Composition

Abstract

This specification discloses compositions, fire extinguishing devices, and their applications. The compositions and fire extinguishing devices are applied to products that may experience abnormal heat generation, ignition, and / or explosion during operation, storage, and / or maintenance, and can effectively respond to such heat generation, ignition, and explosion. The compositions and fire extinguishing devices are applied, for example, to articles containing multiple such products, and can respond to abnormal heat generation, explosion, and / or ignition originating from any one of the products, preventing the propagation of such heat generation, explosion, and / or ignition to other adjacent products. The compositions and fire extinguishing devices also have excellent handling and storage stability. This specification also discloses applications of the compositions and fire extinguishing devices.

Description

[Technical Field]

[0001] This application claims priority under Korean Patent Application No. 10-2023-0041414 dated March 29, 2023, and all content disclosed in the documents of said patent application is incorporated herein as part of this specification.

[0002] This specification discloses compositions, fire extinguishing devices, and their uses. [Background technology]

[0003] Technologies are needed to ensure the stability of products that pose a risk of abnormal heat generation, ignition, and explosion (hereinafter referred to as "hazardous products"). In particular, when multiple hazardous products are included, abnormal heat generation, ignition, and / or explosion originating from one product can have a chain reaction affecting other adjacent products, which can cause significant problems from a stability standpoint. Typical examples of this situation include the so-called TR (Thermal Runaway) or TP (Thermal Propagation) phenomenon that occurs in battery modules and 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 occur in any one battery cell and / or battery module, the phenomenon in which such heat generation, ignition, and / or explosion propagate in a chain reaction to other adjacent battery cells, etc., is called the TR or TP phenomenon.

[0005] The development of products that require a lot of energy to operate, such as electric vehicles, has led to a significant increase in the energy capacity of the aforementioned battery modules or battery packs, and consequently, 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 in electric vehicles, chain reactions of heat generation, ignition, and explosion like TR or TP must be controlled. [Overview of the Initiative] [Problems that the invention aims to solve]

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

[0008] This specification aims to disclose compositions and fire extinguishing devices and their applications that are applicable to products that may experience abnormal heat generation, ignition, and / or explosion during operation, storage, and / or maintenance, and that can effectively respond to such heat generation, ignition, and explosion.

[0009] For example, the compositions and fire extinguishing devices disclosed herein are applied to articles containing multiple such products and can respond to abnormal heat generation, explosion, and / or ignition occurring from any one of the products, and prevent the propagation of such heat generation, explosion, and / or ignition to other adjacent products.

[0010] This specification also aims to disclose the composition and fire extinguishing system having excellent handling and storage stability. This specification also aims to disclose the uses of the composition and fire extinguishing system. [Means for solving the problem]

[0011] In this specification, properties that are affected by temperature are those measured at room temperature unless otherwise specified.

[0012] The term "room temperature" refers to the natural temperature that is not artificially heated or cooled, and means, for example, any single temperature within the range of approximately 10°C to 30°C, or a temperature of approximately 23°C or 25°C.

[0013] Unless otherwise specified in this specification, the unit of temperature is °C.

[0014] Among the physical properties mentioned in this specification, the physical properties affected by pressure are the physical properties measured under normal pressure unless otherwise specified.

[0015] The term "normal pressure" refers to the natural pressure without artificial pressurization and depressurization, and usually, the range of about 700 mmHg to 800 mmHg is referred to as normal pressure.

[0016] Among the physical properties mentioned in this specification, the physical properties affected by humidity are the physical properties measured under the humidity of the standard state unless otherwise specified.

[0017] The humidity of the standard state is relative humidity and means about 40%, 50%, 60% or 65%.

[0018] This specification discloses a composition.

[0019] The term "composition" means an object containing two or more components. Such a composition can be a fire extinguishing composition. A fire extinguishing composition is a composition that can cope with abnormal heat generation, flames, explosions, etc. to be suppressed.

[0020] Such a composition can exhibit excellent effects in combination with the structure of the fire extinguishing device described later.

[0021] Therefore, this specification also discloses a fire extinguishing device.

[0022] First, the fire extinguishing device will be described.

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

[0024] The composition can be the fire extinguishing composition described above, and the vaporizable substance can be a component of the composition.

[0025] The case is a container for maintaining the vaporized substance or composition. The case has or is prepared to have the sealed space inside. In this case, "prepared to have the sealed space inside" means that the sealed space is already formed inside the case, or that there is a certain space inside the case that is not sealed, but the case is prepared to have the sealed space formed in a manner that seals the open portion.

[0026] In such cases, the sealed space may have a vent region. The term “vent region” may mean a region that, in a first state, is sealed and exists in such a way that the sealed state of the space can be maintained, but in a second state is open and allows for the discharge of substances inside the space. The second state may mean, for example, a state in which abnormal ignition, abnormal heat generation and / or explosion occurs in an environment to which the composition or fire extinguishing device is applied, and the first state may mean a state in which such abnormal ignition, abnormal heat generation and abnormal explosion do not occur.

[0027] Such vent regions can be formed using the method described later.

[0028] In one example, the case may have a predetermined range of WVTR (Water Vapor Transmission Rate), 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 predetermined range of WVTR (Water Vapor Transmission Rate). For example, the upper limit of the WVTR of the 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 may be within the range of any one of the upper limits mentioned above, or greater than or greater than any one of the lower limits mentioned above, and less than or less than any one of the upper limits mentioned above. The closer the WVTR is to the range disclosed in the Examples section of this specification within the range described above, the better the effect can be ensured.

[0029] The unit of WVTR is g / m 2 This is measured in days, and is measured using the method described in "9. Evaluation of WVTR (Water Vapor Transmission Rate)" in the Examples section of this specification.

[0030] In one example, when a sealed space is formed within the case, a certain level or more of the total area of ​​the case forming the sealed space can have a WVTR within the range described above.

[0031] For example, the WVTR within the aforementioned range can be confirmed in an area exceeding a certain percentage of the total area of ​​the case. For example, the lower limit of the percentage of the total area of ​​the case that has the WVTR within the aforementioned range may be around 80%, 85%, 90%, 95%, 97%, or 99%, and the upper limit may be around 100%. The percentage may be within the range of any one of the aforementioned lower limits or exceeding it; or within the range of any one of the aforementioned lower limits or exceeding it, and less than or equal to the aforementioned upper limit.

[0032] In other examples, a certain level of area of ​​the portion of the case forming the sealed space may have a WVTR (Water Vapor Transmission Rate) within the range described above. For example, the lower limit of the ratio of the area of ​​the case portion forming the sealed space that exhibits a WVTR within 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 the range of any one of the lower limits described above, or within the range of any one of the lower limits described above, or within the range of any one of the lower limits described above, and less than or equal to the upper limit described above.

[0033] The above means that the sealed space inside the case is essentially entirely surrounded by an area having WVTR within the range described above. This configuration effectively induces an instantaneous increase in internal pressure inside the fire extinguishing system, as described later.

[0034] The fire extinguishing device is configured to stably maintain the internal vaporizable substance or composition in a normal state, and to release all or part of the vaporizable substance or composition or its vaporized form 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.

[0035] The explanation will assume that the fire extinguishing device is applied to a battery module.

[0036] Figure 1 is a schematic diagram of the case when the fire extinguishing device S is applied to a battery module. As shown in Figure 1, the battery module may be configured by arranging a plurality of battery cells 11, 12, 13, 14, 15, 16 adjacent to each other, but the fire extinguishing device S may be placed between the battery cells (for example, between 12 and 13 in Figure 1 and between 14 and 15 in Figure 1), as shown in the figure.

[0037] Under normal conditions, the fire extinguishing device S maintains vaporized substances inside. In abnormal conditions, the vaporized substances in the fire extinguishing device S are ejected in a directional manner (dotted arrow in Figure 1), for example, through the aforementioned vent area, thereby responding to high temperatures and flames caused by abnormal heat generation, ignition, and / or explosion. Figure 1 shows a case where the substance is ejected in both the upper and lower ends of the fire extinguishing device S, but the ejection direction is not limited to that shown in Figure 1. The ejection direction may be in one direction of the fire extinguishing device S, or it may be in two or more directions. Such ejection directions can be adjusted through the formation of a vent area.

[0038] For a fire extinguishing system to effectively perform its function in an abnormal state, it is required that the vaporized substances, etc., present inside the case in a normal state be stably maintained, and that when an abnormal state occurs, the vaporized substances, etc., be rapidly discharged to the outside in as vaporized a state as possible and used up completely. The fire extinguishing system can satisfy the above requirements.

[0039] The principle by which the aforementioned fire extinguishing device works will be explained.

[0040] Figure 2 is a diagram showing only the fire extinguishing device S from Figure 1 separately. In the configuration shown in Figure 1, if abnormal heat generation, ignition, and / or explosion occurs in at least one of the battery cells, a certain level of high heat is instantaneously applied to the fire extinguishing device, as shown by the solid arrows in Figure 2. The vaporizable substance present inside the fire extinguishing device vaporizes due to the applied heat. The vaporized substance propagates randomly in all directions within the sealed space inside the case 1001 of the fire extinguishing device, as shown by the dotted arrows in Figure 2. However, if the sealed space of the case 1001 is substantially surrounded by the WVTR section described above, the vaporized substance cannot be released to the outside, and the inside of the case 1001 becomes instantaneously under very high pressure. When the vent area 1002 of the case is instantaneously opened at a high pressure above a certain level, the gas inside is rapidly discharged to the outside through the opened vent area 1002.

[0041] If the WVTR of the case surrounding the sealed space is high, the internal pressure of case 1001 may not increase effectively in the aforementioned state, or the rate of increase may be slow, preventing the vent area 1002 from opening effectively. Even when the vent area 1002 is opened, the internal pressure may not be sufficient, causing some of the vaporized substance to be discharged to the outside and remain unused, or the discharge rate to be excessively slow.

[0042] Maintaining a low WVTR of the case also has the added benefit of ensuring the storage stability of the internal materials under normal conditions.

[0043] The method for forming the vent region is not particularly limited. The vent region can be formed by designing it so that it can be opened when the internal pressure of the case forming the sealed space reaches a certain level. For example, if a portion of the case forming the sealed space is configured to have lower strength than other portions, the portion with lower strength can be opened by the increased internal pressure. Alternatively, a method can be used in which the sealed space is formed by sealing with a hot melt material, so that opening occurs due to melting at a predetermined temperature. Another method is to form the vent region by making only a certain portion of the case forming the sealed space thinner than other portions. Such methods for forming a vent region can be easily adopted by those skilled in the art.

