Composition

Abstract

The invention discloses a composition, a fire extinguishing device and application of the fire extinguishing device. The composition and the fire extinguishing device can be applied to products having the likelihood of abnormal heat, fire and / or explosion during driving, storage and / or maintenance processes to effectively respond to heat, fire and explosion. The composition and the fire extinguishing device can be applied to, for example, articles including a plurality of products in response to abnormal heat, explosion and / or fire occurring in any one of the products, and can prevent such heat, explosion and / or fire from propagating to other adjacent products. The composition and the fire extinguishing device also have excellent operability and storage stability. The invention further discloses application of the composition and the fire extinguishing device.

Description

Technical Field

[0001] This application claims the benefit of priority based on Korean Patent Application Nos. 10-2023-0041413 and 10-2023-0041416, filed on March 29, 2023, the disclosures of which are incorporated herein by reference in their entirety.

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

[0003] Technology is needed to ensure the stability of products that pose a risk of abnormal heating, fire, or explosion (hereinafter referred to as "hazardous products"). In particular, in the case of multiple hazardous products, if abnormal heating, fire, and / or explosion occurring in any one product has a knock-on effect on other adjacent products, major stability issues may occur. Representative examples of such phenomena are so-called TR (Thermal Runaway) or TP (Thermal Propagation) phenomena that occur in battery modules, battery packs, and the like.

[0004] A battery module or battery pack includes a plurality of battery cells or battery modules arranged adjacent to each other. In such a structure, if abnormal heating, fire, and / or explosion occurs in any battery cell and / or battery module, the phenomenon in which such heating, fire, and / or explosion spreads to other adjacent battery cells in a chain reaction is called TR or TP phenomenon.

[0005] With the development of products requiring a large amount of energy for driving, such as electric vehicles, the energy capacity of battery modules or battery packs has significantly increased, and thus the risk of TR or TP phenomena has also significantly increased.

[0006] In particular, in situations where the stability of the user is directly affected by TR or TP phenomena (such as electric vehicles), the chain reaction of heating, fire and explosion (such as TR or TP) must be managed. Summary of the Invention

[0007] Technical issues

[0008] This specification discloses a composition, a fire extinguishing device and uses thereof.

[0009] The present specification aims to disclose a composition and a fire extinguishing device and their use that can be applied to products having the possibility of abnormal heating, fire and / or explosion during driving, storage and / or maintenance processes to effectively respond to heating, fire and explosion.

[0010] For example, the compositions and fire extinguishing devices disclosed herein can be applied to an article of manufacture comprising a plurality of products to respond to abnormal heating, explosion, and / or fire occurring in any one product and to prevent such heating, explosion, and / or fire from spreading to other adjacent products.

[0011] Another object of the present invention is to disclose a composition and a fire extinguishing device having excellent operability and storage stability. The present invention also aims to disclose uses of the composition and the fire extinguishing device.

[0012] Technical Solution

[0013] Among the physical properties mentioned in this specification, physical properties affected by temperature are physical properties measured at room temperature unless otherwise specified.

[0014] The term room temperature is a natural temperature without artificial heating or cooling, which means, for example, any temperature within the range of about 10°C to 30°C, or a temperature around about 23°C or about 25°C.

[0015] Unless otherwise specified in this specification, temperatures are in °C.

[0016] Among the physical properties mentioned in this specification, physical properties affected by pressure are physical properties measured under normal pressure unless otherwise specified.

[0017] The term normal pressure refers to a natural pressure without artificial pressure increase or decrease, wherein a pressure within a range of about 700 mmHg to 800 mmHg is generally referred to as normal pressure.

[0018] Among the physical properties mentioned in this specification, physical properties affected by humidity are physical properties measured under standard humidity unless otherwise specified.

[0019] Standard state humidity means approximately 40%, 50%, 60% or 65% in terms of relative humidity.

[0020] This specification discloses compositions.

[0021] The term composition refers to an object comprising two or more components. Such a composition can be a fire extinguishing composition. A fire extinguishing composition is a composition that is capable of responding to abnormal heat, flames, explosions, etc. to be suppressed.

[0022] Such a composition can be particularly combined with the structure of the fire extinguishing device described below to exhibit excellent effects.

[0023] Therefore, this specification also discloses a fire extinguishing device.

[0024] First, the fire extinguishing apparatus will be described.

[0025] The fire extinguishing device includes a housing having a sealed space therein and a vaporizable substance or composition in the sealed space.

[0026] The composition may be the fire extinguishing composition described above, and the vaporizable substance may be a component of the composition.

[0027] The housing is a container for holding a vaporizable substance or composition. The housing has a sealed space inside, or is configured to form a sealed space. Here, "the housing is configured to form a sealed space inside" means that the housing exists in a state where a sealed space is formed inside the housing, or that the housing exists so that a certain space exists inside the housing, and this space is not sealed, but a sealed space can be formed by sealing the opening portion.

[0028] The sealed space of such a housing may have a ventilation area. The term ventilation area may refer to an area that is sealed in a first state to maintain the sealed state of the space, but is open in a second state to allow the material inside the space to be discharged. The second state may refer to a state in which abnormal fire, heat generation, and / or explosion occurs, for example, in the environment in which the composition or fire extinguishing device is used, and the first state may refer to a state in which abnormal fire, abnormal heat generation, and abnormal explosion do not occur.

[0029] Such ventilation areas may be formed in the manner described below.

[0030] In one embodiment, the housing may have a WVTR (Water Vapor Transmission Rate) within a predetermined range, or may include a portion having such a WVTR. For example, at least a portion of the housing forming the sealed space may have a WVTR (Water Vapor Transmission Rate) within a predetermined range. For example, the upper limit of the WVTR of the housing 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 its lower limit may be approximately 0, 0.1, 0.2, 0.3, 0.4, or 0.5. The WVTR may be within a range of less than or equal to, or less than, any of the above upper limits; or within a range of less than or equal to, or less than, any of the above upper limits and greater than or equal to, or greater than any of the above lower limits. The closer the WVTR is to the range disclosed in the Examples section of this specification within the above range, the better the effect can be ensured. The unit of WVTR is g / m 2Days, which were measured in the manner described in "9. WVTR (Water Vapor Transmission Rate) Evaluation" of the Example section in this specification.

[0031] In one example, when at least a sealed space has been formed within the housing, a certain level or more of the entire area of ​​the housing forming the sealed space may have a WVTR within the above range.

[0032] For example, a WVTR within the aforementioned range can be determined for an area that is greater than or equal to a certain ratio of the total area of ​​the housing. For example, the lower limit of the ratio of the area of ​​the portion of the total area of ​​the housing having a WVTR within the aforementioned range can be approximately 80%, 85%, 90%, 95%, 97%, or 99%, and the upper limit can be approximately 100%. This ratio can be within a range greater than, equal to, or greater than any of the aforementioned lower limits; or within a range less than, equal to, or less than any of the aforementioned upper limits, while also within a range greater than, equal to, or greater than any of the aforementioned lower limits.

[0033] In another example, the WVTR (water vapor transmission rate) of a certain level or more of the area of ​​the portion of the housing forming the sealed space may be within the aforementioned range. For example, the lower limit of the ratio of the portion of the area of ​​the housing forming the sealed space exhibiting a WVTR within the aforementioned range may be approximately 80%, 85%, 90%, 95%, 97%, or 99%, and the upper limit thereof may be approximately 100%. This ratio may be within a range greater than, equal to, or greater than either of the aforementioned lower limits; or within a range less than, equal to, or less than either of the aforementioned upper limits, and within a range greater than, equal to, or greater than either of the aforementioned lower limits.

[0034] This means that the sealed space inside the housing is completely surrounded by a region substantially having a WVTR within the above range. By this configuration, an instantaneous increase in the internal pressure inside the fire extinguishing device to be described below can be effectively caused.

[0035] The fire extinguishing device is configured so that it can stably maintain the vaporizable substance or composition inside in a normal state, and then release all or part of the vaporizable substance or composition, or its vapor, to the outside in an abnormal state. The abnormal state can be, for example, the second state, and the normal state can be, for example, the first state.

[0036] Description will be made assuming a case where the fire extinguishing apparatus is applied to a battery module.

[0037] Figure 1 FIG. 1 is a schematic diagram showing a fire extinguishing device S applied to a battery module. Figure 1As shown, a battery module can be configured by arranging a plurality of battery cells 11, 12, 13, 14, 15, 16 adjacent to each other, wherein a fire extinguishing device S can be arranged between the battery cells as shown (e.g., Figure 1 Between 12 and 13 and Figure 1 between 14 and 15 in the table).

[0038] The fire extinguishing device S maintains the vaporizable substances etc. in the normal state. In the abnormal state, the vaporizable substances etc. in the fire extinguishing device S can be ejected ( Figure 1 The dotted arrow in the figure also has directionality, such as spraying through the above-mentioned ventilation area, etc., in response to high temperature or flames caused by abnormal heating, fire and / or explosion. Figure 1 In the embodiment, the case where the material is sprayed from the upper end and the lower end of the fire extinguishing device S is described, but the spraying direction is not limited to Figure 1 The spray direction may also be in one direction of the fire extinguishing device S, or in two or more directions. Such a spray direction can be adjusted by forming a ventilation area.

[0039] In order for a fire extinguishing device to effectively function under abnormal conditions, it is required that the vaporizable substance, etc., present in the interior of the housing under normal conditions be stably maintained, and that when an abnormal condition occurs, the vaporizable substance, etc., be rapidly depleted by discharging as much of the vaporizable substance, etc., as possible to the outside in a vaporized state. The fire extinguishing device can meet these requirements.

[0040] Explain the principle of how fire extinguishing devices work.

[0041] Figure 2 Only a single Figure 1 Fire extinguishing device S. In such Figure 1 In the configuration of Figure 2 As shown by the solid arrow in , a certain level or more of high heat is instantaneously applied to the fire extinguishing device. The vaporizable substance present in the fire extinguishing device is vaporized by the applied heat. Figure 2 In the embodiment of the present invention, as indicated by the dotted arrows in the sealed space within the fire extinguishing device housing 1001, the vaporized material thus propagates randomly in all directions within the space. If the sealed space of the housing 1001 is substantially surrounded by the portion having the aforementioned WVTR, the vaporized material cannot be released to the outside, causing the interior of the housing 1001 to instantaneously reach a very high pressure state. When the housing's ventilation area 1002 is momentarily opened at a high pressure of a certain level or higher, the internal gas is rapidly discharged to the outside through the opened ventilation area 1002.

[0042] If the WVTR of the shell around the sealed space is not high, the internal pressure of the shell 1001 may not be effectively increased in this state, or the increase speed may be slow, so that the opening of the ventilation area 1002 may not be effectively carried out, or even when the ventilation area 1002 is opened, the internal pressure may be insufficient, so that some vaporized materials may remain without being consumed by being discharged to the outside, or the discharge speed may be too slow.

[0043] If the WVTR of the housing is kept low, this has the additional effect of ensuring the storage stability of the internal material under normal conditions.

[0044] There is no particular limitation on the method for forming the ventilation area. The ventilation area can be formed by designing the shell that forms the sealed space so that the shell can be opened when the internal pressure of the shell reaches a certain level. For example, if some areas of the shell that forms the sealed space are configured to have a lower strength than other areas, the parts with lower strength can be opened by increasing the internal pressure. In addition, the sealed space can be formed by sealing using a hot-melt material or the like, and a method in which the opening occurs by melting at a predetermined temperature can also be used. In another method, the ventilation area can be formed by making only a specific part of the shell that forms the sealed space have a thinner thickness relative to other areas. Such a method of forming the ventilation area can be easily adopted by those skilled in the art.

[0045] For example, when the fire extinguishing device is used in a battery module or battery pack, the housing can be rectangular, pouch-shaped, and / or cylindrical, the same shape as the battery cells, for ease of application. In this case, a vent area can also be formed by controlling the bonding strength of the lid that forms the sealed space within the rectangular or cylindrical housing.

[0046] The housing may be formed using a known material as long as it can satisfy the above-mentioned WVTR, wherein the material may have a single-layer structure or two or more layers.

[0047] For example, the housing may be formed using appropriate materials for the organic layer and / or the inorganic layer, which may exhibit a WVTR within the above range.

