Composition

Abstract

The present specification discloses a composition, a fire extinguishing device, and uses thereof. The composition and the fire extinguishing device can be applied to products having a possibility of abnormal heat generation, ignition and / or explosion during operation, storage and / or maintenance thereof to effectively respond to the heat generation, ignition and explosion. The composition and the fire extinguishing device can be applied to, for example, an article comprising a plurality of the products, to respond to abnormal heat generation, explosion and / or ignition occurring in one of the products and to prevent such heat generation, explosion and / or ignition from spreading to other adjacent products. The composition and the fire extinguishing device also have excellent handleability and storage stability. The present specification also discloses uses of the composition and the fire extinguishing device.

Description

Composition

[0001] This application claims the benefit of priority to Republic of Korea Patent Application Nos. 10-2023-0041413 and 10-2023-0041416, filed March 29, 2023, the entire contents of which are incorporated herein by reference.

[0002] The present specification discloses compositions, digestive devices and uses thereof.

[0003] Technology is needed to ensure the safety of products that pose a risk of abnormal overheating, ignition, or explosion (hereinafter referred to as "hazardous products"). In particular, when multiple hazardous products are included, significant safety issues can arise if abnormal overheating, ignition, and / or explosion occurring in one product cascades across adjacent products. A representative example of this phenomenon is the so-called TR (Thermal Runaway) or TP (Thermal Propagation) phenomenon, which occurs in battery modules or battery packs.

[0004] A battery module or battery pack comprises a plurality of battery cells or battery modules arranged adjacent to each other. In such a structure, if abnormal heat generation, ignition, and / or explosion occurs in one battery cell and / or battery module, the phenomenon of such heat generation, ignition, and / or explosion spreading to other adjacent battery cells in a chain reaction is called the TR or TP phenomenon.

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

[0006] In particular, in cases where the user's safety is directly affected by TR or TP phenomena, such as in electric vehicles, chain reactions of heat generation, ignition, and explosion such as TR or TP must be managed.

[0007] The present specification discloses compositions, digestive devices and their uses.

[0008] The present specification aims to disclose a composition and a fire extinguishing device and their use that can effectively respond to abnormal heat generation, ignition and / or explosion in products that have the possibility of abnormal heat generation, ignition and / or explosion during operation, storage and / or maintenance.

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

[0010] The present specification also aims to disclose a composition and a fire extinguishing device having excellent handling and storage stability. The present specification also aims to disclose uses of the composition and the fire extinguishing device.

[0011] Among the properties mentioned in this specification, properties that are affected by temperature are properties measured at room temperature, unless otherwise specified.

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

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

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

[0015] The term atmospheric pressure refers to natural pressure that has not been artificially pressurized or depressurized, and is usually in the range of about 700 mmHg to 800 mmHg.

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

[0017] Standard humidity refers to a relative humidity of approximately 40%, 50%, 60%, or 65%.

[0018] The present specification discloses a composition.

[0019] The term "composition" refers to a substance comprising two or more components. Such a composition may be a fire-fighting composition. A fire-fighting composition is a composition capable of responding to abnormal heat, flames, explosions, and other conditions that require suppression.

[0020] These compositions can exhibit excellent effects, especially when combined with the structure of the digestive device described below.

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

[0022] First, let's explain the digestive system.

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

[0024] The above composition may be the aforementioned fire extinguishing composition, and the volatile material may be a component of the composition.

[0025] The case is a container for holding the volatile substance or composition. The case has a sealed space inside, or is prepared to form a sealed space inside. In this case, the case being prepared to form a sealed space inside means that the sealed space is formed inside the case, or that a certain space exists inside the case, and although the space is not sealed, the case exists so that the sealed space can be formed by sealing the open portion.

[0026] The sealed space of such a case may have a vent area. The term "vent area" may refer to an area that is sealed in a first state so that the sealed state of the space can be maintained, but is open in a second state so that the material within the space can be discharged. The second state may refer to a state in which, for example, abnormal ignition, abnormal heating, and / or explosion occurs in an environment in which the composition or fire extinguishing device is applied, and the first state may refer to a state in which the abnormal ignition, abnormal heating, and abnormal explosion do not occur.

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

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

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

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

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

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

[0033] The above-mentioned fire extinguishing device is configured to stably maintain the vaporizable substance or composition inside the device under normal conditions, and to release all or part of the vaporizable substance or composition or its vaporized substances to the outside under abnormal conditions. The abnormal condition may be, for example, the second condition, and the normal condition may be, for example, the first condition.

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

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

[0036] The above-described fire extinguishing device (S) maintains volatile substances, etc., inside it in a normal state. In an abnormal state, the volatile substances, etc., of the fire extinguishing device (S) are ejected (dotted arrows in Fig. 1) in a directionally manner through, for example, the aforementioned vent area, etc., thereby responding to high temperatures or flames resulting from abnormal heating, ignition, and / or explosion. In Fig. 1, a case is described in which the substances are ejected from both the upper and lower directions of the fire extinguishing device (S), but the ejection direction is not limited to Fig. 1. The ejection direction may be in one direction of the fire extinguishing device (S), or in two or more directions. These ejection directions can be controlled by forming a vent area.

[0037] In order for a fire extinguishing device to effectively perform the above function under abnormal conditions, it is required that volatile substances, etc. existing inside the case under normal conditions be stably maintained, and that when an abnormal condition occurs, the volatile substances, etc. be able to be quickly exhausted to the outside in a vaporized state as much as possible. The fire extinguishing device can satisfy the above requirements.

[0038] The above digestive device explains the principle of its function.

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

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

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

[0042] The method for forming the above-mentioned vent area is not particularly limited. The vent area can be formed by designing the case forming the sealed space to be opened when the internal pressure reaches a certain level. For example, if a certain area of ​​the case forming the sealed space is configured to have lower strength than other areas, the portion having the lower strength can be opened due to increased internal pressure. In addition, a method of forming the sealed space through sealing using a hot melt material or the like, thereby causing opening by melting at a certain temperature, can also be used. Alternatively, the vent area can be formed by making only a certain area of ​​the case forming the sealed space thinner than other areas. Such methods for forming the vent area can be readily employed by those skilled in the art.

[0043] For example, when the above-described fire extinguishing device is applied to a battery module or pack, for convenience of application, the case may be a square case, pouch-shaped case, and / or cylindrical case, each having the same shape as the battery cell. In such cases, a vent area may also be formed by controlling the bonding strength of the cover forming a sealed space in the square or cylindrical case.

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

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

[0046] 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 (cyclo olefin copolymer) film; an acrylic polymer film; a polyolefin film; a PVA (polyvinyl alcohol) film; a PVC (poly(vinyl chloride)) film, a PES (poly ether sulfone) film; a PEEK (polyetheretherketon) film; a PPS (polyphenylsulfone) film; a PEI (polyetherimide) film; a PEN (polyethylenemaphthatlate) film; a PET (poly(ethylene terephthalate)) film; a PI (polyimide) film; a PSF (polysulfone) film and / or a PAR (polyarylate) film.

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

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

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

[0050] The above digestive device may include additional components to perform the above action more effectively.

[0051] For example, the fire extinguishing device may further include a thermally conductive layer. This thermally conductive layer may be located at an appropriate location within the fire extinguishing device. For example, the thermally conductive layer may be located between the case and the volatile material or composition within the fire extinguishing device, or may be located adjacent to the case.

[0052] Fig. 3 is an example of a case where the heat-conducting layer (2001) is added to the digestive device of Fig. 2. The heat-conducting layer may be present at different locations inside the case, and the number of layers may be one or two or more.

[0053] The term thermally conductive layer refers to a layer having a thermal conductivity (at 20°C) within the range described below. The lower limit of the thermal conductivity (at 20°C) of the thermally conductive layer may be about 15, 18, 20, 50, 100, 150, 200, 250, 300, 350, or 400, and the upper limit may be about 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 that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The unit of the above thermal conductivity is W / mK, and can be evaluated in the manner described in “15. Evaluation of thermal conductivity” in the Examples section of this specification.

[0054] The type of thermally conductive layer is not particularly limited as long as it possesses the above-mentioned thermal conductivity. Typically, metal materials with excellent thermal conductivity can be used as thermally conductive layers. For example, layers made of metal materials such as aluminum, gold, pure silver, tungsten, copper, nickel, or platinum can be applied.