[0044] For example, when the fire extinguishing device is applied to a battery module or pack, for ease of application, the case can be a rectangular case, a pouch-type case, and / or a cylindrical case, such as a battery cell. In such cases, a vent area can also be formed by controlling the bonding strength of the cover that forms a sealed space in the rectangular or cylindrical case.

[0045] The aforementioned case can be constructed using known materials, provided that they can satisfy the aforementioned WVTR, and the materials may have a single layer or a multilayer structure of two or more layers.

[0046] For example, the case can be formed using a material capable of exhibiting a WVTR within the specified range among suitable organic and / or inorganic layers.

[0047] As the organic layer, for example, a known polymer film or sheet may be used. Examples of organic films include cellulose polymer films; COP (cycloolefin copolymer) films; acrylic polymer films; polyolefin films; PVA (polyvinyl alcohol) films; PVC (poly(vinyl chloride)) films, PES (poly ether sulfone) films; PEEK (polyetheretherketon) films; PPS (polyphenylsulfone) films; PEI (polyetherimide) films; PEN (polyethylenemaphthatlate) films; polyester films such as PET (poly(ethylene terephthalate)) films; PI (polyimide) films; PSF (polysulfone) films and / or PAR (polyarylate) films.

[0048] 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 containing one or more elements 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 material may be applied, or a layer formed by vapor deposition or the like on a suitable substrate may be used.

[0049] 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 aforementioned layers are laminated.

[0050] The thickness of the 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 around 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, and the upper limit may be around 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 may be within the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and any one upper limit or less than any one of the upper limits mentioned above.

[0051] The fire extinguishing device may include further configurations to ensure that the above action is performed more effectively.

[0052] For example, the fire extinguishing device may further include a heat conductive layer. Such a heat conductive layer may be located in an appropriate position within the fire extinguishing device. For example, the heat conductive layer may be located between the case and the vaporized substance or composition in the fire extinguishing device, or it may be located adjacent to the case.

[0053] Figure 3 is an example of the fire extinguishing device in Figure 2 in which the heat conductive layer 2001 is added. The heat conductive layer may be located at other locations inside the case, and its number may be one or more.

[0054] The term "thermal conduction layer" refers to a layer whose thermal conductivity (based on 20°C) is within the range described below. The lower limit of the thermal conductivity (based on 20°C) of the thermal conduction layer may be approximately 15, 18, 20, 50, 100, 150, 200, 250, 300, 350, or 400, and its 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 the range of any one of the lower limits mentioned above or exceeding it; or within the range of any one of the lower limits mentioned above or exceeding it, and any one of the upper limits mentioned above or less. The unit of the thermal conductivity is W / mK, and it can be evaluated using the method described in "15. Evaluation of Thermal Conductivity" in the Examples section of this specification.

[0055] The type of thermal conductive layer is not particularly limited as long as it has the aforementioned thermal conductivity. Generally, metal materials can be used as thermal conductive layers because they have excellent thermal conductivity. For example, layers made of metal materials such as aluminum, gold, pure silver, tungsten, copper, nickel, or platinum may be used. There are no special restrictions on the thickness of the heat conductive layer, and an appropriate thickness can be set considering the specifications of the fire extinguishing system, etc. For example, the lower limit of the thickness of the heat conductive layer may be around 1 μm, 5 μm, 10 μm, 15 μm, 50 μm, 75 μm, or 90 μm, and the upper limit may be around 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, 50 μm, 40 μm, or 30 μm. The thickness may be within the range of any one upper limit or less than any of the upper limits mentioned above; or within the range of any one lower limit or more than any of the lower limits mentioned above; or within the range of any one lower limit or more than any of the lower limits mentioned above, and any one upper limit or less than any of the upper limits mentioned above.

[0056] As shown in Figure 3, in some cases, the heat generated under abnormal conditions may not be applied uniformly to the fire extinguishing system, but rather locally to a specific area. However, in order for the vaporizable substances inside the fire extinguishing system to vaporize rapidly and achieve a high-pressure state, the heat from the abnormal conditions must be applied uniformly to the fire extinguishing system. When a heat conduction layer is present, even if the heat from the abnormal conditions is applied locally, the heat can be rapidly and evenly transferred to the fire extinguishing system, thereby enabling the fire extinguishing action of the fire extinguishing system to occur quickly and efficiently.

[0057] In order for the fire extinguishing system to more efficiently ensure the aforementioned effect, the amount of the vaporizable substance or the composition containing the vaporizable substance (described later) present in the internal space or sealed space of the case can be adjusted. For example, the lower limit of the volume of the vaporizable substance or composition in relation to the total volume of the internal space or sealed space of the case may be around 70%, 75%, 80%, 85%, 90%, or 95%, and the upper limit may be around 100%. The percentage may be within the range of any one of the aforementioned lower limits being greater than or greater than; or within the range of any one of the aforementioned lower limits being greater than or greater than, and any one of the aforementioned upper limits being less than or less than. Under such a percentage, the rapid rise in internal pressure described above can be more effectively induced.

[0058] The fire-extinguishing composition will be described below.

[0059] The fire extinguishing composition may be contained in a sealed space inside the fire extinguishing device and may be composed in such a way that the effects described with reference to Figures 2 and 3 are more effectively exhibited.

[0060] The aforementioned composition is non-flammable and can be formulated to be environmentally and human-friendly.

[0061] For example, the 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 represented by a so-called fire diamond, designed to enable rapid response to hazardous materials in emergency situations. The flammability rating is represented in the red area. The standard is classified into 0, 1, 2, 3, and 4 grades, with 0 meaning no flammability and 1 meaning that it will ignite when sufficiently heated, with an approximate flash point of 93°C or higher. The evaluation method for such flammability ratings follows the NFPA (National Fire Protection Association) 704 standard.

[0062] The 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 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 represented in the blue area of ​​the NFPA 704 standard's fire diamond. The standard is classified into 0, 1, 2, 3, and 4, where 0 means there is no health threat and no special precautions are required, 1 means there is a possibility of causing minor injury upon exposure, and 2 means there is a possibility of causing temporary injury or illness with persistent / general contact, not chronic contact.

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

[0064] The composition comprises at least the vaporizable substance. Such a vaporizable substance vaporizes under certain temperature and / or pressure conditions and, as described above, plays a role in increasing the internal pressure. In addition, such a vaporizable substance can be ejected to the outside in its vaporized state to extinguish fires and / or provide cooling.

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

[0066] Such vaporized substances can be used without any special restrictions, as long as they are non-flammable. For example, the vaporized substance can be a substance having a predetermined range of freezing point and / or boiling point.

[0067] For example, the lower limit of the freezing point of the vaporized substance may be around -5°C, -4°C, -3°C, -2°C, -1°C, or 0°C, and the upper limit may be around 10°C, 9°C, 8°C, 7°C, 6°C, 5°C, 4°C, 3°C, or 2°C. The freezing point may be above or above any one of the lower limits mentioned above, and below or below any one of the upper limits mentioned above. The freezing point is the freezing point at 1 atmosphere.

[0068] The volatile substance may have a boiling point within a certain range in order to exhibit appropriate vaporization. For example, the lower limit of the boiling point of the volatile substance may be around 80°C, 85°C, 90°C, or 95°C, and the upper limit may be around 120°C, 115°C, 110°C, or 105°C. The boiling point may be above or above any one of the lower limits mentioned above, and below or below any one of the upper limits mentioned above. The boiling point is the boiling point at 1 atmosphere.

[0069] As for the vaporized substance, any suitable type can be selected and used without special limitations, as long as it has a freezing point and / or boiling point within the aforementioned range and is non-flammable. A typical example of a non-flammable vaporized substance having a freezing point and / or boiling point within the aforementioned range is water, and therefore, water can be used as the vaporized substance, but the types of vaporized substances that can be applied are not limited as described above.

[0070] In order for the composition to be applied to the sealed space of the fire extinguishing device and to increase the internal pressure at the appropriate rate at the required 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 in the composition or in the sealed space of the fire extinguishing device may be approximately 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, or 80% by weight, and the upper limit may be approximately 95% by weight, 90% by weight, 85% by weight, 80% by weight, 75% by weight, 70% by weight, 65% by weight, or 60% by weight. The proportion may be within the range of any one of the lower limits mentioned above, or within the range of any one of the lower limits mentioned above, and less than or equal to any one of the upper limits mentioned above. The effect may be improved as the content of the vaporizable substance within the ranges mentioned above approaches the ranges disclosed in the examples. The proportion is a percentage based on the sum of the weights of all components present in the composition or all components present in the sealed space.

[0072] The composition or sealed space may contain only a vaporizing substance, or it may further contain other components.

[0073] For example, the composition or sealed space may further contain a freezing point modifier. The term "freezing point modifier" refers to a component that controls the freezing point and / or boiling point of the composition through a so-called freezing point depression phenomenon. For the fire extinguishing device to effectively exhibit the operation described with reference to Figures 2 and 3, instantaneous vaporization of the vaporizable substance must occur at the necessary time, and for this purpose, a freezing point modifier may be applied. Furthermore, since it is advantageous for the vaporizable substance to exist in liquid form at the time the abnormal condition occurs, such a state can also be ensured by a freezing point modifier. In addition, when the composition is applied to highly integrated products such as battery modules and battery cells, if a phase transition occurs due to cooling of the composition in a low-temperature environment, it may adversely affect adjacent products due to volume and hardness changes of the composition, and this problem can also be solved by adding a freezing point modifier.

[0074] The application of the freezing point modifier can be controlled in order to ensure the aforementioned effects, particularly the effect of instantaneous and complete rapid vaporization of the vaporizable substance at the required time.

[0075] For example, the freezing point modifier is ΔT in the following formula 1. f It can exist such that it can be within a predetermined range. [Formula 1] △T f =K f ×M×I In Equation 1, K f This is the freezing point depression constant of the aforementioned vaporized substance.

[0076] The aforementioned K f The unit is °C / m, and for example, if the vaporizing substance is water, then the K f It is approximately 1.86.

[0077] In Equation 1, M is the molar concentration of the freezing point regulator, which is the molar concentration with respect to the volatile substance. Therefore, M is the number of moles of the freezing point regulator present per 1 kg of the volatile substance in the composition or the sealed space.