[0048] As the organic layer, for example, a known polymer film or sheet can be used. Examples of the organic film include: a cellulose-based polymer film; a COP (cyclic olefin copolymer) film; an acrylic polymer film; a polyolefin film; a PVA (polyvinyl alcohol) film; a PVC (polyvinyl chloride) film; a PES (polyethersulfone) film; a PEEK (polyetheretherketone) film; a PPS (polyphenylsulfone) film; a PEI (polyetherimide) film; a PEN (polyethylene naphthalate) film; a polyester film such as a PET (polyethylene terephthalate) film; a PI (polyimide) film; a PSF (polysulfone) film; and / or a PAR (polyarylate) film.

[0049] For example, as the inorganic layer, a metal layer, a metal oxide layer, a metal nitride layer, or a metal oxynitride layer can be used. For example, the inorganic layer can be a metal layer, a metal oxide layer, a metal nitride layer, or a metal oxynitride layer, which contains one or more selected from the following: In, Sn, Pb, Au, Cu, Ag, Zr, Hf, Zn, Al, Si, La, Ti, and Ni. For example, a foil, sheet, or film of the above-mentioned material can be used, or a layer formed by depositing a metal layer, metal oxide layer, metal nitride layer, or metal oxynitride layer on a suitable substrate can be used.

[0050] The material forming the shell may be any single layer selected from an inorganic layer and an organic layer, or a multilayer structure in which two or more layers are laminated.

[0051] The thickness of the inorganic and / or organic layers is selected based on physical properties (e.g., desired WVTR) and is not particularly limited. For example, the lower limit of the thickness may be approximately 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, and the upper limit thereof may be approximately 5,000 μm, 4,000 μm, 3,000 μm, 2,000 μm, 1,000 μm, 500 μm, 200 μm, 150 μm, 100 μm, 90 μm, 80 μm, 70 μm, 60 μm, 50 μm, 40 μm, or 30 μm. The thickness may be within a range of less than or equal to, or less than, any of the aforementioned upper limits; or within a range of greater than or equal to, or greater than, any of the aforementioned lower limits; or within a range of less than or equal to, or less than, any of the aforementioned upper limits and greater than or equal to, or greater than, any of the aforementioned lower limits.

[0052] The fire extinguishing device may include additional features to enable it to perform more effectively.

[0053] For example, the fire extinguishing device may further include a heat-conducting layer. Such a heat-conducting layer may be present at an appropriate location within the fire extinguishing device. For example, the heat-conducting layer may be present between the housing of the fire extinguishing device and the vaporizable substance or composition, or the heat-conducting layer may be present adjacent to the housing.

[0054] Figure 3 For Figure 2 The heat conducting layer 2001 is added to the fire extinguishing device of FIG. The heat conducting layer can be present at different positions in the shell, and the number thereof can also be one, or two or more.

[0055] The term "thermal conductive layer" refers to a layer having a thermal conductivity (based on 20°C) within the range described below. The lower limit of the thermal conductivity (based on 20°C) of the thermal conductive layer may be around 15, 18, 20, 50, 100, 150, 200, 250, 300, 350, or 400, and the upper limit may be around 2,000, 1,500, 1,000, 900, 800, 700, 600, 500, 400, 300, 200, 100, or 50. The thermal conductivity may be within a range greater than or equal to, or greater than any of the above lower limits; or within a range less than or equal to, or less than any of the above upper limits while being within a range greater than or equal to, or greater than any of the above lower limits. The unit of thermal conductivity is W / mK, which can be evaluated in the manner described in "15. Thermal Conductivity Evaluation" of the Examples section of this specification.

[0056] The type of thermally conductive layer is not particularly limited, as long as it has the thermal conductivity described. Generally, a metal material can be used as the thermally conductive layer because it has excellent thermal conductivity characteristics. For example, a layer made of a metal material (such as aluminum, gold, pure silver, tungsten, copper, nickel or platinum) can be used.

[0057] The thickness of the thermally conductive layer is not particularly limited, and an appropriate thickness can be set taking into account the specifications of the fire extinguishing device, etc. For example, the lower limit of the thickness of the thermally conductive layer can be approximately 1 μm, 5 μm, 10 μm, 15 μm, 50 μm, 75 μm, or 90 μm, and the upper limit can be approximately 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, 50 μm, 40 μm, or 30 μm. The thickness can be within a range of less than, equal to, or less than any of the aforementioned upper limits; or within a range of greater than, equal to, or greater than any of the aforementioned lower limits; or within a range of less than, equal to, or less than any of the aforementioned upper limits and within a range of greater than, equal to, or greater than any of the aforementioned lower limits.

[0058] like Figure 3As shown, in some cases, heat generated during an abnormal state may not be uniformly applied to the fire extinguishing device, but may be applied only locally to a specific area. However, in order to quickly vaporize the vaporizable material within the fire extinguishing device and achieve a high-pressure state, the heat generated during the abnormal state must be uniformly applied to the fire extinguishing device. With the presence of a thermally conductive layer, even if the heat generated during the abnormal state is locally applied, the thermally conductive layer can quickly transfer the heat throughout the fire extinguishing device, thereby enabling the fire extinguishing effect of the fire extinguishing device, as described above, to occur quickly and effectively.

[0059] To ensure the fire extinguishing device works more effectively, the amount of vaporizable substance, or the composition containing a vaporizable substance described below, present in the interior space or sealed space of the housing of the fire extinguishing device can be adjusted. For example, the lower limit of the ratio of the volume of the vaporizable substance or composition to the total volume of the interior space or sealed space of the housing can be approximately 70%, 75%, 80%, 85%, 90%, or 95%, and the upper limit can be approximately 100%. This ratio can be within a range greater than, equal to, or greater than any of the aforementioned lower limits; or within a range less than, equal to, or less than any of the aforementioned upper limits, and within a range greater than, equal to, or greater than any of the aforementioned lower limits. At such a ratio, the rapid increase in internal pressure described above can be more effectively induced.

[0060] Hereinafter, the fire extinguishing composition will be described.

[0061] The fire extinguishing composition may be contained in a sealed space within a fire extinguishing device and may be specially formulated so as to more effectively perform the above Figure 2 and Figure 3 The role described in .

[0062] The composition may be non-flammable and formulated to be environmentally and human-friendly.

[0063] For example, according to the NFPA (National Fire Protection Association) 704 standard, the flammability rating of a composition may be 0 or 1. The NFPA 704 standard is a standard announced by the National Fire Protection Association (NFPA) of the United States, which is a standard represented by a so-called fire diamond created to enable rapid response to hazardous materials in an emergency, and the flammability rating is represented by a red area. The standard is divided into 0, 1, 2, 3, and 4 levels, where 0 means no flammability, and 1 means a case where it ignites when heated sufficiently, which is approximately a case where the flash point is 93°C or higher. Such a flammability rating evaluation method follows the NFPA (National Fire Protection Association) 704 standard.

[0064] According to the NFPA (National Fire Protection Association) 704 standard, the composition can exhibit non-flammability with a flammability rating of 0 or 1. For example, according to the NFPA (National Fire Protection Association) 704 standard, the composition can have a health hazard rating of 0, 1, or 2. The health hazard rating is represented by the blue area in the fire diamond of the NFPA 704 standard. The standard is divided into levels 0, 1, 2, 3, and 4, where Level 0 is a situation where there is no health hazard and no special precautions are required, Level 1 is a situation where there is a possibility of causing minor injury upon exposure, and Level 2 is a situation where there is a possibility of causing temporary disability or injury upon continuous / normal contact but not prolonged contact.

[0065] In order for the composition to exhibit the aforementioned ratings, the components constituting the composition may also use materials that exhibit the aforementioned flammability and / or health hazard ratings.

[0066] The composition comprises at least a vaporizable substance. As described above, such a vaporizable substance vaporizes under certain temperature and / or pressure conditions, thereby increasing the internal pressure. Furthermore, the vaporizable substance can be sprayed to the exterior in a vaporized state, thereby also performing a fire extinguishing and / or cooling function.

[0067] A suitable type of vaporizable substance can be selected and used. For example, the vaporizable substance can be a substance known as a so-called vaporizable substance. For example, the vaporizable substance can exist in a liquid phase at least at room temperature (about 25° C.). The vaporizable substance can be used to increase the internal pressure of a sealed space by instantaneous vaporization, reduce heat by heat exchange, or extinguish a flame in response to abnormal heating, flame, or explosion occurring in an adjacent target.

[0068] As the vaporizable substance, any incombustible substance can be used without particular limitation. For example, as the vaporizable substance, a substance having a freezing point and / or boiling point within a predetermined range can be used.

[0069] For example, the lower limit of the freezing point of the vaporizable substance may be around -5°C, -4°C, -3°C, -2°C, -1°C, or 0°C, and the upper limit thereof 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 within a range less than or equal to, or less than, any of the above upper limits, while also being within a range greater than or equal to, or greater than, any of the above lower limits. The freezing point is the freezing point at 1 atmosphere of pressure.

[0070] The boiling point of the vaporizable substance may be within a certain range to exhibit appropriate vaporizability. For example, the lower limit of the boiling point of the vaporizable substance may be approximately 80°C, 85°C, 90°C, or 95°C, and the upper limit thereof may be approximately 120°C, 115°C, 110°C, or 105°C. The boiling point may be within a range less than, equal to, or less than any of the aforementioned upper limits, while also being within a range greater than, equal to, or greater than any of the aforementioned lower limits. The boiling point is the boiling point at 1 atmosphere of pressure.

[0071] As the vaporizable substance, any suitable type can be selected and used without particular limitation, as long as it has a freezing point and / or boiling point within the above ranges and is non-flammable. A representative example of a non-flammable vaporizable substance having a freezing point and / or boiling point within the above ranges is water, and thus water can be used as the vaporizable substance, but the type of applicable vaporizable substance is not limited thereto.

[0072] In order to apply the composition to the sealed space of the fire extinguishing device to increase the internal pressure at an appropriate rate at a necessary time point, it is necessary to control the content of the vaporizable substance in the sealed space or in the composition.

[0073] For example, the lower limit of the ratio of vaporizable substances in the composition or sealed space of the fire extinguishing device can be about 50 weight %, 55 weight %, 60 weight %, 65 weight %, 70 weight %, 75 weight % or 80 weight %, and its upper limit can be about 95 weight %, 90 weight %, 85 weight %, 80 weight %, 75 weight %, 70 weight %, 65 weight % or 60 weight %. The ratio can be within the range of greater than or equal to, or greater than any one of the above lower limits; or within the range of less than or equal to, or less than any one of the above upper limits and at the same time within the range of greater than or equal to, or greater than any one of the above lower limits. As the content of vaporizable substances approaches the range disclosed in the embodiments from the above range, the effect can be improved. The ratio is a percentage based on the total weight of all components present in the composition or all components present in the sealed space.

[0074] The composition or enclosed space may contain only the vaporizable substance, or may also contain other components.

[0075] For example, the composition or the sealed space may also contain a freezing point modifier. The term freezing point modifier is a component that controls the freezing point and / or boiling point of the composition by the so-called freezing point depression phenomenon. In order for the fire extinguishing device to effectively perform the reference Figure 2 and Figure 3To achieve the desired effect, instantaneous vaporization of the vaporizable substance must occur at the necessary time, for which a freezing point modifier can be used. Furthermore, it is advantageous for the vaporizable substance, etc., to be in a liquid phase at the time of the abnormal state, so that such a state can also be ensured using a freezing point modifier. Furthermore, when the composition is applied to highly integrated products such as battery modules or battery cells, if a phase change occurs due to cooling of the composition in a low-temperature environment, it may also adversely affect adjacent products due to changes in the volume and hardness of the composition. This problem can also be addressed by adding a freezing point modifier.

[0076] In order to ensure the above-mentioned effects, particularly the effect of instantaneous and complete rapid vaporization of the vaporizable substance at a necessary time point, by applying the freezing point adjuster, the form in which the freezing point adjuster is applied may be controlled.

[0077] For example, a freezing point modifier may be present such that the ΔT of Equation 1 below f Can be within the predetermined range.

