weight. The ratio is within a range lower than or equal to any of the upper limits described above; or within a range greater than or equal to any of the lower limits described above. Alternatively, it may be within a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above. The ratio of amylose to amylopectin may be measured according to the method described in "8. Measurement of content of amylopectin and amylose" of the Examples section of this specification.

[0117] As the above starch, starch having a molecular weight, for example, a weight-average molecular weight (Mw), within a predetermined range may be used.For example, the lower limit of the weight-average molecular weight of the above starch is 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, 550,000 g / mol, 600,000 g / mol, 650,000 g / mol, 700,000 g / mol, 750,000 g / mol, 800,000 g / mol, 850,000 g / mol, 900,000 g / mol, 950,000 g / mol, 1,000,000 g / mol, 1,500,000 g / mol, 2,000,000 g / mol, 2,500,000 g / mol, 3,000,000 g / mol, 3,500,000 g / mol, 4,000,000 g / mol, 4,500,000 g / mol, 5,000,000 g / mol, 5,500,000 g / mol, 6,000,000 g / mol, 6,500,000 g / mol, 7,000,000 g / mol, 7,500,000 g / mol, 8,000,000 g / mol, 8,500,000 g / mol, 9,000,000 g / mol, 9,500,000 g / mol, 10,000,000 g / mol, 20,000,000 g / mol, It may be approximately 30,000,000 g / mol, 40,000,000 g / mol, or 50,000,000 g / mol, and the upper limit is 1,000,000,000 / mol, 900,000,000 / mol, 800,000,000 / mol, 700,000,000 / mol, 600,000,000 / mol, 500,000,000 / mol, 400,000,000 / mol, 300,000,000 / mol, 200,000,000 / mol, 150,000,000 / mol, 100,000,000 / mol, 90,000,000 / mol, 80,000,000 It can be about 70,000,000 / mol or 60,000,000 / mol.The above molecular weight may be within a range below or less than any of the upper limits described above; or within a range above or greater than any of the lower limits described above; or above or greater than any of the lower limits described above and below or less than any of the upper limits described above. Starch having the above molecular weight (Mw) can form a carbonized material having a desired function (e.g., thermal insulation) more effectively when exposed to heat or flame. Such molecular weight may be measured in the manner described in “7. Measurement of Molecular Weight” of the Examples section of this specification.

[0118] When included, the lower limit of the weight ratio of the carbonizable organic material relative to 100 parts by weight of the vaporizable material may be approximately 0.01 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 9.5 parts by weight, or 10 parts by weight, and the upper limit may be 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 29 parts by weight, 28 parts by weight, 27 parts by weight, 26 parts by weight, 25 parts by weight, 24 parts by weight, 23 parts by weight, 22 parts by weight, 21 parts by weight, 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, 12 The amount may be approximately 11 parts by weight, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, or 5 parts by weight. The above ratio may be within a range below or less than any of the upper limits described above; or within a range above or greater than any of the lower limits described above; or within a range above or greater than any of the lower limits described above and below or less than any of the upper limits described above. Carbonizable organic material included in such a ratio can effectively form carbons within the composition when necessary, and can enable the composition as a whole to have excellent handling and storage stability.

[0119] The sealed space of the above composition or fire extinguishing device may also include a gas-generating material as an additional component. The gas-generating material that may be included in the composition is a substance that generates gas when exposed to heat or flame. The gas generated in this way may act to directly extinguish the heat or flame, and may also perform the function of making the charred material more porous during the process of forming the charred material by the carbonizable organic material.

[0120] The action of such gas-generating substances can be induced or promoted by the aforementioned fire extinguishing agent. That is, the fire extinguishing agent decomposes at high temperatures to produce acid, salt, or ionic components, and these acid, salt, or ionic components can promote the generation of gas by the gas-generating substances.

[0121] The type of gas generated by the above gas generating material is not particularly limited as long as it is a non-flammable gas, and may be, for example, nitrogen gas, carbon dioxide and / or water vapor.

[0122] Various substances that generate the above gases are known. For example, substances that generate the above nitrogen gas may be exemplified as melamine, guanidine, urea, melamine pyrophosphate, dicyandiamide, guanyleurea phosphate, and glycine, substances that generate carbon dioxide may be exemplified as potassium bicarbonate, sodium bicarbonate, calcium bicarbonate, and magnesium bicarbonate, and substances that generate water vapor may be exemplified as calcium hydroxide, magnesium dihydroxide, and aluminum trihydroxide, but the substances applicable in this application are not limited to these.

[0123] As a gas generating material, one type or a mixture of two or more types selected from the types described above may be used.

[0124] To produce an appropriate effect, the above gas generating material may be a substance that generates nitrogen gas, for example, melamine, guanidine, urea, melamine pyrophosphate and / or guanyleurea phosphate. These materials are advantageous in that they more effectively exert a foaming effect on the carbonized material during the process of the carbonized organic material forming the carbonized material, thereby effectively forming the desired porous carbonized material.

[0125] When included, the lower limit of the weight ratio of the gas generating substance relative to 100 parts by weight of the vaporizable substance may be approximately 0.01 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, or 40 parts by weight, and the upper limit may be approximately 100 parts by weight, 95 parts by weight, 90 parts by weight, 85 parts by weight, 80 parts by weight, 75 parts by weight, 70 parts by weight, 65 parts by weight, 60 parts by weight, 55 parts by weight, 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 The amount may be approximately 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, 8 parts by weight, or 7 parts by weight. The above ratio may be within a range below or less than any of the upper limits described above; or within a range above or greater than any of the lower limits described above; or within a range above or greater than any of the lower limits described above and below or less than any of the upper limits described above. The gas-generating material included in such a ratio can exhibit an effective suppression effect against heat or flame and a porous carbon formation effect when necessary, and the composition as a whole can have excellent handling and storage stability.

[0126] The above composition may include an absorbent polymer as an additional component.

[0127] An absorbent polymer is a polymer that has the property of being able to absorb water. In one example, the absorbent polymer may be a so-called hydrogel polymer or hydrogel, which is generally defined as a cross-linked hydrophilic polymer. Such a polymer is also known as a Super Absorbent Polymer (SAP).

[0128] The above-mentioned absorbent polymer is a material capable of absorbing moisture tens to thousands of times its own weight. Such a material enables the composition to exist in a gel state as a whole, thereby ensuring handling and storage stability.

[0129] There are no specific restrictions on the type of absorbent polymer mentioned above, and any polymer that can generally be applied as an SAP can be used without restriction.

[0130] Typically, a polyacrylate-based vinyl polymer is used as the above material. The polyacrylate-based polymer mentioned above is a polymer prepared from acrylate-based monomers, and if necessary, other comonomers may be additionally used to form the polymer.

[0131] The absorption properties of the above-mentioned absorbent polymer can be controlled so that it can exhibit suitable characteristics.

[0132] For example, the lower limit of the centrifugal retention capacity (CRC) of the above absorbent polymer according to the EDANA (European Disposables and Nonwovens Association) method WSP 241.3 may be approximately 12 g / g, 13 g / g, 14 g / g, 15 g / g, 16 g / g, 17 g / g, 18 g / g, 19 g / g, 20 g / g, 21 g / g, 22 g / g, 23 g / g, 24 g / g, 25 g / g, 26 g / g, 27 g / g, 28 g / g, 29 g / g, 30 g / g, 31 g / g, 32 g / g, or 33 g / g, and the upper limit may be approximately 60 g / g, 55 g / g, 50 g / g, 45 g / g, 40 It may be g / g or approximately 35 g / g. The above retention capacity (CRC) may be within a range below or less than any of the upper limits described above; or within a range above or greater than any of the lower limits described above; or within a range above or greater than any of the lower limits described above and below or less than any of the upper limits described above. The above retention capacity (CRC) may be evaluated in the manner described in "5. CRC (Centrifuge Retention Capacity)" of the Examples section of this specification.