[0078] In Equation 1, I is the number (number of moles) of ions formed by 1 mole of the freezing point regulator when the freezing point regulator dissociates, where dissociation means a state in which the freezing point regulator is completely dissociated. Therefore, for example, when the freezing point regulator is not an ionic compound, I is 1.

[0079] When two or more freezing point regulators or ionic compounds are present in the composition, for each compound, the ΔT f is calculated, and the sum of these values is taken as the ΔT f value for the composition.

[0080] The lower limit of ΔT in Equation 1 f can be, for example, about 5, 10, 15, 20, 22 or 24, and the upper limit can be about 50, 45, 40, 35, 30, 25, 20 or 15. The unit of the ΔT f is °C. The ΔT f can be in a range that is greater than or exceeds any one of the aforementioned lower limits and less than or below any one of the aforementioned upper limits.

[0081] By applying the freezing point regulator within the above range, the volatile substance can be rapidly and substantially completely vaporized at the required time, the internal pressure of the sealed space can be rapidly increased, and at the required time, the volatile substance can exist in a liquid state, preventing changes in the volume and hardness of the composition and the fire extinguishing device that can affect the operation of the product in the normal state. The ΔT f can show a more excellent effect as it is closer to the range of the examples within the above range.

[0082] As the freezing point modifier, for example, an alcohol or an ionic compound may be used. The category of ionic compounds includes substances that are ionic by themselves or that can generate ions, such as salts.

[0083] For example, the alcohol can be any alcohol whose boiling point is within a predetermined range. For example, the lower limit of the boiling point of the alcohol may be around 150°C, 170°C, or 190°C, and the upper limit may be around 300°C, 280°C, 260°C, 240°C, 220°C, or 200°C. The boiling point may be within the range of any one of the lower limits mentioned above, or exceeding it, and any one of the upper limits mentioned above, or being less than it.

[0084] For example, the alcohol can be any alcohol whose molar weight is within a predetermined range. For example, the lower limit of the molar weight of the alcohol may be around 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 around 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 weight may be greater than or exceeding any one of the lower limits mentioned above, and less than or equal to any one of the upper limits mentioned above.

[0085] There are no special restrictions on the type of alcohol; for example, polyhydric alcohols such as ethylene glycol or glycerin may be used.

[0086] Examples of ionic compounds that can be applied as freezing point modifiers include one or more salts selected from the group consisting of formate, acetate, carbonate, and sulfate. Specifically, one or more 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) can be used.

[0087] The freezing point modifier can be present in such a way that its concentration, calculated based on the vaporized substance, falls within a predetermined range. This concentration is a molar concentration, specifically the number of moles of the freezing point modifier present per kilogram of the vaporized substance in the composition. In one example, the lower limit of the molar concentration may be 1, 1.5, 2, 4, 6, 8, 10, 12, 14, or 16, and its 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 molar concentration may be greater than or exceeding any one of the aforementioned lower limits, and less than or equal to any one of the aforementioned upper limits. The molar concentration is expressed as ΔT in formula 1. f It can be adjusted taking this into consideration.

[0088] As a freezing point modifier, it is appropriate to use a component that has a flammability rating of 0 or 1 according to the NFPA (National Fire Protection Association) 704 standard, and / or a health hazard rating of 0, 1, or 2 according to the NFPA (National Fire Protection Association) 704 standard. Although a variety of freezing point modifiers that can induce freezing point depression are known, most are flammable and / or toxic, so when it is necessary to achieve the desired NFPA rating, etc., the NFPA rating should also be considered when selecting a freezing point modifier.

[0089] The freezing point modifier should preferably have a certain level of solubility in relation to the vaporized substance. Selecting a freezing point modifier with appropriate solubility allows for greater flexibility in the amount of the additive, enabling the selection of an amount that ensures the desired freezing point without hindering or improving the fire extinguishing function.

[0090] For example, the lower limit of the solubility of the freezing point modifier in 100g of the vaporizable substance or water at 0°C may be around 20g, 25g, 30g, 35g, 40g, 45g, 50g, 55g, 60g, 65g, 70g, 75g, 80g, 85g, 90g, 95g, 100g, 110g, 115g, 120g, 125g, 130g, 135g, 140g, 145g, 150g, 155g, 160g, 165g, 170g, 175g, 180g, 185g, 190g, 195g, 200g, 205g, 210g, or 215g, and the upper limit may be around 1000g, 900g, 8 Possible amounts include 00g, 700g, 600g, 500g, 400g, 300g, 250g, 245g, 240g, 235g, 230g, 225g, 220g, 215g, 210g, 205g, 200g, 195g, 190g, 185g, 180g, 175g, 170g, 165g, 160g, 155g, 150g, 145g, 140g, 135g, 130g, 125g, 120g, 115g, 110g, 105g, 100g, 95g, 90g, 85g, 80g, 75g, 70g, 65g, 60g, 55g, 50g, 45g, 40g, 35g, or approximately 30g. The solubility may be within the range of any one of the lower limits mentioned above, or above or above any one of the lower limits mentioned above, and below or below any one of the upper limits mentioned above. The solubility is the weight (g) of the freezing point modifier that can be dissolved in 100g of a vaporizing substance or water at 0°C. Such solubility can be evaluated using the method described in "10. Evaluation of Solubility".

[0091] The lower limit of solubility of the freezing point modifier in 100g of the vaporizing substance or water at 25°C is 70g, 75g, 80g, 85g, 90g, 95g, 100g, 110g, 115g, 120g, 125g, 130g, 135g, 140g, 145g, 150g, 155g, 160g, 165g, 17 0g, 175g, 180g, 185g, 190g, 195g, 200g, 205g, 210g, 215g, 225g, 230g, 235g, 24 0g, 255g, 260g, 265g, 270g, 275g, 280g, 285g, 290g, 295g, 300g, 305g, 310g, 315 It can be around g or 320g, with upper limits being 1000g, 900g, 800g, 700g, 600g, 500g, 400g, 350g, 345g, 340g, 335g, 330g, 325g, 320g, 315g, 310g, 305g, 300g, 295g, 290g, 280g, 275g, 270g, 265g, 260g, 255g The solubility may be approximately g, 250g, 245g, 240g, 235g, 230g, 225g, 220g, 215g, 210g, 205g, 200g, 195g, 190g, 185g, 180g, 175g, 170g, 165g, 160g, 155g, 150g, 145g, 140g, 135g, 130g, 125g, 120g, 115g, 110g, 105g, or 100g. The solubility may be within the range of any one of the lower limits mentioned above, or above, or above, or above, or above, any one of the lower limits mentioned above, and below, or below, any one of the upper limits mentioned above. The solubility is the weight (g) of the freezing point modifier that can be dissolved in 100g of vaporizing substance or water at 25°C. Such solubility can be evaluated using the method described in "10. Evaluation of Solubility".

[0092] As the freezing point modifier, any component with a molar weight within a predetermined range can be used. Maintaining the molar weight of the freezing point modifier at an appropriate level can maintain and improve the functions of other components in the composition (e.g., fire extinguishing function). For example, the lower limit of the molar weight of the freezing point modifier may be around 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 300 g / mol. The molar mass may be approximately 1 / 4 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 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 greater than or exceeding any one of the lower limits mentioned above, and less than or equal to any one of the upper limits mentioned above.

[0093] To ensure that a freezing point modifier exhibits the flammability and health hazard ratings of NFPA 704, components that do not contain specific functional groups may be used. For example, the freezing point modifier may contain components that do not contain hydroxyl groups and / or chlorine, and other components that do not generate sulfur dioxide, ammonia, and ethylene oxide, or components that do not generate such components. Freezing point modifiers containing such components or functional groups may not exhibit the flammability rating (red items) and health hazard rating (blue items) of the aforementioned NFPA 704 standard.

[0094] Examples of such coagulation point modifiers include, for example, one or more ionic compounds selected from the group consisting of formate, acetate, carbonate, and sulfate, among the types mentioned above.

[0095] The specific content of the freezing point modifier is given by ΔT in formula 1. f The ratio may be adjusted with consideration to the following. For example, the lower limit of the weight ratio of the freezing point modifier to 100 parts by weight of the vaporizing substance may be approximately 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65 parts by weight, and the upper limit may be approximately 200, 180, 160, 140, 120, 100, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, or 40 parts by weight. The ratio may be greater than or greater than any one of the lower limits mentioned above, and less than or equal to any one of the upper limits mentioned above.

[0096] The sealed space of the aforementioned composition or fire extinguishing device may contain, if necessary, additional components, such as a fire extinguishing agent, to ensure proper fire extinguishing function. If a fire extinguishing agent is included, the fire extinguishing agent may promote the carbonization of carbonizable organic matter described later and / or promote the gas generation of gaseous substances described later.

[0097] Because the fire extinguishing agent promotes the carbonization of the carbonizable organic matter, the fire extinguishing agent may also be called a carbonization catalyst.

[0098] For such fire extinguishing agents, it is appropriate to use one that has a certain level of solubility or higher for the aforementioned vaporized substance (e.g., water). By adjusting the solubility, the carbonization and gas generation processes described above can be carried out more effectively without causing aggregation or phase separation phenomena within the composition.

[0099] For example, the lower limit of the solubility of the fire extinguishing agent may be around 5g, 10g, 15g, 20g, 25g, 30g, 35g, or 40g, and the upper limit may be around 1000g, 900g, 800g, 700g, 600g, 500g, 400g, 300g, 200g, 100g, 90g, 80g, 70g, 60g, 50g, 40g, or 30g. The solubility may be within the range of any one of the lower limits mentioned above, or within the range of any one of the lower limits mentioned above, or within the range of any one of the upper limits mentioned above, or less than or equal to any one of the upper limits mentioned above. The solubility is the weight (g) of the fire extinguishing agent that can be dissolved in 100g of water at 25°C, and this can be measured by the method described in "10. Evaluation of Solubility".

[0100] As the fire extinguishing agent, one having the aforementioned solubility can be appropriately selected and used, and examples include phosphoric acid, phosphates, phosphonate compounds, or phosphate compounds. The fire extinguishing agent may be, for example, primary or secondary ammonium phosphate, urea phosphate, guanylurea phosphate, or ammonium polyphosphate, and one or more of the above may be selected and used.