[0078] [Equation 1]

[0079] ΔT f =K f ×M×I

[0080] In Equation 1, K f is the freezing point depression constant of the vaporizable substance.

[0081] K f The unit is ℃ / m, for example, if the vaporizable substance is water, then K f It is about 1.86.

[0082] M in Equation 1 is the molar concentration of the freezing point modifier relative to the molar concentration of the vaporizable substance. Therefore, M is the number of moles of the freezing point modifier present per 1 kg of the vaporizable substance in the composition or sealed space.

[0083] In Equation 1, I represents the number of ions (in moles) formed from 1 mole of the freezing point adjuster when the freezing point adjuster has dissociated, where dissociation refers to a state in which the freezing point adjuster is completely dissociated. Thus, for example, when the freezing point adjuster is not an ionic compound, I is 1.

[0084] In the case where two or more freezing point modifiers or ionic compounds are present in the composition, calculate the ΔT for each compound. f , and use the sum of these values ​​as the composition ΔT f value.

[0085] ΔT in Equation 1 fThe lower limit of ΔT may be, for example, about 5, 10, 15, 20, 22, or 24, and the upper limit thereof may be about 50, 45, 40, 35, 30, 25, 20, or 15. f The unit is °C. ΔT f It can be within the range of less than or equal to, or less than any of the above upper limits while being within the range of greater than or equal to, or greater than any of the above lower limits.

[0086] By applying the freezing point adjuster within the above range, the vaporizable substance can be quickly and substantially completely vaporized at a necessary time point to quickly increase the internal pressure of the sealed space, and the vaporizable substance can exist in a liquid phase at a necessary time point, and the volume change and hardness change of the composition or fire extinguishing device, which may affect the driving of the product in a normal state, can be prevented. When ΔT f When the above range is closer to the range of the embodiment, more excellent effects can be exhibited.

[0087] As the freezing point adjuster, for example, alcohol or ionic compound can be used. The category of ionic compound includes ionic substances themselves or substances that can generate ions, such as salts.

[0088] For example, alcohols having a boiling point within a predetermined range can be used as alcohols. 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 thereof may be around 300°C, 280°C, 260°C, 240°C, 220°C, or 200°C. The boiling point may be within a range of less than or equal to, or less than, any of the aforementioned upper limits, while also being within a range of greater than or equal to, or greater than, any of the aforementioned lower limits.

[0089] For example, as alcohol, the alcohol of molar mass in predetermined range can be used.For example, the lower limit of the molar mass of alcohol can be about 20g / mol, 30g / mol, 40g / mol, 50g / mol, 60g / mol, 70g / mol, 80g / mol or 90g / mol, and its upper limit can be about 300g / mol, 280g / mol, 260g / mol, 240g / mol, 220g / mol, 200g / mol, 180g / mol, 160g / mol, 140g / mol, 120g / mol, 100g / mol, 90g / mol, 80g / mol or 70g / mol.Molar mass can be less than or equal to or less than the scope of any one in the above-mentioned upper limit simultaneously in the scope of any one in greater than or equal to or greater than the above-mentioned lower limit.

[0090] The type of alcohol is not particularly limited, and for example, polyols such as ethylene glycol or glycerin may be used.

[0091] As ionic compounds that can be applied as freezing point adjusters, for example, there are one or more salts selected from formates, acetates, carbonates and sulfates, and specifically, one or more of the following salts can be used: for example, 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).

[0092] The freezing point modifier may be present such that the concentration calculated based on the vaporizable substance is within a predetermined range. Here, the concentration is a molar concentration, which is specifically the number of moles of freezing point modifier present per 1 kg of vaporizable substance present in the composition. In one example, the lower limit of the molar concentration may be about 1, 1.5, 2, 4, 6, 8, 10, 12, 14, or 16, and the upper limit thereof may be about 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 within a range of less than or equal to, or less than any of the above upper limits while being within a range of greater than or equal to, or greater than any of the above lower limits. The molar concentration may take into account the ΔT of Equation 1 above. f To adjust.

[0093] It may be appropriate to use as a freezing point adjuster a component having 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. Various freezing point adjusters that can cause the freezing point depression phenomenon are known, but most of them have flammability and / or toxicity, so that when it is necessary to achieve the NFPA rating, etc. for the purpose, the NFPA rating also needs to be considered when selecting the freezing point adjuster.

[0094] It may be appropriate for the freezing point adjuster to have a certain level of solubility in the vaporizable substance. By selecting a freezing point adjuster with appropriate solubility, the degree of freedom of the addition amount of the freezing point adjuster increases, and an addition amount that can ensure the desired freezing point while improving the fire extinguishing function without any inhibition can be selected.

[0095] For example, the lower limit of the solubility of the freezing point modifier in 100 g of the vaporizable substance or water at 0° C. may be about 20 g, 25 g, 30 g, 35 g, 40 g, 45 g, 50 g, 55 g, 60 g, 65 g, 70 g, 75 g, 80 g, 85 g, 90 g, 95 g, 100 g, 110 g, 115 g, 120 g, 125 g, 130 g, 135 g, 140 g, 145 g, 150 g, 155 g, 160 g, 165 g, 170 g, 175 g, 180 g, 185 g, 190 g, 195 g, 200 g, 205 g, 210 g or 215 g, and the upper limit thereof may be 1000 g, 900 g, 800 g, g, 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 about 30g. The solubility can be within a range greater than, equal to, or greater than either of the aforementioned lower limits; or within a range less than, equal to, or less than either of the aforementioned upper limits and within a range greater than, equal to, or greater than either of the aforementioned lower limits. The solubility is the maximum weight (g) of the freezing point adjuster that can be dissolved in 100 g of the vaporizable substance or water at 0°C. Such solubility can be evaluated in the manner described in "10. Solubility Evaluation" in the Examples section of this specification.

[0096] The lower limit of the solubility of the freezing point modifier in 100 g of the vaporizable substance or water at 25°C may be 70 g, 75 g, 80 g, 85 g, 90 g, 95 g, 100 g, 110 g, 115 g, 120 g, 125 g, 130 g, 135 g, 140 g, 145 g, 150 g, 155 g, 160 g, 165 g, 170 g, 175 g, 180 g, 185 g, 5g, 190g, 195g, 200g, 205g, 210g, 215g, 225g, 230g, 235g, 240g, 255g, 260g, 265g, 270g, 275g, 280g, 285g, 290g, 295g, 300g, 305g, 310g, 315g or 320g, and the upper limit thereof can be 1000g, 9 00g, 800g, 700g, 600g, 500g, 400g, 350g, 345g, 340g, 335g, 330g, 325g, 320g, 315g, 3 10g, 305g, 300g, 295g, 290g, 280g, 275g, 270g, 265g, 260g, 255g, 250g, 245g, 240g, 2 The solubility may be about 35g, 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 a range greater than, equal to, or greater than any of the above lower limits; or within a range less than, equal to, or less than any of the above upper limits and within a range greater than, equal to, or greater than any of the above lower limits. The solubility is the maximum weight (g) of the freezing point modifier that can be dissolved in 100g of the vaporizable substance or water at 25°C. Such solubility can be evaluated in the manner described in "10. Solubility evaluation" of the Example section in this specification.

[0097] As freezing point modifiers, components with a molar mass within a predetermined range can be used. When the molar amount of the freezing point modifier is maintained at an appropriate level, the functions of other components of the composition (e.g., fire extinguishing function) can be maintained and improved. For example, the lower limit of the molar mass of the freezing point modifier can be about 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 can be about 300 g / mol. The molar mass can be about 100 g / mol, 250 g / mol, 200 g / mol, 150 g / mol, 145 g / mol, 140 g / mol, 135 g / mol, 130 g / mol, 125 g / mol, 120 g / mol, 115 g / mol, 110 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 can be about 100 g / mol, 250 g / mol, 200 g / mol, 150 g / mol, 145 g / mol, 140 g / mol, 135 g / mol, 130 g / mol, 125 g / mol, 120 g / mol, 115 g / mol, 110 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.

[0098] In order to make the freezing point adjuster exhibit the flammability and health hazard ratings of NFPA 704, a component that does not contain any specific functional groups can be used. For example, as the freezing point adjuster, a component that does not contain hydroxyl groups and / or chlorine can be used, and a component that does not contain any component that generates other sulfur dioxide gas, ammonia, and ethylene oxide, or generates related components can be used. A freezing point adjuster containing such components or functional groups may not exhibit the flammability rating (red items) and health hazard rating (blue items) of the NFPA 704 standard as described above.

[0099] Such freezing point adjusters can be exemplified by, for example, one or more selected from ionic compounds such as formates, acetates, carbonates, and sulfates among the above-mentioned types.

[0100] The specific content of the freezing point modifier can be considered in terms of ΔT in the above equation 1. fFor example, the lower limit of the weight ratio of the freezing point modifier relative to 100 parts by weight of the vaporizable substance may be about 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, or 65 parts by weight, and the upper limit thereof may be about 200 parts by weight, 180 parts by weight, 160 parts by weight, 140 parts by weight, 120 parts by weight, 100 parts by weight, 90 parts by weight, 85 parts by weight, 80 parts by weight, 75 parts by weight, 70 parts by weight, 65 parts by weight, 60 parts by weight, 55 parts by weight, 50 parts by weight, 45 parts by weight, or 40 parts by weight. This ratio may be within a range less than or equal to, or less than, any of the above upper limits, while being within a range greater than or equal to, or greater than, any of the above lower limits.

[0101] When an ionic compound added for another purpose (e.g., an ionic compound as a carbonization catalyst) is present in the composition or sealed space in addition to the freezing point adjuster, all the freezing point adjusters and other ionic compounds present in the composition or sealed space may be present in such a manner that ΔT of the above equation 1 is f In this case, ΔT is calculated. f The specific method is the same as that for the freezing point modifier. When two or more types of freezing point modifiers and ionic compounds are present in the composition or sealed space, the above ΔT of each compound is calculated. f , and use the sum of these values ​​as the composition or ΔT of the sealed space f value.

[0102] For all freezing point modifiers and other ionic compounds present in the composition or sealed space, the ΔT of Equation 1 f The lower limit of the sum of the values ​​may be, for example, about 3, 5, 10, 15 or 20, and the upper limit thereof may be about 50, 45, 40, 35, 30, 25, 20, 15 or 10. f It may be within a range greater than or equal to, or greater than any of the above lower limits; or within a range less than or equal to, or less than any of the above upper limits; or within a range less than or equal to, or less than any of the above upper limits and within a range greater than or equal to, or greater than any of the above lower limits. ΔT in Equation 1 f The unit is ° C. By adjusting the contents of the freezing point adjuster and the ionic compound within the above range, the vaporization rate of the vaporizable substance can be appropriately controlled, and desired characteristics can be expressed.

[0103] If necessary, the composition or sealed space of the fire extinguishing device may contain, for example, a fire extinguishing agent as an additional component to ensure proper fire extinguishing function. When the fire extinguishing agent is contained, the fire extinguishing agent may promote the carbonization of the carbonizable organic material described below and / or promote the gas generation of the gas generating material described below.

[0104] The fire extinguishing agent performs the function of promoting carbonization of the carbonizable organic material, and thus the fire extinguishing agent may also be referred to as a carbonization catalyst.

[0105] As such a fire extinguishing agent, it may be appropriate to use a fire extinguishing agent having a certain level or higher solubility relative to a vaporizable substance (for example, a vaporizable substance such as water). By adjusting the solubility, the carbonization or gas generation effect as described above can be more effectively performed without causing agglomeration or phase separation in the composition.

[0106] For example, the lower limit of the solubility of the fire extinguishing agent can be about 5g, 10g, 15g, 20g, 25g, 30g, 35g, or 40g, and the upper limit can be about 1000g, 900g, 800g, 700g, 600g, 500g, 400g, 300g, 200g, 100g, 90g, 80g, 70g, 60g, 50g, 40g, or 30g. The solubility can be within a range greater than, equal to, or greater than any of the above lower limits; or within a range less than, equal to, or less than any of the above upper limits and within a range greater than, equal to, or greater than any of the above lower limits. The solubility is the maximum weight (g) of the fire extinguishing agent that can be dissolved in 100g of water at 25°C, which can be measured as described in "10. Solubility Evaluation".

