Composite material

Abstract

Disclosed in the present specification are a composite material and a fire suppression device, which can be applied to a product or element in an abnormal state or having the potential to enter an abnormal state, enabling effective response to the abnormal state. For example, the composite material and the like may be applied to an article comprising a plurality of such products or elements, to respond to abnormal heat generation, explosion, or ignition occurring in any one of the products or elements, and prevent or minimize the propagation of such heat generation, explosion, or ignition to adjacent products or elements. The composite material and the like also exhibit excellent handling characteristics and storage stability. The present specification may also provide uses of the composite material and the like.

Description

composite materials

[0001] This application claims the benefit of priority to Republic of Korea Patent Application No. 10-2024-0043103, filed March 29, 2024, and Republic of Korea Patent Application No. 10-2024-00174265, filed November 28, 2024, the entire contents of which are incorporated herein by reference.

[0002] The present specification discloses a composite material, a fire extinguishing device comprising the composite material, and uses of the composite material and the fire extinguishing device.

[0003] The importance of technology to manage heat generated from products is increasing, but it is a difficult problem to manage, control, and manage heat in products composed of multiple heat-generating elements (heat-generating elements).

[0004] For example, it is very important to prevent so-called thermal runaway (TR) or thermal propagation (TP) phenomena that occur in battery modules or battery packs. A battery module or battery pack includes multiple battery cells or multiple battery modules, which are positioned relatively close to each other.

[0005] In this structure, the phenomenon in which abnormal heat generation, ignition, and / or explosion occurring in one battery cell and / or battery module spreads to adjacent battery cells in a chain reaction is called the TR or TP phenomenon. This chain reaction of ignition or explosion caused by the TR or TP phenomenon must be managed from a safety perspective.

[0006] The present specification discloses composite materials, fire extinguishing devices, and their uses. The purpose of the present specification is to disclose composite materials and fire extinguishing devices that can be applied to products or devices that have experienced an abnormal condition or are at risk of experiencing such an abnormal condition, thereby effectively responding to such an abnormal condition.

[0007] For example, the composite material and fire extinguishing device disclosed herein can be applied to an article including a plurality of the products or elements, thereby preventing or minimizing an abnormal condition occurring in one product or element from spreading to other products or elements.

[0008] The present specification also aims to disclose a composite material and a fire extinguishing device having excellent handling and storage stability. The present specification also aims to disclose uses of the composite material and the fire extinguishing device.

[0009] Among the properties mentioned in this specification, properties that are affected by temperature are properties measured at room temperature, unless otherwise specified.

[0010] 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, for example, a temperature of about 23°C or about 25°C.

[0011] Unless otherwise specified, the unit of temperature referred to in this specification is ℃.

[0012] Among the properties mentioned in this specification, if pressure affects the result, the property is a property measured at atmospheric pressure unless otherwise specified.

[0013] The term atmospheric pressure refers to the natural pressure that has not been artificially pressurized or depressurized, and is usually a pressure in the range of about 700 mmHg to 800 mmHg.

[0014] Among the properties mentioned in this specification, if humidity affects the results, unless otherwise specified, the properties are properties measured at a humidity that has not been artificially adjusted under the above-mentioned room temperature and pressure conditions.

[0015] In this specification, the term “abnormal condition” refers to a condition in which abnormal heating, ignition and / or explosion occurs in a product or component, or there is a risk of such abnormal heating, ignition and / or explosion.

[0016] In this specification, the term normal state refers to a state of a product or element that is not in the above abnormal state.

[0017] The present specification discloses a composite material.

[0018] The present specification also discloses a fire extinguishing device comprising the composite material.

[0019] The above-mentioned fire extinguishing device includes a case having a sealed space inside and a composite material existing in the sealed space inside.

[0020] For example, the fire extinguishing device may include a case, and the composite material may be present within the case. The case may have an internal sealed space, and the composite material may be present within the sealed space.

[0021] The case is a container for holding the composite material. The case has a sealed space inside. The case having 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 an open portion. The sealed space means a space formed so that the components of the composite material, etc., do not substantially leak out to the outside under normal conditions.

[0022] In one example, the case may include a region having a water vapor transmission rate (WVTR) within a predetermined range described below. For example, at least the enclosed space in which the composite material exists may be substantially surrounded by a region having a water vapor transmission rate (WVTR) within the predetermined range described below.

[0023] The above case has a vent area. The term "vent area" may refer to an area that is sealed in a first state so that the sealed state can be maintained, but is opened in a second state so that all or part of the material within the space can be discharged. The second state may refer to, for example, an abnormal state described below, and the first state may refer to a normal state described below. Such a vent area may be formed in the manner described below.

[0024] In one example, the case may include a portion having a WVTR (Water Vapor Transmission Rate) within a predetermined range. For example, a sealed space within the case may be entirely surrounded by a material having a WVTR within a range described below in a sealed state. In the above, the fact that the sealed space is entirely surrounded by a material having a specific WVTR in a sealed state means that the space is substantially surrounded by the material, and for example, means that 80% to 100%, 85% to 100%, 90% to 100%, 95% to 100%, or substantially 100% of the area of ​​the case forming the sealed space has the specific WVTR. The upper limit of the WVTR (Water Vapor Transmission Rate) 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, 0.01, 0.005, or 0.001, 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 less than or equal to any one upper limit arbitrarily selected from the upper limits listed above; Alternatively, it may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. By having such a WVTR, storage stability of the composite material present within the confined space can be secured, and the fire extinguishing device can more efficiently exhibit the intended fire extinguishing effect. From this perspective, a lower WVTR is advantageous.

[0025] The unit of the above WVTR (Water Vapor Transmission Rate) is g / m 2· day, and can be evaluated in the manner described in “7. WVTR (Water Vapor Transmission Rate) Evaluation” of the Examples section of this specification.

[0026] The fire extinguishing device is configured to maintain a composite material in a sealed space under normal conditions and to effectively release certain components of the composite material inside, for example, volatile substances, to the outside under abnormal conditions.

[0027] This action is explained assuming that the above-mentioned digestive device is applied to a battery module.

[0028] Fig. 1 is a schematic diagram of a case where a 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. The fire extinguishing device (S) can be arranged between battery cells (for example, between 12 and 13 and / or between 14 and 15 in Fig. 1).

[0029] The fire extinguishing device (S) maintains a composite material, etc., inside under normal conditions. When an abnormal condition occurs, the internal material of the fire extinguishing device (S) is ejected through the vent area (dashed arrow in Fig. 1), and the ejected internal material can respond to heat generation, flame, and / or explosion under the abnormal condition. In Fig. 1, a case is described in which the internal material is ejected from both the top and bottom directions of the fire extinguishing device (S), but the direction of the ejection is not limited to Fig. 1. The direction of the ejection may be one direction with respect to the fire extinguishing device (S), or may be two or more directions.

[0030] In order for the fire extinguishing device to effectively perform the above function in an abnormal state, it is required that the components of the composite material existing inside the case in a normal state, such as volatile substances, be stably maintained, that the internal substances can be quickly discharged to the outside when an abnormal state occurs, and that most of the necessary components existing inside the case in an abnormal state, such as volatile substances, can be discharged to the outside in a vaporized state and consumed.

[0031] For a digestive device to effectively perform its functions under abnormal conditions, the vaporization rate of the vaporizable substance must be maintained appropriately. If the vaporizable substance vaporizes at an appropriate rate, the internal pores can be prevented from collapsing due to changes in surface tension and other factors following the consumption of latent heat.

[0032] The fire extinguishing device disclosed in this specification can satisfy the above requirements.

[0033] The above digestive device explains the principle of its function.

[0034] FIG. 2 shows only the fire extinguishing device (S) in FIG. 1 separately. In a configuration such as FIG. 1, if abnormal heating, abnormal ignition, and / or abnormal explosion occurs in at least one of the battery cells adjacent to the fire extinguishing device (S), a certain level of heat or more is instantaneously applied to the fire extinguishing device, as indicated by the solid arrow in FIG. 2. As indicated by the dotted arrow in the internal sealed space of the case (1001) of the fire extinguishing device in FIG. 2, volatile substances propagate randomly in all directions within the space. At this time, if the WVTR of the portion forming the sealed space of the case (1001) is within the aforementioned range, the vaporized gas cannot be released to the outside, and thus the inside of the case (1001) becomes very high-pressure. At this time, if the vent area (1002) of the case is configured to be instantaneously opened at a certain level or higher of high pressure, the vent area (1002) is instantaneously opened in the high-pressure state, and the gas inside is quickly discharged to the outside through the opened vent area (1002).