[0101] The fire extinguishing agent may be present in the composition in an appropriate amount considering the intended effect. For example, the lower limit of the weight ratio of the fire extinguishing agent to 100 parts by weight of the vaporizing substance may be about 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 about 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 the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and any one upper limit or less than any one of the upper limits mentioned above.

[0102] The sealed space of the aforementioned composition or fire extinguishing device may also contain carbonizable organic matter as a further component.

[0103] The carbonizable organic matter is an organic substance that carbonizes and forms a carbide when exposed to a flame or heat at a predetermined temperature. The carbide formed by such an organic substance is often porous, and thus can have an insulating function. Therefore, when a composition or fire extinguishing device is exposed to heat generation, ignition, or explosion, the organic substance can form an appropriate carbide and exhibit an insulating function. For example, when applied together with the gas-generating substance, when exposed to heat generation, ignition, or explosion, the porous carbide can be more effectively formed through the action of the gas generated by the gas-generating substance during the process in which the organic substance forms a carbide.

[0104] The carbonization of the carbonizable organic matter can be induced or promoted by the fire extinguishing agent described above. That is, the fire extinguishing agent decomposes at high temperatures, generating acids, salts, or ionic components, and these acids, salts, or ionic components can promote the carbonization of the carbonizable organic matter through catalytic action.

[0105] As for the aforementioned carbonizable organic matter, any substance that forms carbon when exposed to heat or flame can be used without any special restrictions; an appropriate type may be applied.

[0106] Examples of such organic substances include sugars such as sorbitol and mannitol, polysaccharides such as starch or dextrins (e.g., maleated cyclodexdrin and metal salts of 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 and urea-modified liginin, etc.), and methylol melamine (methylol Examples include, but are not limited to, melamine compounds such as melamine, phenol-formaldehyde resins, and / or char-forming polymers such as PA6T (Poly-hexa methylene terephthalamide).

[0107] A typical example of a carbonizable organic substance is starch. Starch is relatively easy to obtain and can form suitable carbonized materials when exposed to heat or flame.

[0108] The type of starch can be adjusted in order to efficiently form the aforementioned char and to ensure that the formed char effectively exhibits the desired fire extinguishing and heat insulating effects.

[0109] For example, the starch used may contain amylose and amylopectin, with their proportions adjusted to an appropriate level. As is well known, amylopectin and amylose are types of polysaccharides mainly found in plants, and starch, among polysaccharides, is composed of amylose and amylopectin. Amylose is composed of glucose molecules linked by α(1→4) glycosidic bonds and has a linear chain structure, while amylopectin has relatively short, highly branched chains. Amylose crystallizes relatively easily compared to amylopectin, and amylopectin has relatively higher solubility in water compared to amylose.

[0110] By using starch containing amylose and amylopectin having the aforementioned properties in appropriate proportions, the desired composition can be provided more efficiently.

[0111] For example, in the starch containing amylose and amylopectin, the lower limit of the weight ratio of amylopectin to 100 parts by weight of amylose may be around 150 parts by weight, 200 parts by weight, 250 parts by weight, or 300 parts by weight, and the upper limit may be around 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 may be within the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and any one upper limit or less than any one of the upper limits mentioned above. The ratio of amylose to amylovectin can be measured by the method described in "8. Measurement of Amylovectin and Amylose Content" in the Examples section of this specification.

[0112] As the starch, a starch with 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 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. mol, 950,000g / mol, 1,000,000g / mol, 1,500,000g / mol, 2,000,000g / mol, 2,500,000g / mol, 3,000,000g / mol, 3,500,000g / mol, 4,000,000g / mol, 4,500,000g / mol, 5,000,000g / mol, 5,500,000g / mol, 6,000,000g / mol, 6,500,000g / mol, 7,000,000g / mol, 7, It can be found in concentrations of 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, 30,000,000 g / mol, 40,000,000 g / mol, or 50,000,000 g / mol, with upper limits of 1,000,000,000 g / mol, 900,000,000 g / mol, and 800,000,000 g / mol. Possible concentrations include approximately 1 / 20 g / mol, 700,000,000 g / mol, 600,000,000 g / mol, 500,000,000 g / mol, 400,000,000 g / mol, 300,000,000 g / mol, 200,000,000 g / mol, 150,000,000 g / mol, 100,000,000 g / mol, 90,000,000 g / mol, 80,000,000 g / mol, 70,000,000 g / mol, or 60,000,000 g / mol.The molecular weight may be within the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and less than or equal to any one upper limit mentioned above. Starch having the molecular weight (Mw) can form carbides that have the desired function (e.g., heat insulation) more effectively when exposed to heat or flame. Such molecular weight can be measured by the method described in "7. Measurement of Molecular Weight" in the Examples section of this specification.

[0113] If present, the lower limit of the weight ratio of the carbonizable organic matter 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, or 10 parts by weight, and the upper limit may be approximately 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 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 proportion may be within the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and any one upper limit or less than any one of the upper limits mentioned above. Carbonizable organic matter included in such proportions can effectively form carbides in the composition when needed, and the composition as a whole can have excellent handling and storage stability.

[0114] The sealed space of the aforementioned composition or fire extinguishing device may also contain a gas-generating substance as a further component. The gas-generating substance that may be included in the composition is a substance that generates gas when exposed to heat or flames. The gas thus generated can either directly extinguish the heat or flames, or it can function to make the carbides more porous during the process in which the carbidizing organic matter forms carbides.

[0115] The action of such gaseous substances can be induced or promoted by the aforementioned fire extinguishing agents. Specifically, the fire extinguishing agents decompose at high temperatures, producing acids, salts, or ionic components, and these acids, salts, or ionic components can promote gas generation from the gaseous substances.

[0116] The type of gas produced by the gas-generating substance 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.

[0117] A wide variety of substances are known that generate the aforementioned gases. For example, examples of substances that generate nitrogen gas include melamine, guanidine, urea, melamine pyrophosphate, dicyandiamide, guanylurea phosphate, and glycine; examples of substances that generate carbon dioxide include potassium bicarbonate, sodium bicarbonate, calcium bicarbonate, and magnesium bicarbonate; and examples of substances that generate water vapor include calcium hydroxide, magnesium dihydrate, and aluminum trihydrate. However, the substances applicable in this application are not limited to these.

[0118] As the gas-generating substance, one or more types selected from the aforementioned types may be used as a mixture of two or more.

[0119] For the appropriate effect to occur, the gas-generating substance can be a substance that generates nitrogen gas, such as melamine, guanidine, urea, melamine pyrophosphate and / or guanylurea phosphate. Such substances are advantageous in that they exert a foaming effect on the carbide more effectively during the process in which the carbonizing organic matter forms the carbide, thereby effectively forming the desired porous carbide.

[0120] If included, the lower limit of the weight ratio of the gas-generating substance 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 parts by weight, 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 aforementioned proportion may be within the range of any one upper limit or less than any one of the aforementioned upper limits; or within the range of any one lower limit or more than any one of the aforementioned lower limits; or within the range of any one lower limit or more than any one of the aforementioned lower limits and any one upper limit or less than any one of the aforementioned upper limits. Gas-generating substances included in such proportions can exert an effective suppressive effect against heat and flames and a porous carbide formation effect when needed, and the composition as a whole can have excellent handling and storage stability.

[0121] The aforementioned composition may further contain a water-absorbing polymer as an additional component.

[0122] Superabsorbent polymers are polymers that have the property of absorbing water. In one example, such a superabsorbent polymer may be a so-called hydrogel polymer or hydrogel, which is generally defined as a cross-linked hydrophilic polymer. Such polymers are also known as SAPs (Super Absorbent Polymers).

[0123] The superabsorbent polymer is a material capable of absorbing tens to thousands of times its own weight in water. Such a material can enable the composition to exist as a whole in a gel state, thereby ensuring handling and storage stability.

[0124] There are no particular restrictions on the type of superabsorbent polymer; any polymer that can be applied to SAP in general may be used without limitation.

[0125] Typically, polyacrylate-based vinyl polymers are used as the material. The polyacrylate-based polymer is a polymer made from acrylate monomers, and other comonomers may be used in the formation of the polymer if necessary.

[0126] The absorbent properties of the superabsorbent polymer can be adjusted so that it exhibits suitable properties.

[0127] For example, the lower limit of the centrifugal retention capacity (CRC) of the superabsorbent polymer according to the EDANA (European Disposables and Nonwovens Association) method WSP 241.3 may be around 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 around 60 g / g, 55 g / g, 50 g / g, 45 g / g, 40 g / g, or 35 g / g. The CRC may be within the range of any one upper limit of the aforementioned upper limits or less; or within the range of any one lower limit of the aforementioned lower limits or greater than or greater than; or within the range of any one lower limit of the aforementioned lower limits or greater than or greater than, and any one upper limit of the aforementioned upper limits or less. The CRC can be evaluated using the method described in "5. CRC (Centrifuge Retention Capacity)" in the Examples section of this specification.

[0128] For example, the lower limit of the pressure absorption capacity (AUP) of the superabsorbent polymer at 0.3 psi according to the EDANA (European Disposables and Nonwovens Association) method WSP 242.3 may be around 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 around 40 g / g, 38 g / g, 36 g / g, 34 g / g, 32 g / g, or 30 g / g. The absorption capacity (AUP) may be within the range of any one upper limit of the aforementioned upper limits or less than or equal to any one lower limit of the aforementioned lower limits or greater than or equal to any one lower limit of the aforementioned lower limits and within the range of any one upper limit of the aforementioned upper limits or less than or equal to any one of the aforementioned upper limits.

[0129] The absorption capacity (AUP) can be evaluated using the method described in "6. AUP (Absorption Under Pressure)" of the Examples section of this specification. A water-absorbing polymer having the above-described absorbent capacity can exhibit the desired properties when combined with other components of the composition.

[0130] The superabsorbent polymer may, in one example, be a particulate polymer, in which case the lower limit of the average particle size of the superabsorbent polymer may be about 10 μm, 50 μm, 100 μm, or 140 μm, and the upper limit may be about 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 may be within the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and any one upper limit or less than any one of the upper limits mentioned above. Such average particle size can be measured by the method specified in NWSP 210.0.R2(15).

[0131] If included, the lower limit of the weight ratio of the superabsorbent polymer to 100 parts by weight of the volatile 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, or 9 parts by weight, and the upper limit may be approximately 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 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 aforementioned percentage may be within the range of any one upper limit mentioned above or less than or equal to any one lower limit mentioned above or greater than or equal to any one lower limit mentioned above or greater than or equal to any one lower limit mentioned above and within the range of any one upper limit mentioned above or less than or equal to any one upper limit mentioned above.

