Fire extinguishing material, and device having fire extinguishing function

Abstract

This fire extinguishing material comprises a sheet including a fire extinguishing agent layer, and a packaging material that houses the sheet, wherein: the fire extinguishing agent layer includes a binder resin, and a fire extinguishing agent containing at least one salt among an organic salt and an inorganic salt that have deliquescent properties; the packaging material has a laminated structure including an aluminum foil and an insulating layer; the aluminum foil is disposed between the sheet and the insulating layer; and the melting temperature of the insulating layer is 150 °C to 500 °C.

Description

Fire extinguishing materials and devices with fire extinguishing functions

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to fire extinguishing materials and devices having fire extinguishing capabilities.

[0002] Patent Document 1 discloses a fire extinguishing body obtained by mixing a fire extinguishing composition that generates an aerosol upon combustion with a binder and molding the mixture into a sheet. Patent Document 2 discloses a fire extinguishing film that can be easily installed in areas where there is a risk of fire and that is highly effective in extinguishing a fire in the early stages of an outbreak. The fire extinguishing film 40 shown in Figure 6 of Patent Document 2 includes a fire extinguishing agent-containing layer 1 and surface layers 6a and 6b arranged to sandwich the fire extinguishing agent-containing layer 1. Paragraph

[0040] of Patent Document 2 discloses that, for example, a resin substrate can be used for the surface layers 6a and 6b.

[0003] International Publication No. 2018 / 047762 Japanese Patent Application Laid-Open No. 2021-137345

[0004] However, when a fire-extinguishing material including a fire-extinguishing agent layer is placed in a high-temperature, high-humidity environment, the performance of the fire-extinguishing agent may be reduced due to the intrusion of moisture. Therefore, as shown in Fig. 6 of Patent Document 2, it is conceivable to suppress the performance reduction of the fire-extinguishing agent by sandwiching the fire-extinguishing agent layer between a pair of resin substrates for protection. According to the studies of the present inventors, a fire-extinguishing film having such a configuration still has room for improvement in terms of the effect of suppressing the performance reduction of the fire-extinguishing agent due to the intrusion of moisture.

[0005] The present inventors have investigated the protection of the fire extinguishing agent layer with a packaging material using aluminum foil as a gas barrier layer to prevent the performance of the fire extinguishing agent from deteriorating. However, when the object to be extinguished that may catch fire is an electrical device or the like, a new problem of concern arises in that the fire extinguishing material may cause a short circuit in the electrical circuit. Although the possibility of such a short circuit occurring is considered extremely low, a short circuit can cause equipment failure or a fire, and therefore the present inventors have further investigated means for solving the above problem.

[0006] The present disclosure has been made in consideration of the above circumstances and provides a fire extinguishing material that uses aluminum foil, which has excellent gas barrier properties, as part of a packaging material and can solve problems caused by the conductivity of the aluminum foil. The present disclosure also provides a device having a fire extinguishing function and that includes the fire extinguishing material.

[0007] [1] A fire extinguishing material comprising: a sheet including a fire extinguishing agent layer; and a packaging material containing the sheet, wherein the fire extinguishing agent layer includes a binder resin and a fire extinguishing agent including at least one salt selected from a deliquescent organic salt and an inorganic salt, the packaging material has a laminated structure including aluminum foil and an insulating layer, the aluminum foil is disposed between the sheet and the insulating layer, and the melting temperature of the insulating layer is 150°C to 500°C. [2] A fire extinguishing material comprising: a sheet including a fire extinguishing agent layer; １５ The fire extinguishing material according to [1], wherein the insulating layer has a thermal conductivity of 0.1 W / (m K) or more. [3] The fire extinguishing material according to [1] or [2], wherein the insulating layer has a thermal conductivity of 0.1 W / (m K) or more. [4] The fire extinguishing material according to any one of [1] to [3], wherein the insulating layer contains at least one resin selected from the group consisting of polyethylene terephthalate resin, nylon resin, polyvinyl chloride resin, and polypropylene resin. [5] The fire extinguishing material according to any one of [1] to [4], wherein the sheet further comprises a substrate. [6] The fire extinguishing material according to any one of [1] to [5], wherein the aluminum foil has a thickness of 15 μm or less. [7] The fire extinguishing material according to any one of [1] to [6], wherein the aluminum foil has a thickness of 3 μm or more. [8] The fire extinguishing material according to any one of [1] to [7], wherein the aluminum foil has a puncture strength of 10 N or less. [9] The fire extinguishing material according to any one of [1] to [8], wherein the aluminum foil has a tensile breaking strength of 25 N or less.

[10] The fire extinguishing material according to any one of [1] to [9], further comprising a sealant layer between the sheet and the aluminum foil.

[11] The fire extinguishing material according to

[10] , wherein the peripheral portion is formed by a sealing portion formed by the sealant layer.

[12] A device having a fire extinguishing function, comprising: at least one object to be extinguished that may catch fire selected from the group consisting of electrical equipment, a distribution board, a panel board, and a battery; and the fire extinguishing material according to any one of [1] to

[11] .

[0008] According to the present disclosure, there is provided a fire extinguishing material that uses aluminum foil having excellent gas barrier properties as a part of a packaging material, and that can solve problems caused by the conductivity of the aluminum foil. Also, according to the present disclosure, there is provided a device having a fire extinguishing function that includes the fire extinguishing material.