[0133] For example, the lower limit of the pressure absorption capacity (AUP) of the above-mentioned absorbent polymer at 0.3 psi according to the EDANA (European Disposables and Nonwovens Association) method WSP 242.3 may be approximately 4 g / g, 6 g / g, 8 g / g, 10 g / g, 12 g / g, 14 g / g, 16 g / g, 18 g / g, 20 g / g, 22 g / g, 24 g / g, 26 g / g, 27 g / g, or 28 g / g, and the upper limit may be approximately 40 g / g, 38 g / g, 36 g / g, 34 g / g, 32 g / g, or 30 g / g. The above-mentioned absorption capacity (AUP) is within a range less than or equal to any one of the upper limits described above; Or within a range greater than or equal to any of the lower limits described above; or within a range greater than or equal to any of the lower limits described above and less than or equal to any of the upper limits described above. The absorption capacity (AUP) may be evaluated in the manner described in "6. AUP (Absorption Under Pressure)" of the Examples section of this specification.

[0134] An absorbent polymer having such absorption capacity as described above can be combined with other components of the above composition to exhibit desired characteristics.

[0135] In one example, the absorbent polymer may be a particulate polymer, wherein the lower limit of the average particle size of the absorbent polymer may be approximately 10 μm, 50 μm, 100 μm, or 140 μm, and the upper limit may be approximately 1000 μm, 950 μm, 900 μm, 850 μm, 800 μm, 750 μm, 700 μm, 650 μm, 600 μm, 550 μm, 500 μm, 450 μm, 400 μm, 350 μm, 300 μm, 250 μm, or 200 μm. The average particle size is within a range less than or equal to any of the upper limits described above; or within a range greater than or equal to any of the lower limits described above. Or it may be within a range greater than or equal to any of the lower limits described above and less than or equal to any of the upper limits described above. Such average particle size may be measured according to the method specified in NWSP 210.0.R2(15).

[0136] When included, the lower limit of the weight ratio of the absorbent polymer relative to 100 parts by weight of the volatile material may be approximately 0.01 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, and the upper limit may be 50 parts by weight, 45 parts by weight, 40 parts by weight, 35 parts by weight, 30 parts by weight, 29 parts by weight, 28 parts by weight, 27 parts by weight, 26 parts by weight, 25 parts by weight, 24 parts by weight, 23 parts by weight, 22 parts by weight, 21 parts by weight, 20 parts by weight, 19 parts by weight, 18 parts by weight, 17 parts by weight, 16 parts by weight, 15 parts by weight, 14 parts by weight, 13 parts by weight, 12 parts by weight, 11 parts by weight, 10 The ratio may be in parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, or 2 parts by weight. The ratio may be within a range below or less than any of the upper limits described above; or within a range above or greater than any of the lower limits described above; or within a range above or greater than any of the lower limits described above and below or less than any of the upper limits described above.

[0137] The composition includes the above components and may include additional components if necessary.

[0138] For example, the above composition may additionally include a buffer.

[0139] Referring to FIGS. 2 and 3, heat may be applied to the fire extinguishing device in an abnormal state, and additionally, instantaneous high pressure may be applied. For example, in a structure like FIG. 1, if a battery cell (12, 13, 14, 15) adjacent to the fire extinguishing device (100) explodes or expands rapidly, high pressure is applied to the fire extinguishing device (100). If the fire extinguishing device (100) contracts instantaneously due to the pressure applied in this way, the vaporizable material inside may be discharged to the outside before it can vaporize, and such discharge may reduce the efficiency of the fire extinguishing operation.

[0140] The above buffer can act as a buffer against pressure applied instantaneously as described above, and as a result, can allow sufficient vaporization of the internal vaporizable substance to occur.

[0141] In addition, the buffer may also serve to support volatile substances depending on the case. That is, as described below, if the buffer has porosity or is in the form of a woven fabric, non-woven fabric, or felt, the buffer may exhibit the characteristic of absorbing or supporting volatile substances.

[0142] There are no special restrictions on the type of buffer as long as it can perform the above function, and, for example, one having an appropriate density and / or pyrolysis temperature may be used.

[0143] For example, the upper limit of the density of the buffer may be approximately 1.5, 1.3, 1.1, 0.9, 0.7, 0.5, 0.3, 0.1, 0.08, 0.06, or 0.04, and the lower limit may be approximately 0.001, 0.005, 0.01, 0.05, 0.1, or 0.15. The density may be within a range lower than or less than any of the upper limits described above; or within a range greater than or exceeding any of the lower limits described above; or within a range greater than or exceeding any of the lower limits described above while being lower than or less than any of the upper limits described above. The unit of the density is g / cm³ 3 am.

[0144] For example, the upper limit of the thermal decomposition temperature of the buffer may be approximately 2,000°C, 1,800°C, 1,600°C, 1,400°C, 1,200°C, 1,000°C, 900°C, 800°C, 600°C, 500°C, or 400°C, and the lower limit may be approximately 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, or 800°C. The thermal decomposition temperature is within a range lower than or equal to any of the upper limits described above; or within a range greater than or equal to any of the lower limits described above. Alternatively, it may be within a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above. A method for measuring the pyrolysis temperature is described in "11. Pyrolysis Temperature" of the Examples section of the specification.

[0145] As a buffer, any known material may be used without special limitations as long as it has the above density and / or pyrolysis temperature. For example, as a buffer, known glass fibers, ceramic fibers, and / or mineral fibers known as insulating materials may be used. These inorganic fibers may be in the form of woven or non-woven fabrics, such as porous films, porous sheets, porous foils, wool, or felt.

[0146] In addition, as a cushioning material, for example, woven fabrics, nonwoven fabrics, or felts made of inorganic foam such as various metal foams, glass wool, mineral wool, glass fibers, or mineral fibers, or foams, woven fabrics, nonwoven fabrics, or felts formed of carbonized organic materials described later may also be used.

[0147] As a buffer, any one type or a combination of two or more types selected from the above various types may be used.

[0148] The size of the buffer is determined according to the size of the sealed space, and there are no specific limitations. For example, if the buffer is in the form of the aforementioned porous film, porous sheet, porous foil, wool, woven fabric, nonwoven fabric, or felt, the lower limit of the thickness of the buffer may be approximately 0.1 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm, or 2.5 mm, and the upper limit may be approximately 20 mm, 15 mm, 10 mm, 9 mm, 8 mm, 7 mm, 6 mm, 5 mm, 4 mm, or 3 mm. The thickness may be within a range below or less than any of the upper limits described above; or within a range above or greater than any of the lower limits described above; or within a range above or greater than any of the lower limits described above and below or less than any of the upper limits described above.

[0149] The above composition can exhibit unique physical properties through a combination of the aforementioned components.

[0150] For example, the above composition may exhibit a generally controlled freezing point. For example, the lower limit of the freezing point of the above composition may be approximately -50°C, -45°C, -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, or -10°C, and the upper limit may be approximately 10°C, 8°C, 6°C, 4°C, 2°C, 0°C, -5°C, -10°C, -15°C, -20°C, -25°C, -30°C, -35°C, or -40°C. The freezing point may be within a range lower than or less than any of the upper limits described above; or within a range greater than or greater than any of the lower limits described above; or within a range greater than or greater than any of the lower limits described above and lower than or less than any of the upper limits described above.