[0055] There is no special limitation on the thickness of the thermal conductive layer, and an appropriate thickness can be set in consideration of the specifications of the fire extinguishing device, etc. For example, the lower limit of the thickness of the thermal conductive layer may be about 1 μm, 5 μm, 10 μm, 15 μm, 50 μm, 75 μm, or 90 μm, and the upper limit may be about 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, 50 μm, 40 μm, or 30 μm. The thickness may be within a range that is less than or equal to any one of the upper limits described above; within a range that is greater than or equal to any one of the lower limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

[0056] As shown in Fig. 3, in some cases, heat generated under abnormal conditions may not be uniformly applied to the fire extinguishing device, but may be applied locally to a certain area. However, in order for the volatile substances within the fire extinguishing device to rapidly vaporize and achieve a high-pressure state, the heat under abnormal conditions must be uniformly applied to the fire extinguishing device. In the case where a heat conductive layer exists, even if the heat under abnormal conditions is applied locally, the heat can be quickly and efficiently transferred to the entire fire extinguishing device, thereby enabling the fire extinguishing action of the fire extinguishing device described above to occur quickly and efficiently.

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

[0058] The above digestive composition is described below.

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

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

[0061] For example, the composition may have a flammability rating of 0 or 1 according to the National Fire Protection Association (NFPA) 704 standard. The NFPA 704 standard is a standard published by the National Fire Protection Association (NFPA), and is a standard expressed as a so-called fire diamond created to enable a rapid response to hazardous materials in emergency situations, and the flammability rating is indicated by a red area. The standard is classified into grades 0, 1, 2, 3, and 4, among which grade 0 means no flammability, and grade 1 means a case where it ignites when sufficiently heated, and is approximately a case where the flash point is 93℃ or higher. The evaluation method of this flammability rating follows the NFPA (National Fire Protection Association) 704 standard.

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

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

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

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

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

[0067] For example, the lower limit of the freezing point of the above-mentioned volatile substance may be about -5°C, -4°C, -3°C, -2°C, -1°C, or 0°C, and the upper limit may be about 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 that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The freezing point is the freezing point under 1 atm.

[0068] The above-mentioned volatile substance may have a boiling point within a certain range in order to exhibit appropriate volatile properties. For example, the lower limit of the boiling point of the above-mentioned volatile 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 that is equal to or greater than any one of the above-mentioned lower limits and equal to or less than any one of the above-mentioned upper limits. The above-mentioned boiling point is a boiling point under 1 atm.

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

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

[0071] For example, the lower limit of the proportion of the vaporizable substance within the composition or within the enclosed space of the fire extinguishing device may be about 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt% or 80 wt%, and the upper limit may be about 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt%, 65 wt% or 60 wt%. The proportion may be within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The closer the content of the vaporizable substance approaches the range disclosed in the embodiments within the above-described range, the better the effect may be. The proportion is a percentage based on the sum total of the weights of all components present in the composition or all components present within the enclosed space.

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

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

[0074] The form in which the freezing point regulator is applied can be controlled to secure the above-described effect, particularly the effect of instantaneous and complete rapid vaporization of the volatile substance at the required time.

[0075] For example, the above freezing point regulator is △T of the following equation 1 f It can exist so that it can be within a certain range.

[0076] [Formula 1]

[0077] △T f = K f × M × I

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

[0079] Above K f The unit is ℃ / m, and for example, if the volatile substance is water, the above K f is approximately 1.86.

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

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

[0082] In the case where two or more types of freezing point regulators or ionic compounds are present in the above composition, the △T for each compound f Calculate and add up the values ​​to get △T for the composition f It's worth it.

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

[0084] By applying the freezing point regulator in the above range, the volatile substance can be rapidly and substantially completely vaporized at the required time to quickly increase the internal pressure of the sealed space, and the volatile substance can exist in a liquid state at the required time, and changes in the volume and hardness of the composition or the extinguishing device that can affect the operation of the product in the normal state can be prevented. The above △T fThe closer it is to the range of the embodiment in the above range, the more excellent the effect can be.

[0085] As the freezing point regulator, for example, alcohol or an ionic compound can be used. The category of the ionic compound includes substances that are ionic in themselves or can generate ions, such as salts.

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

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

[0088] There is no particular limitation on the type of the alcohol, and for example, polyhydric alcohols such as ethylene glycol or glycerin can be applied.

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

[0090] The above freezing point regulator may be present so that the concentration calculated based on the volatile substance is within a predetermined range. The concentration at this time is a molal concentration, and specifically, it is the number of moles of the freezing point regulator present per 1 kg of the volatile substance present in the composition. In one example, the lower limit of the molal concentration may be 1, 1.5, 2, 4, 6, 8, 10, 12, 14, or 16, and the upper limit may be 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 molal concentration may be in a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The molal concentration may be in a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The molal concentration may be in a range that is equal to or greater than △T of the above equation 1. f can be adjusted taking into account.

[0091] As a freezing point regulator, it may be appropriate to use a component having a flammability rating of 0 or 1 according to the National Fire Protection Association (NFPA) 704 standard and / or a health hazard rating of 0, 1, or 2 according to the National Fire Protection Association (NFPA) 704 standard. Various freezing point regulators capable of inducing freezing point depression are known, but most of them are flammable and / or toxic, so when selecting a freezing point regulator, it is necessary to consider the NFPA rating, etc., when achieving the intended NFPA rating.

[0092] The above freezing point regulator may preferably have a certain level of solubility in the volatile substance. To select a freezing point regulator with an appropriate solubility, the degree of freedom in the amount of the freezing point regulator added is increased, and an amount that secures the desired freezing point while improving the extinguishing function without impairing it can be selected.

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

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

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

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

[0097] Examples of such freezing point regulators include, for example, ionic compounds of the types described above, such as one or more selected from the group consisting of formates, acetates, carbonates, and sulfates.

[0098] The specific content of the above freezing point regulator is △T of the above formula 1 f It can be adjusted in consideration of. For example, the lower limit of the weight ratio of the freezing point regulator to 100 parts by weight of the volatile material 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 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. The above ratio may be within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0099] In addition, when an ionic compound (e.g., an ionic compound as a carbonization catalyst) added for a purpose other than the freezing point regulator is present in the composition or the closed space, all the freezing point regulators and the other ionic compounds present in the composition or the closed space have a △T of the above formula 1. f can exist in a quantity that falls within a certain range. At this time, △T f The specific method for calculating is the same as for the above freezing point regulator. When two or more types of freezing point regulators and ionic compounds are present in the above composition or enclosed space, the above △T is calculated for each compound. f Calculate and add up the values ​​to obtain △T for the composition or enclosed space. f It's worth it.

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

[0101] The enclosed space of the above composition or fire extinguishing device may, if necessary, contain additional components, for example, a fire extinguishing agent, to ensure proper fire extinguishing function. When a fire extinguishing agent is included, the fire extinguishing agent may perform the function of promoting the carbonization of carbonizable organic matter, as described below, and / or the function of promoting the gas production of gas-generating substances, as described below.

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

[0103] For these extinguishing agents, it may be appropriate to use agents that have a certain level of solubility in the aforementioned volatile substances (e.g., volatile substances such as water). By controlling the solubility, coagulation or phase separation phenomena within the composition can be prevented, and the aforementioned carbonization or gas generation can proceed more effectively.

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

[0105] As a fire extinguishing agent, an agent having the above solubility can be appropriately selected and used, and examples thereof include phosphoric acid, phosphate, phosphonate compounds, or phosphate compounds. The fire extinguishing agent may be, for example, primary or secondary ammonium phosphate, urea phosphate, guanyl urea phosphate, or ammonium polyphosphate, and one or more of the above may be selected and used.

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

[0107] The enclosed space of the above composition or fire extinguishing device may contain carbonizable organic matter as an additional component.

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

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

[0110] As for the above carbonizable organic material, any suitable type may be applied without special restrictions as long as it is a material that forms carbon when exposed to heat or flame.

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

[0112] A representative example of a carbonizable organic material is starch. Starch is relatively readily available and can form suitable carbonized materials when exposed to heat or flame.

[0113] The type of starch can be controlled to efficiently form the above-mentioned carbide and to ensure that the formed carbide effectively exerts the desired digestion or insulation effect.

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

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

[0116] For example, in the starch containing the amylose and amylopectin, the lower limit of the weight ratio of the amylopectin to 100 parts by weight of the 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 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 300 parts by weight. The ratio may be within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The ratio of amylose and amylopectin can be measured according to the method described in “8. Measurement of Amylopectin and Amylose Contents” in the Examples section of this specification.