[0132] The composition comprises the aforementioned components and may contain further components as needed.

[0133] For example, the composition may further contain a buffer.

[0134] Referring to Figures 2 and 3, under abnormal conditions, heat may be applied to the fire extinguishing device, and furthermore, instantaneous high pressure may be applied. For example, in a structure like that shown in Figure 1, if battery cells 12, 13, 14, and 15 adjacent to the fire extinguishing device 100 explode or rapidly expand, high pressure will be applied to the fire extinguishing device 100. When the fire extinguishing device 100 contracts instantaneously due to this applied pressure, vaporizable substances inside may be discharged to the outside before they vaporize, but such discharge can reduce the efficiency of the fire extinguishing action.

[0135] As described above, the buffer can provide a buffering effect against instantaneously applied pressure, and as a result, the vaporization of the vaporizable substance inside can be sufficiently facilitated.

[0136] Furthermore, the buffer may, in some cases, serve to support vaporized substances. That is, if the buffer is porous, as described later, or in the form of a woven fabric, nonwoven fabric, or felt, the buffer can exhibit the property of absorbing or supporting vaporized substances.

[0137] There are no special restrictions on the type of buffer, as long as it can perform the aforementioned function; for example, one with an appropriate density and / or thermal decomposition temperature can be used.

[0138] For example, the upper limit of the density of the buffer material 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 its lower limit may be approximately 0.001, 0.005, 0.01, 0.05, 0.1, or 0.15. The density may be within the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and any one upper limit or less than any one of the upper limits mentioned above. The unit of density is g / cm³ 3 That is the case.

[0139] For example, the upper limit of the thermal decomposition temperature of the buffer may be around 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 around 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 may be within the range of any one upper limit or less than any of the upper limits mentioned above; or within the range of any one lower limit or more than any of the lower limits mentioned above; or within the range of any one lower limit or more than any of the lower limits mentioned above, and any one upper limit or less than any of the upper limits mentioned above. The method for measuring the aforementioned thermal decomposition temperature is described in "11. Thermal Decomposition Temperature" in the Examples section of the specification.

[0140] As the buffer, any known material can be used without special limitations, as long as it has the density and / or thermal decomposition temperature. For example, glass fibers, ceramic fibers, and / or mineral fibers known as thermal insulation materials can be used as the buffer. Such inorganic fibers may be in the form of woven or nonwoven fabrics, such as porous films, porous sheets, porous foils, wool, or felt.

[0141] Furthermore, as buffers, for example, inorganic foams such as various metal foams, glass wool, mineral wool, woven fabrics, nonwoven fabrics, or felts made of glass fibers or mineral fibers, or foams, woven fabrics, nonwoven fabrics, or felts formed from carbonizable organic materials as described later may also be used.

[0142] As the buffer material, one or more types selected from the various types mentioned above may be used.

[0143] The size of the buffer is determined by the size of the sealed space and is not limited in any particular way. For example, if the buffer is in the form of a 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 the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and any one upper limit or less than any one of the upper limits mentioned above.

[0144] The aforementioned composition can exhibit unique physical properties through the combination of the components described above.

[0145] For example, the composition may exhibit a generally controlled freezing point. For instance, the lower limit of the freezing point of the composition may be around -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 around 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 or below any one of the upper limits mentioned above; or within or above any one of the lower limits mentioned above; or within or above any one of the lower limits mentioned above, and within or below any one of the upper limits mentioned above.

[0146] The composition may have a controlled viscosity and / or thixotropy.

[0147] For example, the lower limit of viscosity of the composition is 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. 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, 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 the range of any one upper limit or less than any one of the upper limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above; or within the range of any one lower limit or more than any one of the lower limits mentioned above, and within the range of any one upper limit or less than any one of the upper limits mentioned above. Such viscosity values ​​are measured at room temperature (approximately 25°C) and a rotational speed of 0.5 rpm.

[0148] For example, the lower limit of the thixotropy of the composition may be around 2, 4, 6, 8, 10, or 10.5, and its upper limit may be around 20, 18, 16, 14, 12, 10, 8, or 6. The thixotropy may be within or below any one of the upper limits mentioned above; or within or above any one of the lower limits mentioned above; or within or above any one of the lower limits mentioned above, and within or below any one of the upper limits mentioned above. Such a thixotropy is a value obtained by dividing the viscosity measured at room temperature (approximately 25°C) and a rotation speed of 0.5 rpm by the viscosity measured at room temperature (approximately 25°C) and a rotation speed of 5 rpm.

[0149] Compositions having the viscosity and / or thixotropy described above can exhibit excellent handling and storage stability.

[0150] The composition may exhibit a predetermined latent heat characteristic. Latent heat is generally defined as the amount of heat required for a substance to undergo a phase transition without a change in temperature. However, when the composition exhibits the latent heat, it is not necessarily the case that the entire substance must undergo a phase transition. The latent heat may be generated during the phase transition of at least a portion of the composition or of components contained in the composition.

[0151] The statement that a composition exhibits latent heat means that, in DSC (Differential Scanning Calorimeter) analysis, the composition shows an endothermic peak within a predetermined temperature range. The method for conducting the DSC is described in "4. Measurement of Latent Heat" in 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 exothermic products to control the heat while maintaining a uniform temperature of the product, and to minimize or prevent the impact of abnormal heat generation, explosion, and / or ignition from one product on other adjacent products.

[0152] The lower limit of the latent heat exhibited by the above composition may be, for example, around 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 its upper limit may be around 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 within the range of any one upper limit mentioned above or less than or equal to any one lower limit mentioned above; or within the range of any one lower limit mentioned above or greater than or equal to any one lower limit mentioned above and within the range of any one upper limit mentioned above or less than or equal to any one upper limit mentioned above.

[0153] The lower limit of the range of on-set temperatures at which the composition begins to exhibit the latent heat may be, for example, around 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 around 200°C, 180°C, 160°C, 140°C, 120°C, 100°C, 90°C, or 80°C. The on-set temperature may be within or below any one of the upper limits mentioned above; or within or above any one of the lower limits mentioned above; or within or above any one of the lower limits mentioned above and within or below any one of the upper limits mentioned above. The on-set temperature refers to the temperature at the left on-set point of the endothermic peak interval of the DSC analysis.

[0154] The lower limit of the temperature range in which the latent heat of the composition is exhibited may be, for example, around 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 around 300°C, 280°C, 260°C, 240°C, 220°C, 200°C, 180°C, or 160°C. The temperature range may be within or below any one of the upper limits mentioned above; or within or above any one of the lower limits mentioned above; or within or above any one of the lower limits mentioned above and within or below any one of the upper limits mentioned above. The aforementioned temperature interval is the value obtained by subtracting the temperature at the left on-set point from the temperature at the right on-set point of the endothermic peak interval of the DSC analysis.

[0155] Through the aforementioned properties, the composition can be applied to a variety of uses and can effectively address the heat generation, ignition, and / or explosions that occur in each application.

[0156] The freezing point, viscosity, thixotropy, and latent heat properties of the aforementioned compositions can be ensured through the combination of components of each composition described above.

[0157] Furthermore, the composition may further contain a variety of known additives, provided that the aforementioned physical properties are not impaired.

[0158] For example, the aforementioned vaporizing substance or composition can be loaded into the sealed space inside the aforementioned case to manufacture the aforementioned fire extinguishing device.

[0159] This specification also discloses electronic equipment or devices to which the fire extinguishing system is applied.

[0160] The type of electronic equipment or device is not particularly limited. For example, the composition or fire extinguishing device may be applied to equipment or devices that pose a risk of abnormal heat generation, ignition, and / or explosion during operation, maintenance, and / or storage, and where such abnormal phenomena must be controlled.

[0161] A typical example of the aforementioned equipment or device is a battery. In particular, in battery modules composed of multiple battery cells, it is important to prevent abnormal heat generation, ignition, and / or explosion originating from one battery cell from spreading to other adjacent battery cells.

[0162] Accordingly, this specification discloses a battery module or battery pack, etc., including the fire extinguishing device.

[0163] Such battery modules may basically include multiple battery cells and the fire extinguishing device positioned between the battery cells.

[0164] As long as the fire extinguishing device is applied, the specific configuration of the battery module, etc., such as the type of battery cell, is not particularly limited, and known materials may be used. For example, known pouch-type, rectangular, or cylindrical battery cells may be used as the battery cells.

[0165] The method for manufacturing the battery module is not particularly limited, and for example, as mentioned above, a method may be used in which a fire extinguishing device, such as in the form of a battery cell, is manufactured first, and then the fire extinguishing device is positioned at the required location during the manufacturing process of the battery module. [Effects of the Invention]

[0166] This specification discloses compositions, fire extinguishing devices, and their applications. The compositions and fire extinguishing devices are applied to products that may experience abnormal heat generation, ignition, and / or explosion during operation, storage, and / or maintenance, and can effectively respond to such heat generation, ignition, and explosion. The compositions and fire extinguishing devices are applied, for example, to articles containing multiple such products, and can respond to abnormal heat generation, explosion, and / or ignition originating from any one of the products, preventing the propagation of such heat generation, explosion, and / or ignition to other adjacent products. The compositions and fire extinguishing devices also have excellent handling and storage stability. This specification also discloses applications of the compositions and fire extinguishing devices. [Brief explanation of the drawing]

[0167] Figure 1 is an exemplary cross-sectional view of a battery module to which a fire extinguishing system has been applied. Figure 2 is an illustrative diagram illustrating the operating principle of the fire extinguishing system. Figure 3 is an illustrative diagram illustrating the operating principle of the fire extinguishing system. 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. Figure 6 shows one exemplary form of the case applied in the embodiment. [Modes for carrying out the invention]

[0168] The compositions and fire extinguishing devices will be described in detail below with reference to the examples, but the scope of the compositions and fire extinguishing devices is not limited by the examples below.