[0035] When the WVTR of the case is high, the pressure inside the case (1001) may not effectively increase in an abnormal state, so that the vent area (1002) may not be opened effectively, or even when the vent area (1002) is opened, the internal pressure may not be sufficient, so that the internal gas may not be completely discharged to the outside and exhausted, or the discharge speed may not be properly secured.

[0036] By keeping the WVTR of the case low, the storage stability of the internal material under normal conditions can also be effectively secured.

[0037] The method for forming the above-mentioned vent area (1002) is not particularly limited. The vent area can be formed by designing a certain area of ​​the case forming the sealed space to be opened when a certain level of pressure and / or heat is applied. For example, if a certain area of ​​the case forming the sealed space is configured to have lower strength than other areas, the area 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 so that opening occurs by melting at a predetermined 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 easily adopted by those skilled in the art.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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, 5, 10, 15, 20, 25 or 30, and the upper limit may be about 5,000, 4,000, 3,000, 2,000, 1,000, 500, 200, 150, 100, 90, 80, 70, 60, 50, 40 or 30. The unit of the thickness is μm. The thickness is within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above. Or, it may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0045] The above digestive device may include additional components to perform the above action more effectively.

[0046] For example, the fire extinguishing device may further include a heat-conducting layer. This heat-conducting layer may be located at an appropriate location within the fire extinguishing device, for example, the heat-conducting layer may be located between the case and the composite material described below within the fire extinguishing device.

[0047] Fig. 3 is an example of a case in which the heat-conducting layer (2001) is added to the fire extinguishing device of Fig. 2. The heat-conducting layer may be located between the case (1001) and the composite material as shown in Fig. 3, but is not limited thereto in terms of location. The heat-conducting layer may be located in other locations, such as inside the case, and the number of heat-conducting layers may be one or two or more.

[0048] 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 is within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; Or, it may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The unit of the thermal conductivity is W / mK, and it can be evaluated in the manner described in “9. Evaluation of Thermal Conductivity” of the Examples section of this specification.

[0049] 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.

[0050] 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, 5, 10, 15, 50, 75, or 90, and the upper limit may be about 500, 400, 300, 200, 100, 50, 40, or 30. The unit of the thickness is μm. The thickness may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above.

[0051] As shown in Fig. 3, in some cases, heat generated in an abnormal state may not be uniformly applied to the fire extinguishing device, but may be locally applied to only a certain area. However, in order for the volatile substances inside the fire extinguishing device to quickly vaporize and achieve a high-pressure state, the heat in the abnormal state must be uniformly applied to the fire extinguishing device. In the case where a heat conductive layer exists, even if the heat in the abnormal state is locally applied, 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.

[0052] The present specification discloses a composite material that may be present in the enclosed space of the above fire extinguishing device.

[0053] The term composite refers to a material comprising two or more components. While the material comprises at least two components, it may additionally comprise other components.

[0054] The above composite material may function as a buffer in some cases.

[0055] In the case of a buffer, the composite material may have an appropriate level of hardness. As described above, in an abnormal state, the fire extinguishing device may be subjected to high temperatures momentarily and, at the same time, very high pressures. Therefore, if the fire extinguishing device cannot properly respond to such momentary high pressures, complete exhaustion of substances within the confined space (particularly, exhaustion of volatile substances into a gaseous state) may become difficult, and even if exhaustion is achieved, the exhaustion rate may not be properly controlled. Furthermore, if the fire extinguishing device is excessively hard, it may have a negative impact on objects adjacent to the fire extinguishing device, depending on its intended use. For example, if the fire extinguishing device is placed between battery cells and the device is excessively hard, it may not be able to effectively respond to volume changes that occur during the charging and discharging of the battery cells.

[0056] The above-mentioned problems can be effectively addressed by controlling the hardness of the composite material present in the above-mentioned digestive device.

[0057] For example, the composite may have a ratio of hardness at room temperature and low temperature within a predetermined range. For example, the lower limit of the ratio A / B of the 25°C hardness A of the composite to the -20°C hardness B may be approximately 0.7, 0.75, 0.8, 0.85, 0.9, or 0.95, and the upper limit may be approximately 10, 8, 6, 4, 2, 1.5, or 1. The ratio may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The hardness may be evaluated by the method described in “10. Hardness Evaluation” of the Examples section of the present specification. The hardness may be Shore A hardness.

[0058] The above-mentioned hardness ratio of the composite indicates that the rate of increase in hardness when exposed to a low-temperature environment is controlled compared to a high-temperature environment. Under this ratio, the aforementioned appropriate vaporization rate of the volatile material is secured, and adverse effects on adjacent objects are reduced.

[0059] The lower limit of the 25°C hardness (Shore A hardness) of the above composite may be about 20, 25, 30, 35, 40, 45, 50, 55, 60, or 65, and the upper limit may be about 150, 145, 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 80, 75, 70, or 65. The above ratio may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The above hardness may be evaluated by the method described in “10. Hardness Evaluation” of the Examples section of the present specification.

[0060] Within this hardness range, the composite material can appropriately perform its assigned function. For example, a composite material having the above hardness can effectively respond to the instantaneous high pressure and heat applied to the fire extinguishing device under abnormal conditions without causing excessive stress or other adverse effects on adjacent elements of the fire extinguishing device under normal conditions, thereby allowing the substances within the confined space to be completely consumed at an appropriate rate (e.g., the release of flammable substances into a gaseous state).

[0061] In order for the composite to have the above hardness, the components and ratio of the composite can be controlled. In addition, the method of forming the composite can be controlled.

[0062] The above composite material may include a vaporizable substance. This vaporizable substance may, in some cases, be contained within an inorganic gel and / or inorganic fiber, as described below. The term "vaporizable substance" refers to a substance that vaporizes at a given temperature. This vaporizable substance may exist in a liquid state at room temperature (25°C). This vaporizable substance may be used to reduce heat through heat exchange or heat absorption in an abnormal state of an object adjacent to the fire extinguishing device, or to eliminate flames generated by ignition and / or explosion. This vaporizable substance may rapidly vaporize in an abnormal state, thereby increasing the pressure in a confined space, opening the vent area, and being discharged to the outside through the opened vent area.

[0063] As the above-mentioned volatile substance, any substance that can be vaporized and is non-flammable may be used without any special restrictions. For example, the above-mentioned volatile substance may be a solvent having a freezing point and / or boiling point within a certain range.

[0064] For example, the lower limit of the freezing point of the 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 less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above. The freezing point is a freezing point under 1 atm.

[0065] In order for the above-mentioned volatile substance to efficiently respond to an abnormal state, it may be advantageous for it to be vaporized at least by heat generated in the abnormal state, and for this purpose, the boiling point of the above-mentioned volatile substance may be controlled.

[0066] The lower limit of the boiling point of the above-mentioned volatile substance may be about 80°C, 85°C, 90°C, or 95°C, and the upper limit may be about 120°C, 115°C, 110°C, or 105°C. The boiling point may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above. The boiling point is a boiling point under 1 atm.

[0067] Any volatile substance having a freezing point and / or boiling point within the above range and being non-flammable may be selected and used without any special restrictions. A representative example of such a volatile substance is water, and thus water can be used as the volatile substance. However, the types of applicable volatile substances are not limited to the above.

[0068] The lower limit of the proportion of the volatile material in the composite may be, for example, about 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 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%, 60 wt%, 55 wt%, 50 wt%, 45 wt% or 40 wt%. The proportion is within a range that is greater than or equal to any lower limit arbitrarily selected from among the lower limits listed above; Or, it may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. By adjusting the content of the volatile material, the desired characteristics such as heat absorption can be achieved.

[0069] The above ratio is a ratio calculated with the sum of the weights of all substances present in the composite material being 100 wt%.

[0070] The above composite may contain additional components to ensure proper digestion function and hardness.

[0071] The above composite may further comprise an inorganic gel and / or inorganic fibers. These inorganic gels and / or inorganic fibers may serve to impart the above-described hardness characteristics to the composite and, if necessary, to support some or all of the components, such as the volatile substances, described above.

[0072] The above-mentioned inorganic gel may be, for example, an oxide network formed by a so-called sol-gel process. This oxide network may include a network in which inorganic elements are connected via oxygen atoms. As the inorganic elements, one or more selected from the group consisting of silicon, titanium, zirconium, niobium, tantalum, molybdenum, and tungsten may be exemplified. For example, if the inorganic element is silicon, the inorganic gel may be silica gel.

[0073] It is possible to achieve the desired hardness by controlling the density and content of the network of the above-mentioned inorganic gel.