[0107] As the fire extinguishing agent, an agent having the above solubility can be appropriately selected and used, and examples thereof include phosphoric acid, phosphates, phosphonate / ester compounds or phosphate ester compounds. The fire extinguishing agent can be, for example, ammonium dihydrogen phosphate or diammonium hydrogen phosphate, urea phosphate, guanyl urea phosphate or ammonium polyphosphate, and one or two or more of the foregoing can be selected and used.

[0108] The fire extinguishing agent can be present in the composition in an appropriate amount taking into account the expected effect. For example, the lower limit of the weight ratio of the fire extinguishing agent relative to 100 parts by weight of the vaporizable substance can 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 thereof can 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 can be within a range less than or equal to, or less than any of the above upper limits; or within a range greater than or equal to, or greater than any of the above lower limits; or within a range less than or equal to, or less than any of the above upper limits and within a range greater than or equal to, or greater than any of the above lower limits.

[0109] The composition or the enclosed space of the fire extinguishing device may contain a carbonizable organic material as a further component.

[0110] Carbonizable organic material is an organic material that carbonizes to form a carbide when exposed to a flame or heat of a predetermined temperature. The carbide formed by such an organic material is often porous, so it can have a heat-insulating function. Therefore, when a composition or a fire extinguishing device is exposed to heating, catching fire or an explosion, the organic material can form a suitable carbide and show a heat-insulating function. For example, when the organic material is used together with a gas generating material, when the organic material is exposed to heating, catching fire or an explosion, in the process of forming the carbide, by the effect of the gas produced by the gas generating material, a porous carbide can be formed more effectively.

[0111] The carbonization of the carbonizable organic material can be caused or promoted by the fire extinguishing agent. That is, the fire extinguishing agent can decompose at high temperature to produce acid, salt or ion components, and these acid, salt or ion components can promote the carbonization of the carbonizable organic material through catalysis.

[0112] As the carbonizable organic material, any appropriate type can be applied without particular limitation as long as it is a material that forms a carbide when exposed to heat or flame.

[0113] Examples of such organic materials can be exemplified by: sugars such as sorbitol or mannitol; polysaccharides such as starch or dextrin (e.g., MC (maleated cyclodextrin) or a metal salt of MC); polyols such as pentaerythritol, dipentaerythritol, tripentaerythritol or THEIC (tris(hydroxyethyl)isocyanurate); cellulose; BSPPO (bis(4-methoxy-1-phospha-2,6,7-trioxabicyclo[2.2.2]-octane-1-sulfide)phenyl phosphate); lignin (alkali lignin or urea-modified lignin); melamine compounds such as hydroxymethyl melamine; phenolic resins; and / or carbonizable polymers (char-forming polymers) such as PA6T (polyhexamethylene terephthalamide); and the like, but are not limited thereto.

[0114] Typically, starch is used as the carbonizable organic material. Starch is relatively easy to obtain and can form suitable carbonization products when exposed to heat or flame.

[0115] In order for the carbide to be formed effectively and for the formed carbide to effectively exert the desired fire extinguishing or heat insulating effect, the type of starch may be adjusted.

[0116] For example, as starch, a starch containing amylose and amylopectin whose ratio is adjusted to an appropriate level can be used. As is known, amylopectin and amylose are types of polysaccharides mainly present in plants, and the starch of the polysaccharide is composed of amylose and amylopectin. Amylose is composed of glucose molecules connected by α (1 → 4) glycosidic bonds and has a linear chain structure, while amylopectin has a relatively short and highly branched chain. Compared with amylopectin, amylose is relatively easy to crystallize, and amylopectin has a relatively higher solubility in water than amylose.

[0117] By using starch having the above-described properties and containing amylose and amylopectin at an appropriate ratio, a desired composition can be provided more efficiently.

[0118] For example, in a starch comprising amylose and amylopectin, the lower limit of the weight ratio of amylopectin relative to 100 parts by weight of amylose may be about 150 parts by weight, 200 parts by weight, 250 parts by weight or 300 parts by weight, and the upper limit thereof may be about 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 about 300 parts by weight. The ratio may be within a range of less than or equal to, or less than any one of the above upper limits; or within a range of greater than or equal to, or greater than any one of the above lower limits; or within a range of less than or equal to, or less than any one of the above upper limits and at the same time within a range of greater than or equal to, or greater than any one of the above lower limits. The ratio of amylose to amylopectin may be measured according to the method described in "8. Measurement of amylopectin and amylose content" of the Examples section of this specification.

[0119] As starch, a starch having a molecular weight, for example, a weight average molecular weight (Mw) within a predetermined range can be used. For example, the lower limit of the weight average molecular weight of starch can be 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, g / mol, 950,000g / mol, 1,000,000g / mol, 1,500,000g / mol, 2,000,000g / mol, 2,500,000g / mol, 3,000,000g / mol, 3,500,000 g / 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, 7,000,00 0 g / mol, 7,500,000 g / mol, 8,000,000 g / mol, 8,500,000 g / mol, 9,000,000 g / mol, 9,500,000 g / mol, 10,000,000 g / mol, 20,000,000 g / mol, 30,000,000 g / mol, 40,000,000 g / mol, or 50,000,000 g / mol, and the upper limit thereof may be 1,000,000,000 / mol, 900,000,000 / mol, The molecular weight can be in the range of less than or equal to, or less than any one of the above upper limits; or in the range of greater than or equal to, or greater than any one of the above lower limits; or in the range of less than or equal to, or less than any one of the above upper limits and in the range of greater than or equal to, or greater than any one of the above lower limits.When exposed to heat or flame, starch having such a molecular weight (Mw) can more effectively form carbides having desired functions (e.g., thermal insulation functions).Molecular weight can be measured in the manner described in "7. Molecular weight measurement" of the Examples section in this specification.

[0120] In the case of including a carbonizable organic material, the lower limit of the weight ratio of the carbonizable organic material relative to 100 parts by weight of the vaporizable substance may be approximately 0.01 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 9.5 parts by weight or 10 parts by weight, and the upper limit thereof 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. This ratio may be within a range of less than or equal to, or less than, any of the aforementioned upper limits; or within a range of greater than or equal to, or greater than, any of the aforementioned lower limits; or within a range of less than or equal to, or less than, any of the aforementioned upper limits and greater than or equal to, or greater than, any of the aforementioned lower limits. The carbonizable organic material contained in such a ratio can effectively form carbides in the composition as needed, and can ensure excellent handleability and storage stability of the composition as a whole.

[0121] The composition or sealed space of the fire extinguishing device may also include a gas generating material as an additional component. The gas generating material that can be included in the composition is a material that generates gas when exposed to heat or flame. The gas thus generated can be used to directly extinguish the heat or flame and, in the process of forming the carbide from the carbonizable organic material, can also perform the function of making the carbide more porous.

[0122] The effect of such a gas generating material can be caused or promoted by the fire extinguishing agent. That is, the fire extinguishing agent can decompose at high temperature to produce acid, salt or ion components, and such acid, salt or ion components can promote the gas generation of the gas generating material.

[0123] The type of gas generated by the gas generating material is not particularly limited as long as it is a non-combustible gas, and may be, for example, nitrogen, carbon dioxide, and / or water vapor.

[0124] Various materials for generating gases are known. For example, materials for generating nitrogen include melamine, guanidine, urea, melamine pyrophosphate, dicyandiamide, guanyl urea phosphate, and glycine; materials for generating carbon dioxide include potassium bicarbonate, sodium bicarbonate, calcium bicarbonate, and magnesium bicarbonate; and materials for generating water vapor include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. However, the materials suitable for this application are not limited thereto.

[0125] As the gas generating material, one or a mixture of two or more selected from the above types may be used.

[0126] In order to produce an appropriate effect, as the gas generating material, a material that generates nitrogen gas can be used, for example, melamine, guanidine, urea, melamine pyrophosphate and / or guanyl urea phosphate, etc. Such a material is advantageous in that, in particular, during the process of forming a carbide from the carbonizable organic material, it effectively exerts a foaming effect on the carbide, thereby effectively forming the desired porous carbide.

[0127] In the case of including a gas generating material, the lower limit of the weight ratio of the gas generating material relative to 100 parts by weight of the vaporizable substance may be about 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 thereof 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, 15 parts by weight, 10 parts by weight, 8 parts by weight or 7 parts by weight. The ratio may be within a range of less than or equal to, or less than, any of the aforementioned upper limits; or within a range of greater than or equal to, or greater than, any of the aforementioned lower limits; or within a range of less than or equal to, or less than, any of the aforementioned upper limits and greater than or equal to, or greater than, any of the aforementioned lower limits. The gas generating material contained in such a ratio can effectively suppress heat or flame and form porous carbides as needed, while ensuring excellent handleability and storage stability of the composition as a whole.

[0128] The composition may comprise water-absorbing polymers as further components.

[0129] A water-absorbing polymer is a polymer that has the property of absorbing water. In one example, the water-absorbing polymer may be a so-called hydrogel polymer or hydrogel, which is generally defined as a cross-linked hydrophilic polymer. Such polymers are also referred to as SAP (Super Absorbent Polymer).

[0130] Water-absorbing polymers are materials that can absorb tens to thousands of times their own weight in water. Such materials make the composition as a whole exist in a gel state, thus playing a role in ensuring handleability and storage stability.

[0131] The type of the water-absorbing polymer is not particularly limited, and any polymer generally usable as a SAP can be used without limitation.

[0132] Typically, a polyacrylate-based vinyl polymer is used as the above material. Here, the polyacrylate-based polymer is a polymer made from an acrylate-based monomer, and if necessary, other comonomers may be used to form the polymer.

[0133] The water absorption characteristics can be adjusted so that the water-absorbing polymer exhibits appropriate characteristics.

[0134] For example, the lower limit of the centrifuge retention capacity (CRC) of the water-absorbing polymer according to EDANA (European Disposables and Nonwovens Association) method WSP 241.3 can 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 thereof can be around 60 g / g, 55 g / g, 50 g / g, 45 g / g, 40 g / g or 35 g / g. The retention capacity (CRC) may be within a range of less than or equal to, or less than any of the above upper limits; or within a range of greater than or equal to, or greater than any of the above lower limits; or within a range of less than or equal to, or less than any of the above upper limits and greater than or equal to, or greater than any of the above lower limits. The centrifuge retention capacity (CRC) can be evaluated in the manner described in "5. CRC (Centrifuge Retention Capacity)" of the Examples section of this specification.

[0135] For example, the water-absorbent polymer may have an absorption under pressure (AUP) of about 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 at a lower limit according to EDANA (European Disposables and Nonwovens Association) method WSP 242.3 at 0.3 psi, and an upper limit thereof may be about 40 g / g, 38 g / g, 36 g / g, 34 g / g, 32 g / g, or 30 g / g. The absorption rate (AUP) may be within a range of less than or equal to, or less than any of the aforementioned upper limits; or within a range of greater than or equal to, or greater than any of the aforementioned lower limits; or within a range of less than or equal to, or less than any of the aforementioned upper limits and within a range of greater than or equal to, or greater than any of the aforementioned lower limits. The absorbency (AUP) can be evaluated in the manner described in "6. AUP (Absorption Under Pressure)" of the Examples section in this specification.

[0136] The water-absorbent polymer having the above absorbency may be combined with other components of the composition to exhibit desired characteristics.

[0137] In one example, the water-absorbing polymer may be a particulate polymer, wherein the lower limit of the average particle size of the water-absorbing polymer may be approximately 10 μm, 50 μm, 100 μm, or 140 μm, and the upper limit thereof may be approximately 1000 μm, 950 μm, 900 μm, 850 μm, 800 μm, 750 μm, 700 μm, 650 μm, 600 μm, 550 μm, 500 μm, 450 μm, 400 μm, 350 μm, 300 μm, 250 μm, or 200 μm. The average particle size may be within a range of less than or equal to, or less than, any of the aforementioned upper limits; or within a range of greater than or equal to, or greater than, any of the aforementioned lower limits; or within a range of less than or equal to, or less than, any of the aforementioned upper limits and within a range of greater than or equal to, or greater than, any of the aforementioned lower limits. The above average particle size can be measured according to the method specified in NWSP 210.0.R2 (15).