[0009] FIG. 1 is a plan view schematically showing a fire extinguishing material according to one embodiment of the present disclosure. FIG. 2 is a schematic cross-sectional view of the fire extinguishing material shown in FIG. 1 taken along line II-II. FIG. 3 is a perspective view schematically showing one embodiment of a device having a fire extinguishing function according to the present disclosure. FIG. 4 is a schematic cross-sectional view of a fire extinguishing material according to another embodiment. FIG. 5 is a schematic cross-sectional view of a fire extinguishing material according to another embodiment. FIG. 6 is a schematic cross-sectional view of a fire extinguishing material according to another embodiment. FIG. 7 is a schematic cross-sectional view of a fire extinguishing material according to another embodiment. FIGS. 8(a) and 8(b) are cross-sectional views schematically showing steps for manufacturing the fire extinguishing material shown in FIG. 7.

[0010] Hereinafter, embodiments of the present disclosure will be described in detail, with reference to the drawings as needed. However, the present invention is not limited to the following embodiments.

[0011] <Fire Extinguishing Material> FIG. 1 is a plan view schematically illustrating a fire extinguishing material according to this embodiment, and FIG. 2 is a schematic cross-sectional view of the fire extinguishing material 100A shown in FIG. 1 taken along line II-II. As shown in FIG. 1, the fire extinguishing material 100A includes a main surface 100f and a peripheral edge portion 100a. As shown in FIG. 2, the fire extinguishing material 100A includes a sheet 10 and a packaging material 20 that houses the sheet 10. The sheet 10 has a laminated structure including a substrate 11 and a fire extinguishing agent layer 12. The packaging material 20 has a laminated structure including, in this order, a sealant layer 21a, an adhesive layer 22a, an aluminum foil 23, an adhesive layer 22b, and an insulating layer 24. The melting temperature of the insulating layer 24 is 150 to 500°C. The peripheral edge portion 100a of the fire extinguishing material 100A is formed by a sealed portion 21 formed by the sealant layers 21a of a pair of packaging materials 20 (see FIG. 2).

[0012] The fire extinguishing material 100A can suppress performance degradation of the fire extinguishing agent contained in the fire extinguishing agent layer 12 and also suppress short circuits with the fire extinguishing object. The inventors speculate as follows about the reason for this effect. Specifically, in the fire extinguishing material 100A, the sheet 10 is contained in a packaging material 20 containing aluminum foil 23. This suppresses deliquescence of the fire extinguishing material due to moisture from the external environment, suppressing performance degradation of the fire extinguishing material 100A. Furthermore, generally, when a packaging material contains aluminum foil, a short circuit may occur between the fire extinguishing material and the fire extinguishing object. In the fire extinguishing material 100A, the packaging material 20 includes an insulating layer 24, and the melting temperature of the insulating layer 24 is 150 to 500°C. By having the melting temperature of the insulating layer 24 be 150°C or higher, even if the fire extinguishing object experiences thermal runaway to a degree that does not result in ignition, the insulating layer can be prevented from melting and the aluminum foil 23 can be prevented from being exposed to the outermost surface of the fire extinguishing material 100A. This sufficiently suppresses the occurrence of short circuits. Furthermore, since the melting temperature of the insulating layer 24 is 500°C or less, the insulating layer 24 is less likely to obstruct the ejection of the aerosol-like fire extinguishing agent in the event of a fire. As a result, the fire extinguishing material 100A can suppress a decrease in the performance of the fire extinguishing agent and also suppress short circuits with the object to be extinguished, thereby achieving excellent fire extinguishing performance. Each component of the fire extinguishing material 100A will be described below.

[0013] (Substrate) The sheet 10 includes a substrate 11. This further improves the stability of the fire extinguishing agent and also tends to improve the rigidity of the fire extinguishing material 100A. Considering that the temperature of a flame is generally about 700°C to 900°C, the substrate 11 is preferably a resin substrate. Examples of materials for the substrate 11 include polyolefin resins (LLDPE, PP, COP, CPP, etc.), polyester resins (PET, etc.), fluororesins (PTFE, ETFE, EFEP, PFA, FEP, PCTFE, etc.), PVC resins, PVA resins, acrylic resins, epoxy resins, polyamide resins, and polyimide resins. These resins can be perforated by heat. The substrate 11 may contain a fire extinguishing agent. From the viewpoint of adjusting the water vapor permeability, the substrate 11 may be provided with a vapor deposition layer (alumina vapor deposition layer and / or silica vapor deposition layer) having water vapor barrier properties.

[0014] The thickness of the substrate 11 can be appropriately selected depending on the amount of heat at the time of fire outbreak, impact, allowable space, etc. The thickness of the substrate 11 may be 5 μm or more, or may be 10 μm or more. The thickness of the substrate 11 may be 100 μm or less, or may be 30 μm or less.

[0015] (Fire-extinguishing agent layer) The fire-extinguishing agent layer 12 is formed by molding a composition containing a fire-extinguishing agent and a binder resin. The use of the binder resin makes it easier to maintain the properties of the fire-extinguishing agent, thereby reducing the frequency of replacing the fire-extinguishing material. The composition may further contain a liquid medium in addition to the resin and binder resin.

[0016] The fire extinguishing agent contains at least one of a deliquescent organic salt and an inorganic salt. The organic salt and the inorganic salt may be used alone or in combination of two or more.

[0017] Examples of organic salts include potassium salts, sodium salts, and ammonium salts. Potassium salts can be used as the organic salt. Examples of organic potassium salts include potassium carboxylates such as potassium acetate, potassium citrate (monopotassium citrate, dipotassium citrate, tripotassium citrate), potassium tartrate, potassium lactate, potassium oxalate, and potassium maleate.