[0169] 1. Convection Exam A fire extinguishing device of an example or comparative example was positioned between two aluminum plates, and an insulating material was laminated onto one of the two aluminum plates to produce a laminate in which the insulating material, aluminum plate, fire extinguishing device, and aluminum plate were sequentially laminated. As the aluminum plate, a plate with a thickness of about 3 mm was used, and as the insulating material, mineral wool (KCC, insulation board No. 1) with a thickness of about 2 mm was used. Next, both sides of the laminate were pressed together with a jig at a pressure of about 350 kPa to fix it in place. Next, a temperature sensor (k-type thermocoupler, Fluke IR thermometers model 566) was positioned on the insulating material side of the laminate, and the temperature was measured with the temperature sensor while applying a flame toward the aluminum plate on the opposite side. The flame was applied at a distance of about 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. <Evaluation Criteria> PASS: If the temperature sensor's measured temperature is maintained below 200°C. NG: If the temperature sensor measures a temperature of 200°C or higher, or if the aluminum plate is observed to melt. 2. Chain reaction test

[0170] Rectangular batteries were arranged at intervals of approximately 3 mm, with a fire extinguishing device positioned between them. CATL products (120Ah, 3.2V, size = thickness x width x height = 48 x 174 x 165 mm) were used as rectangular batteries and were applied to the test in a 100% charged state. In the above arrangement, battery ignition was induced in one rectangular battery according to the SAE J2464:2009 standard, and the presence or absence of chain ignition in other cells was checked. The ignition of the aforementioned battery was induced by penetrating the rectangular battery with a nail approximately 5 mm in diameter at a speed of 25 mm / sec (nail penetration method).

[0171] <Evaluation Criteria> PASS: If no fire occurs in any battery cells other than the one pierced by the nail. NG: If a fire occurs in a battery cell other than the one pierced by the nail.

[0172] 3. Evaluation of storage stability 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. A weight change of 1% or more was evaluated as NG, and a change of less than 1% or no weight change was evaluated as PASS.

[0173] 4. Measurement of latent heat Approximately 3-5 mg of the composition of the example or comparative example was taken and loaded into the measuring equipment. A Differential Scanning Calorimeter (DSC) (TA instrument, Q200 model) was used as the measuring equipment. The temperature range for latent heat evaluation was set from 25°C to 300°C. The endothermic peak was measured while the temperature was increased from 25°C to 300°C at a rate of approximately 20°C / min. The left on-set point and 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 data over this range.

[0174] 5.CRC(Centrifuge Retention Capacity) CRC was measured using EDANA WSP 241.3. Approximately 0.2 g (W0) of superabsorbent polymer was placed in a nonwoven fabric bag, sealed, and then immersed in physiological saline solution at room temperature. A 0.9 wt% NaCl aqueous solution was used as the physiological saline solution. This condition was maintained for approximately 30 minutes, and after removing moisture from the bag for 3 minutes under a 250 g condition using a centrifuge, the mass of the bag (g, W2) was measured.

[0175] The same procedure was performed on the same nonwoven fabric bags that did not contain superabsorbent polymers, and their mass (g, W1) was measured.

[0176] The measurement results were substituted into formula A below to calculate CRC (g / g). The aforementioned evaluation was conducted under constant temperature and humidity conditions (23±1°C, relative humidity: 50±10%). [Formula A] CRC(g / g)={[W2(g)-W1(g)] / W0(g)}-1 6.AUP(Absorption Under Pressure) AUP was measured using the EDANA method WSP 242.3. A stainless steel 400-mesh wire mesh was attached to the bottom of a plastic cylinder with an inner diameter of approximately 60 mm. 0.0 g (W0) (0.90 g) of superabsorbent polymer was uniformly scattered on the wire mesh, and a piston capable of uniformly applying a load of 0.3 psi was placed on top of it. The piston had an outer diameter slightly smaller than 60 mm and was installed so as to be able to move up and down without any gaps between it and the inner wall of the cylinder. The weight (g, W3) of the apparatus was measured.

[0177] Glass filters with diameters of 90 mm and thicknesses of 5 mm were placed inside a 150 mm diameter petroleum dish, and physiological saline solution was added until it was level with the top surface of the glass filters. A 0.9 wt% NaCl aqueous solution was used as the physiological saline solution. A 90 mm diameter filter paper was placed on top of the saline solution. The measuring device was mounted on the filter paper and allowed to absorb the physiological saline solution under a load of 0.3 psi for 1 hour. After that, the measuring device was lifted and its weight (g, W4) was measured.

[0178] The obtained values ​​were substituted into equation B below to evaluate AUP(g / g). The aforementioned evaluation was conducted under constant temperature and humidity conditions (23±1°C, relative humidity: 50±10%). [Formula B] AUP(g / g) = [W4(g) - W3(g)] / W0(g)

[0179] 7. Measurement of molecular weight The molecular weight of starch was evaluated using the following method.

[0180] (1) Manufacturing of the mobile phase Mobile phase A was prepared by filtering 1000 mL of a 150 ml NaNO3 aqueous solution containing 0.02 wt% NaN3 using a solvent clarification system (Millipore Millisolve Kit, MilliporeSigma).

[0181] (2) Preparation of sample solution A 25 mg sample was taken from the sample whose molecular weight was to be measured, mixed with 5 mL of 150 ml of NaNO3 aqueous solution 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 the sample solution.

[0182] (3) GPC (Gel Permeation Chromatography) / MALS (Multi-Anglue Light Scattering Detection) conditions The molecular weight was evaluated using the sample solution and mobile phase A in the following manner. Measurement device: Agilent GPC (Agilent 1200 series, US) Stationary phase: Shodex OH-Pak 804 column and Shodex OH-Pak 80 column linked together Mobile phase: A; 0.02% NaN3, 150mm NaNO3 aqueous solution = 100 (v / v%) Flow rate: 0.4mL / min Stationary phase temperature: 25℃ Injection volume: 100μl (0.45μm filtered) Analysis time: 120 minutes

[0183] 8. Measurement of amylovectin and amylose content The amylovectin and amylose content of starch was evaluated according to the method described in the paper (Potato Research 31(1988)241-246).

[0184] First, approximately 5 mg of starch was dissolved in approximately 1 mL of sterile water to prepare the sample (Step 1), and then it was heated in a water bath at 95°C for approximately 15 minutes (Step 2).

[0185] Next, approximately 20 μl of the sample was placed in a cuvette (step 3), and approximately 980 μl of iodine solution was added and mixed (step 4).

[0186] Next, the absorbance of the sample mixed with the iodine solution was measured and recorded at wavelengths of 525 nm and 700 nm (Step 5). The absorbance was measured using the KLAB OPTIZEN POP model.

[0187] Approximately 20 μl of water was placed in another cuvette, 980 μl of iodine solution was added, and the mixture was mixed (Step 6). The absorbance of the solution from Step 6 was measured and recorded at wavelengths of 525 nm and 700 nm, in the same manner as in Step 5 (Step 7).

[0188] The absorbance obtained in step 7 was subtracted from the absorbance obtained in step 5, and the percentage of amylose was confirmed using the following formula C (step 8).

number

[0189] In formula C, PA is the percentage of amylose, and OD 700 This is the value obtained by subtracting the absorbance at 700 nm measured in step 7 from the absorbance at 700 nm measured in step 5, and OD 525 This value is obtained by subtracting the absorbance at 525 nm measured in step 7 from the absorbance at 525 nm measured in step 5.

[0190] 9. Evaluation of WVTR (Water Vapor Transmission Rate) The case's WVTR was evaluated according to the ASTM F1249 standard under conditions of 38°C and 100% relative humidity.

[0191] 10. Evaluation of solubility Solubility was evaluated based on the ASTM E1148-02 standard. The amount of the sample that dissolves to the maximum extent in 100g of a vaporizing substance (water) at 0°C or room temperature (approximately 25°C) was evaluated according to the aforementioned standard, and the solubility was confirmed.

[0192] 11.Pyrolysis temperature The thermal decomposition temperature was determined by TGA (Thermogravimetric Analysis). Using a Mettler-Toledo TGA e850, the sample temperature 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 thermal decomposition temperature.

[0193] 12. Evaluation of Flammability The flammability of the freezing point modifier was evaluated according to ASTM D93 standards. The sample (ignition source) was placed in a 100 mL brass test cup in an amount of approximately 90% of the cup's volume, stirred at approximately 100 times / min, and the ignition source diameter was set to approximately 3.2 mm to 4.8 mm. The flash point was evaluated while the temperature was increased at a rate of 5 °C / min. If the sample vaporized without igniting during the evaluation, the sample was evaluated as non-flammable. If ignition occurred, the temperature at the time of ignition was defined as the flash point.

[0194] 13. Assessment of whether or not toxic gases are generated. The presence or absence of toxic gases was evaluated using a length-of-stain colorimetric dosimeter according to the ASTM D4599-21 standard. The length-of-stain colorimetric dosimeter is a tube that allows for concentration measurement by color, and a measurement tube is specified for each toxic gas. Gas samples generated from the target substance were collected for approximately 1 minute and quantified. After injecting the sample into the open end of the length-of-stain colorimetric dosimeter using a 100 ml syringe, the sample was maintained for approximately 8 hours, and then the concentration was measured for each gas. The toxic gases measured using this method were chlorine gas, ammonia gas, and hydrofluoric acid gas.

[0195] 14. Whether or not it is flammable. The fire extinguishing composition was placed in an aluminum can and its flammability was evaluated. The aluminum can used was manufactured using aluminum foil with a thickness of approximately 3 mm and had an open top. The width and height of the can were approximately 9 cm and 12 cm, respectively, and the internal volume was approximately 32.4 cm³. 3 The results were as follows: The composition was filled into the can, and with the top of the can open, a flame was applied vertically to one side of the can from a distance of about 1 inch. The flame was applied using butane gas (a 220g capacity can of butane gas (unused product)) and a torch. While applying the flame for about 5 minutes, the flammability was evaluated by observing whether or not a flame was generated at the open top end.

[0196] 15. Evaluation of thermal conductivity Thermal conductivity was evaluated at 20°C using a measuring instrument (Hot Disk, TPS2200) in accordance with the ISO22007-2 standard.