[0138] In the case of containing a water-absorbing polymer, the lower limit of the weight ratio of the water-absorbing polymer relative to 100 parts by weight of the vaporizable substance may be approximately 0.01 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, and the upper limit thereof 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 ratio may be within a range of less than or equal to, or less than any of the above upper limits; or within a range of greater than or equal to, or greater than any of the above lower limits; or within a range of less than or equal to, or less than any of the above upper limits and within a range of greater than or equal to, or greater than any of the above lower limits.

[0139] The composition contains the above components and, if necessary, may further contain additional components.

[0140] For example, the composition may further comprise a buffer.

[0141] Reference Figure 2 and Figure 3 , in an abnormal state, heat may be applied to the fire extinguishing device, and in addition, instantaneous high pressure may also be applied. For example, in an abnormal state such as Figure 1 In the structure, if the battery cells 12, 13, 14, 15 adjacent to the fire extinguishing device 100 explode or expand rapidly, high pressure is applied to the fire extinguishing device 100. If the fire extinguishing device 100 contracts instantaneously due to the pressure thus applied, the vaporizable substance present inside may be discharged to the outside before it vaporizes, and such discharge may reduce the efficiency of the fire extinguishing effect.

[0142] The buffer may buffer the instantaneously applied pressure as described above, and thus, it may allow vaporization of the internal vaporizable substance to occur sufficiently.

[0143] In addition, the buffer may also optionally serve to carry the vaporizable substance. That is, if the buffer has a porosity as described below, or is in the form of a woven fabric, non-woven fabric, or felt, the buffer may exhibit the characteristics of absorbing or carrying the vaporizable substance.

[0144] The type of buffer is not particularly limited as long as it can play the role described, and for example, a buffer having an appropriate density and / or thermal decomposition temperature can be used.

[0145] For example, the upper limit of the density of the cushioning material may be about 1.5, 1.3, 1.1, 0.9, 0.7, 0.5, 0.3, 0.1, 0.08, 0.06, or 0.04, and the lower limit thereof may be about 0.001, 0.005, 0.01, 0.05, 0.1, or 0.15. The density may be within a range of less than or equal to, or less than any of the aforementioned upper limits; or within a range of greater than or equal to, or greater than any of the aforementioned lower limits; or within a range of less than or equal to, or less than any of the aforementioned upper limits and within a range of greater than or equal to, or greater than any of the aforementioned lower limits. The unit of density is g / cm 3 .

[0146] For example, the upper limit of the thermal decomposition temperature of the buffer may be about 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 thereof may be about 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 a range less than or equal to, or less than, any of the above upper limits; or within a range greater than or equal to, or greater than, any of the above lower limits; or within a range less than or equal to, or less than, any of the above upper limits and within a range greater than or equal to, or greater than, any of the above lower limits. A method for measuring the thermal decomposition temperature is described in "11. Thermal Decomposition Temperature" of the Examples section of this specification.

[0147] As the buffer, any known material can be used without particular limitation, as long as it has the above-described 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 can be in the form of a porous film, a porous sheet, a porous foil, a wool fabric, or a woven or non-woven fabric, such as a felt.

[0148] In addition, as a buffer, for example, inorganic foams such as various metal foams; woven fabrics, non-woven fabrics or felts made of glass wool, mineral wool, glass fibers or mineral fibers; or foams, woven fabrics, non-woven fabrics or felts formed from carbonizable organic materials to be described below can also be used.

[0149] As the buffer, any one selected from various types or a combination of two or more types can be used.

[0150] The size of the buffer is determined according to the size of the sealed space and is not particularly limited. For example, when the buffer is in the form of a porous membrane, porous sheet, porous foil, wool fabric, woven fabric, non-woven fabric or felt as described above, the lower limit of the thickness of the relevant buffer may be about 0.1 mm, 0.5 mm, 1 mm, 1.5 mm, 2 mm or 2.5 mm, and the upper limit thereof may be about 20 mm, 15 mm, 10 mm, 9 mm, 8 mm, 7 mm, 6 mm, 5 mm, 4 mm or 3 mm. The thickness may be within a range less than or equal to, or less than any one of the above upper limits; or within a range greater than or equal to, or greater than any one of the above lower limits; or within a range less than or equal to, or less than any one of the above upper limits and within a range greater than or equal to, or greater than any one of the above lower limits.

[0151] The composition can exhibit unique physical properties through the combination of the above components.

[0152] For example, the composition as a whole can exhibit a controlled freezing point. For example, the lower limit of the freezing point of the composition can 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 thereof can 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 can be within a range of less than, equal to, or less than any of the aforementioned upper limits; or within a range of greater than, equal to, or greater than any of the aforementioned lower limits; or within a range of less than, equal to, or less than any of the aforementioned upper limits and within a range of greater than, equal to, or greater than any of the aforementioned lower limits.

[0153] The composition may have a controlled viscosity and / or thixotropic index.

[0154] For example, the lower limit of the viscosity of the composition may be 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 viscosity may be within a range of less than or equal to, or less than any one of the above upper limits; or within a range of greater than or equal to, or greater than any one of the above lower limits; or within a range of less than or equal to, or less than any one of the above upper limits and within a range of greater than or equal to, or greater than any one of the above lower limits. Such viscosity is a value measured at room temperature (about 25° C.) and a rotation speed of 0.5 rpm.

[0155] For example, the lower limit of the thixotropic index of the composition may be about 2, 4, 6, 8, 10 or 10.5, and the upper limit thereof may be about 20, 18, 16, 14, 12, 10, 8 or 6. The thixotropic index may be in the range of less than or equal to, less than any of the above upper limits; or in the range of greater than or equal to, or greater than any of the above lower limits; or in the range of less than or equal to, or less than any of the above upper limits and greater than or equal to, or greater than any of the above lower limits. Such a thixotropic index is a value obtained by dividing the viscosity measured at room temperature (about 25° C.) and a rotation speed of 0.5 rpm by the viscosity measured at room temperature (about 25° C.) and a rotation speed of 5 rpm.

[0156] A composition having such a viscosity and / or thixotropic index can exhibit excellent workability, storage stability, and the like.

[0157] Compositions may exhibit certain latent heat properties. Latent heat is generally defined as the amount of heat required for any material to undergo a change of state (phase change) in the absence of any change in temperature. However, when a composition exhibits latent heat, it does not necessarily have to undergo a change of state as a whole. Latent heat can be generated during the process of changing the state of at least a portion of the composition or a component included in the composition.

[0158] Here, the situation that the composition shows latent heat means that in DSC (differential scanning calorimeter) analysis, the composition shows an endothermic peak within a predetermined temperature range. The method for performing DSC is described in "4. Measurement of Latent Heat" of the Examples section. The process in which the composition shows latent heat can be an isothermal process or a process similar thereto. Therefore, the composition can be applied to heat-generating products to control heat while uniformly maintaining the temperature of the product, and can minimize or prevent the influence of abnormal heating, explosion and / or fire occurring in one product on other adjacent products.

[0159] The lower limit of the latent heat exhibited by the above composition can 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 the upper limit thereof can 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 a range of less than or equal to, or less than any of the above upper limits; or within a range of greater than or equal to, or greater than any of the above lower limits; or within a range of less than or equal to, or less than any of the above upper limits and within a range of greater than or equal to, or greater than any of the above lower limits.

[0160] The lower limit of the range of the onset temperature at which the composition begins to express 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 thereof may be around 200°C, 180°C, 160°C, 140°C, 120°C, 100°C, 90°C, or 80°C. The onset temperature may be within a range of less than or equal to, or less than, any of the aforementioned upper limits; or within a range of greater than or equal to, or greater than, any of the aforementioned lower limits; or within a range of less than or equal to, or less than, any of the aforementioned upper limits while also within a range of greater than or equal to, or greater than, any of the aforementioned lower limits. The onset temperature refers to the temperature at the left starting point of the endothermic peak interval in DSC analysis.

[0161] The lower limit of the temperature interval representing the latent heat of the composition may be, for example, approximately 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, or 180°C, and the upper limit may be approximately 300°C, 280°C, 260°C, 240°C, 220°C, 200°C, 180°C, or 160°C. This temperature interval may be within a range less than or equal to, or less than, any of the aforementioned upper limits; or within a range greater than or equal to, or greater than, any of the aforementioned lower limits; or within a range less than or equal to, or less than, any of the aforementioned upper limits and within a range greater than or equal to, or greater than, any of the aforementioned lower limits. This temperature interval is the value obtained by subtracting the temperature of the left starting point from the temperature of the right starting point in the endothermic peak interval analyzed by DSC.

[0162] Through the above characteristics, the composition can be applied to various applications to effectively respond to heat generation, fire and / or explosion occurring in various applications.

[0163] The freezing point, viscosity, thixotropic index and latent heat characteristics of the composition as described above can be ensured by the combination of the components of each composition as described above.

[0164] In addition, the composition may further contain various types of known additives as long as the above-mentioned physical properties are not impaired.

[0165] For example, the fire extinguishing device can be manufactured by loading the vaporizable substance or composition into the sealed space inside the housing.

[0166] This specification also discloses an electronic device or device using the fire extinguishing device.

[0167] The type of electronic device or apparatus is not particularly limited. For example, the composition or fire extinguishing device can be applied to equipment or apparatus that has a risk of abnormal heating, fire, and / or explosion during operation, maintenance, and / or storage and must control the related abnormal phenomena.

[0168] Examples of the equipment or device typically include batteries. In particular, in a battery module constructed using a plurality of battery cells, it is important to prevent abnormal heating, fire, and / or explosion occurring in one battery cell from spreading to other adjacent battery cells.

[0169] Therefore, this specification discloses a battery module or battery pack, etc., including a fire extinguishing device.

[0170] Such a battery module or the like may basically include: a plurality of battery cells; and a fire extinguishing device disposed between the battery cells.

[0171] If the fire extinguishing device is applied, the specific configuration of the battery module, etc. (such as the type of battery cell, etc.) is not particularly limited, and known materials can be applied. For example, known pouch-shaped, rectangular or cylindrical battery cells can be used as battery cells.

[0172] The manufacturing method of the battery module is not particularly limited, and for example, as described above, a method may be used in which the fire extinguishing device is manufactured in the form of a battery cell and then placed at a desired position during the manufacturing process of the battery module or the like.

[0173] Beneficial effects

[0174] This specification discloses a composition, a fire extinguishing device and its use. The composition and the fire extinguishing device can be applied to products with the possibility of abnormal heating, fire and / or explosion during driving, storage and / or maintenance processes, so as to effectively respond to heating, fire and explosion. The composition and the fire extinguishing device can be applied to products comprising, for example, a plurality of products, so as to respond to abnormal heating, explosion and / or fire occurring in any one product, and can prevent such heating, explosion and / or fire from propagating to other adjacent products. The composition and the fire extinguishing device also have excellent operability and storage stability. The specification also discloses the use of the composition and the fire extinguishing device. BRIEF DESCRIPTION OF THE DRAWINGS

[0175] Figure 1 An exemplary cross-sectional view of a battery module with a fire extinguishing device applied.

[0176] Figure 2 It is an exemplary diagram for explaining the working principle of the fire extinguishing device.

[0177] Figure 3 It is an exemplary diagram for explaining the working principle of the fire extinguishing device.

[0178] Figure 4 It is a figure for demonstrating the process of manufacturing the fire extinguishing apparatus in Example.

[0179] Figure 5 It is a figure for demonstrating the process of manufacturing the fire extinguishing apparatus in Example.

[0180] Figure 6 FIG. 1 is a diagram showing an exemplary form of a housing used in the embodiment. DETAILED DESCRIPTION

[0181] Hereinafter, the composition, the fire extinguishing apparatus, and the like will be specifically described with reference to Examples, but the scope of the composition, the fire extinguishing apparatus, and the like is not limited to the following Examples.