[0117] As the above 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 the starch is 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, 550,000 g / mol, 600,000 g / mol, 650,000 g / mol, 700,000 g / mol, 750,000 g / mol, 800,000 g / mol, 850,000 g / mol, 900,000 g / mol, 950,000 g / mol, 1,000,000 g / mol, 1,500,000 g / mol, 2,000,000 g / mol, 2,500,000 g / mol, 3,000,000 g / mol, 3,500,000 g / mol, 4,000,000 g / mol, 4,500,000 g / mol, 5,000,000 g / mol, 5,500,000 g / mol, 6,000,000 g / mol, 6,500,000 g / mol, 7,000,000 g / mol, 7,500,000 g / mol, 8,000,000 g / mol, 8,500,000 g / mol, 9,000,000 g / mol, 9,500,000 g / mol, 10,000,000 g / mol, It can be about 20,000,000 g / mol, 30,000,000 g / mol, 40,000,000 g / mol or 50,000,000 g / mol, and its upper limit is 1,000,000,000 / mol, 900,000,000 / mol, 800,000,000 / mol, 700,000,000 / mol, 600,000,000 / mol, 500,000,000 / mol, 400,000,000 / mol, 300,000,000 / mol, 200,000,000 / mol, 150,000,000 / mol, 100,000,000 / mol, It could be around 90,000,000 / mol, 80,000,000 / mol, 70,000,000 / mol, or 60,000,000 / mol.The above molecular weight may be within a range that is less than or equal to any one of the upper limits described above; within a range that is greater than or equal to any one of the lower limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above. A starch having the above molecular weight (Mw) can form a carbide having a desired function (e.g., an insulating function) more effectively when exposed to heat or flame. The above molecular weight can be measured by the method described in “7. Molecular Weight Measurement” of the Examples section of the present specification.

[0118] When included, the lower limit of the weight ratio of the carbonizable organic material to 100 parts by weight of the vaporizable material 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 or 10 parts by weight, and the upper limit may be about 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, It can be about 12 parts by weight, 11 parts by weight, 10 parts by weight, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, or 5 parts by weight. The ratio can be within a range that is less than or equal to any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and less than or equal to any one of the upper limits described above. The carbonizable organic material included in this ratio can effectively form carbonized materials when necessary in the composition, and can enable the composition to have excellent handling properties and storage stability as a whole.

[0119] The enclosed space of the above composition or fire extinguishing device may also include a gas-generating substance as an additional component. The gas-generating substance included in the composition is a substance that generates gas when exposed to heat or flame. The gas thus generated may directly extinguish the heat or flame, or may function to make the carbonized material more porous during the process of forming the carbonized material.

[0120] The action of these gas-generating substances may be induced or accelerated by the aforementioned extinguishing agent. That is, the extinguishing agent decomposes at high temperatures to produce acid, salt, or ionic components, which may accelerate the production of gas by the gas-generating substance.

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

[0122] Various substances that generate the above gases are known. For example, substances that generate nitrogen gas include melamine, guanidine, urea, melamine pyrophosphate, dicyandiamide, guanylurea phosphate, and glycine. Substances that generate carbon dioxide include potassium bicarbonate, sodium bicarbonate, calcium bicarbonate, and magnesium bicarbonate. Substances that generate water vapor include calcium hydroxide, magnesium dihydroxide, and aluminum trihydroxide. However, the substances applicable to the present application are not limited thereto.

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

[0124] For the purpose of generating an appropriate effect, the gas-generating material may be a material that generates nitrogen gas, and examples thereof include melamine, guanidine, urea, melamine pyrophosphate, and / or guanylurea phosphate. These materials are advantageous in that they more effectively exert a foaming effect on the carbide during the process in which the carbonizable organic material forms the carbide, thereby effectively forming the desired porous carbide.

[0125] When included, the lower limit of the weight ratio of the gas-generating substance to 100 parts by weight of the vaporizable substance may be about 0.01 parts by weight, 0.5 parts by weight, 1 parts by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, and the upper limit may be 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, It can be about 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 can be within a range that is less than or equal to any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and less than or equal to any one of the upper limits described above. The gas-generating material included in this ratio can exhibit an effective suppression effect against heat or flame and a formation effect of porous carbide when necessary, and can enable the composition to have excellent handling properties and storage stability overall.

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

[0127] Absorbent polymers are polymers that have the ability to absorb water. In one example, the absorbent polymer may be a so-called hydrogel polymer or hydrogel, which is generally defined as a cross-linked hydrophilic polymer. Such polymers are also known as SAPs (Super Absorbent Polymers).

[0128] The above absorbent polymer is a material capable of absorbing tens to thousands of times its own weight in moisture. This material allows the composition to remain in a gel state throughout, thereby ensuring ease of handling and storage stability.

[0129] There is no particular limitation on the type of the above absorbent polymer, and any polymer that can be generally applied as SAP can be used without limitation.

[0130] Typically, the above material is a vinyl polymer of the polyacrylate series. The polyacrylate series polymer is a polymer manufactured from an acrylate series monomer, and if necessary, other comonomers may be additionally used in the formation of the polymer.

[0131] The absorption properties of the above absorbent polymer can be adjusted so that it can exhibit suitable properties.

[0132] For example, the lower limit of centrifugal water retention capacity (CRC) of the absorbent polymer according to EDANA (European Disposables and Nonwovens Association) law WSP 241.3 may be about 12 g / g, 13 g / g, 14 g / g, 15 g / g, 16 g / g, 17 g / g, 18 g / g, 19 g / g, 20 g / g, 21 g / g, 22 g / g, 23 g / g, 24 g / g, 25 g / g, 26 g / g, 27 g / g, 28 g / g, 29 g / g, 30 g / g, 31 g / g, 32 g / g or 33 g / g, and the upper limit may be about 60 g / g, 55 g / g, 50 g / g, 45 g / g, It can be about 40 g / g or 35 g / g. The centrifuge retention capacity (CRC) can be within a range that is less than or equal to any one of the upper limits described above; within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and less than or equal to any one of the upper limits described above. 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.

[0133] For example, the lower limit of the absorbent polymer's absorbency under pressure (AUP) at 0.3 psi according to EDANA (European Disposables and Nonwovens Association) law WSP 242.3 may be 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, and the upper limit may be about 40 g / g, 38 g / g, 36 g / g, 34 g / g, 32 g / g or 30 g / g. The absorbency (AUP) is within a range that is less than or equal to any one of the upper limits described above; Or within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The above absorption capacity (AUP) can be evaluated in the manner described in “6. AUP (Absorption Under Pressure)” of the Examples section of this specification.

[0134] An absorbent polymer having the above-mentioned absorbency can be combined with other components of the composition to exhibit desired properties.

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

[0136] When included, the lower limit of the weight ratio of the absorbent polymer to 100 parts by weight of the vaporizable material 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 or 9 parts by weight, and the upper limit may be about 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, It can be about 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 can be within a range that is less than or equal to any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above.

[0137] The composition comprises the above components and may comprise additional components if necessary.

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

[0139] Referring to FIGS. 2 and 3, in an abnormal state, heat may be applied to the fire extinguishing device, and additionally, momentary high pressure may be applied. For example, in a structure such as FIG. 1, if a battery cell (12, 13, 14, 15) adjacent to the fire extinguishing device (100) explodes or rapidly expands, high pressure is applied to the fire extinguishing device (100). If the fire extinguishing device (100) contracts momentarily due to the applied pressure, volatile substances present inside may be discharged to the outside before they are vaporized, and such discharge may reduce the efficiency of the fire extinguishing action.

[0140] The above-mentioned buffer can have a buffering effect against the pressure applied instantaneously as described above, and as a result, can enable sufficient vaporization of the vaporizable substance inside.

[0141] Additionally, the buffer may, in some cases, serve to support a volatile substance. That is, when the buffer is porous as described below, or is in the form of a woven fabric, non-woven fabric, or felt, the buffer may exhibit the property of absorbing or supporting a volatile substance.

[0142] There is no particular limitation on the type of buffer as long as it can perform the above function, and for example, one having an appropriate density and / or thermal decomposition temperature can be used.

[0143] For example, the upper limit of the density of the buffer 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 may be about 0.001, 0.005, 0.01, 0.05, 0.1, or 0.15. The density may be within a range that is less than or equal to any one of the upper limits described above; within a range that is greater than or equal to any one of the lower limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above. The unit of the density is g / cm 3 am.