[0018] Examples of inorganic salts include potassium salts and sodium salts. Potassium salts can be used as the inorganic salt. Examples of inorganic potassium salts include potassium carbonate, potassium hydrogen carbonate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate.

[0019] As the organic salt and inorganic salt, tripotassium citrate is preferred. Tripotassium citrate has high fire extinguishing performance, but its high deliquescence can cause a decrease in performance. However, the fire extinguishing material 100A includes aluminum foil 23. Therefore, by using tripotassium citrate, the fire extinguishing material 100A tends to have even better fire extinguishing performance while suppressing the decrease in performance of the fire extinguishing agent.

[0020] The extinguishing agent may contain an oxidizing compound, such as a chlorate salt, such as potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, or magnesium chlorate, which can generate an aerosol from the potassium salts when exposed to the heat of a fire.

[0021] Thermoplastic resins and thermosetting resins can be used as the binder resin. Examples of the thermoplastic resin include polyolefin resins such as polypropylene resins, polyethylene resins, poly(1-)butene resins, and polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene resins, methyl methacrylate-butadiene-styrene resins, ethylene-vinyl acetate resins, ethylene-propylene resins, polycarbonate resins, polyphenylene ether resins, acrylic resins, polyamide resins, polyvinyl chloride resins, polyvinyl alcohol (PVA) resins, and polyvinyl butyral (PVB) resins. Examples of thermosetting resins include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-polybutadiene rubber (1,2-BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber (IIR), ethylene-propylene rubber (EPR, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), multi-vulcanized rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), urethane rubber (U), polyurethane resin, phenolic resin, epoxy resin, polyvinyl ether (PMVE)-maleic anhydride resin, etc. The binder resin may contain a curing agent component.

[0022] The fire extinguishing agent layer 12 may contain a colorant, an antioxidant, a flame retardant, an inorganic filler, etc., and from the viewpoint of property stability, may contain additives such as a surfactant, a silane coupling agent, an antiblocking agent, etc. These components can be appropriately selected depending on the composition of the fire extinguishing agent layer 12 and the type of binder resin.

[0023] The extinguishing agent content of the extinguishing agent layer 12 (based on the total mass of the extinguishing agent layer 12) can be 70 to 97 mass%, alternatively 80 to 95 mass%, or alternatively 85 to 92 mass%. When the extinguishing agent content is 70 mass% or more, excellent fire extinguishing performance is easily achieved, while when it is 97 mass% or less, excellent formability is easily achieved.

[0024] The thickness of the fire extinguishing agent layer 12 can be appropriately set depending on the amount of fire extinguishing agent to be blended. The thickness of the fire extinguishing agent layer 12 can be, for example, 1 mm or less, and may be 30 to 1000 μm, 100 to 500 μm, or 150 to 500 μm.

[0025] Examples of the liquid medium include organic solvents. Examples of the organic solvent include water-soluble solvents, such as alcohols such as methanol, ethanol, isopropyl alcohol, and n-propyl alcohol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and diethylene glycol; and glycol ethers such as N-methylpyrrolidone (NMP), tetrahydrofuran, and butyl cellosolve. In view of the deliquescent properties of the fire extinguishing agent, the liquid medium may be an alcohol-based solvent, specifically isopropyl alcohol.

[0026] The amount of the liquid medium in the composition used to form the fire-extinguishing agent layer may be adjusted appropriately depending on the method of use of the composition, but may be 40 to 95 mass % based on the total amount of the composition. When the composition contains a sufficient amount of the liquid medium, this composition may also be referred to as a coating liquid.

[0027] (Sealant Layer) The sealant layer 21a is used to seal the sheet 10. The sealant layer 21a is made of, for example, a resin material having heat melting properties (thermal adhesive properties). Examples of resin materials having heat melting properties include polyolefin-based resins. That is, the sealant layer 21a may contain a polyolefin-based resin. Examples of polyolefin-based resins include polyolefin-based resins such as low-density polyethylene resin (LDPE), linear low-density polyethylene resin (LLDPE), medium-density polyethylene resin (MDPE), and unstretched polypropylene resin (CPP); polyethylene-based resins such as ethylene-vinyl acetate copolymer and ethylene-α-olefin copolymer; and polypropylene-based resins such as propylene-ethylene random copolymer, propylene-ethylene block copolymer, and propylene-α-olefin copolymer. Among these, the polyolefin resin may include low-density polyethylene resin (LDPE), linear low-density polyethylene resin (LLDPE), or unstretched polypropylene resin (CPP), from the viewpoint of excellent heat-sealing properties, low water vapor permeability, and ease of suppressing deterioration of the fire extinguishing agent.

[0028] The sealant layer 21a is preferably made of a resin material having a melting temperature of 70°C or higher. As shown in FIG. 2, the end surface 100b of the fire extinguishing material 100A is not covered with the aluminum foil 23, and the sealant layer 21a is exposed. If the sealant layer 21a constituting the peripheral edge portion 100a melts or tears before the aluminum foil 23 on the main surface 100f breaks, the extinguishing agent may leak laterally from the end surface 100b. A fire extinguishing material in which the aluminum foil 23 on the main surface 100f is likely to break first has the advantage of achieving a higher probability of initial fire extinguishing compared to a fire extinguishing material in which the peripheral edge portion 100a is likely to break first. For this reason, the melting temperature of the resin constituting the sealant layer 21a is preferably as high as possible, more preferably 75°C or higher, and even more preferably 95°C or higher.