[0151] The above composition may have a controlled viscosity and / or thixotropic index.

[0152] For example, the lower limit of the viscosity of the above composition may be approximately 30,000 cP, 40,000 cP, 50,000 cP, 60,000 cP, 70,000 cP, 80,000 cP, 90,000 cP, 100,000 cP, 110,000 cP, 120,000 cP, 130,000 cP, 140,000 cP, 150,000 cP, or 155,000 cP, and the upper limit may be approximately 600,000 cP, 550,000 cP, 500,000 cP, 450,000 cP, 400,000 cP, 350,000 cP, 300,000 cP, The viscosity may be approximately 250,000 cP, 200,000 cP, 150,000 cP, 100,000 cP, 90,000 cP, 80,000 cP, or 70,000 cP. The viscosity may be within a range below or less than any of the upper limits described above; or within a range above or greater than any of the lower limits described above; or within a range above or greater than any of the lower limits described above and below or less than any of the upper limits described above. This viscosity is a value measured at room temperature (about 25°C) and a rotational speed of 0.5 rpm.

[0153] For example, the lower limit of the thixotropic index of the above composition may be approximately 2, 4, 6, 8, 10, or 10.5, and the upper limit may be approximately 20, 18, 16, 14, 12, 10, 8, or 6. The thixotropic index may be within a range lower than or less than any of the upper limits described above; or within a range greater than or greater than any of the lower limits described above; or within a range greater than or greater than any of the lower limits described above and lower than or less than any of the upper limits described above. This thixotropic index is a value obtained by dividing the viscosity measured at room temperature (about 25°C) and a rotational speed of 0.5 rpm by the viscosity measured at room temperature (about 25°C) and a rotational speed of 5 rpm.

[0154] A composition having the above viscosity and / or thixotropic index can exhibit excellent handling properties and storage stability.

[0155] The above composition may exhibit a specific latent heat characteristic. Latent heat is typically defined as the amount of heat required for a substance to undergo a phase transition without a change in temperature. However, when the above composition exhibits the said latent heat, it is not necessary for the entire composition to undergo a phase transition. The said latent heat may be generated during the process of a phase transition of at least a part of the composition or a component included in the composition.

[0156] In the above, the statement that the composition exhibits latent heat means that the composition exhibits an endothermic peak within a predetermined temperature range in Differential Scanning Calorimeter (DSC) analysis. The method for conducting the DSC is described in "4. Measurement of Latent Heat" of the Examples section. The process by which the composition exhibits the latent heat may be an isothermal process or a similar process. Therefore, the composition can be applied to a heat-generating product to control the heat while maintaining a uniform temperature of the product, and can minimize or prevent the impact of abnormal heat generation, explosion, and / or ignition occurring in one product on adjacent products.

[0157] The lower limit of the latent heat exhibited by the above composition may be, for example, approximately 500 J / g, 550 J / g, 600 J / g, 650 J / g, 700 J / g, 750 J / g, 800 J / g, 850 J / g, 900 J / g, 950 J / g, 1000 J / g, 1100 J / g, 1200 J / g, or 1300 J / g, and the upper limit may be approximately 3000 J / g, 2800 J / g, 2600 J / g, 2400 J / g, 2200 J / g, 2000 J / g, 1800 J / g, 1600 J / g, 1400 J / g, 1200 J / g, 1000 J / g, or 900 J / g The latent heat may be of a certain degree. The latent heat may be within a range lower than or less than any of the upper limits described above; or within a range greater than or greater than any of the lower limits described above; or within a range greater than or greater than any of the lower limits described above and lower than or less than any of the upper limits described above.

[0158] The lower limit of the range of on-set temperatures at which the above composition begins to exhibit the latent heat may be, for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C, and the upper limit may be 200°C, 180°C, 160°C, 140°C, 120°C, 100°C, 90°C, or 80°C. The above on-set temperature may be within a range lower than or equal to any of the upper limits described above; or within a range greater than or equal to any of the lower limits described above; or within a range greater than or equal to any of the lower limits described above while being lower than or equal to any of the upper limits described above. The above on-set temperature refers to the temperature of the left on-set point of the endothermic peak section of the DSC analysis.

[0159] The lower limit of the temperature range exhibiting the latent heat of the above composition may be, for example, approximately 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, or 180°C, and the upper limit may be approximately 300°C, 280°C, 260°C, 240°C, 220°C, 200°C, 180°C, or 160°C. The temperature range is within a range lower than or equal to any of the upper limits described above; or within a range greater than or equal to any of the lower limits described above. Alternatively, it may be within a range greater than or equal to any of the lower limits described above, and less than or equal to any of the upper limits described above. The temperature range is the value obtained by subtracting the temperature of the left on-set point from the temperature of the right on-set point of the endothermic peak range of the DSC analysis.

[0160] Through the above characteristics, the composition can be applied to various uses and effectively respond to heat generation, ignition, and / or explosion occurring in each use.

[0161] The freezing point, viscosity, thixotropic index, and latent heat properties of the above-described composition can be obtained through a combination of the components of each of the above-described compositions.

[0162] In addition, the above composition may further include various types of known additives, provided that the aforementioned physical properties are not compromised.

[0163] For example, the aforementioned extinguishing device can be manufactured by loading the above-described vaporizable substance or the above-described composition into a sealed space inside the above-described case.

[0164] This specification also discloses electronic equipment or devices to which the fire extinguishing device is applied.

[0165] The type of electronic equipment or device is not particularly limited. For example, the above composition or fire extinguishing device may be applied to equipment or devices, etc., where there is a risk of abnormal heat generation, ignition, and / or explosion during operation, maintenance, and / or storage, and such abnormal phenomena must be controlled.

[0166] Examples of the above equipment or devices include, but are not limited to, batteries. In particular, for battery modules composed of multiple battery cells, it is important to prevent abnormal heat generation, ignition, and / or explosion occurring in one battery cell from propagating to adjacent battery cells.

[0167] Accordingly, the present specification discloses a battery module or battery pack, etc., including the above-mentioned fire extinguishing device.

[0168] Such battery modules, etc., may basically include a plurality of battery cells; and a fire extinguishing device disposed between the battery cells.

[0169] As long as the above-mentioned fire extinguishing device is applied, the specific configuration of the battery module, etc., such as the type of battery cell, etc., is not particularly limited, and known materials may be used. For example, known pouch-type, prismatic, or cylindrical battery cells may be used as the battery cell.