[0144] 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 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 that is lower than or equal to any one of the upper limits described above; or within a range that is higher than or equal to any one of the lower limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The method for measuring the thermal decomposition temperature is described in “11. Thermal decomposition temperature” in the Examples section of the specification.

[0145] Any known material can be used as the buffer without any particular limitation, as long as it has the above-mentioned density and / or thermal decomposition temperature. For example, the buffer can be made of known glass fibers, ceramic fibers, and / or mineral fibers, which are known as insulating materials. These inorganic fibers can be in the form of woven or non-woven fabrics, such as porous films, porous sheets, porous foils, wool, or felt.

[0146] In addition, as a buffer, for example, inorganic foam such as various metal foams, woven fabrics, nonwoven fabrics or felts made of glass wool, mineral wool, glass fiber or mineral fiber, etc., or foams, woven fabrics, nonwoven fabrics or felts formed of carbonized organic substances described later can also be used.

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

[0148] The size of the buffer is determined according to the size of the above-mentioned sealed space and is not particularly limited. For example, when the buffer is in the form of the above-mentioned porous film, porous sheet, porous foil, wool, woven fabric, non-woven fabric or felt, the lower limit of the thickness of the 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 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 that is less than or equal to any one of the above-mentioned upper limits; or within a range that is greater than or equal to any one of the above-mentioned lower limits; or within a range that is greater than or equal to any one of the above-mentioned lower limits and less than or equal to any one of the above-mentioned upper limits.

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

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

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

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

[0153] 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 may be about 20, 18, 16, 14, 12, 10, 8, or 6. The thixotropic index may be within a range that is less than or equal to any one of the upper limits described above; or within a range that is equal to or greater than any one of the lower limits described above; or within a range that is equal to or greater than any one of the lower limits described above and less than or equal to any one of the upper limits described above. The 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.

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

[0155] The composition may exhibit a certain latent heat characteristic. Latent heat is typically defined as the amount of heat required for a substance to undergo a phase transition without a temperature change. However, when the composition exhibits latent heat, it does not necessarily undergo a phase transition as a whole. The latent heat may occur during the phase transition of at least a portion of the composition or a component contained within the composition.

[0156] The fact that the composition exhibits latent heat as described above means that the composition exhibits an endothermic peak within a certain temperature range in a DSC (Differential Scanning Calorimeter) analysis. The method of performing the DSC is described in “4. Measurement of latent heat” of the Examples. The process by which the composition exhibits the latent heat may be an isothermal process or a similar process. Therefore, the composition can be applied to a product that generates heat to control the heat while maintaining the temperature of the product uniformly, and can minimize or prevent the impact of abnormal heat generation, explosion, and / or ignition occurring in one product on other adjacent products.

[0157] The lower limit of the latent heat exhibited by the above composition may be, for example, about 500 J / g, 550 J / g, 600 J / g, 650 J / g, 700 J / g, 750 J / g, 800 J / g, 850 J / g, 900 J / g, 950 J / g, 1000 J / g, 1100 J / g, 1200 J / g or 1300 J / g, and the upper limit may be about 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 It may be on the order of J / g. The latent heat may be within a range that is less than or equal to any one of the upper limits described above; within a range that is greater than or equal to any one of the lower limits described above; or within a range that is greater than or equal to any one of the lower limits described above and less than or equal to any one of the upper limits described above.

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

[0159] The lower limit of the temperature range representing the latent heat of the composition may be, for example, about 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 about 300°C, 280°C, 260°C, 240°C, 220°C, 200°C, 180°C or 160°C. The temperature range may be within a range that is less than or equal to any one of the upper limits described above; or within a range that is greater than or equal to any one of the lower limits described above; Or, it may be within a range that is equal to or greater than any one of the lower limits described above and equal to or less than any one of the upper limits described above. The temperature range is the temperature at the right on-set point minus the temperature at the left on-set point of the endothermic peak range of the DSC analysis.

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

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

[0162] Additionally, the composition may further include various types of known additives as long as the aforementioned properties are not impaired.

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

[0164] The present specification also discloses an electronic equipment or device to which the above-described fire extinguishing device is applied.

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

[0166] Examples of the above equipment or devices include batteries. In particular, in battery modules comprised of multiple battery cells, it is crucial to prevent any abnormal heat generation, ignition, and / or explosion occurring in one battery cell from spreading to adjacent battery cells.

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

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

[0169] As long as the above-mentioned fire extinguishing device is applied, the specific configuration of the battery module, etc., for example, the type of the battery cell, etc., is not particularly limited, and any known material may be applied. For example, any known pouch-shaped, square-shaped, or cylindrical battery cell may be applied as the battery cell.

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

[0171] The present disclosure discloses a composition, a fire extinguishing device, and uses thereof. The composition and the fire extinguishing device can be applied to products that have a risk of abnormal heating, ignition, and / or explosion during operation, storage, and / or maintenance, and can effectively respond to such heating, ignition, and explosion. The composition and the fire extinguishing device can be applied, for example, to articles containing multiple such products, to respond to abnormal heating, explosion, and / or ignition occurring in one product, and to prevent the spread of such heating, explosion, and / or ignition to adjacent products. The composition and the fire extinguishing device also have excellent handling and storage stability. The present disclosure also discloses uses of the composition and the fire extinguishing device.

[0172] Figure 1 is an exemplary cross-sectional view of a battery module to which a fire extinguishing device is applied.

[0173] Figure 2 is an exemplary drawing for explaining the operating principle of the digestive device.

[0174] Figure 3 is an exemplary drawing for explaining the operating principle of the digestive device.

[0175] Figure 4 is a drawing for explaining the process of manufacturing a fire extinguishing device in an embodiment.

[0176] Figure 5 is a drawing for explaining the process of manufacturing a fire extinguishing device in an embodiment.

[0177] Figure 6 is a drawing showing one exemplary form of a case applied in the embodiment.

[0178] The composition and the fire extinguishing device are specifically described with reference to the following examples, but the scope of the composition and the fire extinguishing device is not limited by the following examples.

[0179]

[0180] 1. Convection test

[0181] A fire extinguishing device of an embodiment or a comparative example is placed between two aluminum plates, and an insulating material is laminated on one of the two aluminum plates, thereby manufacturing a laminate in which the insulating material, the aluminum plate, the fire extinguishing device, and the aluminum plate are sequentially laminated. As the aluminum plate, a plate having a thickness of about 3 mm was used, and as the insulating material, mineral wool (KCC, Insulating Board No. 1) having a thickness of about 2 mm was used. Then, both sides of the laminate were fixed by pressing them with a jig at a pressure of about 350 kPa. Then, a temperature sensor (k-type thermocouple, Fluke IR thermometers model 566) was placed on the insulating material side of the laminate, and the temperature was measured with the temperature sensor while a flame was applied toward the aluminum plate on the opposite side. The flame was applied at a distance of about 2 inches from the aluminum plate using two butane gas (220 g can-type butane gas (unused product)) and a torch. The temperature was measured with the temperature sensor while applying the above flame for about 5 minutes, and evaluated according to the following criteria.

[0182] <Evaluation Criteria>

[0183] PASS: When the measured temperature of the temperature sensor remains below 200℃

[0184] NG: If a temperature exceeding 200℃ is measured from the temperature sensor or if melting of the aluminum plate is observed.

[0185]

[0186] 2. Chain ignition test

[0187] Square batteries were arranged side by side at intervals of approximately 3 mm, and a fire extinguishing device was placed between them. CATL's product (120 Ah, 3.2 V, size = thickness × width × depth = 48 × 174 × 165) was used as the square battery, and the test was performed in a 100% charged state. In the above arrangement, battery ignition was induced in one square battery according to the SAE J2464:2009 standard, and whether or not a chain ignition occurred in other cells was confirmed. The battery ignition was induced by penetrating a nail with a diameter of approximately 5 mm into the square battery at a speed of 25 mm / sec (Nail Penetration method).

[0188] <Evaluation Criteria>

[0189] PASS: If no ignition occurs in any battery cell other than the one through which the nail was pierced.

[0190] NG: If a fire occurs in a battery cell other than the one penetrated by the nail.

[0191]

[0192] 3. Storage stability evaluation

[0193] The digestive device was stored in an oven at approximately 35°C for 1,000 hours, and the weight change before and after storage in the oven was measured. If the weight change before and after storage was 1% or more, it was evaluated as NG, and if it was less than 1% or there was no weight change, it was evaluated as PASS.