[0029] (Adhesive Layer) Examples of adhesives that constitute the adhesive layers 22a and 22b include acrylic adhesives, epoxy adhesives, silicone adhesives, polyolefin adhesives, urethane adhesives, polyvinyl ether adhesives, and synthetic adhesives thereof. Of these, urethane synthetic adhesives are preferred for use as the adhesive from the viewpoint of achieving both good adhesion and low cost. The thickness of the adhesive layers 22a and 22b is, for example, 1 to 100 μm. Depending on the material that constitutes the adhesive layers 22a and 22b, the thickness may be 1 to 30 μm or 30 to 100 μm.

[0030] (Aluminum foil) The thickness of the aluminum foil 23 is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 8 μm or less. When the thickness of the aluminum foil 23 is 15 μm or less, when the fire extinguishing material 100A exhibits its fire extinguishing performance, the main surface 100f of the fire extinguishing material 100A is torn, and the extinguishing agent is easily ejected from there toward the flame. Compared to fire extinguishing materials in which the aluminum foil is too thick and the main surface 100f is difficult to tear, and the peripheral portion is easily torn first, initial fire extinguishing can be achieved with a high probability. On the other hand, the thickness of the aluminum foil 23 is preferably 3 μm or more, more preferably 5 μm or more. When the thickness of the aluminum foil 23 is 3 μm or more, excellent gas barrier properties can be achieved and the deterioration of the performance of the fire extinguishing agent tends to be further suppressed.

[0031] The puncture strength of the aluminum foil 23 is preferably 10 N or less, more preferably 5 N or less. When the puncture strength of the aluminum foil 23 is 10 N or less, when the fire extinguishing material 100A exerts its fire extinguishing performance, the main surface 100 f of the fire extinguishing material 100A is torn, and the extinguishing agent is easily ejected from there toward the flame. On the other hand, the puncture strength of the aluminum foil 23 is preferably 0.5 N or more, more preferably 1 N or more. When the puncture strength of the aluminum foil 23 is 0.5 N or more, the occurrence of pinholes can be suppressed, and there is a tendency that the deterioration of the performance of the fire extinguishing agent can be further suppressed.

[0032] The tensile breaking strength of the aluminum foil 23 is preferably 25N or less, more preferably 20N or less. When the tensile breaking strength of the aluminum foil 23 is 25N or less, when the fire extinguishing material 100A exerts its fire extinguishing performance, the main surface 100f of the fire extinguishing material 100A is broken, and the extinguishing agent is easily ejected from there toward the flame. On the other hand, the tensile breaking strength of the aluminum foil 23 is preferably 8N or more, more preferably 12N or more. When the tensile breaking strength of the aluminum foil 23 is 8N or more, the occurrence of pinholes can be suppressed, and there is a tendency that the deterioration of the performance of the fire extinguishing agent can be further suppressed.

[0033] Because the sheet 10 is covered with aluminum foil 23, which has excellent thermal conductivity, even if the fire source is some distance away from the fire extinguishing material 100A, the entire fire extinguishing material 100A is heated in a relatively short time, and the packaging material 20 is easily broken by the thermal expansion of the fire extinguishing agent layer 12, thereby easily exhibiting fire extinguishing performance. In addition, because the sheet 10 is covered with aluminum foil 23, which has excellent gas barrier properties, it is possible to prevent moisture from penetrating the inside of the fire extinguishing material 100A, which would otherwise cause a decrease in the performance of the fire extinguishing agent.

[0034] (Insulating Layer) As shown in FIG. 2, the insulating layer 24 constitutes the outermost layer of the fire extinguishing material 100A. The insulating layer 24 may be made of a resin. Examples of resins include polypropylene resin (PP), polyester resin (polyethylene terephthalate (PET) or the like), nylon resin, fluororesin (ethylene tetrafluoroethylene (ETFE) or the like), and polyvinyl chloride resin (PVC). The material of the insulating layer 24 is preferably polypropylene resin, polyester resin, nylon resin, or polyvinyl chloride resin. When the insulating layer 24 is made of these materials, the fire extinguishing material 100A tends to have even better fire extinguishing performance.

[0035] The resin content in the insulating layer 24 may be 80% by mass or more, 90% by mass or more, or 95% by mass or more, based on the total amount of the insulating layer 24, or may be 100% by mass.

[0036] The thickness of the insulating layer 24 is preferably 4 μm or more from the viewpoint of abrasion resistance and mechanical strength retention, and is preferably 50 μm or less from the viewpoint of excellent flexibility and enabling the fire extinguishing material to be installed in a narrow space.

[0037] The melting temperature of the insulating layer 24 is 150°C or higher, and preferably 220°C or higher. When the melting temperature is within the above range, short circuits with the object to be extinguished tend to be further suppressed. The melting temperature of the insulating layer 24 is 500°C or lower, and preferably 400°C or lower. When the melting temperature is within the above range, the fire extinguishing material 100A tends to have even better fire extinguishing performance. The melting temperature is measured by analyzing the endothermic peak by differential scanning calorimetry.

[0038] The volume resistivity of the insulating layer 24 is 10 １５ It is preferable that the resistance is Ω·cm or more, and 10 １９ It is more preferable that the volume resistivity is Ω·cm or more. When the volume resistivity is in this range, there is a tendency that short circuits between the fire extinguishing material and the object to be extinguished can be further suppressed. The volume resistivity is measured in accordance with JIS C2139-3.

[0039] The thermal conductivity of the insulating layer 24 is preferably 0.1 W / (m·K) or more, and more preferably 0.3 W / (m·K) or more. When the thermal conductivity is in this range, heat is easily transferred to the fire-extinguishing agent layer. Therefore, the fire-extinguishing material 100A tends to have even better fire-extinguishing performance. The thermal conductivity is measured in accordance with ASTM C177.