[0170] The method of manufacturing the above battery module is not particularly limited, and, for example, a method may be used in which a fire extinguishing device, such as the shape of a battery cell as described above, is manufactured and then the fire extinguishing device is positioned at a necessary location during the manufacturing process of the battery module. Effects of the invention

[0171] This specification discloses compositions, fire extinguishing devices, and their uses. The compositions and fire extinguishing devices may be applied to products that are likely to generate abnormal heat, ignition, and / or explosion during operation, storage, and / or maintenance, and may effectively respond to said heat, ignition, and explosion. The compositions and fire extinguishing devices may be applied, for example, to articles containing multiple said products to respond to abnormal heat, explosion, and / or ignition occurring in any one of the products and to prevent the propagation of such heat, explosion, and / or ignition to adjacent other products. The compositions and fire extinguishing devices also possess excellent handling and storage stability. This specification also discloses the uses of said compositions and fire extinguishing devices. Brief explanation of the drawing

[0172] FIG. 1 is an exemplary cross-sectional view of a battery module with a fire extinguishing device applied. Figure 2 is an exemplary diagram illustrating the operating principle of a fire extinguishing device. Figure 3 is an exemplary diagram illustrating the operating principle of a fire extinguishing device. Figure 4 is a diagram illustrating the process of manufacturing a fire extinguishing device in an embodiment. Figure 5 is a diagram illustrating the process of manufacturing a fire extinguishing device in an embodiment. FIG. 6 is a drawing showing one exemplary form of a case applied in the embodiment. Specific details for implementing the invention

[0173] The above composition and fire extinguishing device, etc. will be described in detail with reference to the following examples, but the scope of the above composition and fire extinguishing device, etc. is not limited by the following examples.

[0175] 1. Convection test

[0176] A fire extinguishing device of an example or comparative example is positioned between two aluminum plates, and an insulating material is laminated onto one of the two aluminum plates to manufacture a laminate in which the insulating material, the aluminum plate, the fire extinguishing device, and the aluminum plate are sequentially laminated. As the aluminum plate, a plate with a thickness of approximately 3 mm was used, and as the insulating material, mineral wool (KCC, Insulation Board No. 1) with a thickness of approximately 2 mm was used. Subsequently, both sides of the laminate were fixed by compressing them with a jig at a pressure of approximately 350 kPa. Then, a temperature sensor (k-type thermocoupler, Fluke IR thermometers Model 566) was positioned on the insulating side of the laminate, and the temperature was measured using the temperature sensor while applying a flame toward the aluminum plate on the opposite side. The flame was applied at a distance of approximately 2 inches from the aluminum plate using two butane gas canisters (220 g capacity can-type butane gas (unused product)) and a torch. The temperature was measured with the temperature sensor while applying the flame for about 5 minutes, and evaluated according to the following criteria.

[0177] <Evaluation Criteria>

[0178] PASS: When the temperature measured by the temperature sensor is maintained below 200℃

[0179] NG: If a temperature of 200℃ or higher is measured by the temperature sensor, or if melting of the aluminum plate is observed.

[0181] 2. Chain Ignition Test

[0182] Rectangular batteries were arranged side by side at a interval of approximately 3 mm, and a fire extinguishing device was positioned between them. CATL products (120 Ah, 3.2 V, size = thickness × width × depth = 48 × 174 × 165) were used as the prismatic batteries, and the test was conducted in a 100% charged state. In the above arrangement, ignition was induced in one prismatic battery according to the SAE J2464:2009 standard, and the occurrence of chain ignition in other cells was checked. Ignition of the battery was induced by penetrating the prismatic battery with a nail having a diameter of approximately 5 mm at a speed of 25 mm / sec (Nail Penetration method).

[0183] <Evaluation Criteria>

[0184] PASS: Cases where ignition does not occur in battery cells other than the one penetrated by the nail

[0185] NG: Case where ignition occurs in a battery cell other than the one penetrated by the nail

[0187] 3. Storage Stability Evaluation

[0188] The fire extinguishing device was stored in an oven at a temperature of approximately 35°C for 1,000 hours, and the weight change before and after storage in the oven was measured. If the weight change before and after storage was 1% or more, it was evaluated as NG, and if it was less than 1% or there was no weight change, it was evaluated as PASS.

[0190] 4. Measurement of latent heat

[0191] Approximately 3 to 5 mg of the composition of the example or comparative example was taken and loaded into a measuring device. A Differential Scanning Calorimeter (DSC) (TA instrument, Q200 model) was used as the measuring device. The temperature range for evaluating latent heat was set from 25°C to 300°C. The endothermic peak was measured while increasing the temperature from 25°C to 300°C at a rate of approximately 20°C / min. The left on-set point and the right on-set point of the endothermic peak range were designated as the start and end of the phase transition, and the latent heat (unit: J / g) was calculated by integrating the corresponding range.

[0193] 5.CRC(Centrifuge Retention Capacity)

[0194] CRC was measured according to EDANA WSP 241.3. Approximately 0.2 g (W0) of absorbent polymer was placed in a nonwoven bag, sealed, and then immersed in physiological saline at room temperature. An aqueous NaCl solution with a concentration of 0.9 wt% was used as the physiological saline. The condition was maintained for about 30 minutes, and after removing moisture from the bag for 3 minutes at 250 G using a centrifuge, the mass (g, W2) of the bag was measured.

[0195] The same operation was performed on the same nonwoven fabric bag that does not contain an absorbent polymer, and the mass (g, W1) was measured.

[0196] The CRC(g / g) was calculated by substituting the measurement results into Equation A below.

[0197] The above evaluation was conducted under constant temperature and humidity conditions (23±1℃, relative humidity: 50±10%).

[0198] [Equation A]

[0199] CRC (g / g) = {[W2(g) - W1(g)] / W0(g)} - 1

[0201] 6. Absorption Under Pressure (AUP)

[0202] AUP was measured according to the EDANA method WSP 242.3. A stainless steel 400 mesh wire mesh was mounted on the bottom of a plastic cylinder with an inner diameter of approximately 60 mm, and 0.0 g (W0) (0.90 g) of absorbent polymer was uniformly spread over the wire mesh. Then, a piston capable of uniformly applying a load of 0.3 psi was installed on top of it. The piston was installed with an outer diameter slightly smaller than 60 mm, with no gap between it and the inner wall of the cylinder, and was installed to be able to move up and down. The weight (g, W3) of the device was measured.

[0203] A glass filter with a diameter of 90 mm and a thickness of 5 mm was placed on the inside of a petroleum dish with a diameter of 150 mm, and physiological saline solution was added to the same level as the top surface of the glass filter. An aqueous NaCl solution with a concentration of 0.9 wt% was used as the physiological saline solution. A sheet of filter paper with a diameter of 90 mm was placed on top of it. The measuring device was placed on the filter paper, and the physiological saline solution was absorbed for 1 hour under a load of 0.3 psi. Afterward, the measuring device was lifted, and its weight (g, W4) was measured.

[0204] The obtained value was substituted into Equation B below to evaluate AUP(g / g).

[0205] The above evaluation was conducted under constant temperature and humidity conditions (23±1℃, relative humidity: 50±10%).

[0206] [Equation B]

[0207] AUP(g / g) = [W4(g) - W3(g)] / W0(g)

[0209] 7. Measurement of molecular weight

[0210] The molecular weight of starch was evaluated in the following manner.

[0211] (1) Preparation of the mobile phase

[0212] Mobile phase A was prepared by filtering 1000 mL of a 150 mM NaNO3 aqueous solution containing 0.02 wt% NaN3 using a solvent clarification system (Millipore Millisolve Kit, MilliporeSigma).

[0213] (2) Preparation of sample solution

[0214] 25 mg of the sample to be measured for molecular weight was mixed with 5 mL of a 150 mM aqueous solution of NaNO3 containing 0.02 wt% NaN3, heated at 80°C for 20 hours, and then filtered through a 0.4 μm Nylon Syringe Filter to prepare a sample solution.

[0215] (3) GPC (Gel Permeation Chromatography) / MALS (Multi-Anglue Light Scattering Detection) conditions

[0216] The molecular weight was evaluated using the above sample solution and mobile phase A in the following manner.