[0194]

[0195] 4. Measurement of latent heat

[0196] About 3 to 5 mg of the composition of the examples or comparative examples was sampled and loaded into a measuring device. A Differential Scanning Calorimeter (DSC) (TA instrument, Q200 model) was used as the measuring device. The temperature range for evaluating latent heat was from 25°C to 300°C. The endothermic peak was measured while the temperature was increased from 25°C to 300°C at a rate of about 20°C / min. The left on-set point and the right on-set point of the endothermic peak range were designated as the start and end of the phase transition, and the corresponding range was integrated to calculate the latent heat (unit: J / g).

[0197]

[0198] 5.CRC(Centrifuge Retention Capacity)

[0199] CRC was measured according to EDANA WSP 241.3. Approximately 0.2 g (W0) of absorbent polymer was placed in a nonwoven bag, sealed, and immersed in physiological saline solution at room temperature. The physiological saline solution used was a 0.9 wt% NaCl aqueous solution. The above condition was maintained for approximately 30 minutes, and water was removed from the bag using a centrifuge at 250 G for 3 minutes, after which the mass (g, W2) of the bag was measured.

[0200] The same operation was performed on the same nonwoven bag without absorbent polymer and the mass (g, W1) was measured.

[0201] The measurement results were substituted into Equation A below to calculate CRC (g / g).

[0202] The above evaluation was conducted under constant temperature and humidity conditions (23±1℃, relative humidity: 50±10%).

[0203] [Formula A]

[0204] CRC (g / g) = {[W2(g) - W1(g)] / W0(g)} - 1

[0205]

[0206] 6. Absorption Under Pressure (AUP)

[0207] AUP was measured according to EDANA method WSP 242.3. A 400 mesh stainless steel wire mesh was installed on the bottom of a plastic cylinder with an inner diameter of approximately 60 mm, and 0.0 g (W0) (0.90 g) of absorbent polymer was uniformly sprayed on the wire mesh. Then, a piston capable of uniformly applying a load of 0.3 psi was installed on it. The piston had an outer diameter slightly smaller than 60 mm, was installed so that there was no gap with the inner wall of the cylinder, and could move up and down. The weight (g, W3) of the device was measured.

[0208] A glass filter with a diameter and thickness of 90 mm and 5 mm, respectively, was placed inside a 150 mm diameter petroleum dish, and saline solution was added so that it was level with the upper surface of the glass filter. The saline solution used was a 0.9 wt% NaCl aqueous solution. A sheet of filter paper with a diameter of 90 mm was placed on top of it. The measuring device was placed on the filter paper, and the saline solution was absorbed for 1 hour under a load of 0.3 psi. Thereafter, the measuring device was lifted, and its weight (g, W4) was measured.

[0209] The obtained value was substituted into the following formula B to evaluate AUP (g / g).

[0210] The above evaluation was conducted under constant temperature and humidity conditions (23±1℃, relative humidity: 50±10%).

[0211] [Formula B]

[0212] AUP(g / g) = [W4(g) - W3(g)] / W0(g)

[0213]

[0214] 7. Molecular weight measurement

[0215] The molecular weight of starch was evaluated in the following manner.

[0216] (1) Preparation of mobile phase

[0217] 1000 mL of 150 mM NaNO3 aqueous solution containing 0.02 wt% NaN3 was filtered using a solvent clarification system (Millipore Millisolve Kit, MilliporeSigma) to prepare mobile phase A.

[0218] (2) Preparation of sample solution

[0219] A sample whose molecular weight is to be measured was taken in an amount of 25 mg, mixed with 5 mL of a 150 mM NaNO3 aqueous solution containing 0.02 wt% NaN3, heated at 80°C for 20 hours, and then filtered through a 0.4 μm Nylon Syringe Filter to prepare a sample solution.

[0220] (3) GPC (Gel Permeation Chromatography) / MALS (Multi-Anglue Light Scattering Detection) conditions

[0221] The molecular weight was evaluated using the above sample solution and mobile phase A in the following manner.

[0222] Measuring instrument: Agilent GPC (Agilent 1200 series, US)

[0223] Stationary phase: Shodex OH-Pak 804 column and Shodex OH-Pak 80 column connection

[0224] Mobile phase: A; 0.02% NaN3, 150 mM NaNO3 aqueous solution = 100 (v / v %)

[0225] Flow rate: 0.4 mL / min

[0226] Stationary temperature: 25℃

[0227] Injection volume: 100 μl (0.45 μm filtered)

[0228] Analysis time: 120 minutes

[0229]

[0230] 8. Measurement of amylopectin and amylose content

[0231] The amylopectin and amylose contents of starch were evaluated according to the method described in the paper (Potato Research 31 (1988) 241-246).

[0232] First, a sample was prepared by dissolving about 5 mg of starch in about 1 mL of sterile water (step 1), and then heated in a water bath at 95°C for about 15 minutes (step 2).

[0233] Next, about 20 μl of the sample was placed in a cuvette (step 3), and about 980 μl of iodine solution was added and mixed (step 4).

[0234] Next, the absorbance of the sample mixed with the above iodine solution at wavelengths of 525 nm and 700 nm was measured and recorded respectively (Step 5). The absorbance was measured using the OPTIZEN POP model from KLAB.

[0235] Approximately 20 μl of water was placed in another cuvette, 980 μl of iodine solution was added, and mixed (Step 6). For the solution in Step 6, the absorbance at wavelengths of 525 nm and 700 nm was measured and recorded, respectively, in the same manner as in Step 5 (Step 7).

[0236] The absorbance obtained in step 7 was subtracted from the absorbance obtained in step 5, and the ratio (%) of amylose was confirmed according to the following formula C (step 8).

[0237] [Formula C]

[0238]

[0239] In formula C, PA is the percentage of amylose (%) and OD 700is the value obtained by subtracting the absorbance at a wavelength of 700 nm measured in step 7 from the absorbance at a wavelength of 700 nm measured in step 5 above, and OD 525 is the value obtained by subtracting the absorbance at a wavelength of 525 nm measured in step 7 from the absorbance at a wavelength of 525 nm measured in step 5.

[0240]

[0241] 9. WVTR (Water Vapor Transmission Rate) Evaluation

[0242] The WVTR of the case was evaluated according to the standard of ASTM F1249 under the conditions of 38℃ and 100% relative humidity.

[0243]

[0244] 10. Solubility Evaluation

[0245] Solubility was evaluated based on the ASTM E1148-02 standard. Solubility was confirmed by evaluating the maximum amount of sample dissolved in 100 g of a vaporous substance (water) at 0℃ or room temperature (approximately 25℃) according to the above standard.

[0246]

[0247] 11. Thermal decomposition temperature

[0248] The thermal decomposition temperature was confirmed by TGA (Thermogravimetric Analysis). Using a Mettler-Toledo TGA e850 equipment, the temperature of the sample was increased from approximately 20°C at a rate of 5°C / min in an N2 flow atmosphere, and the point at which the weight loss exceeded 5% was defined as the thermal decomposition temperature.

[0249]

[0250] 12. Flammability Assessment

[0251] The flammability of the freezing point regulator was evaluated according to ASTM D93. The sample (ignition source) was placed in a 100 mL brass test cup in an amount of about 90% by volume of the cup, stirred at about 100 times / min, and the ignition source was set to a diameter of about 3.2 mm to 4.8 mm. The temperature was increased at a rate of 5°C / min to evaluate the flash point. If the sample did not ignite but vaporized during the evaluation, the sample was evaluated as non-flammable. If the sample ignited, the temperature at the time of ignition was considered the flash point.

[0252]

[0253] 13. Assessment of toxic gas generation

[0254] The generation of toxic gases was evaluated using length-of-stain colorimetric dosimeters according to ASTM D4599-21. The length-of-stain colorimetric dosimeters are tubes that can measure concentration based on color, and each toxic gas has a designated measurement tube. A gas sample generated from the target substance was collected for approximately 1 minute and quantified. A 100 ml syringe was used to inject the sample into the open end of the length-of-stain colorimetric dosimeters, and the concentration of each gas was measured after maintaining it for approximately 8 hours. The toxic gases measured using the above method were chlorine gas, ammonia gas, and hydrofluoric acid gas.

[0255]

[0256] 14. Flammability

[0257] The fire extinguishing composition was placed in an aluminum can, and its flammability was evaluated. The aluminum can was manufactured with an open top using aluminum foil with a thickness of approximately 3 mm. The length and width of the can were approximately 9 cm and 12 cm, respectively, and the internal volume was approximately 32.4 cm. 3 It was about that degree. The composition was filled inside the can, and with the top of the can open, a flame was applied vertically to one side of the can at a distance of about 1 inch. The flame was applied using butane gas (220 g can-type butane gas (unused product)) and a torch. The ignition property was evaluated by observing whether a flame occurred at the open top while applying the flame for about 5 minutes.