[0040] <Method of Manufacturing Fire Extinguishing Material> A method of manufacturing the fire extinguishing material 100A will be described. The fire extinguishing material 100A can be manufactured, for example, by a roll-to-roll method as follows. That is, a roll (not shown) on which the substrate 11 is wound into a roll is prepared. A coating liquid is applied to a predetermined area on the surface of the substrate 11 supplied from this roll, and the coating liquid is dried to form the fire extinguishing agent layer 12. The application can be performed by a wet coating method. Examples of wet coating methods include gravure coating, comma coating, spray coating, dip coating, curtain coating, spin coating, sponge roll coating, die coating, and brush painting. Through this process, a sheet 10 including the substrate 11 and the fire extinguishing agent layer 12 is obtained.

[0041] On the other hand, two rolls (not shown) each having the packaging material 20 wound into a roll are prepared. The sheet 10 is placed between the packaging material 20 provided from the two rolls. The packaging material 20 is heat-pressed and cut out to obtain the fire extinguishing material 100A.

[0042] <Device with Fire Extinguishing Function> The device with fire extinguishing function includes a fire-extinguishing target that may catch fire and a fire extinguishing material. Examples of the fire-extinguishing target include electrical equipment, a distribution board, a power distribution panel, and a battery (e.g., a lithium-ion battery). In the device according to this embodiment, the fire extinguishing material may be disposed so as to face the fire-extinguishing target. The distance between the fire extinguishing material and the fire-extinguishing target may be, for example, 0 mm or more or 1 mm or more, and may be 5 mm or less or 10 mm or less.

[0043] Fig. 3 is a perspective view that schematically shows one embodiment of a device having a fire extinguishing function. Fig. 3 shows a distribution board as an example of electrical equipment. Electrical equipment 200 mainly comprises a housing 201 that has a storage section 201a and an opening / closing door 201b that stores electrical equipment, and a breaker 203 and wiring 204 as electrical equipment. Some of the wiring 204 is housed together in a wiring cover 202. Electrical equipment 200 is provided with fire extinguishing material 100A in the following areas: - Area of ​​opening / closing door 201b facing the electrical equipment - Area on the top surface of storage section 201a facing the electrical equipment - Area on the bottom surface of wiring cover 202 facing the electrical equipment - Side of the back of storage section 201a facing the electrical equipment, i.e., area on the back side of the electrical equipment

[0044] The position where the fire extinguishing material 100A is disposed is not limited to the embodiment shown in FIG. 3, and the position can be adjusted appropriately depending on the location of electrical equipment or the like which is a location at risk of fire.

[0045] Although the embodiments of the present disclosure have been described in detail above, the present invention is not limited to the above embodiments. For example, in the above embodiments, the ends of the aluminum foil 23 are exposed from the end faces of the fire extinguishing material 100A, but the ends of the aluminum foil 23 may be covered with the insulating layer 24. In the fire extinguishing material 100B shown in Figure 4, the sealant layer 21a, the adhesive layer 22a, and the end faces of the aluminum foil 23 are covered with the insulating layer 24, and the entire fire extinguishing material 100B is covered with the insulating layer 24. In other words, the fire extinguishing material 100B has a configuration in which its internal structure is sealed with the insulating layer 24.

[0046] The fire extinguishing material according to the present disclosure may further include a sealant layer between the aluminum foil 23 and the insulating layer 24. In the fire extinguishing material 100C shown in Fig. 5, a sealant layer 21b is provided on the outer side of the aluminum foil 23, and an adhesive layer 22b and an insulating layer 24 are provided in this order on the outer side of the sealant layer 21b.

[0047] The fire extinguishing material according to the present disclosure may not include the sealant layer 21a and the adhesive layers 22a and 22b. In the fire extinguishing material 100D shown in FIG. 6, the aluminum foil 23 directly covers the sheet 10, and the insulating layer 24 is provided so as to be in direct contact with the outer surface of the aluminum foil 23. In this case, the insulating layer 24 can be formed by applying a composition containing an insulating resin to the aluminum foil 23 to form a coating film, and then drying the coating film. Furthermore, the sheet 10 can be sealed inside the aluminum foil 23 by welding the ends of the aluminum foil 23.

[0048] The fire extinguishing material according to the present disclosure does not need to include the adhesive layers 22a, 22b. A fire extinguishing material 100E shown in Fig. 7 includes a sheet 10 and a packaging material that houses the sheet 10, and the packaging material is composed of an insulating layer 24 constituting the outermost layer, an aluminum foil 23, and a sealant layer 21a. As shown in Fig. 7, the peripheral edge of the fire extinguishing material 100E is composed of a sealed portion 21 formed by the sealant layers 21a, 21a of a pair of packaging materials 20, 20.

[0049] The fire extinguishing material 100E shown in Fig. 7 can be manufactured by the roll-to-roll method as described above, as follows. That is, a roll (not shown) of the substrate 11 wound into a roll is prepared. A fire extinguishing agent-forming coating liquid is applied to a predetermined area on the surface of the substrate 11 supplied from this roll, and the applied coating liquid is dried to form the fire extinguishing agent layer 12 (see Fig. 8(a)). Through this process, a sheet 10 including the substrate 11 and the fire extinguishing agent layer 12 is obtained. Meanwhile, two rolls (not shown) of the packaging material 20 are prepared, each wound into a roll. The sheet 10 is placed between the packaging materials 20 supplied from the two rolls (see Fig. 8(b)). The layered product shown in Fig. 8(b) is pressed while applying heat and then cut out to obtain the fire extinguishing material 100E.