[0074] The lower limit of the proportion of the inorganic gel in the composite may be, for example, about 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, or 2.5 wt%, and the upper limit may be about 13 wt%, 12 wt%, 11 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, or 2 wt%. The proportion may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The proportion is a proportion calculated when the sum of the weights of all substances present in the composite is 100 wt%.

[0075] In another example, the lower limit of the content of the inorganic gel relative to 100 parts by weight of the volatile material may be about 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts 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 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, or 0.5 parts by weight. The above ratio may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0076] Achieving the desired hardness may be possible by including an inorganic gel having an appropriate network within the above range.

[0077] As the above-mentioned inorganic fibers, for example, inorganic fibers commonly used in the formation of insulating materials can be used, such as so-called glass fibers and / or ceramic fibers. Such inorganic fibers can exist, for example, in the form of woven or non-woven fabrics. The category of woven or non-woven fabrics can also include objects referred to as paper, wool, or blankets.

[0078] For example, as the inorganic fiber, ceramic paper, ceramic paper using an organic / inorganic binder, binder-free fiber, ceramic fiber, glass fiber, glass felt, basalt fiber, basalt felt, aramid fabric, silica felt, oxpan carbon felt, carbon fiber felt, and / or melamine fiber can be used, and an organic binder can be used. When the inorganic fiber is used, the insulation property is excellent, and the sol is easily absorbed, so that materials such as gels and heat absorbents can be evenly positioned within the substrate, thereby increasing stability.

[0079] The properties of the above inorganic fibers can be adjusted according to the purpose.

[0080] For example, the lower limit of the tensile strength of the inorganic fiber may be about 0.5, 1, 5, 10, 50, 70, 90, 95 or 100, and the upper limit may be about 500, 450, 400, 350, 300, 250, 200, 150, 100, 80, 60, 40, 20, 15 or 10. The tensile strength may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The unit of the tensile strength is kPa.

[0081] For example, the lower limit of the compressive strength of the inorganic fiber may be about 1, 5, 8, 10, 50, 100, 110, 120, 130, 140, 145 or 150, and the upper limit may be about 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 40, 30, 20, 15 or 10. The compressive strength may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The unit of the compressive strength is kPa.

[0082] For example, the lower limit of the Young's modulus of the inorganic fiber may be about 0.1, 0.5, 1, 1.5, 2, 2.5, or 3, and the upper limit may be about 20, 18, 16, 14, 12, 10, 8, 6, or 4. The Young's modulus may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above. The unit of the Young's modulus is MPa.

[0083] The inorganic fibers, when included in the composite, may exhibit one or more of the tensile strength, compressive strength, and Young's modulus within the above range. Thus, for example, if the inorganic fibers are included in the composite in the form of the woven or nonwoven fabric, the woven or nonwoven fabric may exhibit one or more of the tensile strength, compressive strength, and Young's modulus within the above range. The tensile strength, compressive strength, and Young's modulus may be measured according to the KS K ISO 9073-3 standard.

[0084] It is possible to form a composite having the desired properties by applying inorganic fibers exhibiting tensile strength, compressive strength and / or Young's modulus in the above range.

[0085] The lower limit of the density of the above-mentioned inorganic fiber may be about 0.01, 0.05, or 0.1, and the upper limit may be about 10, 8, 6, 4, 2, 1, 0.5, or 0.3. The density may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above. The unit of the density is g / cm 3 am.

[0086] The inorganic fibers, when included in the composite, can exhibit a density within the above range. Thus, for example, if the inorganic fibers are included in the composite in the form of a woven or nonwoven fabric, the woven or nonwoven fabric can exhibit the above density.

[0087] When the above-mentioned inorganic fiber is included in the form of a woven fabric or a non-woven fabric, the thickness of the woven fabric or the non-woven fabric may be selected within a range capable of exhibiting the above-described characteristics. For example, the lower limit of the thickness may be about 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, 2.5, or 3, and the upper limit may be about 100, 50, 30, 10, 8, 6, or 4. The unit of the thickness is mm. The thickness may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above.

[0088] The lower limit of the proportion of the inorganic fiber in the composite may be, for example, about 0.5 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, or 20 wt%, and the upper limit may be about 60 wt%, 40 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, or 10 wt%. The proportion may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The proportion is a proportion calculated when the sum of the weights of all substances present in the composite is 100 wt%.

[0089] In another example, the lower limit of the weight ratio of the inorganic fiber to 100 parts by weight of the volatile material may be about 0.5 parts by weight, 1 part by weight, 5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, or 75 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, or 20 parts by weight. The above ratio may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0090] When the above-described inorganic fibers and inorganic gel exist simultaneously, the inorganic gel may be attached to the inorganic fibers, or the inorganic gel and the inorganic fibers may exist in a state of being entangled with each other. For example, as described below, by performing the gelation process in the presence of the inorganic fibers, the structure described above can be implemented, thereby enabling the composite material to more effectively perform the desired performance and function, such as hardness.

[0091] The composite may further include an ionic compound. An ionic compound is a compound that can dissociate to form ions, such as an acid, a base, or a salt.

[0092] The ionic compound may be a catalyst applied to form the inorganic gel, a freezing point regulator described below, or a carbonization catalyst. The ionic compound may be included in the composite in an undissociated state, i.e., a state in which no ions are formed, or may be included in the composite in a state in which it is dissociated and forms ions.

[0093] Ionic compounds play an important role in forming inorganic gels having the desired network structure, achieving the aforementioned hardness properties, and enabling the composite to exhibit the desired effects over a wide temperature range.

[0094] As described below, the inorganic gel can be formed by polymerizing a metal alkoxide within the vaporizable substance (sol-gel process). The ionic compound, when present, can induce a so-called freezing point depression phenomenon in the vaporizable substance, etc. The freezing point of the medium in which polymerization is performed is related to the attractive forces between the constituent molecules of the medium and the energy of the molecules. Therefore, the ionic compound affects the polymerization efficiency in conjunction with the polymerization temperature, and the result becomes a factor determining the density and degree of crosslinking of the network of the inorganic gel.

[0095] The composite can stably exhibit the desired effect even at relatively low temperatures by determining the freezing point according to the addition of the ionic compound, and the efficiency of forming a carbonized layer of the carbonizable organic material described below can also be determined.

[0096] For example, the ionic compound has the following formula 1 △T f It can exist in a quantity that is within a certain range.

[0097] [Formula 1]

[0098] △T f = K f × M × I

[0099] K in Equation 1 fis the freezing point depression constant of the volatile substance, M is the molal concentration of the ionic compound with respect to the volatile substance, and I is the number of moles of ions generated when 1 mole of the ionic compound is dissociated.

[0100] K in Equation 1 f is the freezing point depression constant of a volatile substance, and its unit is K / m or ℃ / m. For example, if the volatile substance is water, the above K f is 1.86.

[0101] M in Equation 1 is the molal concentration of the freezing point regulator, which is the molal concentration with respect to the volatile substance. Therefore, M is the number of moles of the ionic compound present per 1 kg of the volatile substance in the composite.

[0102] I in Equation 1 is the number of ions (moles) formed by 1 mole of the ionic compound when the ionic compound is dissociated, and in this case, dissociation means a state in which the freezing point regulator is completely dissociated.

[0103] In the case where two or more ionic compounds exist in the above composite material, the above △T for each compound f Calculate and add up the values ​​to get △T for the composite material. f It's worth it.

[0104] △T in Equation 1 f The lower limit of may be, for example, 5, 10, 15, 20 or 25, and the upper limit may be, for example, 50, 45, 40, 35, 30, 25, 20 or 15. The above △T fIt may be within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above. △T in Equation 1 f The unit is ℃. By adjusting the content of the ionic compound within the above range, the above-described purpose can be achieved.

[0105] In order for the ionic compound included in the above content to exert an appropriate effect, the solubility of the ionic compound in the volatile substance (e.g., water) can be adjusted.

[0106] For example, the lower limit of solubility of the ionic compound in 100 g of water at 25°C is 10 g, 15 g, 20 g, 25 g, 30 g, 35 g, 40 g, 45 g, 50 g, 55 g, 60 g, 65 g, 70 g, 75 g, 80 g, 85 g, 90 g, 95 g, 100 g, 110 g, 115 g, 120 g, 125 g, 130 g, 135 g, 140 g, 145 g, 150 g, 155 g, 160 g, 165 g, 170 g, 175 g, 180 g, 185 g, 190 g, 195 g, 200 g, 205 g, 210 g, 215 g, 225 g, 230 g, 235 g, 240 g, 255 g, 260 g, 265 g, 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 1,000 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, 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, 100 g, 95 g, 90 g, 85 g, It can be 80 g, 75 g, 70 g, 65 g, 60 g, 55 g, 50 g, 45 g, 40 g, 35 g or 30 g.The solubility may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The solubility is the weight (g) of the ionic compound that can be dissolved at most in 100 g of water at 25°C. The solubility may be evaluated in the manner described in “8. Solubility Evaluation” of the Examples section of the present specification.