[0258]

[0259] 15. Thermal conductivity evaluation

[0260] Thermal conductivity was evaluated at 20℃ using a measuring device (Hot Disk, TPS2200) according to the ISO22007-2 standard.

[0261]

[0262] Example 1.

[0263] Digestive composition

[0264] Water (W) and a freezing point regulator (ethylene glycol (molar mass: 62.07 g / mol)) (E) were mixed in a weight ratio (W:E) of 60:40. The mixing was performed at room temperature (about 25°C) at 300 rpm for about 30 minutes. The ethylene glycol has a flash point of about 111°C, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method were all 0 ppm. In addition, the ethylene glycol was miscible with water. Then, the mixture was placed in a sealed container, and glass wool was placed in the sealed container, and the mixture was maintained at room temperature (about 25°C) for about 24 hours to impregnate the glass wool, thereby preparing a fire extinguishing composition. The glass wool had a thickness of about 2.5 mm and a density of about 0.03 g / cm. 3 The temperature is about 400℃, and glass wool (Glass wool blanket, Rosewool) was used.

[0265]

[0266] Digestive system

[0267] The composition was placed inside a can (case) used for manufacturing square batteries, and the opening was sealed to manufacture a fire extinguishing device. The WVTR of the can used for the square batteries was approximately 0.11 g / m 2·It was about day. As shown in Fig. 4, two thermally conductive layers (2001, 2002) were inserted into the inside of the aluminum can (1001), and the composition (glass wool containing the mixture) (300) was injected between the thermally conductive layers (2001, 2002), and then a cover (1002) was covered to manufacture a fire extinguishing device. When manufacturing the fire extinguishing device, the composition was injected so that it filled at least 90% of the volume of the empty space inside the can. As the thermally conductive layers (2001, 2002), a copper film (thickness of about 18 μm) having a thermal conductivity of about 401 W / m·K (based on 20°C) was used. In cases where the fire extinguishing composition is not in the form of a sheet such as glass wool containing the mixture as described above, a fire extinguishing device can also be manufactured by placing two heat-conducting layers (2001, 2002) in a case as shown in Fig. 5 and injecting the composition between the heat-conducting layers. As the square battery case, a case measuring approximately 9 cm in width, 12 cm in length, and 3 mm in thickness was used.

[0268]

[0269] Example 2.

[0270] Digestive composition

[0271] 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.

[0272]

[0273] Digestive system

[0274] As a square battery case, it is made of aluminum and has a WVTR of approximately 0 g / m. 2· A fire extinguishing device was manufactured in the same manner as in Example 1, except that a case of about day was used.

[0275]

[0276] Example 3.

[0277] Digestive composition

[0278] Water (W), potassium acetate (K) (molar mass: 98.15 g / mol) (CH3COOK) and starch (S) were mixed in a weight ratio (W:K:S) of 55:36:10. As the starch, corn starch was used having a weight average molecular weight of approximately 51,000,000 g / mol and a weight ratio of amylose to amylopectin (amylose:amylopectin) of approximately 25:75. The potassium acetate, which is a freezing point regulator, is a non-flammable substance having no flash point, and the concentrations of chlorine gas, ammonia gas and hydrofluoric acid gas measured according to a toxic gas evaluation method were all 0 ppm, indicating that it was a non-toxic substance. In addition, the solubility of potassium acetate, which is the 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. Then, the mixture is placed in a sealed container, and additionally, mineral wool (thickness: about 2.5 mm, density: about 0.2 g / cm) is placed in the sealed container. 3 , thermal decomposition temperature: about 800℃) (KCC, Mineral Wool Insulation Board No. 1) was added, and the mixture was maintained at room temperature (about 25℃) for about 24 hours to impregnate the mineral wool, thereby preparing a fire-extinguishing composition.

[0279]

[0280] Fire extinguishing device

[0281] A can (case) used in the manufacture of square batteries, with a WVTR of approximately 0.27 g / m 2· A fire extinguishing device was manufactured in the same manner as in Example 1 using a can of about day. In this process, aluminum foil having a thermal conductivity of about 234 W / mK (at 20°C) and a thickness of about 50 μm was used as the heat conductive layer.

[0282]

[0283] Example 4.

[0284] Digestive composition

[0285] A first mixture was prepared by mixing water (W), ammonium phosphate (N)(NH4H2PO4)(Daejung Chemicals), and a freezing point regulator (F) in a weight ratio of 100:20:30 (W:N:F). The mixing was performed at room temperature (approximately 25°C) under mixing conditions of 300 rpm for approximately 10 minutes. Potassium formate (HCOOK)(Daejung Chemicals) (molar mass 84.12 g / mol) was used as the freezing point regulator. The potassium formate is a non-flammable substance having no flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method were all 0 ppm, making it a non-toxic substance. In addition, the solubility of the potassium formate in 100 g of water at 0°C is approximately 32.8 g, and the solubility in 100 g of water at 25°C is approximately 331 g.

[0286] The above first ammonium phosphate (N) (NH4H2PO4) has a solubility in water of about 29 g at 25°C. Next, starch (S) (Sigma-Aldrich) and melamine (M) (ACROS ORGANICS) were additionally mixed into the first mixture to prepare a second mixture. In the second mixture, the ratio of water (W) to the starch (S) and melamine (M) (W:S:M) was adjusted to about 100:10:10. The mixing was performed at room temperature (about 25°C) under mixing conditions of 300 rpm for about 30 minutes. In the preparation of the second mixture, corn starch used in Example 3 was used as the starch. Next, an absorbent polymer (SAP) was additionally mixed into the second mixture to prepare a composition. The mixing of the above absorbent polymer was performed by mixing the second mixture and the absorbent polymer, and mixing for about 2 hours at room temperature (about 25°C) and mixing conditions of 300 rpm. The mixing was performed so that the weight ratio (W:P) of the water (W) and the absorbent polymer (P) of the mixture was about 100:5. As the absorbent polymer, LG Chemical's SAP GS-803ND product was used, and it was applied to a size of about 150 μm through a grinding and classification process. The CRC (Centrifuge Retention Capacity) of this absorbent polymer was about 33.5 g / g, and the AUP (Absorption Under Pressure) was about 28.1 g / g.

[0287]

[0288] Digestive system

[0289] A fire extinguishing device was manufactured in the same manner as in Example 2 using the aluminum can (case) used in the manufacture of the square battery applied in Example 2. In this process, a thermal conductive layer was not applied.

[0290]

[0291] Example 5.

[0292] A fire extinguishing composition and a fire extinguishing device were prepared in the same manner as in Example 4, except that sodium formate (HCOONa) (Daemyung Chemical) (molar mass: 68.01 g / mol) was used instead of potassium formate (HCOOK) (Daejung Chemicals) as a freezing point regulator. The sodium formate is a non-flammable substance having no flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method were all 0 ppm, making it a non-toxic substance. In addition, the solubility of the sodium formate as a freezing point regulator in 100 g of water at 0°C is about 43.82 g, and in 100 g of water at 25°C is about 97.2 g.

[0293]

[0294] Example 6.

[0295] A fire extinguishing composition and a fire extinguishing device were prepared in the same manner as in Example 4, except that potassium acetate (CH3COONa) (Daejunggeum) (molar mass: 98.15 g / mol) was used instead of potassium formate (HCOOK) (Daejunggeum) as a freezing point regulator. The potassium acetate is a non-flammable substance having no flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to a toxic gas evaluation method were all 0 ppm, making it a non-toxic substance.

[0296]

[0297] Example 7.

[0298] Digestive composition

[0299] A first mixture was prepared by mixing water (W) and ammonium phosphate (N) (NH4H2PO4) at a weight ratio (W:N) of 100:22. The mixing was performed at room temperature (about 25°C) at a mixing speed of 300 rpm for about 10 minutes. A second mixture was prepared by further mixing starch (S) and melamine (M) into the first mixture. In the second mixture, the ratio (W:S:M) of water (W) and the starch (S) and melamine (M) was adjusted to 100:6:6. The mixing was performed at room temperature (about 25°C) at a mixing speed of 300 rpm for about 30 minutes. In the preparation of the second mixture, the same corn starch as used in Example 3 was used as the starch. Subsequently, an absorbent polymer (SAP) was further mixed into the second mixture to prepare a composition. The mixing of the absorbent polymer was performed by mixing the second mixture and the absorbent polymer, and mixing for about 2 hours at room temperature (about 25°C) and mixing conditions of 300 rpm. The mixing was performed so that the weight ratio (W:P) of the water (W) and the absorbent polymer (P) of the mixture was about 100:5. The same polymer as that used in Example 4 was used as the absorbent polymer. The latent heat of the fire extinguishing composition manufactured in this way was about 1615 J / g.