[0217] Measuring instrument: Agilent GPC (Agilent 1200 series, US)

[0218] Stationary phase: Shodex OH-Pak 804 column and Shodex OH-Pak 80 column connection

[0219] Mobile phase: A; 0.02% NaN3, 150 mM NaNO3 aqueous solution = 100(v / v %)

[0220] Flow rate: 0.4 mL / min

[0221] Stationary bed temperature: 25℃

[0222] Injection volume: 100 μl (0.45 μm filtered)

[0223] Analysis time: 120 minutes

[0225] 8. Measurement of Amylopectin and Amylose Content

[0226] The content of amylopectin and amylose in starch was evaluated according to the method described in the paper (Potato Research 31 (1988) 241-246).

[0227] First, about 5 mg of the sample starch was dissolved in about 1 mL of sterile water to prepare the sample (Step 1), and heated in a water bath at 95°C for about 15 minutes (Step 2).

[0228] Next, about 20 μl of the above sample was placed in a cuvette (step 3), about 980 μl of iodine solution was added, and mixed (step 4).

[0229] Next, the absorbance of the sample mixed with the iodine solution at wavelengths of 525 nm and 700 nm was measured and recorded (Step 5). The absorbance was measured using the OPTIZEN POP model from KLAB.

[0230] About 20 μl of water was placed in another cuvette, 980 μl of iodine solution was added, and mixed (Step 6). For the solution from Step 6, the absorbance at wavelengths of 525 nm and 700 nm was measured and recorded, respectively, in the same manner as in Step 5 (Step 7).

[0231] The absorbance obtained in Step 7 was subtracted from the absorbance obtained in Step 5, and the ratio (%) of amylose was determined according to the following formula C (Step 8).

[0232] [Equation C]

[0233]

[0234] In Equation C, PA is the percentage of amylose (%), and OD 700 is the value obtained by subtracting the absorbance at a wavelength of 700 nm measured in Step 7 from the absorbance at a wavelength of 700 nm measured in Step 5 above, and OD 525is the value obtained by subtracting the absorbance at a wavelength of 525 nm measured in step 7 from the absorbance at a wavelength of 525 nm measured in step 5 above.

[0236] 9. WVTR (Water Vapor Transmission Rate) Evaluation

[0237] The WVTR of the case was evaluated according to ASTM F1249 standards under conditions of 38°C and 100% relative humidity.

[0239] 10. Solubility Evaluation

[0240] Solubility was evaluated based on ASTM E1148-02 standards. Solubility was confirmed by evaluating the maximum amount of sample dissolved in 100 g of a volatile substance (water) at 0°C or room temperature (approx. 25°C) according to the above standards.

[0242] 11. Pyrolysis temperature

[0243] The pyrolysis temperature was determined by TGA (Thermogravimetric Analysis). Using a Mettler-Toledo TGA e850 instrument, the temperature of the sample was increased from approximately 20°C at a rate of 5°C / min in an N2 flow atmosphere, and the point at which the weight loss exceeded 5% was defined as the pyrolysis temperature.

[0245] 12. Flammability Assessment

[0246] The flammability of the freezing point modifier was evaluated according to ASTM D93 standards. An ignition source was placed in a 100 mL brass test cup to fill approximately 90% of the cup's volume, stirred at a rate of about 100 revolutions / min, and the ignition source diameter was set to approximately 3.2 mm to 4.8 mm. The flash point was evaluated while increasing the temperature at a rate of 5°C / min. During the evaluation, if the sample vaporized without igniting, it was evaluated as non-flammable; if it ignited, the temperature at the time of ignition was defined as the flash point.

[0248] 13. Assessment of toxic gas generation

[0249] The presence of toxic gases was evaluated using length-of-stain colorimetric dosimeters in accordance with ASTM D4599-21. These length-of-stain colorimetric dosimeters are tubes capable of measuring concentration based on color, with specific measuring tubes designated for each toxic gas. Gas samples generated from the target substance were collected for approximately one minute and quantified. After injecting the sample into the open end of the length-of-stain colorimetric dosimeters using a 100ml syringe and maintaining the sample for about eight hours, the concentration of each gas was measured. The toxic gases measured by this method were chlorine gas, ammonia gas, and hydrofluoric acid gas.

[0251] 14. Flammability

[0252] A fire extinguishing composition was placed in an aluminum can, and its flammability was evaluated. The aluminum can used was manufactured with an open top using aluminum foil approximately 3 mm thick. The width and length of the can were approximately 9 cm and 12 cm, respectively, and the internal volume was approximately 32.4 cm³. 3 The composition was filled into the interior of the can, and a flame was applied vertically to one side of the can with the top open, at a distance of about 1 inch. The flame was applied using butane gas (220 g capacity can-type butane gas (unused product)) and a torch. Ignition was evaluated by observing whether a flame occurred on the open top while applying the flame for about 5 minutes.

[0254] 15. Thermal Conductivity Evaluation

[0255] Thermal conductivity was evaluated at 20°C using a measuring instrument (Hot Disk, TPS2200) in accordance with ISO22007-2 standards.

[0257] Example 1.

[0258] Fire extinguishing composition

[0259] Water (W) and a freezing point regulator (ethylene glycol (molar mass: 62.07 g / mol)) (E) were mixed in a weight ratio of 60:40 (W:E). The mixing was performed for approximately 30 minutes at room temperature (approx. 25°C) under conditions of 300 rpm. The ethylene glycol has a flash point of approximately 111°C, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas, measured according to the toxic gas evaluation method, are all 0 ppm. Additionally, the ethylene glycol was miscible with water. Subsequently, the mixture was placed in a sealed container, glass wool was placed in the sealed container, and the mixture was impregnated onto the glass wool by maintaining the container at room temperature (approx. 25°C) for approximately 24 hours to prepare a fire extinguishing composition. The glass wool used had a thickness of approximately 2.5 mm and a density of approximately 0.03 g / cm³. 3 Glass wool (Glass wool blanket, Rosewool) was used, which has a thermal decomposition temperature of about 400℃.

[0261] fire extinguishing device

[0262] A fire extinguishing device was manufactured by placing the above composition inside a can (case) used in the manufacture of prismatic batteries and sealing the opening. The WVTR of the can used in the prismatic batteries is approximately 0.11 g / m². 2·It was about a day. As shown in FIG. 4, a fire extinguishing device was manufactured by inserting two heat-conducting layers (2001, 2002) into the interior of the aluminum can (1001), injecting the composition (glass wool containing the mixture) (300) between the heat-conducting layers (2001, 2002), and then covering it with a lid (1002). When manufacturing the fire extinguishing device, the composition was injected so that it filled at least 90% of the volume of the empty space inside the can. As for the heat-conducting layers (2001, 2002), a copper film (thickness about 18 μm) with a thermal conductivity of about 401 W / m·K (at 20°C) was used. In cases where the fire extinguishing composition is not in the form of a sheet such as glass wool containing the mixture as described above, the fire extinguishing device can also be manufactured by placing two heat-conducting layers (2001, 2002) in a case as shown in FIG. 5 and injecting the composition between the heat-conducting layers. For the case for the prismatic battery, a case with a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm was used.

[0264] Example 2.

[0265] Fire extinguishing composition

[0266] A fire extinguishing composition was prepared in the same manner as in Example 1, except that water (W) and ethylene glycol (molar mass: 62.07 g / mol) (E) were mixed in a weight ratio (W:E) of 72:28.