[0107] The lower limit of solubility of the above ionic compound in 100 g of water at 0℃ is 10 g, 15 g, 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 1,000 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 lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The solubility is the weight (g) of the ionic compound that can be dissolved at most in 100 g of water at 0°C. The solubility can be evaluated in the manner described in “8. Solubility Evaluation” of the Examples section of the present specification.

[0108] The type of the above ionic compound is determined according to the purpose and is not particularly limited. For example, as an ionic compound having a freezing point depression effect, one or more selected from the group consisting of formates, acetates, carbonates, and sulfates can be exemplified. Specifically, for example, at least one of substances composed of sodium acetate (CH3COONa), sodium formate (HCOONa), potassium acetate (CH3COOK), potassium formate (HCOOK), calcium formate ((HCOO)2Ca), magnesium formate ((HCOO)2Mg), potassium carbonate (K2CO3), and ammonium sulfate ((NH4)2SO4) can be used as the ionic compound.

[0109] For example, the lower limit of the weight part of the ionic compound applied to control the freezing point relative to 100 parts by weight of the vaporizable substance may be about 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 or 55 parts by weight, and the upper limit may be about 200 parts by weight, 150 parts by weight, 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 or 30 parts by weight. The above ratio may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0110] In the case where other ionic compounds (e.g., ionic compounds as carbonization catalysts described below or acids or bases added for the formation of inorganic gels) are added in addition to those added as the freezing point regulator in the composite, all ionic compounds present in the composite have a △T of Equation 1. fIt can exist in an amount within the above-mentioned range.

[0111] The composite may include, as additional components, a carbonization catalyst and a carbonizable organic material. The combination of the components allows the carbonization of the carbonizable organic material to occur at a desired time (e.g., in the abnormal state). The carbonized material thus formed can block heat transfer. The carbonization catalyst can promote the carbonization process of the carbonizable organic material, etc. The carbonization catalyst forms an acid or an acid-based salt or ion at high temperatures, and such a component can promote the carbonization process and gas generation process. In addition, depending on the type of carbonization catalyst, the carbonized material may be flame retardant or form a component that exhibits flame retardancy on its own. For example, the carbonization catalyst forms a phosphoric acid-based substance by decomposition at high temperatures, and such a substance can polymerize to have flame retardancy. Accordingly, the carbonization catalyst can be included in the composite to enable the composite to effectively respond to an abnormal state.

[0112] The above carbonization catalyst and the carbonizable organic material need to be applied together with the vaporizable material, and at this time, the carbonization catalyst should have a solubility above a certain level in the vaporizable material (e.g., water). That is, the components dispersed within the vaporizable material can more effectively contact and interact with each other at the necessary time to efficiently form the desired carbonized material, etc. In addition, by controlling the solubility of the carbonization catalyst in the vaporizable material, the agglomeration or phase separation of the components within the composite material can be prevented, and the formation of the above-mentioned carbonized material and / or the formation of the flame retardant can proceed more effectively. For example, the lower limit of the solubility of the carbonization catalyst in the vaporizable substance or water 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 lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The above solubility is the weight (g) of the carbonization catalyst that can be dissolved to the maximum extent in 100 g of the solvent (e.g., water) at 25°C. The above solubility is measured in the manner described in “8. Solubility Evaluation” of the Examples section of this specification.

[0113] As the above carbonization catalyst, any catalyst that can be decomposed at high temperatures to form an acid or an acid-based salt or ion, etc., and has the above solubility can be used without special limitations. Examples of the above carbonization catalyst include phosphoric acid compounds such as phosphoric acid and phosphate, phosphonate compounds, or phosphate compounds. The above carbonization catalyst may be, for example, primary or secondary ammonium phosphate, urea phosphate, guanyl urea phosphate, or ammonium polyphosphate, and one or two or more of the above may be selected and used.

[0114] The above carbonization catalyst may be present in an appropriate amount considering the desired effect. For example, the lower limit of the weight ratio of the carbonization catalyst to 100 parts by weight of the vaporizable material may be about 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight or 500 parts by weight, and the upper limit of the weight ratio may be about The ratio may be about 1,000 parts by weight, 900 parts by weight, 800 parts by weight, 700 parts by weight, 600 parts by weight, 500 parts by weight, 400 parts by weight, 100 parts by weight, 50 parts by weight, 40 parts by weight, 30 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, or 5 parts by weight. The ratio may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above. If the content of the carbonization catalyst is excessively large, the content of the vaporizable material that can be applied to the composite material is limited, and the vaporization characteristics of the vaporizable material are affected by the carbonization catalyst, making it difficult to secure the desired characteristics. Therefore, the amount of the carbonization catalyst may be adjusted taking this into consideration.

[0115] The above carbonizable organic material is an organic material that carbonizes to form a carbide when exposed to a flame or heat of a certain temperature. The carbide formed by such an organic material is often porous and can thus have an insulating function. Therefore, when the composite material or the like is exposed to abnormal heat generation, ignition, or explosion, the organic material can form an appropriate carbide to exhibit an insulating function. As described above, by adding the specific carbonization catalyst and the carbonizable organic material to the volatile material, even when a small amount of the carbonizable organic material is applied, it is possible to form a carbide that can effectively respond to abnormal heat generation, ignition, and / or explosion.

[0116] As for the above organic matter, any suitable type may be applied without special restrictions as long as it is a substance that forms carbon when exposed to heat or flame.

[0117] 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).

[0118] 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.

[0119] 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.

[0120] 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.

[0121] By using starch in which amylose and amylopectin with the above characteristics exist in an appropriate ratio, the desired composite material can be provided more efficiently.

[0122] 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 upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above. Or, it may be a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The ratio of amylose and amylopectin can be measured according to the method described in “6. Measurement of Amylopectin and Amylose Contents” in the Examples section of the present specification.

[0123] 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, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, 550,000, 600,000, 650,000, 700,000, 750,000, 800,000, 850,000, 900,000, 950,000, 1,000,000, 1,500,000, 2,000,000, 2,500,000, 3,000,000, 3,500,000, 4,000,000, It can be 4,500,000, 5,000,000, 5,500,000, 6,000,000, 6,500,000, 7,000,000, 7,500,000, 8,000,000, 8,500,000, 9,000,000, 9,500,000, 10,000,000, 20,000,000, 30,000,000, 40,000,000, or 50,000,000, with an upper limit of 1,000,000,000, 900,000,000, 800,000,000, 700,000,000, The molecular weight may be about 600,000,000, 500,000,000, 400,000,000, 300,000,000, 200,000,000, 150,000,000, 100,000,000, 90,000,000, 80,000,000, 70,000,000 or 60,000,000. The unit of the molecular weight is g / mol. The molecular weight may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above.Starch having the above molecular weight (Mw) can form carbides having a desired function (e.g., insulating function) more effectively when exposed to heat or flame. The above molecular weight can be measured by the method described in “5. Molecular Weight Measurement” of the Examples section of this specification.

[0124] The carbonizable organic material (e.g., starch) may be used with a gelatinization viscosity within a certain range. This gelatinization viscosity is related to the characteristics of the carbonizable organic material when present in a volatile substance, and by controlling the gelatinization viscosity, carbonized materials can be formed more effectively. The lower limit of the gelatinization viscosity of the above-mentioned carbonizable organic matter (e.g., starch) may be about 150, 200, 250, 300, 350, 400, 450, 500, 550, 650, 700, 750, 800, 850, 900, 950 or 1,000, and the upper limit may be about 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, It can be about 350 or 300. The gelatinization viscosity can be within a range that is less than or equal to an upper limit arbitrarily selected from the upper limits listed above; within a range that is greater than or equal to an upper limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to an lower limit arbitrarily selected from the lower limits listed above and less than or equal to an upper limit arbitrarily selected from the upper limits listed above. The unit of the gelatinization viscosity is BU (Brabeder unit).

[0125] The lower limit of the weight ratio of the carbonizable organic material to 100 parts by weight of the vaporizable material may be about 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight or 6 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, 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, 5 parts by weight, 4, parts by weight, 3 parts by weight, 2 parts by weight or 1 part by weight. The above ratio may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above. The carbonizable organic material included in this ratio may enable the composite to effectively form carbides when necessary and to have excellent overall handling properties and storage stability.