[0300]

[0301] Digestive system

[0302] A fire extinguishing device was manufactured in the same manner as in Example 4 using the above fire extinguishing composition.

[0303]

[0304] Comparative Example 1.

[0305] Digestive composition

[0306] Water (W) and potassium acetate (K) (molar mass: 98.15 g / mol) (CH3COOK) were mixed in a weight ratio (W:K) of 45:55. The potassium acetate, which is a freezing point regulator, is a non-flammable substance with no flash point, and the concentrations of chlorine gas, ammonia gas, and hydrofluoric acid gas measured according to the toxic gas evaluation method were all 0 ppm, meaning it was a non-toxic substance. Then, the mixture was placed in a sealed container, and mineral wool (thickness: about 2.5 mm, density: about 0.2 g / cm3, pyrolysis temperature: about 800°C) (KCC, Mineral Wool Insulating Board No. 1) was additionally placed in the sealed container, and then maintained at room temperature (about 25°C) for about 24 hours to prepare a fire extinguishing composition.

[0307]

[0308] Fire extinguishing device

[0309] A can (case) used in the manufacture of square batteries, with a WVTR of approximately 0.27 g / m 2· A fire extinguishing device was manufactured in the same manner as in Example 1 using a can of about day. In this process, aluminum foil having a thermal conductivity of about 234 W / mK (at 20°C) and a thickness of about 50 μm was used as the heat conductive layer.

[0310]

[0311] Comparative Example 2.

[0312] As a square battery case, the WVTR is approximately 7.5 g / m 2· A fire extinguishing device was manufactured in the same manner as in Example 1, except that a case of about day was used.

[0313]

[0314] Comparative Example 3.

[0315] As a square battery case, the WVTR is approximately 7.5 g / m 2· A fire extinguishing device was manufactured in the same manner as in Example 7, except that a case of about day was used.

[0316]

[0317] The evaluation results for the above examples and comparative examples are summarized and described in Tables 1 and 2 below. In Tables 1 and 2 below, M is the sum of the molal concentrations of the freezing point regulator and other ionic compounds (primary ammonium phosphate) for the volatile substance (water) in the composition, and △T f For each freezing point regulator and other ionic compounds (primary ammonium phosphate), Equation 1(K f× It is the sum of the values ​​calculated as (M × I). In addition, the water content in Tables 1 and 2 is the weight of water included when the weight of the fire extinguishing composition of the example or comparative example is 100%, and WVTR is the WVTR (unit: g / m) of the case used in the manufacture of the fire extinguishing device. 2· day).

[0318] Example 1234567 Water content (weight%) 607254.557.157.157.171.9 WVTR 0.1100.270000 M 10.76.36.75.36.14.8 1.9 △T f 2011.724.819.722.917.87.1Convection TestPassPassPassPassPassPassChain Ignition TestPassPassPassPassPassPassPassStorage StabilityPassPassPassPassPassPassPass

[0319] Comparative Example 123 Water content (weight%) 456071.9WVTR0.277.57.5M12.510.712.5△T f 46.32046.3Convection testNGNGNGChain ignition testNGNGNGStorage stabilityPassNGNG

[0320] From the results in Table 1, it can be confirmed that excellent results are achieved in the convection test and chain ignition test when a certain amount of water is included in the composition and the WVTR of the case of the fire extinguishing device is controlled. In addition, considering the temperature detected by the temperature sensor in the convection test, Examples 1 to 6, in which the vaporization rate was adjusted by adding a freezing point regulator, showed an excellent effect compared to Example 7. From the results in Table 2, it can be seen that even if the WVTR of the case is controlled, if the water content in the composition is not controlled (Comparative Example 1) or if the water content is not controlled together with the WVTR control (Comparative Examples 2 and 3), the intended effect cannot be obtained. In addition, the compositions of the examples and comparative examples were confirmed to be ignitable when ethylene glycol was applied as a freezing point depressant.

[0321]

[0322] Example 8.

[0323] As a case for the fire extinguishing device, a fire extinguishing device was manufactured in the same manner as in Example 1, except that a pouch-type case was used. The case 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 the above 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. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. After attaching a heat-conducting layer to the concave portion (I) of the upper and lower outer skins (121, 122), a fire-extinguishing composition was placed on the heat-conducting layer, and after laminating the upper and lower outer skins (121, 122), the PP hot melt films were fused to each other at the sealing portion (S) to manufacture a fire-extinguishing device. After that, among the four sealing portions (S), three of the sealing portions on each side were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 0.11 g / m 2 ·It was about day. The same thermal conductive layer as that used in Example 1 was used. The case was manufactured to be about 9 cm wide, 12 cm long, and 3 mm thick.

[0324]

[0325] Example 9.

[0326] As a case for the fire extinguishing device, a fire extinguishing device was manufactured in the same manner as in Example 2, except that a pouch-type case was used. The case was manufactured using an outer shell manufactured by laminating a PET (poly(ethylene 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 the above 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. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. After attaching a heat-conducting layer to the concave portion (I) of the upper and lower outer skins (121, 122), a fire-extinguishing composition was placed on the heat-conducting layer, and after laminating the upper and lower outer skins (121, 122), the PP hot melt films were fused to each other at the sealing portion (S) to manufacture a fire-extinguishing device. After that, among the four sealing portions (S), three of the sealing portions on each side were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 0 g / m 2 ·It was about day. The same thermal conductive layer as that used in Example 1 was used. The case was manufactured to be about 9 cm wide, 12 cm long, and 3 mm thick.

[0327]

[0328] Example 10.

[0329] As a case for the fire extinguishing device, the fire extinguishing device was manufactured in the same manner as in Example 3, except that a pouch-type case was used. The case 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 the above order. The outer shell was manufactured by laminating the PET film on one side of the EVOH film with an adhesive, and laminating the PE hot melt film on the other side at a temperature of about 200°C. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. After attaching a heat-conducting layer to the concave portion (I) of the upper and lower outer skins (121, 122), a fire-extinguishing composition was placed on the heat-conducting layer, and after laminating the upper and lower outer skins (121, 122), the PE hot melt films were fused to each other at the sealing portion (S) to manufacture a fire-extinguishing device. After that, among the four sealing portions (S), three of the sealing portions on each side were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 0.27 g / m 2 ·It was about day. The same thermal conductive layer as that used in Example 3 was used. The case was manufactured to be about 9 cm wide, 12 cm long, and 3 mm thick.

[0330]

[0331] Example 11.

[0332] As a case for the fire extinguishing device, the fire extinguishing device was manufactured in the same manner as in Example 4, except that a pouch-type case was used. The case was manufactured using an outer shell manufactured by laminating a PET (poly(ethylene 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 the above 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. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. A fire extinguishing composition was placed in the lower outer shell (122), and after the upper and lower outer shells (121, 122) were laminated, the PP hot melt film was fused to each other at the sealing portion (S) to manufacture a fire extinguishing device. After that, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 0 g / m 2 ·It was about a day. In the above process, no thermal conductive layer was applied. The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0333]

[0334] Example 12.

[0335] As a case for the fire extinguishing device, a fire extinguishing device was manufactured in the same manner as in Example 5, except that a pouch-type case was used. The case was manufactured using an outer shell manufactured by laminating a PET (poly(ethylene 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 the above 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. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. A fire extinguishing composition was placed in the lower outer shell (122), and after the upper and lower outer shells (121, 122) were laminated, the PP hot melt film was fused to each other at the sealing portion (S) to manufacture a fire extinguishing device. After that, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 0 g / m 2 ·It was about a day. In the above process, no thermal conductive layer was applied. The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0336]

[0337] Example 13.

[0338] As a case for the fire extinguishing device, the fire extinguishing device was manufactured in the same manner as in Example 6, except that a pouch-type case was used. The case was manufactured using an outer shell manufactured by laminating a PET (poly(ethylene 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 the above 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. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. A fire extinguishing composition was placed in the lower outer shell (122), and after the upper and lower outer shells (121, 122) were laminated, the PP hot melt film was fused to each other at the sealing portion (S) to manufacture a fire extinguishing device. After that, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 0 g / m 2 ·It was about a day. In the above process, no thermal conductive layer was applied. The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0339]

[0340] Example 14.