[0182] 1. Convection test

[0183] The fire extinguishing device of embodiment or comparative example is positioned between two aluminum plates respectively, and heat-insulating material is laminated on one of two aluminum plates, thereby manufacture the laminated body that is sequentially laminated with heat-insulating material, aluminum plate, fire extinguishing device and aluminum plate.As aluminum plate, use the plate with a thickness of about 3mm or so, and as heat-insulating material, use the mineral wool (KCC, heat-insulating plate No. 1) with a thickness of about 2mm or so. Subsequently, with fixture, press the both sides of laminated body under the pressure of about 350kPa and fix. Subsequently, temperature sensor (k type thermocouple, IR thermometer 566 type of Fluke) is positioned on the heat-insulating material side of laminated body, and when the aluminum plate on the opposite side is applied to flame, use temperature sensor to measure temperature. Use two kinds of butane gas (can type butane gas (unused product) that capacity is 220g) and blowtorch to apply flame at a distance of about 2 inches from aluminum plate. Use temperature sensor to measure temperature when applying flame about 5 minutes, and according to the following standard assessment temperature.

[0184] <Evaluation Criteria>

[0185] PASS: When the measured temperature of the temperature sensor remains below 200°C

[0186] NG: When the temperature sensor measures a temperature of 200°C or above, or the aluminum plate is observed to be melted

[0187] 2. Chain fire test

[0188] Rectangular batteries are arranged side by side at intervals of about 3 mm, and a fire extinguishing device containing the composition is placed therebetween. As a rectangular battery, a product of CATL (120Ah, 3.2V, size = thickness × width × width = 48 × 174 × 165) is used, and is applied to the test in a 100% charged state. In the above arrangement, a battery fire is initiated in one rectangular battery according to the SAE J2464:2009 standard, and a chain fire in another battery cell is checked. The battery fire is caused by piercing a nail with a diameter of about 5 mm into the rectangular battery at a speed of 25 mm / sec (nail penetration method).

[0189] <Evaluation Criteria>

[0190] PASS: When no fire occurs in any battery cell other than the one pierced by the nail

[0191] NG: When a fire occurs in a battery cell other than the one pierced by the nail

[0192] 3. Storage stability evaluation

[0193] 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 was measured. If the weight change before and after storage was 1% or greater, it was evaluated as NG, and if the weight change was less than 1% or there was no weight change, it was evaluated as PASS.

[0194] 4. Measurement of latent heat

[0195] Each composition of the embodiment or comparative example was collected in an amount of about 3 mg to 5 mg and loaded into a measuring device. As a measuring device, a DSC (differential scanning calorimeter) device (TA Instruments, Q200 model) was used. When evaluating the latent heat, the temperature interval was set to 25°C to 300°C. While the temperature was raised from 25°C to 300°C at a rate of about 20°C / min, the endothermic peak was measured. The left starting point and the right starting point of the endothermic peak interval were designated as the start and end points of the endothermic ...

[0196] 5. CRC (centrifugal retention capacity)

[0197] CRC was measured according to EDA NSW SP 241.3. Approximately 0.2 g (W0) of a water-absorbing polymer was placed in a nonwoven envelope, sealed, and then immersed in a physiological saline solution at room temperature. A 0.9 wt% NaCl aqueous solution was used as the physiological saline solution. This state was maintained for approximately 30 minutes. Water was then removed from the envelope using a centrifuge at 250 G for 3 minutes, and the envelope's mass (g, W2) was then measured.

[0198] The same operation was performed on the same nonwoven envelope without any water-absorbing polymer, and the mass (g, W1) was measured.

[0199] CRC(g / g) is calculated by substituting the measurement results into the following equation A.

[0200] The evaluation was performed under constant temperature and humidity conditions (23±1° C., relative humidity: 50±10%).

[0201] [Equation A]

[0202] CRC(g / g)={[W2(g)-W1(g)] / W0(g)}-1

[0203] 6.AUP (Absorption Under Pressure)

[0204] AUP was measured according to EDANA method WSP 242.3. A 400-mesh stainless steel screen was mounted at the bottom of a plastic cylinder with an inner diameter of approximately 60 mm. 0.0 g (W0) (0.90 g) of water-absorbent polymer was evenly sprayed onto the screen. A piston, which applied a uniform 0.3 psi load, was then mounted on the screen. The piston had an outer diameter slightly less than 60 mm, maintained a gap with the inner wall of the cylinder, and was mounted so that it could move up and down. The weight of the device (g, W3) was measured.

[0205] A glass filter having a diameter of 90 mm and a thickness of 5 mm was placed in a culture dish having a diameter of 150 mm, and physiological saline solution was added so that the upper surface thereof and the glass filter were at the same level. As physiological saline solution, a NaCl aqueous solution having a concentration of 0.9 % by weight was used. A filter paper having a diameter of 90 mm was placed thereon. A measuring device was placed on the filter paper and, under a load of 0.3 psi, physiological saline solution was absorbed for 1 hour. After this, the measuring device was raised and its weight (g, W4) was measured.

[0206] AUP (g / g) was estimated by substituting the obtained value into the following equation B.

[0207] The evaluation was performed under constant temperature and humidity conditions (23±1° C., relative humidity: 50±10%).

[0208] [Equation B]

[0209] AUP(g / g)=[W4(g)-W3(g)] / W0(g)

[0210] 7. Molecular Weight Measurement

[0211] The molecular weight of starch was evaluated in the following manner.

[0212] (1) Preparation of mobile phase

[0213] Mobile phase A was prepared by filtering 1000 mL of a 150 mM NaNO 3 aqueous solution containing 0.02 wt % NaN 3 using a solvent purification system (Millipore Millisolve Kit, MilliporeSigma).

[0214] (2) Preparation of sample solution

[0215] The sample to be measured was collected in an amount of 25 mg and mixed with 5 mL of a 150 mM NaNO 3 aqueous solution containing 0.02 wt % NaN 3 , and then a sample solution was prepared by heating the mixture at 80° C. for 20 hours and then filtering it with a 0.4 μm nylon syringe filter.

[0216] (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.

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

[0218] Stationary phase: Connecting Shodex OH-Pak 804 column and Shodex OH-Pak 80 column Mobile phase: A; 0.02% NaN3, 150mM NaNO3 aqueous solution = 100 (volume / volume%)

[0219] Flow rate: 0.4 mL / min

[0220] Stationary phase temperature: 25°C

[0221] Injection volume: 100 μl (0.45 μm filtered)

[0222] Analysis time: 120 minutes

[0223] 8. Measurement of Amylopectin and Amylose Content

[0224] The amylopectin and amylose contents in starch were evaluated according to the method described in the paper (Potato Research 31 (1988) 241-246).

[0225] First, the sample was prepared by dissolving about 5 mg of starch in about 1 mL of sterile water (step 1) and heating to 95°C in a constant temperature water bath for about 15 minutes (step 2).

[0226] Subsequently, about 20 μl of the sample was placed in a cuvette (step 3), and about 980 μl of the iodine solution was added thereto and mixed (step 4).

[0227] Subsequently, the absorbance of the sample mixed with the iodine solution at wavelengths of 525 nm and 700 nm was measured and recorded, respectively (Step 5). The absorbance was measured using KLAB's OPTIZEN POP model.

[0228] About 20 μl of water is placed in another cuvette, 980 μl of iodine solution is added thereto, and mixed (step 6). For the solution of step 6, the absorbance at wavelengths of 525 nm and 700 nm is measured and recorded in the same manner as in step 5 (step 7).

[0229] The absorbance obtained in step 7 is subtracted from the absorbance obtained in step 5, and the ratio (%) of amylose is determined according to the following equation C (step 8).

[0230] [Equation C]

[0231]

[0232] In equation C, PA is the ratio of amylose (%), OD is 700 is the value obtained by subtracting the absorbance at a wavelength of 700 nm measured in step 7 from the absorbance at a wavelength of 700 nm measured in step 5, and OD 525 is a value obtained by subtracting the absorbance at a wavelength of 525 nm measured in step 7 from the absorbance at a wavelength of 525 nm measured in step 5.

[0233] 9.WVTR (Water Vapor Transmission Rate) Evaluation

[0234] The WVTR (water vapor transmission rate) of the housing was evaluated according to ASTM F1249 under conditions of 38° C. and 100% relative humidity.

[0235] 10. Solubility Assessment

[0236] The solubility was evaluated based on the ASTM E1148-02 standard. According to this standard, the solubility is determined by evaluating the maximum amount of a sample that dissolves in 100 g of a vaporizable substance (water) at 0°C or room temperature (about 25°C).

[0237] 11. Thermal decomposition temperature

[0238] The thermal decomposition temperature was determined by TGA (Thermogravimetric Analysis). Using a TGAe850 device from Mettler-Toledo, the temperature of the sample was raised from about 20° C. at a rate of 5° C. / min in a N 2 flow atmosphere, and the point at which the weight loss was 5% or more was defined as the thermal decomposition temperature.

[0239] 12. Flammability assessment

[0240] The flammability of freezing point modifiers was evaluated according to ASTM D93. A sample (ignition source) was placed in a 100 mL brass test cup at approximately 90% of its volume. The sample was stirred at approximately 100 times / minute, and the diameter of the ignition source was set to approximately 3.2 mm to 4.8 mm. The flash point was then evaluated while the temperature was raised at a rate of 5°C / minute. If the sample vaporized without igniting, the sample was considered non-flammable. If it ignited, the temperature at the time of ignition was determined to be the flash point.

[0241] 13. Assessment of toxic gas generation

[0242] According to ASTM D4599-21, the production of toxic gases was assessed using a dye length colorimetric dosimeter. A dye length colorimetric dosimeter is a tube that can measure concentration based on color, and the measuring tube is designated for various toxic gases. The gas sample produced by the target substance is collected for about 1 minute and quantified. After injecting the sample into the open end of the dye length colorimetric dosimeter using a 100ml syringe and then holding it for about 8 hours, the concentration of each gas is measured. The toxic gases measured using this method are chlorine, ammonia, and hydrofluoric acid gas.

[0243] 14. The existence of the quality of fire

[0244] The fire extinguishing composition was placed in an aluminum can and its ignition quality was evaluated. An open-top aluminum can made of aluminum foil with a thickness of approximately 3 mm was used. The horizontal and vertical lengths of the can were approximately 9 cm and 12 cm, respectively, and the internal volume was approximately 32.4 cm. 3 The composition was filled into a can, and with the top of the can open, a flame was applied vertically to one of the can's side surfaces at intervals of approximately 1 inch. The flame was applied using butane gas (a can of butane gas with a capacity of 220 g (unused product)) and a blowtorch. Ignition quality was evaluated by observing whether a flame appeared at the open top while applying the flame for approximately 5 minutes.

[0245] 15. Thermal conductivity evaluation

[0246] The thermal conductivity was evaluated at 20° C. using a measuring device (Hot Disk, TPS2200) according to ISO 22007-2 standard.

[0247] Example 1.

[0248] Fire extinguishing composition

[0249] Water (W) and a freezing point regulator (ethylene glycol (molar mass: 62.07 g / mol)) (E) are mixed in a weight ratio (W:E) of 60:40. The mixing is carried out at 300 rpm at room temperature (about 25°C) for about 30 minutes. The flash point of ethylene glycol is about 111°C, and the concentrations of chlorine, ammonia and hydrofluoric acid gas measured according to the toxic gas assessment method are all 0 ppm. In addition, ethylene glycol is miscible with water. Subsequently, the mixture is placed in a sealed container, and glass wool is placed in the sealed container, and then maintained at room temperature (about 25°C) for about 24 hours, thereby impregnating the mixture in the glass wool to prepare a fire extinguishing composition. As glass wool, glass wool having a thickness of about 2.5 mm and a viscosity of about 0.03 g / cm 3Glass wool (glass wool blanket, Rosewool) with a density of about 1000 nm and a thermal decomposition temperature of about 400°C.

[0250] Fire extinguishing equipment

[0251] The composition was placed inside a can (housing) for making rectangular batteries and the opening was sealed to make a fire extinguishing device. The WVTR of the can for rectangular batteries was about 0.11 g / m 2 · About a day. Figure 4 As shown, two heat-conducting layers 2001 and 2002 are inserted into the interior of an aluminum can 1001, and a composition (glass wool impregnated with the mixture) 300 is injected between the heat-conducting layers 2001 and 2002, and then covered with a lid 1002 to manufacture a fire extinguishing device. When manufacturing the fire extinguishing device, the composition is injected so that at least 90% of the volume of the empty space inside the can is filled with the composition. As the heat-conducting layers 2001 and 2002, a copper film (thickness of about 18 μm) with a thermal conductivity of about 401 W / mK (based on 20°C) is used. In the case where the fire extinguishing composition is not in the form of a sheet, such as glass wool impregnated with the mixture as above, it can also be obtained by Figure 5 The fire extinguishing device is manufactured by placing two heat-conducting layers 2001 and 2002 in a housing and injecting a composition between the heat-conducting layers. As a rectangular battery housing, a housing with a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm is used.