[0050] The present disclosure will be explained in more detail by the following examples, but the present invention is not limited to these examples.

[0051] <Preparation of Sheets> (Examples 1 to 5 and Comparative Examples 1 to 9) Potassium citrate and potassium chlorate were mixed and ground in an agate mortar to obtain a mixture. The mixture was sieved through an 800 mesh to adjust the particle size D50 to 8 to 12 μm. This resulted in the preparation of a fire extinguishing agent.

[0052] The following components were mixed to prepare a coating liquid for forming a fire-extinguishing agent layer. Fire-extinguishing agent: the mixture of potassium citrate and potassium chlorate obtained above (87.4 parts by mass); Binder resin: ether-based urethane resin (12.6 parts by mass); Liquid medium: ethanol (87 parts by mass) and isopropyl alcohol (27 parts by mass).

[0053] A polyethylene terephthalate (PET) film (product name: E7002, manufactured by Toyobo Co., Ltd., thickness: 50 μm) was prepared as a substrate. The coating liquid was applied to one main surface of the PET film using an applicator (gap 450 μm). The coating film on the PET film was dried in an oven (conditions: 75°C, 7 minutes). This resulted in a sheet in which a fire-extinguishing agent layer (thickness: 190 to 210 μm) was formed on the substrate (PET film).

[0054] <Preparation of Packaging Materials> (Examples 1 to 5 and Comparative Examples 1 to 4, 7, and 9) Urethane adhesives A-1143 and A-3 manufactured by Mitsui Chemicals, Inc. were prepared as adhesives to form the adhesive layer, and ethyl acetate was prepared as a dilution solvent. These were mixed in a ratio of A-1143:A-3:ethyl acetate = 9:1:20.7 and stirred for 1 minute. This yielded an adhesive (solid content: 20% by mass).

[0055] The material (resin film) shown in Table 1 was prepared as the insulating layer. An adhesive was applied to one surface of the insulating layer by a bar coating method using a wire bar #14 to form a coating film. The coating film was dried in an oven at 80°C for 30 seconds. This resulted in a first adhesive layer (dry coating amount 3 g / m ２ An aluminum foil (1N30 aluminum foil, 7 μm thick, manufactured by Toyo Aluminum) was laminated onto the surface of the first adhesive layer opposite the insulating layer. The lamination was performed using a tabletop laminator FA-570 manufactured by Taisei Laminator Co., Ltd., under conditions of a lamination temperature of 50°C and a pressure of 0.1 MPa.

[0056] In the same manner as the first adhesive layer, a second adhesive layer was formed on the surface of the aluminum foil opposite the first adhesive layer. A sealant layer (linear low-density polyethylene resin, thickness 30 μm) was laminated on the surface of the second adhesive layer opposite the aluminum foil. The lamination was performed using a Taisei Laminator Co., Ltd. tabletop laminator FA-570 under conditions of a lamination temperature of 50 ° C and a pressure of 0.1 MPa. This resulted in a packaging material comprising, in this order, an insulating layer, a first adhesive layer, aluminum foil, a second adhesive layer, and a sealant layer.

[0057] Comparative Example 5 A packaging material was obtained in the same manner as in Example 1, except that the non-combustible paper shown in Table 1 was used instead of the resin film.

[0058] Comparative Example 6 A packaging material was obtained in the same manner as in Example 1, except that a glass cloth shown in Table 1 was used instead of the resin film.

[0059] Comparative Example 8 A packaging material was obtained in the same manner as in Example 1, except that a graphite sheet shown in Table 1 was used instead of the resin film.

[0060]

[0061] <Production of Fire Extinguishing Materials> (Examples 1 to 5 and Comparative Examples 1 to 9) The sheet obtained above was sandwiched between a pair of packaging materials, and the four sides of the packaging materials were heat-sealed to enclose the sheet. The heat-sealing conditions were 140°C and 2 seconds. In this way, evaluation samples of the fire extinguishing materials were obtained.

[0062] <Fire Extinguishing Test Evaluation> An iron container measuring 20 cm in length, 30 cm in width, and 40 cm in height was prepared. To prevent ignition of the solid fuel from suffocating, five circular vents with a diameter of 8.5 mm were provided on each side of the container at heights of 5, 12.5, 20.0, 27.5, and 35.0 cm from the top. An evaluation sample with an area of ​​50 mm x 50 mm was attached to the center of the top of the container with double-sided tape. 1.5 g of solid fuel (Captain Stag Co., Ltd. Solid Fuel Fire Block Ignition Agent) measuring 15 mm in length, 15 mm in width, and 10 mm in height was placed in the center of the bottom of the container. The distance between the solid fuel and the evaluation sample was 20 cm. When the solid fuel was ignited, it was determined whether the evaluation sample could extinguish the fire within 180 seconds after ignition. Five samples from each example and comparative example were tested for fire extinguishing ability. The percentage of the five samples that were successfully extinguished is shown in Table 2.