[0126] The above composite material may optionally include an absorbent polymer as an additional component. An absorbent polymer is a polymer that has the property of absorbing water.

[0127] 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 SAP (Super Absorbent Polymer).

[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 composite to remain in a gel state throughout, thereby ensuring ease of handling and storage stability.

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

[0130] Typically, the above material uses 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 above absorbent polymer may be a particulate polymer, for example. To achieve desired viscosity characteristics and digestive functions through the application of the absorbent polymer, the weight-based size distribution of the particulate absorbent polymer may be controlled. In this specification, the weight-based size distribution of the term absorbent polymer is a size distribution measured according to the EDANA method WSP 220.3 standard, and the sample of the particulate absorbent polymer is divided into a fraction having a size of less than 150 μm (hereinafter referred to as "A fraction"), a fraction within a range of 150 μm to 300 μm (hereinafter referred to as "B fraction"), a fraction within a range of 300 μm to 600 μm (hereinafter referred to as "C fraction"), a fraction within a range of 600 μm to 850 μm (hereinafter referred to as "D fraction"), and a fraction exceeding 850 μm (hereinafter referred to as "E fraction"), and the weight of each fraction is expressed as a percentage (the weight of each fraction) relative to the weight of the entire particulate absorbent polymer sample. It refers to the size distribution expressed as a ratio.

[0132] The particulate absorbent polymer may have a maximum weight size in the weight-based size distribution within a range of 150 μm to 850 μm. The maximum weight size herein refers to the size of the fraction having the highest weight ratio among the weight ratio of the A fraction, the weight ratio of the B fraction, the weight ratio of the C fraction, the weight ratio of the D fraction, and the weight ratio of the E fraction. That is, the fact that the maximum weight size is within a range of 150 μm to 850 μm means that the weight ratio of the particulate absorbent polymer belonging to one or more of the B fraction, the C fraction, and the D fraction has the largest value. Since the weight ratios of each of the two fractions are the same and may represent the highest value among the weight ratios of each of the entire fractions, the fraction having the maximum weight size may be one or two or more. In one example, the fraction having the maximum weight size may be the C fraction among the B, C, and D fractions. Therefore, the maximum weight size in the above weight-based size distribution may be within the range of 300 μm to 600 μm.

[0133] The lower limit of the weight ratio in the fraction exhibiting the maximum weight size in the weight-based size distribution of the above particulate absorbent polymer (i.e., the weight ratio of the absorbent polymer belonging to the maximum weight size in the weight-based size distribution) may be about 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt% or 74 wt%, and the upper limit may be about 95 wt%, 90 wt%, 85 wt%, 80 wt%, 79 wt%, 78 wt%, 77 wt%, 76 wt% or 75 wt%. The weight ratio is within a range that is equal to or greater than any one lower limit arbitrarily selected from among the lower limits listed above; Or, it may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0134] If the above maximum weight size is too small, and / or the weight ratio in the fraction representing the above maximum weight size is too small, the composite may not properly form the desired gel, resulting in poor handling and storage properties or failure to exhibit the desired digestive function. Therefore, an appropriate particulate absorbent polymer may be selected taking this into consideration.

[0135] 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 upper limit arbitrarily selected from the upper limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above.

[0136] The sealed space or composite material inside the above digestive device may contain the above components and, if necessary, additional components.

[0137] The present specification discloses a method for producing the above composite material.

[0138] For example, the manufacturing method may include a step of polymerizing a precursor solution comprising the inorganic gel precursor and a vaporizable material.

[0139] The polymerization process involves the formation of a high-molecular-weight component by forming a network of relatively low-molecular-weight substances, such as monomers or oligomers. In this case, the monomer or oligomer may be the precursor. Furthermore, there are no particular limitations on the specific method by which the polymerization is performed. For example, if the inorganic gel precursor is a condensation precursor, as described below, the polymerization process may be a so-called sol-gel process.

[0140] As the precursor, for example, a metal alkoxide can be used. This precursor is a condensation precursor and can form an inorganic gel through the sol-gel process. Specifically, the metal alkoxide may be one or more alkoxides selected from the group consisting of silicon, titanium, zirconium, niobium, tantalum, molybdenum, and tungsten. The lower limit of the number of carbon atoms present in the alkoxide may be about 4, 6, 8, or 10, and the upper limit may be about 20, 18, 16, 14, 12, 10, or 8. The above carbon number may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. As the precursor, for example, a component called sodium silicate may be used, and such a component can form silica gel as an inorganic gel.

[0141] As the above-mentioned volatile material, components such as water described above can be used.

[0142] The composition of the precursor solution can be adjusted to form the desired inorganic gel and composite.

[0143] For example, the content of the vaporizable substance in the precursor solution can be adjusted. For example, the lower limit of the content of the vaporizable substance in the precursor solution can be about 30 wt%, 40 wt%, 50 wt%, 60 wt%, or 65 wt%, and the upper limit can be about 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt%, 65 wt%, or 60 wt%. The content can be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0144] The lower limit of the weight ratio of the precursor to 100 parts by weight of the vaporizable substance in the precursor solution may be about 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts 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 25 parts by weight, 20 parts by weight, 15 parts by weight, 10 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, or 0.5 parts by weight. The above content may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0145] The above-described precursor solution may be formulated to exhibit a pH within a predetermined range. For example, the lower limit of the pH of the above-described precursor solution may be about 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or 7, and the upper limit may be about 14, 13, 12, 11, 10, 9, 8, or 7. The pH may be within a range that is equal to or greater than any lower limit arbitrarily selected from the above-described lower limits and equal to or less than any upper limit arbitrarily selected from the above-described upper limits.

[0146] To adjust the pH, the precursor solution may additionally contain a catalyst. This catalyst may be one of the ionic compounds described above. There is no particular limitation on the type of applicable catalyst, and for example, an acid catalyst or a base catalyst applicable to a general sol-gel process may be used. Examples of such acid catalysts include one or a mixture of two or more selected from hydrochloric acid, sulfuric acid, fluorosulfuric acid, nitric acid, phosphoric acid, acetic acid, hexafluorophosphoric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid, and examples of base catalysts include, but are not limited to, alkaline catalysts such as sodium hydroxide, ammonium hydroxide, or ammonium chloride.

[0147] The content of the catalyst can be controlled within a range where the above-mentioned pH can be achieved. For example, the lower limit of the molal concentration of the catalyst (i.e., the number of moles of catalyst present per 1 kg of the vaporizable substance) based on the vaporizable substance in the precursor solution may be about 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.5, 1, or 1.5, and the upper limit may be about 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.8, 0.6, or 0.4. The molal concentration may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and is equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0148] The above precursor solution may additionally contain an ionic compound in addition to the catalyst. Such an ionic compound may be added to adjust the molecular energy or intermolecular attraction of the vaporizable substance, as described above, to form the desired inorganic gel. Examples of the ionic compound include the aforementioned freezing point regulator or carbonization catalyst.

[0149] The content of all ionic compounds present in the precursor solution, including the catalyst, can be adjusted. Adjusting this content controls the fluidity of the vaporizable material, and this controlled fluidity can affect the polymerization efficiency of the precursor, thereby forming the desired inorganic gel at a specified polymerization temperature.

[0150] For example, the ionic compound has △T of the above-mentioned formula 1 f It can be added so as to be within the above-described predetermined range.

[0151] In addition to the above components, the precursor solution may contain any other necessary components. For example, the polymerization may be performed in the presence of the inorganic fibers. The inorganic fibers also affect the polymerization efficiency of the precursor. In such cases, the precursor solution may contain the inorganic fibers described above.

[0152] The lower limit of the weight ratio of the inorganic fiber to 100 parts by weight of the vaporizable substance in the precursor solution may be about 0.5 parts by weight, 1 part by weight, 5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, or 75 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, or 20 parts by weight. The above weight ratio may be within a range that is equal to or greater than any one arbitrarily selected lower limit among the lower limits listed above, and at the same time less than or equal to any one arbitrarily selected upper limit among the upper limits listed above.

[0153] The temperature for polymerization of the above-mentioned bulb solution can be controlled. This controlled temperature is the above-mentioned △T f It contributes to the formation of an inorganic gel of the desired shape by linking with an ionic compound having a value of .