[0252] Example 2.

[0253] Fire extinguishing composition

[0254] A fire extinguishing composition was prepared in the same manner as in Example 1, except that water (W) and ethylene glycol (molar mass: 62.07 g / mol) (E) were mixed in a weight ratio (W:E) of 72:28.

[0255] Fire extinguishing equipment

[0256] The fire extinguishing device was manufactured in the same manner as in Example 1, except that a fire extinguishing device made of an aluminum material having a thickness of about 0 g / m 2 The housing of the WVTR of about 1 day is used as a rectangular battery housing.

[0257] Example 3.

[0258] Fire extinguishing composition

[0259] Water (W), potassium acetate (K) (molar mass: 98.15 g / mol) (CH3COOK) and starch (S) are mixed in a weight ratio (W:K:S) of 55:36:10. As starch, corn starch having a weight average molecular weight of about 51,000,000 g / mol and a weight ratio of amylose to amylopectin (amylose: amylopectin) of about 25:75 is used. Potassium acetate, which is a freezing point regulator, is a non-flammable substance with no flash point and is a non-toxic substance, wherein the concentrations of chlorine, ammonia and hydrofluoric acid gas measured according to the toxic gas evaluation method are all 0 ppm. In addition, the solubility of potassium acetate, which is a freezing point regulator, in 100 g of water at 0°C is about 216 g, and the solubility in 100 g of water at 25°C is about 268.6 g. Subsequently, the mixture was placed in a sealed container, and mineral wool (thickness: about 2.5 mm, density: about 0.2 g / cm 3 , thermal decomposition temperature: about 800° C.) (KCC, mineral wool insulation board No. 1) was placed in a sealed container and then maintained at room temperature (about 25° C.) for about 24 hours, thereby impregnating the mixture into the mineral wool to prepare a fire extinguishing composition.

[0260] Fire extinguishing equipment

[0261] The fire extinguishing device was manufactured in the same manner as in Example 1, using a WVTR of about 0.27 g / m 2 A can of about 10000 sq. ft. was used as a can (casing) for manufacturing a rectangular battery. In this process, aluminum foil having a thermal conductivity of about 234 W / mK (based on 20° C.) and a thickness of about 50 μm was used as a heat-conducting layer.

[0262] Example 4.

[0263] Fire extinguishing composition

[0264] Water (W), ammonium dihydrogen phosphate (N) (NH4H2PO4) (DAEJUNG Chemicals & Metals) and a freezing point regulator (F) are mixed in a weight ratio (W:N:F) of 100:20:30 to prepare a first mixture. Mixing is carried out at room temperature (about 25°C) under a mixing condition of 300 rpm for about 10 minutes. As a freezing point regulator, potassium formate (HCOOK) (DAEJUNG Chemicals & Metals) (molar mass 84.12 g / mol) is used. Potassium formate is a non-flammable substance with no flash point and is a non-toxic substance, wherein the concentrations of chlorine, ammonia and hydrofluoric acid gas measured according to the toxic gas assessment method are all 0 ppm. In addition, the solubility of potassium formate in 100 g of water at 0°C is about 32.8 g, and the solubility in 100 g of water at 25°C is about 331 g.

[0265] The solubility of ammonium dihydrogen phosphate (N) (NH4H2PO4) in water at 25°C is about 29g. Subsequently, starch (S) (Sigma-Aldrich) and melamine (M) (ACROS ORGANICS) are additionally mixed into the first mixture to prepare a second mixture. In the second mixture, the ratio (W:S:M) of water (W) to starch (S) to melamine (M) is adjusted to about 100:10:10. Mixing is performed at room temperature (about 25°C) under a mixing condition of 300 rpm for about 30 minutes. When making the second mixture, the corn starch used in Example 3 is used as starch. Subsequently, a water-absorbing polymer (SAP) is additionally mixed into the second mixture to prepare a composition. The mixing of the water-absorbing polymer is performed by mixing the second mixture and the water-absorbing polymer and mixing them at room temperature (about 25°C) under a mixing condition of 300 rpm for about 2 hours. Mixing was performed so that the weight ratio (W:P) of water (W) to water-absorbent polymer (P) was approximately 100:5. LG Chemical's SAP GS-803ND was used as the water-absorbent polymer, which had been crushed and classified to a size of approximately 150 μm. This water-absorbent polymer had a CRC (centrifuge retention capacity) of approximately 33.5 g / g and an AUP (absorption under pressure) of approximately 28.1 g / g.

[0266] Fire extinguishing equipment

[0267] A fire extinguishing device was manufactured in the same manner as in Example 2 using the aluminum can (casing) for manufacturing a rectangular battery applied in Example 2. In this process, no heat conductive layer was applied.

[0268] Example 5.

[0269] A fire extinguishing composition and a fire extinguishing device were each manufactured in the same manner as in Example 4, except that sodium formate (HCOONa) (DAEMYUNG Chemical) (molar mass: 68.01 g / mol) was used instead of potassium formate (HCOOK) (DAEJUNG Chemicals & Metals) as a freezing point adjuster. Sodium formate is a non-flammable substance without any flash point and is a non-toxic substance, wherein all concentrations of chlorine, ammonia, and hydrofluoric acid gas measured according to the toxic gas evaluation method are 0 ppm. In addition, the solubility of sodium formate in 100 g of water at 0° C. is about 43.82 g, and the solubility in 100 g of water at 25° C. is about 97.2 g.

[0270] Example 6.

[0271] A fire extinguishing composition and a fire extinguishing apparatus were each manufactured in the same manner as in Example 4, except that potassium acetate (CH3COONa) (DAEJUNG Chemicals & Metals) (molar mass: 98.15 g / mol) was used instead of potassium formate (HCOOK) (DAEWUNG Chemicals & Metals) as the freezing point adjuster. Potassium acetate is a non-flammable substance having no flash point and is a non-toxic substance, with all concentrations of chlorine, ammonia, and hydrofluoric acid gas measured according to the toxic gas evaluation method being 0 ppm.

[0272] Example 7.

[0273] Fire extinguishing composition

[0274] Water (W) and diammonium phosphate (N) (NH4H2PO4) were mixed in a weight ratio (W:N) of 100:22 to prepare a first mixture. The mixture was mixed at 300 rpm for about 10 minutes at room temperature (about 25°C). A second mixture was prepared by adding starch (S) and melamine (M) to the first mixture. In the second mixture, the ratio (W:S:M) of water (W), starch (S) and melamine (M) was adjusted to 100:6:6. The mixture was mixed at 300 rpm for about 30 minutes at room temperature (about 25°C). When preparing the second mixture, the same corn starch as used in Example 3 was used as starch. Subsequently, a water-absorbing polymer (SAP) was added to the second mixture to prepare a composition. The water-absorbing polymer was mixed by mixing the second mixture and the water-absorbing polymer and mixing them at 300 rpm for about 2 hours at room temperature (about 25°C). Mixing was performed so that the weight ratio (W:P) of water (W) to water-absorbing polymer (P) in the mixture was approximately 100:5. The same polymer as used in Example 4 was used as the water-absorbing polymer. The fire extinguishing composition thus prepared had a latent heat of approximately 1615 J / g.

[0275] Fire extinguishing equipment

[0276] A fire extinguishing device was manufactured in the same manner as in Example 4 using this fire extinguishing composition.

[0277] Comparative Example 1.

[0278] Fire extinguishing composition

[0279] Water (W) and potassium acetate (K) (molar mass: 98.15 g / mol) (CH3COOK) are mixed in a weight ratio (W:K) of 45:55. Potassium acetate, which is a freezing point regulator, is a non-flammable substance with no flash point and is a non-toxic substance, wherein the concentrations of chlorine, ammonia and hydrofluoric acid gas measured according to the toxic gas evaluation method are all 0 ppm. Subsequently, the mixture is placed in a sealed container, and mineral wool (thickness: about 2.5 mm, density: about 0.2 g / cm 3 , thermal decomposition temperature: about 800° C.) (KCC, mineral wool insulation board No. 1) was placed in a sealed container and then maintained at room temperature (about 25° C.) for about 24 hours to prepare a fire extinguishing composition.

[0280] Fire extinguishing equipment

[0281] The WVTR is about 0.27 g / m 2 A can (casing) of about 10000 Å was used as a can (casing) for manufacturing a rectangular battery, and a fire extinguishing device was manufactured in the same manner as in Example 1. In this process, aluminum foil having a thermal conductivity of about 234 W / mK (based on 20° C.) and a thickness of about 50 μm was used as the heat conductive layer.

[0282] Comparative Example 2.

[0283] A fire extinguishing device was manufactured in the same manner as in Example 1, except that a WVTR of about 7.5 g / m 2 The shell of about 1000 square meters is used as a rectangular battery shell.

[0284] Comparative Example 3.

[0285] A fire extinguishing device was manufactured in the same manner as in Example 7, except that a WVTR of about 7.5 g / m 2 The shell of about 1000 square meters is used as a rectangular battery shell.

[0286] The evaluation results of the Examples and Comparative Examples are summarized and described in the following Tables 1 and 2. In the following Tables 1 and 2, M is the sum of the molar concentrations of the freezing point modifier and other ionic compounds (ammonium dihydrogen phosphate) relative to the vaporizable substance (water) in the composition, and ΔT f The freezing point modifier and the other ionic compound (ammonium dihydrogen phosphate) are each expressed as follows: f In addition, in Tables 1 and 2, the water content is the weight of water contained when the weight of the fire extinguishing composition of the embodiment or comparative example is 100%, and WVTR is the WVTR (unit: g / m2) of the shell used to manufacture the fire extinguishing device. 2 ·sky).

[0287] [Table 1]

[0288]

[0289] [Table 2]

[0290]

[0291] The results in Table 1 confirm that by including a certain amount or more of water in the composition and controlling the WVTR of the fire extinguishing device housing, excellent results were achieved in the convection test and the chain fire test. Furthermore, considering the temperature determined by the temperature sensor during the convection test, Examples 1 to 6, which adjusted the vaporization rate by adding a freezing point modifier, showed superior results compared to Example 7. The results in Table 2 indicate that controlling the WVTR of the housing without controlling the water content in the composition (Comparative Example 1) or without controlling the water content in conjunction with WVTR (Comparative Examples 2 and 3) did not achieve the expected results. Furthermore, when ethylene glycol was used as the freezing point depressant, the compositions of the Examples and Comparative Examples were confirmed to have ignition quality.

[0292] Example 8.

[0293] A fire extinguishing device was manufactured in the same manner as in Example 1, except that a bag-type housing was used as the housing of the fire extinguishing device. The housing was manufactured using an outer shell manufactured by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), a PVDC (polyvinylidene chloride) film (thickness: about 40 μm), and a PP (polypropylene) hot melt film (thickness; about 50 μm) (melting point: about 140°C) in this order. The PET film was laminated on one side of the PVDC film using an adhesive, and the PP hot melt film was laminated on the other side at a temperature of about 200°C to manufacture the outer shell. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare the upper shell 121 and the lower shell 122 respectively. After the heat conductive layer is attached to the recess I of the upper shell 121 and the lower shell 122, the fire extinguishing composition is placed on the heat conductive layer, and after the upper shell 121 and the lower shell 122 are laminated, the PP hot melt films are fused to each other at the sealing portion S to manufacture the fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 0.11 g / m 2 As the heat-conducting layer, the same heat-conducting layer as that used in Example 1 was used. The housing was manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0294] Example 9.