[0341] As a case for the fire extinguishing device, a fire extinguishing device was manufactured in the same manner as in Example 7, except that a pouch-type case was used. The case was manufactured using an outer shell manufactured by laminating a PET (poly(ethylene 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 the above 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. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. A fire extinguishing composition was placed in the lower outer shell (122), and after the upper and lower outer shells (121, 122) were laminated, the PP hot melt film was fused to each other at the sealing portion (S) to manufacture a fire extinguishing device. After that, three of the four sealing portions (S) were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 0 g / m 2 ·It was about a day. In the above process, no thermal conductive layer was applied. The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0342]

[0343] Comparative Example 4.

[0344] As a case for the fire extinguishing device, a fire extinguishing device was manufactured in the same manner as in Comparative Example 1, except that a pouch-type case was used. The case 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 the above order. The outer shell was manufactured by laminating the PET film on one side of the EVOH film with an adhesive, and laminating the PE hot melt film on the other side at a temperature of about 200°C. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. After attaching a heat-conducting layer to the concave portion (I) of the upper and lower outer skins (121, 122), a fire-extinguishing composition was placed on the heat-conducting layer, and after laminating the upper and lower outer skins (121, 122), the PE hot melt films were fused to each other at the sealing portion (S) to manufacture a fire-extinguishing device. After that, among the four sealing portions (S), three of the sealing portions on each side were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 0.27 g / m 2 ·day. Aluminum foil with a thermal conductivity of approximately 234 W / mK (at 20°C) and a thickness of approximately 50 μm was used as the thermal conductive layer. The case was manufactured to be approximately 9 cm wide, 12 cm long, and 3 mm thick.

[0345]

[0346] Comparative Example 5.

[0347] As a case for the fire extinguishing device, the fire extinguishing device was manufactured in the same manner as in Example 1, except that a pouch-type case was used. The case was manufactured using an outer shell manufactured by laminating a PVC (poly(vinyl chloride)) film (thickness: about 20 μm) and a PP hot melt film (thickness: about 70 μm) (melting point: about 140°C). The outer shell was manufactured by laminating the PP hot melt film on one surface of the PVC film at a temperature of about 200°C. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. After attaching a heat-conducting layer to the concave portion (I) of the upper and lower outer skins (121, 122), a fire-extinguishing composition was placed on the heat-conducting layer, and after laminating the upper and lower outer skins (121, 122), the PP hot melt films were fused to each other at the sealing portion (S) to manufacture a fire-extinguishing device. After that, among the four sealing portions (S), three of the sealing portions on each side were folded so that the unfolded sealing portion could function as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave portion (I). The WVTR of the case was about 7.5 g / m 2 ·It was about day. The same thermal conductive layer as that used in Example 1 was used. The case was manufactured to be about 9 cm wide, 12 cm long, and 3 mm thick.

[0348]

[0349] Comparative Example 6.

[0350] As a case for the fire extinguishing device, a fire extinguishing device was manufactured in the same manner as in Example 7, except that a pouch-type case was used. The case was manufactured using an outer shell manufactured by laminating a poly(vinyl chloride) (PVC) 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. As shown in Fig. 6, a concave portion (I) was formed in the central portion of the outer shell, and an upper outer shell (121) and a lower outer shell (122) were prepared, respectively. A fire extinguishing composition was placed in the concave portion (I) of the lower outer shell (122), and after laminating the upper and lower outer shells (121, 122), the PP hot melt films were fused to each other at the sealing portion (S), thereby manufacturing a fire extinguishing device. After that, three of the four sealing parts (S) were folded so that the unfolded sealing parts could act as a vent area. In the above, the composition was injected so as to occupy at least 90% of the volume of the sealed space formed by the concave part (I). The WVTR of the case was about 7.5 g / m 2 ·It was about a day. The case was manufactured to be about 9 cm wide, 12 cm long, and 3 mm thick.

[0351]

[0352] The evaluation results for the above examples and comparative examples are summarized and described in Tables 3 and 4 below. In Tables 3 and 4 below, M and △T f The meaning of is as in Tables 1 and 2. In addition, in Tables 3 and 4, the water content is the weight of water included when the weight of the fire extinguishing composition of the example or comparative example is 100%, and WVTR is the WVTR of the case used in the manufacture of the fire extinguishing device (unit: g / m 2· day).

[0353] Example 891011121314Water content (weight%)607254.557.157.157.171.9WVTR0.1100.270000M10.76.36.75.36.14.81.9△T f 2011.724.819.722.917.87.1Convection TestPassPassPassPassPassPassChain Ignition TestPassPassPassPassPassPassPassStorage StabilityPassPassPassPassPassPassPass

[0354] Comparative Example 456 Water content (weight%) 456 0 7 1.9 W V TR 0.2 7 7.5 7.5 M 12.5 10.7 12.5 △T f 46.32046.3Convection testNGNGNGChain ignition testNGNGNGStorage stabilityPassNGNG

[0355] From the results in Tables 3 and 4, it can be confirmed that although the shape of the case is different, excellent results are achieved in the convection test and chain ignition test by containing a certain amount of water in the composition and controlling the WVTR of the case of the fire extinguishing device.

Claims

1. flammable substances; and Containing at least one freezing point regulator selected from the group consisting of alcohols and ionic compounds, The content of the above volatile material is 50 wt% or more, The above freezing point regulator is △T of the following formula 1 f Compositions containing within the range of 5 to 50: [Formula 1] △T f = K f × M × I K in Equation 1 f is the freezing point depression constant of the volatile substance, M is the molal concentration of the freezing point regulator with respect to the volatile substance, and I is the number of ions formed by the freezing point regulator, but when the freezing point regulator is not an ionic compound, I is 1.

2. In the first paragraph, the volatile material is a composition having a boiling point within a range of 80°C to 120°C.

3. A composition according to claim 1, wherein the volatile material is water.

4. In the first paragraph, the freezing point regulator is a composition having a solubility of 20 g or more in 100 g of a vaporizable substance at 0°C.

5. In the first paragraph, the freezing point regulator is a composition having a solubility of 70 g or more in 100 g of a volatile substance at 25°C.

6. In the first paragraph, the freezing point regulator is a composition having a molar mass of 300 g / mol or less.

7. A composition according to claim 1, wherein the ionic compound is at least one selected from the group consisting of formate, acetate, carbonate, and sulfate.

8. A composition according to claim 1, further comprising at least one selected from the group consisting of a carbonizable organic material and a carbonization catalyst.

9. A case having a sealed space inside; and Contains a volatile substance present in the above-mentioned closed space, The content of volatile substances in the above-mentioned sealed space is 50 wt% or more, Among the areas of the above cases forming the sealed space, the WVTR (Water Vapor Transmission Rate) of 80% or more of the area is 5 g / m 2· day or less, or the WVTR (Water Vapor Transmission Rate) of 80% or more of the area of ​​the above case is 5 g / m 2· Digestive system less than day.

10. In paragraph 9, the sealed space is a fire extinguishing device further comprising at least one freezing point regulator selected from the group consisting of alcohols and ionic compounds.

11. In the 10th paragraph, the freezing point regulator is △T of the following formula 1 f Extinguishing devices that exist within the range of 5 to 50: [Formula 1] △T f = K f × M × I K in Equation 1 f is the freezing point depression constant of the volatile substance, M is the molal concentration of the freezing point regulator with respect to the volatile substance, and I is the number of ions formed by the freezing point regulator, provided that if the freezing point regulator is not an ionic compound, I is 1.

12. In paragraph 9, a fire extinguishing device having a boiling point of the flammable substance within a range of 80°C to 120°C.

13. A fire extinguishing device in accordance with paragraph 9, wherein the flammable substance is water.

14. In the 10th paragraph, the freezing point regulator is a fire extinguishing device having a solubility of 20 g or more in 100 g of a volatile substance at 0°C.

15. In the 10th paragraph, the freezing point regulator is a fire extinguishing device having a solubility of 70 g or more in 100 g of a volatile substance at 25°C.

16. A fire extinguishing device according to claim 10, wherein the ionic compound is at least one selected from the group consisting of formate, acetate, carbonate and sulfate.

17. A fire extinguishing device in accordance with paragraph 9, wherein at least one selected from the group consisting of carbonizable organic matter and carbonization catalyst is additionally present in a sealed space.

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