[0154] For example, the lower limit of the polymerization temperature may be about 10°C, 15°C, 20°C, 25°C, 30°C, or 35°C, and the upper limit may be about 50°C, 45°C, 40°C, 35°C, 30°C, or 25°C. The polymerization temperature may be within a range that is equal to or greater than any arbitrarily selected lower limit among the lower limits listed above, while being less than or equal to any arbitrarily selected upper limit among the upper limits listed above.

[0155] In order to form the desired composite, the polymerization of the precursor or the prepolymer of the precursor may be performed in the presence of inorganic fibers. For this purpose, the polymerization may be performed in multiple stages. For example, the manufacturing method may include a first stage (primary polymerization) of polymerizing the precursor solution to obtain a prepolymer, and a second stage (secondary polymerization) of polymerizing the precursor or prepolymer in the presence of the inorganic fibers to obtain an inorganic gel. The precursor solution applied to the first polymerization may not include the inorganic fibers. That is, the first polymerization may be performed in the absence of inorganic fibers, and the second polymerization of the second stage may be performed in the presence of inorganic fibers. That is, after the first polymerization, the polymerized product may be mixed with the inorganic fibers, and further polymerization may be performed. The precursor of the second stage may refer to a precursor that did not participate in the polymerization during the first polymerization to form a prepolymer.

[0156] The above primary polymer or prepolymer may be, for example, an inorganic sol.

[0157] The polymerization temperature, polymerization time, and / or mixing conditions of the first step may be adjusted.

[0158] The lower limit of the polymerization temperature of the first step may be about 10°C, 15°C, 20°C, 25°C, 30°C, or 35°C, and the upper limit may be about 50°C, 45°C, 40°C, 35°C, 30°C, or 25°C. The polymerization temperature may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, while being less than or equal to any upper limit arbitrarily selected from the upper limits listed above.

[0159] The above first step can be performed while stirring the precursor solution at an appropriate speed. In this process, the lower limit of the stirring speed can be about 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, or 500 rpm, and the upper limit can be about 2,000 rpm, 1,500 rpm, 1,000 rpm, 800 rpm, 600 rpm, 400 rpm, or 300 rpm. The stirring speed can be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0160] The lower limit of the time for performing the above first polymerization may be about 1 second, 5 seconds, 10 seconds, 30 seconds, 1 minute, 5 minutes, 10 minutes, or 15 minutes, and the upper limit may be about 60 minutes, 55 minutes, 50 minutes, 45 minutes, 40 minutes, 35 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes, 8 minutes, 6 minutes, 4 minutes, 2 minutes, 1 minute, or 30 seconds. The time may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0161] By forming a primary polymer (a prepolymer or a mixture of a prepolymer and a precursor) under the above conditions and performing secondary polymerization, the desired composite material can be formed.

[0162] The above primary polymer can be further polymerized secondaryally to form an inorganic gel. As described above, the secondary polymerization can be performed in the presence of the inorganic fibers. That is, after the primary polymerization, the inorganic fibers and the primary polymer are mixed so as to satisfy the ratio described above (ratio of inorganic fibers to 100 parts by weight of the volatile material), and then further polymerization is performed to effectively form the desired inorganic gel.

[0163] The above secondary polymerization can be performed at an appropriate temperature.

[0164] For example, the lower limit of the polymerization temperature may be about 10°C, 15°C, 20°C, or 25°C, and the upper limit may be about 40°C, 35°C, 30°C, or 25°C. The temperature may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0165] By maintaining the mixture of the primary polymer and the inorganic fiber at the above temperature during the secondary polymerization, the desired inorganic gel can be obtained.

[0166] The composite can be prepared by mixing the inorganic gel formed in this manner with other components of the desired composite. These components may be mixed with the inorganic gel after the inorganic gel is prepared, mixed into the precursor solution prior to the preparation of the inorganic gel, or performed at an appropriate point during the preparation of the inorganic gel.

[0167] After manufacturing the composite, it can be placed within a case to form a fire extinguishing device. The composite can be placed within the case after manufacturing, and the entire or partial manufacturing process of the composite can be performed within the case to form the fire extinguishing device. For example, the fire extinguishing device and the composite can be manufactured simultaneously by pre-placing the inorganic fibers within the case, injecting the primary polymer, followed by additional polymerization, and then introducing additional components after polymerization, if necessary.

[0168] The present specification also discloses an electronic equipment or device to which the above-described fire extinguishing device is applied.

[0169] The type of electronic equipment or device is not particularly limited. For example, the composite material or fire extinguishing device may be applied to equipment or devices that pose a risk of abnormal heat generation, ignition, and / or explosion during operation, maintenance, and / or storage, and where such abnormal phenomena must be controlled.

[0170] Examples of the above equipment or devices include batteries. In particular, in battery modules comprised of multiple battery cells, it is crucial to prevent abnormal heat generation, ignition, and / or explosion from occurring in one battery cell from spreading to adjacent battery cells.

[0171] The present specification discloses a battery module including the above-described fire extinguishing device.

[0172] Such a battery module may basically include a plurality of battery cells; and the fire extinguishing device disposed between the battery cells.

[0173] As long as the above-mentioned fire extinguishing device is applied, the specific configuration of the battery module, 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.

[0174] 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.

[0175] The present specification discloses composite materials and fire extinguishing devices that can be applied to products or devices that are in an abnormal state or have the potential for an abnormal state, and can effectively respond to such abnormal states. For example, the composite materials and the like can be applied to articles comprising multiple products or devices, and can respond to abnormal heat generation, explosion, and ignition occurring in one of the devices or products, and prevent or minimize the spread of such heat generation, explosion, and ignition to other adjacent devices or products. The composite materials and the like also exhibit excellent handling and storage stability. The present specification can also provide uses for the composite materials and the like.

[0176] Figure 1 is an exemplary cross-sectional view of a battery module to which a fire extinguishing device is applied.

[0177] Figure 2 is an exemplary drawing for explaining the operating principle of the digestive device.

[0178] Figure 3 is an exemplary drawing for explaining the operating principle of the digestive device.

[0179] Figure 4 is a drawing explaining the manufacturing of a fire extinguishing device in an embodiment.

[0180] Figure 5 is a drawing explaining the manufacturing of a fire extinguishing device in an embodiment.

[0181] The composite material and the like are specifically described with reference to the following examples, but the scope of the composite material and the like is not limited by the following examples.

[0182]

[0183] 1. Convection test

[0184] A fire extinguishing device is placed between two aluminum plates, and insulation is laminated on one of the two aluminum plates, thereby manufacturing a laminate in which the insulation, 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 is used, and as the insulation, mineral wool (KKC, insulating board No. 1) having a thickness of about 2 mm is used. Both sides of the laminate are fixed by pressing them with a jig at a pressure of about 350 kPa. A temperature sensor (k-type thermocouple, Fluke IR thermometers model 566) is placed on the insulation side of the laminate, and a flame is applied toward the aluminum plate on the opposite side, while the temperature is measured with the temperature sensor. The flame is applied at a distance of about 2 inches from the aluminum plate using two butane gas (220 g capacity can type butane gas (unused product)) and a torch. The temperature is measured with the temperature sensor while applying the above flame for about 5 minutes, and evaluated according to the following criteria.

[0185] <Evaluation Criteria>

[0186] Pass: The measured temperature of the temperature sensor remains below 200℃.

[0187] NG: A temperature exceeding 200℃ is measured by the temperature sensor, or melting of the aluminum plate is observed.

[0188]

[0189] 2. Chain ignition test

[0190] Square batteries are arranged side by side at intervals of approximately 3 mm, and a fire extinguishing device is placed between them. CATL's product (120 Ah, 3.2 V, size = thickness × width × depth = 48 × 174 × 165) is used as the square battery, and the test is applied in a 100% charged state. In the above arrangement, a battery ignition is induced in one square battery according to the SAE J2464:2009 standard, and whether a chain ignition occurs in other cells is checked. The battery ignition is 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).

[0191] <Evaluation Criteria>

[0192] Pass: If no ignition occurs in any battery cell other than the one through which the nail was pierced.

[0193] NG: If a fire occurs in a battery cell other than the one penetrated by the nail.

[0194]

[0195] 3. Storage stability evaluation

[0196] 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.

[0197]

[0198] 4. Thermal Cycle Test

[0199] A simple module is fabricated by connecting eight square batteries in parallel and positioning a fire extinguishing device between each battery. The simple module is subjected to a thermal cycle test according to UL 1642 and evaluated according to the following criteria.

[0200] <Evaluation Criteria>

[0201] Pass: When there is no excessive capacity loss, voltage drop, or appearance change (such as Li precipitation) in the battery after the thermal cycle test, and the capacity between the batteries is measured uniformly.