[0268] fire extinguishing device

[0269] As a case for prismatic batteries, it is manufactured from aluminum and has a WVTR of approximately 0 g / m² 2· A fire extinguishing device was manufactured in the same manner as in Example 1, except that a case of about one day was used.

[0271] Example 3.

[0272] Fire extinguishing composition

[0273] Water (W), potassium acetate (K) (molar mass: 98.15 g / mol) (CH3COOK), and starch (S) were mixed in a weight ratio of 55:36:10 (W:K:S). Corn starch was used as the starch, having a weight-average molecular weight of approximately 51,000,000 g / mol and a weight ratio of amylose to amylopectin (amylose:amylopectin) of approximately 25:75. The potassium acetate, which acts as a freezing point regulator, is a non-flammable substance that does not have a flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method were all 0 ppm, indicating that it was a non-toxic substance. In addition, the solubility of the above-mentioned freezing point regulator, potassium acetate, in 100 g of water at 0°C is approximately 216 g, and the solubility in 100 g of water at 25°C is approximately 268.6 g. Subsequently, the above mixture is placed in a sealed container, and additionally, mineral wool (thickness: approximately 2.5 mm, density: approximately 0.2 g / cm³) is placed in the sealed container. 3 After adding the mineral wool insulation board (KCC, Mineral Wool Insulation Board No. 1) (pyrolysis temperature: approximately 800℃), the mixture was impregnated in the mineral wool by maintaining it at room temperature (approx. 25℃) for approximately 24 hours to prepare a fire extinguishing composition.

[0275] Fire extinguishing device

[0276] A can (case) used in the manufacture of prismatic batteries, with a WVTR of approximately 0.27 g / m² 2· A fire extinguishing device was manufactured in the same manner as in Example 1 using a can of about 1 day. In this process, aluminum foil with a thermal conductivity of about 234 W / mK (at 20℃) and a thickness of about 50 μm was used as the thermal conductive layer.

[0278] Example 4.

[0279] Fire extinguishing composition

[0280] A first mixture was prepared by mixing water (W), ammonium dihydrogen phosphate (N) (NH4H2PO4) (Daejeong Chemical), and a freezing point regulator (F) in a weight ratio of 100:20:30 (W:N:F). The mixing was performed for about 10 minutes at room temperature (about 25°C) under mixing conditions of 300 rpm. Potassium formate (HCOOK) (Daejeong Chemical) (molar mass 84.12 g / mol) was used as the freezing point regulator. Potassium formate is a non-flammable substance that does not have a flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method were all 0 ppm, making it a non-toxic substance. In addition, the solubility of the above potassium formate in 100 g of water at 0°C is about 32.8 g, and the solubility in 100 g of water at 25°C is about 331 g.

[0281] The above-mentioned ammonium monophosphate (N) (NH4H2PO4) has a solubility of approximately 29 g in water at 25°C. Subsequently, a second mixture was prepared by additionally mixing starch (S) (Sigma-Aldrich) and melamine (M) (ACROS ORGANICS) into the first mixture. In the second mixture, the ratio of water (W) to the starch (S) and melamine (M) (W:S:M) was adjusted to approximately 100:10:10. The mixing was performed for about 30 minutes at room temperature (approx. 25°C) under mixing conditions of 300 rpm. For the preparation of the second mixture, the corn starch used in Example 3 was used as the starch. Subsequently, an absorbent polymer (SAP) was additionally mixed into the second mixture to prepare a composition. The mixing of the absorbent polymer was performed by mixing the second mixture and the absorbent polymer, and mixing for about 2 hours at room temperature (about 25°C) under mixing conditions of 300 rpm. The mixing was performed so that the weight ratio (W:P) of water (W) and the absorbent polymer (P) in the mixture was about 100:5. As the absorbent polymer, LG Chem's SAP GS-803ND product was used, and after grinding and classification processes, it was applied with a size of about 150 μm. The Centrifuge Retention Capacity (CRC) of this absorbent polymer was about 33.5 g / g, and the Absorption Under Pressure (AUP) was about 28.1 g / g.

[0283] fire extinguishing device

[0284] A fire extinguishing device was manufactured in the same manner as in Example 2 using an aluminum can (case) used for manufacturing the prismatic battery applied in Example 2. In this process, a thermal conductive layer was not applied.

[0286] Example 5.

[0287] A fire extinguishing composition and a fire extinguishing device were prepared in the same manner as in Example 4, except that sodium formate (HCOONa) (Daemyung Chemical) (molar mass: 68.01 g / mol) was used instead of potassium formate (HCOOK) (Daejeong Chemical) as a freezing point regulator. The sodium formate is a non-flammable substance that does not have a flash point, and is a non-toxic substance, with the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method all being 0 ppm. In addition, the sodium formate, which is the freezing point regulator, has a solubility of approximately 43.82 g in 100 g of water at 0°C and a solubility of approximately 97.2 g in 100 g of water at 25°C.

[0289] Example 6.

[0290] A fire extinguishing composition and a fire extinguishing device were prepared in the same manner as in Example 4, except that potassium acetate (CH3COONa) (Daejeong Hwakum) (molar mass: 98.15 g / mol) was used instead of potassium formate (HCOOK) (Daejeong Hwakum) as a freezing point regulator. The potassium acetate is a non-flammable substance that does not have a flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method are all 0 ppm, making it a non-toxic substance.

[0292] Example 7.

[0293] Fire extinguishing composition

[0294] A first mixture was prepared by mixing water (W) and diammonium phosphate (N) (NH4H2PO4) in a weight ratio (W:N) of 100:22. The mixing was performed for about 10 minutes at room temperature (approx. 25°C) under a mixing condition of 300 rpm. A second mixture was prepared by additionally mixing starch (S) and melamine (M) into the first mixture. In the second mixture, the ratio of water (W) to the starch (S) and melamine (M) (W:S:M) was adjusted to 100:6:6. The mixing was performed for about 30 minutes at room temperature (approx. 25°C) under a mixing condition of 300 rpm. For the preparation of the second mixture, the same corn starch used in Example 3 was used as the starch. Subsequently, an absorbent polymer (SAP) was additionally mixed into the second mixture to prepare a composition. The mixing of the absorbent polymer was performed by mixing the second mixture and the absorbent polymer, and mixing for about 2 hours at room temperature (about 25°C) under mixing conditions of 300 rpm. The mixing was performed so that the weight ratio (W:P) of water (W) and the absorbent polymer (P) in the mixture was about 100:5. The same polymer used in Example 4 was used as the absorbent polymer. The latent heat of the fire extinguishing composition prepared in this way was about 1615 J / g.

[0296] fire extinguishing device

[0297] A fire extinguishing device was manufactured in the same manner as in Example 4 using the above fire extinguishing composition.

[0299] Comparative Example 1.

[0300] Fire extinguishing composition

[0301] Water (W) and potassium acetate (K) (molar mass: 98.15 g / mol) (CH3COOK) were mixed in a weight ratio of 45:55 (W:K). The potassium acetate, which acts as a freezing point regulator, is a non-flammable substance that does not have a flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method were all 0 ppm, indicating that it was a non-toxic substance. Subsequently, the mixture was placed in a sealed container, and additionally, mineral wool (thickness: approx. 2.5 mm, density: approx. 0.2 g / cm3, pyrolysis temperature: approx. 800℃) (KCC, Mineral Wool Insulation Board No. 1) was placed in the sealed container, and the mixture was maintained at room temperature (approx. 25℃) for approximately 24 hours to prepare a fire extinguishing composition.