[0063] <Insulation evaluation> An evaluation sample was cut to a size of 50 mm x 50 mm. A voltage of 3.5 kV was applied to both sides of the evaluation sample (temperature: 25°C) for 60 seconds. The results were evaluated based on the following criteria. An AC / DC withstand voltage and insulation resistance tester (manufactured by Kikusui Electric Industry Co., Ltd.) was used to apply the voltage. A voltage was also applied to an evaluation sample heated to 150°C in the same manner. The results were evaluated based on the following criteria. The results are shown in Table 2. (Criteria) A: No current was applied B: Current was applied

[0064] <Fire-extinguishing agent property stability> The total light transmittance of the obtained evaluation sample was measured using a haze meter (BYK-Gardner Haze-Guard Plus, manufactured by BYK) according to a method conforming to JIS K 7361-1. Measurements were performed before placing the sample in a constant temperature and humidity chamber (under conditions of 85°C / 85% RH) (initial total light transmittance) and 24 hours after placing the sample in the chamber (total light transmittance after storage). These total light transmittances were substituted into the following formula (1) to calculate the change Δ in total light transmittance before and after storage. When moisture absorption (deliquescence) occurs in the fire-extinguishing agent, the transparency of the fire-extinguishing agent layer increases. Therefore, the degree of deliquescence can be confirmed by checking the change Δ. The change Δ was evaluated based on the following criteria. The results are shown in Table 2. Change Δ = total light transmittance value after storage - initial total light transmittance value (1)

[0065] (Criteria) A: Change Δ is 35 or less B: Change Δ is more than 35

[0066] <Measurement of Volume Resistivity of Insulating Layer> A film of the insulating layer alone was prepared, and the volume resistivity of the insulating layer was measured in accordance with JIS C2139-3-1. The results are shown in Table 2.

[0067] <Measurement of Thermal Conductivity of Insulating Layer> A film having an insulating layer alone was prepared, and the thermal conductivity of the insulating layer was measured in accordance with ASTM C 177. The results are shown in Table 2.

[0068] <Measurement of Melting Temperature of Insulating Layer> A film of the insulating layer alone was prepared, and differential scanning calorimetry was measured using a differential scanning calorimeter DSC7000X (Hitachi High-Tech Science Corporation). From the results, the melting temperature was calculated from the endothermic peak. The results are shown in Table 2.

[0069]

[0070] <Preparation of Sheet> (Example 6) The following components were mixed to prepare a coating liquid for forming a fire-extinguishing agent layer. Fire-extinguishing agent: 87 parts by mass of a mixture of potassium chlorate and tripotassium citrate Binder resin: 41 parts by mass of an ether-based polyurethane resin solution (a solution obtained by dissolving 100 parts by mass of ether-based polyurethane resin in 210 parts by mass of isopropyl alcohol) Liquid medium: 87 parts by mass of ethanol The mixture of potassium chlorate and tripotassium citrate, a deliquescent salt, was ground in an agate mortar and then filtered through an 800-mesh mesh to adjust the particle diameter D50 to 12 μm before mixing.

[0071] The coating liquid was applied to one side of a 50 μm thick polyethylene terephthalate (PET) substrate (product name: E7002, manufactured by Toyobo Co., Ltd.) using an applicator so that the thickness of the fire extinguishing agent layer after drying would be 150 μm. The coating film was then dried in an oven at 75° C. for 7 minutes. This resulted in a sheet having a fire extinguishing agent layer formed on the surface of the substrate.

[0072] <Preparation of Packaging Material> A laminated film (product name: ALPET, manufactured by Asia Aluminum Co., Ltd.) of aluminum foil (thickness 7 μm) and PET film (thickness 38 μm) was prepared. A sealant layer (LLDPE resin, thickness 30 μm) was laminated on this laminated film to obtain a packaging material having a laminated structure of PET film / aluminum foil (Al foil) / sealant layer.

[0073] <Production of Fire Extinguishing Material> The above sheet (50 mm x 50 mm) was sandwiched between two of the above packaging materials, and the four sides of the packaging material were heat-sealed to obtain a fire extinguishing material. The heat-sealing conditions were 140°C and 2 seconds. The heat-seal width on each side was 10 mm. As a result, a fire extinguishing material with outer dimensions of 70 mm x 70 mm was obtained.

[0074] (Example 7) A fire extinguishing material was obtained in the same manner as in Example 6, except that a laminated film of aluminum foil (thickness 9 μm) and PET film (thickness 12 μm) (product name: ALPET, manufactured by Asia Aluminum Co., Ltd.) was used instead of the laminated film of aluminum foil (thickness 7 μm) and PET film (thickness 38 μm).

[0075] (Example 8) A fire extinguishing material was obtained in the same manner as in Example 6, except that a laminated film of aluminum foil (thickness 7 μm) and PET film (thickness 38 μm) (product name: ALPET, manufactured by Asia Aluminum Co., Ltd.) was used instead of the laminated film of aluminum foil (thickness 7 μm) and PET film (thickness 38 μm).

[0076] (Comparative Example 10) A fire extinguishing material was obtained in the same manner as in Example 6, except that a PET film having a silica vapor deposition layer (thickness: about 20 nm) (hereinafter referred to as "silica vapor deposition PET film") was used instead of the laminated film of aluminum foil (thickness: 7 μm) and PET film (thickness: 38 μm). The silica vapor deposition PET film had a thickness of 12 μm and a water vapor permeability of 0.2 to 0.6 g / (m ２ The water vapor permeability in this disclosure refers to a value measured in accordance with JIS K 7129 under conditions of 40°C / 90% RH.

[0077] (Comparative Example 11) A fire extinguishing material was obtained in the same manner as in Example 6, except that a PET film having an aluminum vapor deposition layer (Al vapor deposition layer, thickness: approximately 30 nm) (hereinafter referred to as "aluminum vapor deposition PET film") was used instead of a laminated film of aluminum foil (thickness 7 μm) and PET film (thickness 38 μm). The aluminum vapor deposition PET film had a thickness of 12 μm and a water vapor permeability of 0.5 to 0.7 g / (m ２ ・day).