[0295] A fire extinguishing device was manufactured in the same manner as in Example 2, except that a bag-type housing was used as the housing of the fire extinguishing device. The housing was manufactured using an outer shell manufactured by laminating a PET (polyethylene terephthalate) film (thickness: about 10 μm), an aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot-melt film (thickness: about 70 μm) (melting point: about 140° C.) in this order. The PET film was laminated on one side of the aluminum foil using an adhesive, and the PP hot-melt film was laminated on the other side at a temperature of about 200° C. to manufacture the outer shell. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare the upper shell 121 and the lower shell 122 respectively. After the heat conductive layer is attached to the recess I of the upper shell 121 and the lower shell 122, the fire extinguishing composition is placed on the heat conductive layer, and after the upper shell 121 and the lower shell 122 are laminated, the PP hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 0 g / m 2 As the heat-conducting layer, the same heat-conducting layer as that used in Example 1 was used. The housing was manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0296] Example 10.

[0297] A fire extinguishing device was manufactured in the same manner as in Example 3, except that a bag-type shell was used as the shell of the fire extinguishing device. The shell was manufactured using an outer shell manufactured by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), an EVOH (ethylene vinyl alcohol) film (thickness: about 40 μm), and a PE (polyethylene) hot melt film (thickness: about 50 μm) (melting point: about 140°C) in this order. The PET film was laminated on one side of the EVOH film using an adhesive, and the PE hot melt film was laminated on the other side at a temperature of about 200°C to manufacture the outer shell. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare the upper shell 121 and the lower shell 122 respectively. After the heat conductive layer is attached to the recess I of the upper shell 121 and the lower shell 122, the fire extinguishing composition is placed on the heat conductive layer, and after the upper shell 121 and the lower shell 122 are laminated, the PE hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 0.27 g / m 2As the heat conducting layer, the same heat conducting layer as that used in Example 3 was used. The housing was manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0298] Example 11.

[0299] A fire extinguishing device was manufactured in the same manner as in Example 4, except that a bag-type housing was used as the housing of the fire extinguishing device. The housing was manufactured using an outer shell manufactured by laminating a PET (polyethylene terephthalate) film (thickness: about 10 μm), an aluminum foil film (thickness; about 20 μm), and a PP (polypropylene) hot melt film (thickness: about 70 μm) (melting point: about 140°C) in this order. The PET film was laminated on one side of the aluminum foil using an adhesive, and the PP hot melt film was laminated on the other side at a temperature of about 200°C to manufacture the outer shell. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare an upper shell 121 and a lower shell 122 respectively. A fire extinguishing composition is placed on the lower shell 122, and after laminating the upper shell 121 and the lower shell 122, the PP hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 0 g / m 2 About 1 day. During this process, no thermal conductive layer was applied. The housing was manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0300] Example 12.

[0301] A fire extinguishing device was manufactured in the same manner as in Example 5, except that a bag-type housing was used as the housing of the fire extinguishing device. The housing was manufactured using an outer shell manufactured by laminating a PET (polyethylene terephthalate) film (thickness: about 10 μm), an aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot melt film (thickness: about 70 μm) (melting point: about 140° C.) in this order. The PET film was laminated on one side of the aluminum foil using an adhesive, and the PP hot melt film was laminated on the other side at a temperature of about 200° C. to manufacture the outer shell. Figure 6As shown, a recess I is formed in the central portion of the shell to prepare an upper shell 121 and a lower shell 122 respectively. A fire extinguishing composition is placed on the lower shell 122, and after laminating the upper shell 121 and the lower shell 122, the PP hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 0 g / m 2 About 1 day. During this process, no thermal conductive layer was applied. The housing was manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0302] Example 13.

[0303] A fire extinguishing device was manufactured in the same manner as in Example 6, except that a bag-type housing was used as the housing of the fire extinguishing device. The housing was manufactured using an outer shell manufactured by laminating a PET (polyethylene terephthalate) film (thickness: about 10 μm), an aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot-melt film (thickness: about 70 μm) (melting point: about 140° C.) in this order. The PET film was laminated on one side of the aluminum foil using an adhesive, and the PP hot-melt film was laminated on the other side at a temperature of about 200° C. to manufacture the outer shell. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare an upper shell 121 and a lower shell 122 respectively. A fire extinguishing composition is placed on the lower shell 122, and after laminating the upper shell 121 and the lower shell 122, the PP hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 0 g / m 2 About 1 day. During this process, no thermal conductive layer was applied. The housing was manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0304] Example 14.

[0305] A fire extinguishing device was manufactured in the same manner as in Example 7, except that a bag-type housing was used as the housing of the fire extinguishing device. The housing was manufactured using an outer shell manufactured by laminating a PET (polyethylene terephthalate) film (thickness: about 10 μm), an aluminum foil (thickness: about 20 μm), and a PP (polypropylene) hot-melt film (thickness: about 70 μm) (melting point: about 140° C.) in this order. The PET film was laminated on one side of the aluminum foil using an adhesive, and the PP hot-melt film was laminated on the other side at a temperature of about 200° C. to manufacture the outer shell. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare an upper shell 121 and a lower shell 122 respectively. A fire extinguishing composition is placed in the lower shell 122, and after laminating the upper shell 121 and the lower shell 122, the PP hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 0 g / m 2 About 1 day. During this process, no thermal conductive layer was applied. The housing was manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0306] Comparative Example 4.

[0307] A fire extinguishing device was manufactured in the same manner as in Comparative Example 1, except that a bag-type shell was used as the shell of the fire extinguishing device. The shell was manufactured using an outer shell manufactured by laminating a PET (poly(ethylene terephthalate)) film (thickness: about 10 μm), an EVOH (ethylene vinyl alcohol) film (thickness: about 40 μm), and a PE (polyethylene) hot-melt film (thickness: about 50 μm) (melting point: about 140°C) in this order. The outer shell was manufactured by laminating a PET film on one side of the EVOH film using an adhesive and laminating a PE hot-melt film on the other side at a temperature of about 200°C. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare the upper shell 121 and the lower shell 122 respectively. After the heat conductive layer is attached to the recess I of the upper shell 121 and the lower shell 122, the fire extinguishing composition is placed on the heat conductive layer, and after the upper shell 121 and the lower shell 122 are laminated, the PE hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 0.27 g / m 2 About 10 days. As the thermal conductive layer, aluminum foil with a thermal conductivity of approximately 234 W / mK (based on 20°C) and a thickness of approximately 50 μm was used. The housing was manufactured to have a width of approximately 9 cm, a length of approximately 12 cm, and a thickness of approximately 3 mm.

[0308] Comparative Example 5.

[0309] The fire extinguishing device was manufactured in the same manner as in Example 1, except that a bag-type housing was used as the housing of the fire extinguishing device. The housing was manufactured using an outer shell manufactured by laminating a PVC (polyvinyl chloride) film (thickness: about 20 μm) and a PP hot melt film (thickness: about 70 μm) (melting point: about 140° C.). The PP hot melt film was laminated on one side of the PVC film at a temperature of about 200° C. to manufacture the outer shell. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare the upper shell 121 and the lower shell 122 respectively. After the heat conductive layer is attached to the recess I of the upper shell 121 and the lower shell 122, the fire extinguishing composition is placed on the heat conductive layer, and after the upper shell 121 and the lower shell 122 are laminated, the PP hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 7.5 g / m 2 As the heat-conducting layer, the same heat-conducting layer as that used in Example 1 was used. The housing was manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0310] Comparative Example 6.

[0311] The fire extinguishing device was manufactured in the same manner as in Example 7, except that a bag-type housing was used as the housing of the fire extinguishing device. The housing was manufactured using an outer shell manufactured by laminating a PVC (polyvinyl chloride) film (thickness: about 20 μm) and a PP hot melt film (thickness: about 70 μm) (melting point: about 140° C.). The PP hot melt film was laminated on one side of the PVC film at a temperature of about 200° C. to manufacture the outer shell. Figure 6 As shown, a recess I is formed in the central portion of the shell to prepare the upper shell 121 and the lower shell 122 respectively. The fire extinguishing composition is placed on the recess I of the lower shell 122, and after the upper shell 121 and the lower shell 122 are laminated, the PP hot melt films are fused to each other at the sealing portion S to manufacture a fire extinguishing device. Thereafter, three of the four side sealing portions S are folded so that the unfolded sealing portion can be used as a ventilation area. Here, the composition is injected to occupy at least 90% of the volume of the sealed space formed by the recess I. The WVTR of the shell is about 7.5 g / m 2 The housing is manufactured to have a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm.

[0312] The evaluation results of Examples and Comparative Examples are summarized and described in the following Tables 3 and 4. In the following Tables 3 and 4, M and ΔT fThe meanings of are the same as those in Tables 1 and 2. In addition, in Tables 3 and 4, the water content is the weight of water contained when the weight of the fire extinguishing composition of the Examples or Comparative Examples is 100%, and WVTR is the WVTR (unit: g / m2) of the shell used to manufacture the fire extinguishing device. 2 ·sky).

[0313] [Table 3]

[0314]

[0315] [Table 4]

[0316]

[0317] It can be confirmed from the results in Tables 3 and 4 that although the shape of the shell is changed, excellent results are shown in the convection test and the chain fire test by including a certain content or more of water in the composition and controlling the WVTR of the shell of the fire extinguishing device.

Claims

1. A composition comprising: vaporizable substances; and a freezing point adjuster, wherein the freezing point adjuster is one or more selected from alcohols and ionic compounds, wherein the amount of the vaporizable substance is 50 wt% or more, and wherein the freezing point modifier is included such that ΔT according to the following equation 1 f For 5 to 50: [Equation 1] ΔT f =K f ×M×I Wherein K f is the freezing point depression constant of the vaporizable substance, M is the molar concentration of the freezing point adjuster relative to the vaporizable substance, and I is the number of ions formed by the freezing point adjuster, or 1 if the freezing point adjuster is not the ionic compound.

2. The composition according to claim 1, wherein the boiling point of the vaporizable substance is in the range of 80°C to 120°C.

3. The composition of claim 1, wherein the vaporizable substance is water.

4. The composition according to claim 1, wherein the solubility of the freezing point adjuster in 100 g of the vaporizable substance at 0°C is 20 g or more. 5 . The composition according to claim 1 , wherein the solubility of the freezing point adjuster in 100 g of the vaporizable substance at 25° C. is 70 g or more.

6. The composition of claim 1, wherein the freezing point modifier has a molar mass of 300 g / mol or less.

7. The composition of claim 1, wherein the ionic compound is one or more selected from the group consisting of formates, acetates, carbonates, and sulfates. 8 . The composition according to claim 1 , further comprising one or more selected from the group consisting of a carbonizable organic material and a carbonization catalyst.

9. A fire extinguishing device comprising: A shell having a sealed space inside; and a vaporizable substance in the sealed space, wherein the amount of the vaporizable substance in the sealed space is 50 wt % or more, and wherein the WVTR (water vapor transmission rate) of a portion of the housing or the housing is 5 g / m 2 days or less, the portion is 80% or more of the area of ​​the housing forming the sealed space. 10 . The fire extinguishing device according to claim 9 , wherein the sealed space further contains a freezing point adjuster, and the freezing point adjuster is one or more selected from alcohols and ionic compounds.

11. The fire extinguishing device of claim 10, wherein the freezing point modifier is present such that ΔT according to the following equation 1 f For 5 to 50: [Equation 1] ΔT f =K f ×M×I Wherein K f is the freezing point depression constant of the vaporizable substance, M is the molar concentration of the freezing point adjuster relative to the vaporizable substance, and I is the number of ions formed by the freezing point adjuster, or 1 if the freezing point adjuster is not the ionic compound.

12. The fire extinguishing device according to claim 9, wherein the boiling point of the vaporizable substance is in the range of 80°C to 120°C.

13. The fire extinguishing device according to claim 9, wherein the vaporizable substance is water.

14. The fire extinguishing apparatus according to claim 10, wherein the solubility of the freezing point adjuster in 100 g of the vaporizable substance at 0°C is 20 g or more.

15. The fire extinguishing apparatus according to claim 10, wherein the solubility of the freezing point adjuster in 100 g of the vaporizable substance at 25°C is 70 g or more.

16. The fire extinguishing device of claim 10, wherein the ionic compound is one or more selected from the group consisting of formates, acetates, carbonates, and sulfates.

17. The fire extinguishing device according to claim 9, wherein at least one selected from a carbonizable organic material and a carbonization catalyst further exists in the sealed space.

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