[0197] Example 1. Fire extinguishing composition A first mixture was prepared by mixing water (W), monoammonium phosphate (N) (NH4H2PO4), starch (S), and melamine (M) in a weight ratio of 100:22:6:6 (W:N:S:M). The mixing was carried out at room temperature (approximately 25°C) at a mixing speed of 500 rpm for approximately 1 minute. The solubility of monoammonium phosphate (N) (NH4H2PO4) in water at 25°C is approximately 29 g. Corn starch was used as the starch, with 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. Next, a superabsorbent polymer (SAP) was further mixed into the first mixture to prepare a fire extinguishing composition. The mixing of the superabsorbent polymer was carried out by mixing the first mixture with the superabsorbent polymer and mixing at room temperature (approximately 25°C) at a mixing speed of 500 rpm for about 2 hours. The mixing was carried out so that the weight ratio (W:P) of water (W) to the superabsorbent polymer (P) in the mixture was approximately 100:5. As the superabsorbent polymer, LG Chem's GS-803ND product was used, and after pulverization and classification processes, it was applied in a size range of approximately 150 μm to 850 μm. The CRC (Centrifuge Retention Capacity) of such a superabsorbent polymer was approximately 33.5 g / g, and the AUP (Absorption Under Pressure) was approximately 28.1 g / g. The latent heat of the fire extinguishing composition was approximately 1615 J / g.

[0198] fire extinguisher The aforementioned composition was placed inside an aluminum can (case) used in the manufacture of a rectangular battery, and the opening was sealed to manufacture a fire extinguishing device. The WVTR of the can used in the rectangular battery was approximately 0 g / m². 2The process took approximately 1 day. As shown in Figure 4, two heat conductive layers 2001 and 2002 were inserted inside the aluminum can 1001, the composition was injected between them, and then the cover 1002 was placed over them to manufacture the fire extinguishing device. During the manufacture of 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. For the heat conductive layers 2001 and 2002, copper films (thickness approximately 15 μm) with a thermal conductivity of approximately 401 W / m·K (at 20°C) were used. For the rectangular battery case, a case with a width of approximately 9 cm, a height of approximately 12 cm, and a thickness of approximately 3 mm was used.

[0199] Example 2. For use as a case for rectangular batteries, WVTR is approximately 0.11 g / m². 2 Except for using a case of approximately 1 day, and using aluminum foil with a thermal conductivity of approximately 235 W / mK (at 20°C) and a thickness of approximately 100 μm as the heat conductive layer, the fire extinguishing device was manufactured in the same manner as in Example 1.

[0200] Example 3. Manufacture of fire extinguishing composition Water (W), monoammonium phosphate (N) (NH4H2PO4), starch (S), and melamine (M) were mixed in a weight ratio of 100:22:10:10 (W:N:S:M) to produce a first mixture. The mixing was carried out at room temperature (approximately 25°C) at a mixing speed of 500 rpm for approximately 1 minute. The same starch as in Example 1 was used. Next, a superabsorbent polymer (SAP) was further mixed into the first mixture to produce a fire extinguishing composition. The superabsorbent polymer was mixed with the first mixture and mixed at room temperature (approximately 25°C) at a mixing speed of 500 rpm for approximately 2 hours. The mixing was carried out so that the weight ratio (W:P) of water (W) to the superabsorbent polymer (P) in the mixture was approximately 100:8. The same superabsorbent polymer as in Example 1 was used. The latent heat of the fire extinguishing composition was approximately 1615 J / g.

[0201] fire extinguisher For use as a case for rectangular batteries, WVTR is approximately 0.27 g / m². 2Except for using a case of approximately 1 day, and using a copper alloy foil with a thermal conductivity of approximately 138 W / mK (at 20°C) and a thickness of approximately 150 μm as the heat conductive layer, the fire extinguishing device was manufactured in the same manner as in Example 1 using the above composition.

[0202] Example 4. Fire extinguishing composition Water (W) and a freezing point modifier (ethylene glycol (molar mass: 62.07 g / mol)) (E) were mixed in a weight ratio of 60:40 (W:E). The mixing was carried out at room temperature (approximately 25°C) at 300 rpm for approximately 30 minutes. The ethylene glycol has a flash point of approximately 111°C, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas, as measured by a toxic gas evaluation method, were all 0 ppm. Furthermore, the ethylene glycol was miscible with water. Next, the mixture was placed in a sealed container, and glass wool was placed in the sealed container. The mixture was then maintained at room temperature (approximately 25°C) for approximately 24 hours to allow it to be supported on the glass wool (latent heat: approximately 1,000 J / g or more). The glass wool had a thickness of approximately 2.5 mm and a density of approximately 0.03 g / cm³. 3 Glass wool (glass wool blanket, rosewool) with a thermal decomposition temperature of approximately 400°C was used.

[0203] fire extinguisher The aforementioned composition was placed inside a can (case) used in the manufacture of a rectangular battery, and the opening was sealed to manufacture a fire extinguishing device. The WVTR of the can used in the rectangular battery was approximately 0.11 g / m³ 2The process took approximately 1.5 days. As shown in Figure 5, two heat conductive layers 2001 and 2002 were inserted inside the aluminum can 1001, and glass wool 300 on which the mixture was supported was placed between the heat conductive layers 2001 and 2002. After this, the cover 1002 was placed over the glass wool to manufacture the fire extinguishing device. During the manufacture of the fire extinguishing device, the size of the glass wool was adjusted so that the composition filled at least 90% of the volume of the empty space inside the can. For the heat conductive layers 2001 and 2002, copper film (thickness approximately 18 μm) with a thermal conductivity of approximately 405 W / m·K (at 20°C) was used. For the rectangular battery case, a case with a width of approximately 9 cm, a height of approximately 12 cm, and a thickness of approximately 3 mm was used.

[0204] Example 5. Fire extinguishing composition Glass wool supported with water and ethylene glycol was obtained in the same manner as in Example 4, except that water (W) and ethylene glycol (molar mass: 62.07 g / mol) (E) were mixed in a weight ratio of 72:28 (W:E) (latent heat: approximately 1,000 J / g or more).

[0205] fire extinguisher Made of aluminum, this case is designed for rectangular batteries and has a WVTR of approximately 0g / m². 2 Except for using a case of approximately 1 day, the fire extinguishing device was manufactured in the same manner as in Example 4.

[0206] Example 6. Fire extinguishing composition 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). As the starch, corn starch was used, with 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 modifier, is a non-flammable substance with no flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured by a toxic gas evaluation method were all 0 ppm, indicating that it is a non-toxic substance. Furthermore, the solubility of potassium acetate, the freezing point modifier, 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. Next, the mixture is placed in a sealed container, and then mineral wool (thickness: approximately 2.5 mm, density: approximately 0.2 g / cm³) is added to the sealed container. 3 After adding the mineral wool (KCC, Mineral Wool Insulation Board No. 1) (thermal decomposition temperature: approximately 800°C), the mixture was maintained at room temperature (approximately 25°C) for approximately 24 hours to allow the mixture to be supported on the mineral wool (latent heat: approximately 1,000 J / g or more).

[0207] Fire extinguishing equipment The WVTR used as a casing in the manufacture of prismatic batteries is approximately 0.27 g / m². 2 A fire extinguishing device was manufactured using a can of approximately 1 day size in the manner described in Example 4. In this process, aluminum foil with a thermal conductivity of approximately 235 W / mK (at 20°C) and a thickness of approximately 50 μm was used for the heat conductive layer.

[0208] Comparative Example 1. The fire extinguishing device was manufactured in the same manner as in Example 4, except that a heat conductive layer was not applied.

[0209] Comparative Example 2. Fire extinguishing composition 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, used as a freezing point modifier, is a non-flammable substance with no flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured by a toxic gas evaluation method were all 0 ppm, indicating that it was a non-toxic substance. Next, the mixture was placed in a sealed container, and then mineral wool (thickness: approximately 2.5 mm, density: approximately 0.2 g / cm³) was placed in the sealed container. 3 After adding (KCC, Mineran-Ul insulation board No. 1) (thermal decomposition temperature: approximately 800°C), the mixture was maintained at room temperature (approximately 25°C) for approximately 24 hours to produce a fire extinguishing composition.

[0210] Fire extinguishing equipment The WVTR used as a casing in the manufacture of prismatic batteries is approximately 0.27 g / m². 2 A fire extinguishing device was manufactured using the same method as in Example 1, with a can of approximately 1 day size. In this process, aluminum foil with a thermal conductivity of approximately 235 W / mK (at 20°C) and a thickness of approximately 50 μm was used as the heat conductive layer.

[0211] Comparative Example 3. Except for changing the thermal conductive layer, the fire extinguishing device was manufactured in the same manner as in Example 1. As the thermal conductive layer, manganese foil with a thermal conductivity of approximately 7.81 W / mK (at 20°C) and a thickness of approximately 20 μm was used.

[0212] Comparative Example 4. A fire extinguishing device was manufactured in the same manner as in Example 1. However, in this case, instead of the fire extinguishing composition, a polyurethane foam pad, which is a known heat insulating material, was inserted into the case to manufacture the fire extinguishing device.

[0213] 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 molar concentration of the freezing point modifier relative to the vaporizing substance (water) in the composition, and △T f This is given by equation 1(K fThe value is calculated using (×M×I). Also, 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 taken as 100%, and WVTR is the WVTR of the case used in the manufacture of the fire extinguishing device (unit: g / m³). 2 It is (day). Also, in Tables 1 and 2 below, the thermal conductivity is the thermal conductivity of the heat conductive layer applied to the fire extinguishing system (unit: W / mK) (based on 20°C).

[0214] [Table 1] [Table 2]

[0215] The results in Table 1 confirm that when water is included in the composition above a certain content and a heat conductive layer is introduced into the fire extinguishing device, excellent results are obtained in the convection test and chain ignition test. Furthermore, considering the temperature confirmed by the temperature sensor in the convection test, Examples 3 to 6, in which the vaporization rate was adjusted by adding a freezing point modifier, showed superior effects compared to the other examples. The results in Table 2 show that even with a high water content, if there is no heat conductive layer (Comparative Example 1) or the thermal conductivity of the heat conductive layer is low (Comparative Example 3), the intended effect cannot be obtained, and even in the presence of a heat conductive layer, if the water content is low (Comparative Examples 2 and 4), the desired effect cannot be ensured.