[0078] <Evaluation Items> (Piercing Strength) The aluminum foil (100 mm long x 30 mm wide) used in Examples 6 to 8 was fixed at a height of 90 mm. A push-pull gauge (manufactured by Aiko Engineering Co., Ltd.) was used to pierce a jig having a diameter of 15 mm, and the strength at which the jig penetrated the aluminum foil was measured.

[0079] (Tensile Breaking Strength) The aluminum foils (125 mm long x 25 mm wide) used in Examples 6 to 8 were set in a universal tensile testing device (Shimadzu Corporation, Autograph AGS-X). A tensile test was carried out under conditions of a chuck spacing of 100 mm and a tensile speed of 200 mm / min, and the strength at which the aluminum foil broke was measured.

[0080] (Deliquescence Resistance Test) The total light transmittance of the fire extinguishing materials according to Examples 6 to 8 and Comparative Examples 10 and 11 was measured using a haze meter (BYK-Gardner Haze-Guard Plus, manufactured by BYK) according to a method conforming to JIS K 7361-1. Measurements were performed before placing the fire extinguishing materials in a constant temperature and humidity chamber (under conditions of 85°C / 85% RH) (initial total light transmittance) and 72 hours after placement (total light transmittance after storage), and the change in total light transmittance Δ before and after storage was calculated according to the following formula. When moisture absorption (deliquescence) occurs, the transparency of the fire extinguishing material increases, so the degree of deliquescence was evaluated by checking this change Δ. The total light transmittance of the sheet obtained by removing the packaging material from the fire extinguishing material was measured. Evaluation was performed based on the following criteria. Change Δ = Total light transmittance value after storage - Initial total light transmittance value A: Change Δ is 35 or less B: Change Δ is more than 35

[0081] (Fire Extinguishing Test) An iron container measuring 20 cm in length, 30 cm in width, and 40 cm in height was prepared. A circular vent hole with a diameter of 8.5 mm was provided on each side of the container at a height distance of 5 cm from the top surface. Similarly, circular vent holes with a diameter of 8.5 mm were provided on each side of the container at positions 12.5 cm, 20.0 cm, 27.5 cm, and 35.0 cm from the top surface. The fire extinguishing materials according to the examples and comparative examples were attached to the center of the top surface of the container with double-sided tape. 1.5 g of solid fuel (Captain Stag Co., Ltd.'s Solid Fuel Fire Block Ignition Agent) measuring 15 mm in length, 15 mm in width, and 10 mm in height was placed in the container so that the distance from the fire extinguishing material was 20 cm in the height direction. At this time, the fire extinguishing material and the solid fuel overlapped each other vertically. The fire extinguishing materials were evaluated to see if they could extinguish the solid fuel fire within 180 seconds after ignition. The number "n" in Table 3 indicates the number of tests, and the extinguishing rate indicates the rate at which the fire was extinguished within 180 seconds after ignition. In all cases where the fire could not be extinguished within 180 seconds after ignition, the extinguishing agent did not spray out from the fire extinguishing material.

[0082]

[0083] 10...sheet, 11...substrate, 12...fire extinguishing agent layer, 20...packaging material, 21...sealing portion, 21a...sealant layer, 23...aluminum foil, 24...insulating layer, 100A, 100B, 100C, 100D, 100E...fire extinguishing material, 200...electrical equipment, 203...breaker, 204...wiring

Claims

1. A fire extinguishing material comprising: a sheet including a fire extinguishing agent layer; and a packaging material housing the sheet, wherein the fire extinguishing agent layer includes a binder resin and an fire extinguishing agent including at least one salt selected from among an organic salt and an inorganic salt having deliquescent properties, the packaging material having a laminated structure including aluminum foil and an insulating layer, the aluminum foil being disposed between the sheet and the insulating layer, and the melting temperature of the insulating layer being 150°C to 500°C.

2. The volume resistivity of the insulating layer is 10 １５ The fire extinguishing material according to claim 1, having a resistance of Ω·cm or more.

3. The fire extinguishing material according to claim 1 or 2, wherein the thermal conductivity of the insulating layer is 0.1 W / (m·K) or more.

4. A fire extinguishing material according to any one of claims 1 to 3, wherein the insulating layer contains at least one resin selected from the group consisting of polyethylene terephthalate resin, nylon resin, polyvinyl chloride resin and polypropylene resin.

5. The fire extinguishing material according to any one of claims 1 to 4, wherein the sheet further comprises a substrate.

6. A fire extinguishing material according to any one of claims 1 to 5, wherein the aluminum foil has a thickness of 15 μm or less.

7. The fire extinguishing material according to any one of claims 1 to 6, wherein the aluminum foil has a thickness of 3 μm or more.

8. A fire extinguishing material according to any one of claims 1 to 7, wherein the puncture strength of the aluminum foil is 10 N or less.

9. A fire extinguishing material according to any one of claims 1 to 8, wherein the tensile breaking strength of the aluminum foil is 25 N or less.

10. The fire extinguishing material according to any one of claims 1 to 9, further comprising a sealant layer between the sheet and the aluminum foil.

11. The fire extinguishing material according to claim 10, wherein a peripheral portion is formed by a sealing portion formed by the sealant layer.

12. A device having a fire extinguishing function, comprising: at least one object to be extinguished that may catch fire and is selected from the group consisting of electrical equipment, a distribution board, a switchboard, and a battery; and the fire extinguishing material according to any one of claims 1 to 11.

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