[0303] Fire extinguishing device

[0304] A can (case) used in the manufacture of prismatic batteries, with a WVTR of approximately 0.27 g / m² 2· A fire extinguishing device was manufactured in the same manner as in Example 1 using a can of about 1 day. In this process, aluminum foil with a thermal conductivity of about 234 W / mK (at 20℃) and a thickness of about 50 μm was used as the thermal conductive layer.

[0306] Comparative Example 2.

[0307] As a case for prismatic batteries, with a WVTR of approximately 7.5 g / m² 2· A fire extinguishing device was manufactured in the same manner as in Example 1, except that a case of about one day was used.

[0309] Comparative Example 3.

[0310] As a case for prismatic batteries, with a WVTR of approximately 7.5 g / m² 2· A fire extinguishing device was manufactured in the same manner as in Example 7, except that a case of about one day was used.

[0312] The evaluation results for the above examples and comparative examples are summarized in Tables 1 and 2 below. In Tables 1 and 2 below, M is the sum of the molal concentrations of the freezing point regulator and other ionic compounds (ammonium dihydrogen phosphate) with respect to the volatile substance (water) in the composition, and △T f For each freezing point regulator and other ionic compound (ammonium dihydrogen phosphate), Equation 1 (K f× It is the sum of values ​​calculated as M×I). In addition, in Tables 1 and 2, the water content is the weight of water contained when the weight of the fire extinguishing composition of the example or comparative example is set to 100%, and WVTR is the WVTR of the case used in the manufacture of the fire extinguishing device (unit: g / m³). 2· day)

[0313] Examples 1 2 3 4 5 6 7 Water content (weight%) 60 72 54.5 57.1 57.1 57.1 71.9 WVTR 0.11 0 0.27 0 0 0 0 M 10.7 6.3 6.7 5.3 6.1 4.8 1.9 △T f 20 11.7 24.8 19.7 22.9 17.8 7.1 Convection test Pass Pass Pass Pass Pass Pass Pass chain ignition test Pass Pass Pass Pass Pass Pass Pass Storage stability Pass Pass Pass Pass Pass Pass Pass

[0314] Comparative example 1 2 3 Water content (weight%) 45 60 71.9 WVTR 0.27 7.5 7.5 M 12.5 10.7 12.5 △T f 46.3 20 46.3 Convection test NG NG NG chain ignition test NG NG NG Storage stability Pass NG NG

[0316] From the results in Table 1, it can be confirmed that excellent results are obtained in the Convection test and chain ignition test when the composition contains water above a certain content and the WVTR of the fire extinguishing device case is controlled. In addition, considering the temperature confirmed by the temperature sensor in the Convectoin test, Examples 1 to 6, in which the vaporization rate was adjusted through the addition of a freezing point regulator, showed superior effects compared to Example 7. From the results in Table 2, it can be seen that the intended effect cannot be obtained when the water content in the composition is not controlled even if the WVTR of the case is controlled (Comparative Example 1), or when the control of the water content is not carried out together with the control of the WVTR (Comparative Examples 2 and 3). Furthermore, the flammability of the compositions of the Examples and Comparative Examples was confirmed when ethylene glycol was applied as a freezing point lowering agent.

[0318] Example 8.

[0319] A fire extinguishing device was manufactured in the same manner as in Example 1, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), a PVDC (polyvinylidene chloride) film (thickness: about 40 μm), and a PP (polypropylene) hot melt film (thickness: about 50 μm) (melting point: about 140°C) in the order described above. The outer shell was manufactured by laminating the PET film on one side of the PVDC film with an adhesive and laminating the PP hot melt film on the other side at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing device was manufactured by attaching a heat-conducting layer to the concave portions (I) of the upper and lower outer shells (121, 122), placing a fire extinguishing composition onto the heat-conducting layer, laminating the upper and lower outer shells (121, 122), and then fusing the PP hot melt films together at the sealing portion (S). Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portions could function as vent areas. The composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portions (I). The WVTR of the case is approximately 0.11 g / m² 2 It was about 1 day. The same material used in Example 1 was used as the thermal conductive layer. The above case was manufactured with a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0321] Example 9.

[0322] A fire extinguishing device was manufactured in the same manner as in Example 2, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot melt film (thickness: about 70 μm) (melting point: about 140°C) in the above order. The outer shell was manufactured by laminating the PET film on one side of the aluminum foil with an adhesive and laminating the PP hot melt film on the other side at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing device was manufactured by attaching a heat-conducting layer to the concave portions (I) of the upper and lower outer shells (121, 122), placing a fire extinguishing composition onto the heat-conducting layer, laminating the upper and lower outer shells (121, 122), and then fusing the PP hot melt films together at the sealing portion (S). Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portions could function as vent areas. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portions (I). The WVTR of the case is approximately 0 g / m² 2 It was about 1 day. The same material used in Example 1 was used as the thermal conductive layer. The above case was manufactured with a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0324] Example 10.

[0325] A fire extinguishing device was manufactured in the same manner as in Example 3, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), an EVOH (Ethylene Vinyl Alcohol) film (thickness: about 40 μm), and a PE (polyethylene) hot melt film (thickness: about 50 μm) (melting point: about 140°C) in the above order. The outer shell was manufactured by laminating the PET film on one side of the EVOH film with an adhesive and laminating the PE hot melt film on the other side at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing device was manufactured by attaching a heat-conducting layer to the concave portions (I) of the upper and lower outer shells (121, 122), placing a fire extinguishing composition on the heat-conducting layer, laminating the upper and lower outer shells (121, 122), and then fusing the PE hot melt films together at the sealing portion (S). Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portions could function as vent areas. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portions (I). The WVTR of the case is approximately 0.27 g / m² 2 It was about 1 day. The same material used in Example 3 was used as the thermal conductive layer. The case was manufactured with a width of about 9 cm, a height of about 12 cm, and a thickness of about 3 mm.

[0327] Example 11.

[0328] A fire extinguishing device was manufactured in the same manner as in Example 4, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot melt film (thickness: about 70 μm) (melting point: about 140°C) in the above order. The outer shell was manufactured by laminating the PET film on one side of the aluminum foil with an adhesive and laminating the PP hot melt film on the other side at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing device was manufactured by placing a fire extinguishing composition into the lower outer shell (122), laminating the upper and lower outer shells (121, 122), and then fusing the PP hot melt films together at the sealing portion (S). Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case is approximately 0 g / m² 2 It was about 9 cm in width and 12 cm in height, and about 3 mm in thickness.

[0330] Example 12.

[0331] A fire extinguishing device was manufactured in the same manner as in Example 5, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot melt film (thickness: about 70 μm) (melting point: about 140°C) in the order described above. The outer shell was manufactured by laminating the PET film on one side of the aluminum foil with an adhesive and laminating the PP hot melt film on the other side at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing device was manufactured by placing a fire extinguishing composition into the lower outer shell (122), laminating the upper and lower outer shells (121, 122), and then fusing the PP hot melt films together at the sealing portion (S). Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case is approximately 0 g / m² 2 It was about 9 cm in width and 12 cm in height, and about 3 mm in thickness.

[0333] Example 13.

[0334] A fire extinguishing device was manufactured in the same manner as in Example 6, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot melt film (thickness: about 70 μm) (melting point: about 140°C) in the above order. The outer shell was manufactured by laminating the PET film on one side of the aluminum foil with an adhesive and laminating the PP hot melt film on the other side at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing device was manufactured by placing a fire extinguishing composition into the lower outer shell (122), laminating the upper and lower outer shells (121, 122), and then fusing the PP hot melt films together at the sealing portion (S). Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case is approximately 0 g / m² 2 It was about 9 cm in width and 12 cm in height, and about 3 mm in thickness.