[0216] Example 7. Except for using a pouch-type case as the fire extinguishing device case, the fire extinguishing device was manufactured in the same manner as in Example 1. The case was manufactured using an outer shell made by laminating PET (poly(ethylene terephthalate)) film (thickness: approximately 10 μm), aluminum foil (thickness: approximately 20 μm), and PP (polypropylene) hot melt film (thickness: approximately 70 μm) (melting point: approximately 140°C) in this order. The outer shell was manufactured by laminating the PET film to one side of the aluminum foil with adhesive, and laminating the PP hot melt film to the other side at a temperature of approximately 200°C. As shown in Figure 6, a recess I was formed in the center of the outer shell, and an upper outer shell 121 and a lower outer shell 122 were prepared, respectively. After bonding a heat conductive layer to the recesses I of the upper and lower outer shells 121 and 122, a fire extinguishing composition was placed on the heat conductive layer, and after laminating the upper and lower outer shells 121 and 122, the PP hot melt films were fused together at the sealing section S to manufacture the fire extinguishing device. Subsequently, three of the four sealing sections S were folded so that the unfolded sealing section could act as a vent area. The composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the recesses I. The WVTR of the case was approximately 0 g / m 2 The temperature was approximately 1 day. The same thermal conductive layer used in Example 1 was used. The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0217] Example 8. A fire extinguishing device was manufactured using the method presented in Example 7, with an outer shell made by laminating PET (poly(ethylene terephthalate)) film (thickness: approximately 10 μm), PVDC (Polyvinylidene chloride) film (thickness: approximately 40 μm), and PP (polypropylene) hot melt film (thickness: approximately 50 μm) (melting point: approximately 140°C) in that order. The fire extinguishing device was manufactured in the same manner as in Example 7, except that an aluminum foil with a thermal conductivity of approximately 235 W / mK (at 20°C) and a thickness of approximately 100 μm was used as the thermal conductive layer. The WVTR of the case was 0.11 g / m 2 It was about a day.

[0218] Example 9. A fire extinguishing device was manufactured using an outer shell produced by laminating a PET (poly(ethylene terephthalate)) film (thickness: approximately 10 μm), an EVOH (Ethylene Vinyl Alcohol) film (thickness: approximately 40 μm), and a PE (polyethylene) hot melt film (thickness: approximately 50 μm) (melting point: approximately 140°C) in this order, in the same manner as in Example 7. The WVTR of the case was approximately 0.27 g / m². 2 The thermal conductivity was approximately 138 W / mK (at 20°C) and the thickness was approximately 150 μm. The fire extinguishing composition used was the same as that used in Example 3.

[0219] Example 10. An outer shell was manufactured by laminating a PET (poly(ethylene terephthalate)) film (thickness: approximately 10 μm), a PVDC (Polyvinylidene chloride) film (thickness: approximately 40 μm), and a PP (polypropylene) hot melt film (thickness: approximately 50 μm) (melting point: approximately 140°C) in this order. As shown in Figure 6, a recess I was formed in the center of the outer shell, and an upper outer shell 121 and a lower outer shell 122 were prepared. After bonding a heat conductive layer to the recess I of the upper and lower outer shells 121 and 122, glass wool supporting water, etc. from Example 4 was placed on the heat conductive layer, and after laminating the upper and lower outer shells 121 and 122, the PP hot melt films were fused together at the sealing section S to manufacture the fire extinguishing device. Subsequently, three of the four sealing sections S were folded so that the unfolded sealing section could act as a vent area. As described above, the glass wool was inserted in a size that occupied at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the case was approximately 0.11 g / m 2 The temperature was approximately 18 μm thick and had a thermal conductivity of approximately 405 W / m·K (at 20°C). The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0220] Example 11. An outer shell was manufactured by laminating a PET (poly(ethylene terephthalate)) film (thickness: approximately 10 μm), aluminum foil (thickness: approximately 20 μm), and a PP (polypropylene) hot melt film (thickness: approximately 70 μm) (melting point: approximately 140°C) in this order. As shown in Figure 6, a recess I was formed in the center of the outer shell, and an upper outer shell 121 and a lower outer shell 122 were prepared. After bonding a heat conductive layer to the recess I of the upper and lower outer shells 121 and 122, glass wool supporting water, etc. from Example 5 was placed on the heat conductive layer, and after laminating the upper and lower outer shells 121 and 122, the PP hot melt films were fused together at the sealing section S to manufacture the fire extinguishing device. Subsequently, three of the four sealing sections S were folded so that the unfolded sealing section could function as a vent area. As described above, the glass wool was inserted in a size that occupied at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the case was approximately 0 g / m 2 The temperature was approximately 18 μm thick and had a thermal conductivity of approximately 405 W / m·K (at 20°C). The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0221] Example 12. An outer shell was manufactured by laminating a PET (poly(ethylene terephthalate)) film (thickness: approximately 10 μm), an EVOH (Ethylene Vinyl Alcohol) film (thickness: approximately 40 μm), and a PE (polyethylene) hot melt film (thickness: approximately 50 μm) (melting point: approximately 140°C) in this order. As shown in Figure 6, a recess I was formed in the center of the outer shell, and an upper outer shell 121 and a lower outer shell 122 were prepared. After bonding a heat conductive layer to the recess I of the upper and lower outer shells 121 and 122, mineral wool supporting water, etc. from Example 6 was placed on the heat conductive layer, and after laminating the upper and lower outer shells 121 and 122, the PP hot melt films were fused together at the sealing section S to manufacture the fire extinguishing device. Subsequently, three of the four sealing sections S were folded so that the unfolded sealing section could act as a vent area. As described above, the mineral wool was inserted in a size that occupied at least 90% of the volume of the sealed space formed by recess I. The WVTR of the case was approximately 0.27 g / m 2 The temperature was approximately 1 day. For the thermal conductive layer, aluminum foil with a thermal conductivity of approximately 235 W / mK (at 20°C) and a thickness of approximately 50 μm was used. The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0222] Comparative Example 5. The fire extinguishing device was manufactured in the same manner as in Example 10, except that a heat conductive layer was not applied.

[0223] Comparative Example 6. The fire extinguishing device was manufactured in the same manner as in Example 12, except that the mineral wool obtained in Comparative Example 2 was used. In this process, aluminum foil with a thermal conductivity of approximately 235 W / mK (at 20°C) and a thickness of approximately 50 μm was used as the heat conductive layer.

[0224] Comparative Example 7. Except for changing the thermal conductive layer, the fire extinguishing device was manufactured in the same manner as in Example 7. As mentioned above, manganese foil with a thermal conductivity of approximately 7.81 W / mK (at 20°C) and a thickness of approximately 20 μm was used as the thermal conductive layer.

[0225] Comparative Example 8. A fire extinguishing device was manufactured in the same manner as in Example 7. However, in this case, instead of the fire extinguishing composition, a polyurethane foam pad, which is a known heat insulating material, was inserted into the case to manufacture the fire extinguishing device.

[0226] 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 the same as in Tables 1 and 2. Also, in Tables 3 and 4, the water content is the weight of water contained when the weight of the fire extinguishing composition of the example or comparative example is taken as 100%, and WVTR is the WVTR of the case used in the manufacture of the fire extinguishing device (unit: g / m³). 2 It is (day). Also, in Tables 3 and 4 below, the thermal conductivity is the thermal conductivity of the heat conductive layer applied to the fire extinguishing system (unit: W / mK) (based on 20°C). [Table 3] [Table 4]

[0227] The results in Tables 3 and 4 show that although there are differences in the form of the fire extinguishing devices, by adjusting the amount of heat conductive layer and water in the fire extinguishing device, excellent results can be obtained in convection tests and chain ignition tests.

Claims

1. Volatile substances; One or more fire extinguishing agents selected from the group consisting of phosphoric acid, phosphates, phosphonate compounds and phosphate compounds; and Contains carbonizable organic matter, A composition exhibiting a latent heat of 500 J / g.

2. The composition according to claim 1, wherein the content of the volatile substance is 50% by weight or more.

3. The composition according to claim 1, wherein the fire extinguishing agent has a solubility of 5 g or more in 100 g of water at 25°C.

4. The freezing point modifier is ΔT in the following formula 1. ｆ The composition according to claim 1, further comprising such that the ratio is in the range of 5 to 50: [Formula 1] △T ｆ =K ｆ ×M×I In Equation 1, K ｆ is the freezing point depression constant of the vaporized substance, M is the molar concentration of the freezing point regulator relative to the vaporized substance, and I is the number of ions formed by the freezing point regulator, where I is 1 if the freezing point regulator is not an ionic compound.

5. A case with a sealed space inside; Vaporizing substances present in the sealed space; and It contains a thermal conductive layer with a thermal conductivity of 10 W / mK or higher at 20°C. A fire extinguishing device in which the content of vaporized substances in the sealed space is 50% by weight or more.

6. In the aforementioned case, the WVTR (Water Vapor Transmission Rate) of 80% or more of the area forming the sealed space is 5 g / m². ２ - The WVTR (Water Vapor Transmission Rate) is 5 g / m² or less, or the WVTR of 80% or more of the area of ​​the case is 5 g / m² or less. ２ - The fire extinguishing device according to claim 5, wherein the number of days is less than or equal to 5 days.

7. The fire extinguishing device according to claim 5, wherein the vaporized substance has a boiling point in the range of 80°C to 120°C.

8. The fire extinguishing device according to claim 5, wherein the vaporizing substance is water.

9. The solidification point modifier further comprises a solidification point modifier present in a sealed space, wherein the solidification point modifier is ΔT of the following formula 1. ｆ The fire extinguishing device according to claim 5, wherein the value is included in a range of 5 to 50: [Formula 1] △T ｆ =K ｆ ×M×I In Equation 1, K ｆ is the freezing point depression constant of the vaporized substance, M is the molar concentration of the freezing point regulator relative to the vaporized substance, and I is the number of ions formed by the freezing point regulator, where I is 1 if the freezing point regulator is not an ionic compound.

10. The fire extinguishing device according to claim 9, wherein the coagulation point adjusting agent has a solubility of 20 g or more per 100 g of vaporizable substance at 0°C.

11. The fire extinguishing device according to claim 9, wherein the coagulation point adjusting agent has a solubility of 70 g or more per 100 g of vaporizing substance at 25°C.

12. The fire extinguishing device according to claim 9, wherein the freezing point adjusting agent has a molar mass of 300 g / mol or less.

13. The fire extinguishing device according to claim 9, wherein the coagulation point modifier is one or more selected from the group consisting of formate, acetate, carbonate, and sulfate.

14. The fire extinguishing device according to claim 5, wherein the heat conductive layer is located between the vaporized substance and the case.

15. The fire extinguishing device according to claim 5, further comprising one or more selected from the group consisting of carbonizable organic matter and carbonizing catalyst present in the sealed space.

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