[0202] NG: If one or more batteries exhibit excessive capacity degradation, voltage drop, and / or appearance changes (e.g., Li precipitation) after the Thermal Cycle test, or if the capacity is measured unevenly between batteries.

[0203]

[0204] 5. Molecular weight measurement

[0205] The molecular weight of starch is evaluated in the following manner.

[0206] (1) Preparation of mobile phase

[0207] 1000 mL of 150 mM NaNO3 aqueous solution containing 0.02 wt% NaN3 is filtered using a solvent clarification system (Millipore Millisolve Kit, MilliporeSigma) to prepare mobile phase A.

[0208] (2) Preparation of sample solution

[0209] Take 25 mg of a sample whose molecular weight you wish to measure, mix with 5 mL of a 150 mM NaNO3 aqueous solution containing 0.02 wt% NaN3, heat at 80°C for 20 hours, and then filter with a 0.4 μm Nylon Syringe Filter to prepare a sample solution.

[0210] (3) GPC (Gel Permeation Chromatography) / MALS (Multi-Anglue Light Scattering Detection) conditions

[0211] The molecular weight is evaluated using the above sample solution and mobile phase A in the following manner.

[0212] Measuring instrument: Agilent GPC (Agilent 1200 series, US)

[0213] Stationary phase: Shodex OH-Pak 804 column and Shodex OH-Pak 80 column connection

[0214] Mobile phase: A; 0.02% NaN3, 150 mM NaNO3 aqueous solution = 100 (v / v %)

[0215] Flow rate: 0.4 mL / min

[0216] Stationary temperature: 25℃

[0217] Injection volume: 100 μl (0.45 μm filtered)

[0218] Analysis time: 120 minutes

[0219]

[0220] 6. Measurement of amylopectin and amylose content

[0221] The amylopectin and amylose contents of starch are evaluated according to the method described in the paper (Potato Research 31 (1988) 241-246). First, a sample (about 5 mg of starch) is dissolved in about 1 mL of sterile water to prepare a sample (step 1), and then heated in a water bath at 95°C for about 15 minutes (step 2).

[0222] Next, about 20 μl of the above sample is placed in a cuvette (step 3), and about 980 μl of iodine solution is added and mixed (step 4).

[0223] Next, the absorbance of the sample mixed with the above iodine solution at wavelengths of 525 nm and 700 nm is measured and recorded respectively (Step 5). The absorbance is measured using the OPTIZEN POP model from KLAB.

[0224] Add approximately 20 μl of water to another cuvette, add 980 μl of iodine solution, and mix (Step 6). Measure the absorbance at wavelengths of 525 nm and 700 nm for the solution in Step 6 in the same manner as in Step 5, and record each (Step 7).

[0225] The absorbance obtained in step 7 is subtracted from the absorbance obtained in step 5, and the percentage of amylose (%) is determined according to the following formula C (step 8).

[0226] [Formula C]

[0227] PA = 3.039 - U / L - 19.192

[0228] In formula C, PA is the proportion (%) of amylose, U is determined by formula D below, and L is determined by formula E below.

[0229] [Formula D]

[0230] U = 7.154 × OD 700 / OD 525

[0231] [Formula E]

[0232] L = 3.048 × OD 700 / OD 525

[0233] OD in formulas D and E 700 is the value obtained by subtracting the absorbance at a wavelength of 700 nm measured in step 7 from the absorbance at a wavelength of 700 nm measured in step 5 above, and OD 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.

[0234]

[0235] 7. WVTR (Water Vapor Transmission Rate) Evaluation

[0236] The WVTR of the case (outer shell) of the fire extinguishing device is evaluated according to the standard of ASTM F1249 under the conditions of 38℃ and 100% relative humidity.

[0237]

[0238] 8. Solubility Evaluation

[0239] Solubility is evaluated based on ASTM E1148-02. The amount of sample that can be dissolved to the maximum extent in 100 g of water at the measurement temperature (0°C or room temperature (approximately 25°C)) is evaluated according to the above standard to determine solubility.

[0240]

[0241] 9. Thermal conductivity evaluation

[0242] Thermal conductivity is evaluated using Hot Disk's TPS2200 equipment according to the ISO22007-2 standard.

[0243]

[0244] 10. Hardness assessment

[0245] Hardness is measured by placing the sample on an aluminum dish according to ASTM D 2240. The sample is a composite manufactured in an example or comparative example (a silicone foam pad in the case of Comparative Example 3), and the composite is cut to have a width, length, and thickness of 9 cm, 12 cm, and 3 mm, respectively. Hardness is measured using an ASKER durometer hardness device according to the above standard, and the initial hardness is measured by applying a load of 1 kg or more (approximately 1.5 kg) to the surface of a flat sample, and the hardness is evaluated by checking the stabilized measurement value after 15 seconds.

[0246] The hardness (room temperature hardness) of the sample was evaluated in the above manner at room temperature (approximately 25°C), and after evaluation, the sample was stored in a freezer at -20°C for approximately 24 hours and then taken out and the hardness (low temperature hardness) was evaluated in the same manner.

[0247] The hardness ratio was calculated by dividing the low-temperature hardness by the room-temperature hardness.

[0248]

[0249] Example 1.

[0250] Manufacturing of composite materials

[0251] A mixture was prepared by mixing distilled water, liquid sodium silicate, aqueous hydrochloric acid solution (hydrochloric acid concentration: approximately 33 wt%), monobasic ammonium phosphate (NH4H2PO4), potassium acetate, and starch, and a silica sol was prepared. As the starch, corn starch having a weight average molecular weight of approximately 51,000,000 g / mol and a weight ratio of amylose to amylopectin (amylose: amylopectin) of approximately 25:75 was used. As the liquid sodium silicate, No. 1 from Youngil Chemical Co., Ltd. was used. 3(KS)(No. 3 KS)(Na2O content: about 9 to 10 wt%, SiO2 content: about 28 to 30 wt%, sodium silicate molar ratio (= 1.032 (SiO2 weight) / (Na2O weight)): about 3.1 to 3.3) was used. The solubility of monoammonium phosphate (N)(NH4H2PO4) in water at 25°C is about 29 g. The solubility of potassium acetate 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.

[0252] The above mixing was performed so that the weight ratio (W:S:H:N:K:T) of distilled water (W), liquid sodium silicate (SiO2 (S), aqueous hydrochloric acid solution (H), monobasic ammonium phosphate (N), potassium acetate (K), and starch (T) was approximately 64:2:2.56:4.5:25:0.7. The pH of the mixture was approximately 5 to 6.

[0253] The molal concentration of hydrochloric acid based on distilled water in the mixture was approximately 0.37, the molal concentration of potassium acetate was approximately 3.88, and the molal concentration of ammonium phosphate monobasic was approximately 0.6. In addition, in the mixture, the △T of the following equation 1 by the hydrochloric acid f was approximately 1.39, and the △T of the following equation 1 by the potassium acetate f was about 14.43, and the △T of the following formula 1 by the first ammonium phosphate f was about 2.22.

[0254] [Formula 1]

[0255] △T f = K f × M × I

[0256] K in Equation 1 f is the freezing point depression constant of distilled water, which is approximately 1.86 K / m, M is the molal concentration of each ionic compound based on distilled water, and I is the number of moles of ions generated when 1 mole of the ionic compound is completely dissociated.

[0257] Silica sol was prepared by stirring the above mixture at room temperature (about 23°C) at a speed of about 500 rpm for about 15 minutes.

[0258] Glass wool (Shenzhen Sailong Fiberglass Co., Ltd.) (thickness: approximately 3 mm) was placed on the conveyor belt of a gel casting equipment, and the silica sol was impregnated into the glass wool using a spike roller. Then, while moving the conveyor belt, additional gelation was performed at room temperature (approximately 25°C) to form a silica gel, thereby manufacturing a composite.

[0259] When manufacturing the above composite material, the ratio G:W of the weight (G) of the silica sol and the weight (W) of the glass wool was set to be approximately 100:15.

[0260] The above glass wool has a tensile strength of about 0.1 MPa, a compressive strength of about 150 kPa, a Young's modulus of about 3 MPa, and a density of about 0.13 g / cm. 3 It was a degree. The above tensile strength, compressive strength and Young's modulus can be measured according to the KS K ISO 9073-3 standard. The glass wool is cut to have a width of about 50 mm and a length of about 200 mm, mounted on a UTM (Universal Testing Machine), and the glass wool is pulled in the longitudinal direction at a speed of about 100 mm / min to obtain a stress-strain curve, and the tensile strength, compressive strength and Young's modulus can be measured based on this curve.