[0336] Example 14.

[0337] A fire extinguishing device was manufactured in the same manner as in Example 7, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot melt film (thickness: about 70 μm) (melting point: about 140°C) in the above order. The outer shell was manufactured by laminating the PET film on one side of the aluminum foil with an adhesive and laminating the PP hot melt film on the other side at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing device was manufactured by placing a fire extinguishing composition into the lower outer shell (122), laminating the upper and lower outer shells (121, 122), and then fusing the PP hot melt films together at the sealing portion (S). Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case is approximately 0 g / m² 2 It was about 9 cm in width and 12 cm in height, and about 3 mm in thickness.

[0339] Comparative Example 4.

[0340] A fire extinguishing device was manufactured in the same manner as Comparative Example 1, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), an EVOH (Ethylene Vinyl Alcohol) film (thickness: about 40 μm), and a PE (polyethylene) hot melt film (thickness: about 50 μm) (melting point: about 140°C) in the above order. The outer shell was manufactured by laminating the PET film on one side of the EVOH film with an adhesive and laminating the PE hot melt film on the other side at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing device was manufactured by attaching a heat-conducting layer to the concave portions (I) of the upper and lower outer shells (121, 122), placing a fire extinguishing composition on the heat-conducting layer, laminating the upper and lower outer shells (121, 122), and then fusing the PE hot melt films together at the sealing portion (S). Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portions could function as vent areas. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portions (I). The WVTR of the case is approximately 0.27 g / m² 2 It was approximately 1 / day. As the thermal conductive layer, aluminum foil with a thermal conductivity of approximately 234 W / mK (at 20℃) and a thickness of approximately 50 μm was used. The above case was manufactured with a width of approximately 9 cm, a length of approximately 12 cm, and a thickness of approximately 3 mm.

[0342] Comparative Example 5.

[0343] A fire extinguishing device was manufactured in the same manner as in Example 1, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell made by laminating a PVC (poly(vinyl chloride)) film (thickness: about 20 μm) and a PP hot melt film (thickness: about 70 μm) (melting point: about 140°C). The outer shell was manufactured by laminating the PP hot melt film on one side of the PVC film at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. After attaching a heat conductive layer to the concave portion (I) of the upper and lower outer shells (121, 122), a fire extinguishing composition was placed on the heat conductive layer, and after laminating the upper and lower outer shells (121, 122), the PP hot melt film was fused together at the sealing portion (S) to manufacture the fire extinguishing device. Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case is approximately 7.5 g / m² 2 It was about 1 day. The same material used in Example 1 was used as the thermal conductive layer. The above case was manufactured with a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0345] Comparative Example 6.

[0346] A fire extinguishing device was manufactured in the same manner as in Example 7, except that a pouch-type case was used as the case of the fire extinguishing device. The case was manufactured using an outer shell made by laminating a PVC (poly(vinyl chloride)) film (thickness: about 20 μm) and a PP hot melt film (thickness: about 70 μm) (melting point: about 140°C). The outer shell was manufactured by laminating the PP hot melt film on one side of the PVC film at a temperature of about 200°C. As shown in FIG. 6, an upper outer shell (121) and a lower outer shell (122) were prepared by forming a concave portion (I) in the center of the outer shell. A fire extinguishing composition was placed in the concave portion (I) of the lower outer shell (122), and after laminating the upper and lower outer shells (121, 122), the PP hot melt films were fused together at the sealing portion (S) to manufacture the fire extinguishing device. Subsequently, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case is approximately 7.5 g / m² 2 It was about a day. The above case was manufactured with a width of about 9 cm, a height of about 12 cm, and a thickness of about 3 mm.

[0348] The evaluation results for the above examples and comparative examples are summarized in Tables 3 and 4 below. In Tables 3 and 4 below, M and △T f The meaning is as in Tables 1 and 2. In addition, in Tables 3 and 4, water content refers to the weight of water contained when the weight of the fire extinguishing composition of the example or comparative example is set to 100%, and WVTR refers to the WVTR of the case used to manufacture the fire extinguishing device (unit: g / m³ 2· day)

[0349] Examples 8 9 10 11 12 13 14 Water content (weight%) 60 72 54.5 57.1 57.1 57.1 71.9 WVTR 0.11 0 0.27 0 0 0 0 M 10.7 6.3 6.7 5.3 6.1 4.8 1.9 △T f 20 11.7 24.8 19.7 22.9 17.8 7.1 Convection test Pass Pass Pass Pass Pass Pass Pass chain ignition test Pass Pass Pass Pass Pass Pass Pass Storage stability Pass Pass Pass Pass Pass Pass Pass

[0350] Comparative example 4 5 6 Water content (weight%) 45 60 71.9 WVTR 0.27 7.5 7.5 M 12.5 10.7 12.5 △T f 46.3 20 46.3 Convection test NG NG NG chain ignition test NG NG NG Storage stability Pass NG NG

[0352] From the results of Tables 3 and 4, it can be confirmed that excellent results were obtained in the Convection test and chain ignition test by controlling the WVTR of the fire extinguishing device case, even though the shape of the case was different, and water was included in the composition at a certain content or higher.

Claims

Claim 1 A case having a sealed space inside; and a composition existing in the sealed space, wherein the Water Vapor Transmission Rate (WVTR) of at least 80% of the area of ​​the portion of the case forming the sealed space or at least 80% of the area of ​​the case is 5 g / m² 2· day or less, and the above composition comprises a volatile substance; and one or more freezing point regulators selected from the group consisting of alcohols and ionic compounds, wherein the content of the volatile substance in the above composition is 50 weight% or more, and the freezing point regulator is △T of Formula 1 below f A fire extinguishing device included in the above composition such that α is in the range of 5 to 50: [Formula 1] △T f = K f K in Equation 1 × M × I f is the freezing point depression constant of the above-mentioned volatile substance, M is the molal concentration of the above-mentioned freezing point regulator with respect to the above-mentioned volatile substance, and I is the number of ions formed by the above-mentioned freezing point regulator, wherein I is 1 when the above-mentioned freezing point regulator is not an ionic compound. Claim 2 In claim 1, the extinguishing device wherein the vaporizable substance has a boiling point within the range of 80°C to 120°C. Claim 3 A fire extinguishing device in which the vaporizable substance in claim 1 is water. Claim 4 In claim 1, the freezing point regulator is a fire extinguishing device having a solubility of 20 g or more per 100 g of vaporizable substance at 0°C. Claim 5 In claim 1, the freezing point regulator is a fire extinguishing device having a solubility of 70 g or more per 100 g of vaporizable substance at 25°C. Claim 6 In claim 1, the freezing point regulator is a fire extinguishing device having a molar mass of 300 g / mol or less. Claim 7 A fire extinguishing device according to claim 1, wherein the ionic compound is one or more selected from the group consisting of formate, acetate, carbonate and sulfate. Claim 8 A fire extinguishing device according to claim 1, wherein the composition further comprises one or more selected from the group consisting of carbonizable organic materials and carbonization catalysts. Claim 9 A fire extinguishing device according to claim 1, wherein the ratio of the volume occupied by the composition within the total volume of the sealed space of the case is 70% or more. Claim 10 delete Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete

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