[0261]

[0262] Manufacturing of digestive devices

[0263] The composite material was placed inside an aluminum can (case) used in the manufacture of square batteries, and the opening was sealed to manufacture a fire extinguishing device. The aluminum can is made of an aluminum alloy, and the WVTR of the case is about 0 g / m 2·It was about day. As shown in Fig. 4, a laminate of a thermally conductive layer (2001), the composite (300), and the thermally conductive layer (2002) was inserted into the inside of the aluminum can (1001), and a lid (1002) was covered to manufacture a fire extinguishing device. In cases where the composite does not maintain a sheet shape, a method of inserting thermally conductive layers (2001, 2002) into the inside of the can (1001) and placing the composite between them, as shown in Fig. 5, can also be applied. As the thermally conductive layers (2001, 2002), a copper film (thickness of about 15 μm) having a thermal conductivity of about 401 W / m·K was used. As the square battery case, a case having a width of about 9 cm, a length of about 12 cm, and a thickness of about 3 mm was used.

[0264]

[0265] Example 2.

[0266] A mixture was prepared by mixing distilled water, liquid sodium silicate, aqueous hydrochloric acid solution (hydrochloric acid concentration: about 33 wt%), aqueous NaOH solution (NaOH concentration: about 33 wt%), monobasic ammonium phosphate, ammonium sulfate, and starch, and a silica sol was prepared in the same manner as in Example 1. The starch, liquid sodium silicate, and monobasic ammonium phosphate were the same materials as in Example 1. The solubility of the ammonium sulfate in 100 g of water at 0°C is about 70.6 g, and the solubility in 100 g of water at 25°C is about 76 g.

[0267] The above mixing was performed so that the weight ratio (W:S:H:B:N:C:T) of the distilled water (W), liquid sodium silicate (SiO2 (S), aqueous hydrochloric acid solution (H), aqueous NaOH solution (B), monobasic ammonium phosphate (N), ammonium sulfate (C), and starch (T) was approximately 64:2:0.91:0.09:4.5:16:0.7.

[0268] The pH of the above mixture was about 6 to 8.

[0269] In the above mixture, the molal concentration of the hydrochloric acid based on distilled water was about 0.01, the molal concentration of NaOH was about 0.01, the molal concentration of ammonium phosphate was about 0.61, and the molal concentration of ammonium sulfate was about 1.87. In addition, in the above mixture, the △T of the above equation 1 by the hydrochloric acid f was about 0.5, and the △T of the above equation 1 by the above NaOH f was about 0.04, and the △T of the above formula 1 by the first ammonium phosphate f was approximately 2.25, and the △T of the above formula 1 by the ammonium sulfate f It was around 10.45.

[0270] A composite was prepared in the same manner as in Example 1 using the above silica sol.

[0271] Next, a fire extinguishing device was manufactured using the above composite material in the same manner as in Example 1. As a heat-conducting layer, a film (approximately 100 μm thick) made of aluminum with a thermal conductivity of approximately 235 W / m·K was used.

[0272]

[0273] Comparative Example 1.

[0274] A mixture was prepared by mixing distilled water, liquid sodium silicate, aqueous hydrochloric acid solution (hydrochloric acid concentration: about 33 wt%), monobasic ammonium phosphate (NH4H2PO4), potassium acetate, and starch, and a silica sol was prepared in the same manner as in Example 1. The starch, liquid sodium silicate, and monobasic ammonium phosphate (N)(NH4H2PO4) were the same materials as in Example 1.

[0275] The above mixing was performed so that the weight ratio (W:S:H:N:K:T) of the distilled water (W), the liquid sodium silicate (SiO2 (S), the hydrochloric acid solution (H), the monobasic ammonium phosphate (N), the potassium acetate (K), and the starch (T) was approximately 88:2:3.52:4.5:4:0.7. The pH of the mixture was approximately 5 to 6.

[0276] In the above mixture, the molal concentration of the hydrochloric acid based on distilled water was about 0.37, the molal concentration of potassium acetate was about 0.45, and the molal concentration of ammonium phosphate monobasic was about 0.43. In addition, in the above mixture, the △T of the above equation 1 by the hydrochloric acid f was approximately 1.39, and the △T of the above formula 1 by the potassium acetate f was approximately 1.68, and the △T of the above formula 1 by the first ammonium phosphate f was about 1.61.

[0277] A composite material and a fire extinguishing device were manufactured using the above silica sol in the same manner as in Example 1. As a thermally conductive layer, a copper film (thickness of about 300 μm) having a thermal conductivity of about 401 W / m·K was used.

[0278]

[0279] Comparative Example 2.

[0280] A mixture was prepared by mixing distilled water, liquid sodium silicate, and aqueous hydrochloric acid (hydrochloric acid concentration: approximately 33 wt%), and a silica sol was prepared in the same manner as in Example 1. The liquid sodium silicate was the same material as in Example 1.

[0281] The above mixing was performed so that the weight ratio (W:S:H) of the distilled water (W), the liquid sodium silicate (SiO2 (S)) and the hydrochloric acid aqueous solution (H) was approximately 9:1:0.36. The pH of the mixture was approximately 5 to 6.

[0282] The molal concentration of the hydrochloric acid based on distilled water in the above mixture was approximately 0.37. In addition, the △T of the above equation 1 by the hydrochloric acid in the above mixture f was about 1.39.

[0283] A composite material and a fire extinguishing device were prepared using the above silica sol in the same manner as in Example 1.

[0284]

[0285] Comparative Example 3.

[0286] A fire extinguishing device was manufactured in the same manner as in Example 1, except that a silica foam pad (L2Y) was used instead of the composite.

[0287]

[0288] The evaluation results for the above digestive device are shown in Table 1 below.

[0289] Example Comparative Example 12123 Room temperature hardness 656261605 Low temperature hardness 67.764.688.4875.2 Hardness ratio 0.960.960.690.690.96 Thermal Cycle PassPassNGNGPass Convection PassPassPassNGNG Chain ignition test PassPassPassNGNG Storage stability PassPassPassPassPassPass

[0290]

[0291] In Table 1, the room temperature and low temperature hardness are Shore A hardness.

[0292] From Table 1, it can be confirmed that the composite material of the example containing an inorganic gel and inorganic fibers and exhibiting the desired hardness characteristics (low hardness increase ratio at low temperatures) effectively secures the desired performance. On the other hand, Comparative Examples 1 and 2 contain an inorganic gel and inorganic fibers, but the desired network was not formed during the polymerization process performed in an environment with a low proportion of ionic compounds, so the hardness characteristics were not properly secured, resulting in poor performance. Comparative Example 3 is a case where an inorganic gel and inorganic fibers are not included.

Claims

1. flammable substances; and Containing at least one selected from the group consisting of inorganic gels and inorganic fibers, A composite material having a ratio of hardness at 25°C to hardness at -20°C of 0.7 or greater.

2. A composite material in accordance with claim 1, wherein the hardness at 25°C is in the range of 20 to 150 in terms of Shore A hardness.

3. In paragraph 1, the volatile material is a composite material having a boiling point at 1 atm within a range of 80°C to 120°C.

4. In the first paragraph, the volatile material is a composite material that is water.

5. A composite material in which the content of the volatile material is in the range of 40 to 90 wt% in the first paragraph.

6. A composite material comprising 0.1 to 25 parts by weight of an inorganic gel relative to 100 parts by weight of a volatile material in the first paragraph.

7. A composite material comprising 5 to 70 parts by weight of inorganic fibers relative to 100 parts by weight of a volatile material in the first paragraph.

8. A composite material comprising an inorganic gel and an inorganic fiber in the first paragraph.

9. A composite material in which the inorganic gel is attached to the inorganic fibers in the 8th paragraph, or the inorganic gel and the inorganic fibers are entangled with each other.

10. A composite material further comprising an ionic compound according to claim 1.

11. In the 10th paragraph, △T of the following equation 1 f Composites with a 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 ionic compound relative to the volatile substance, and I is the number of moles of ions produced by dissociation of 1 mole of the ionic compound.

12. A composite material in which the solubility of the ionic compound in 100 g of water at 25°C is 10 or more in the 10th paragraph.

13. A composite material in accordance with claim 10, wherein the ionic compound is at least one selected from the group consisting of formate, acetate, carbonate, and sulfate.

14. A composite material further comprising a carbonizable organic material in the first paragraph.

15. A composite material further comprising a carbonization catalyst in accordance with claim 14.

16. Case; and A fire extinguishing device comprising a composite material according to any one of claims 1 to 15 present within the case.

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