Composition for fire extinction material, fire extinction material, and manufacturing method thereof

Abstract

To provide a fire extinction material having excellent flexibility.SOLUTION: Provided is a fire extinction material including a base material and a fire extinguisher layer formed on at least one surface of the base material. The fire extinguisher layer contains a fire extinguisher and a binder resin. A content of the fire extinguisher in the fire extinguisher layer is 60 mass% or more and 98 mass% or less with a mass of the fire extinguisher layer as a reference. A tensile breaking elongation of the binder resin is 45 mm or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a composition for a fire extinguishing material, a fire extinguishing material, and a method for manufacturing the same.

Background Art

[0002] A lithium-ion battery is one of typical secondary batteries. A lithium-ion battery can cause thermal runaway due to a short circuit caused by a strong external impact or overcharging. When a lithium-ion battery causes thermal runaway, a large amount of flammable gas is released, which can lead to a serious fire. Patent Document 1 discloses disposing a flame-retardant heat-insulating sheet between a plurality of power storage units in order to prevent heat transfer between the plurality of power storage units. On the other hand, it has also been considered to previously dispose a fire extinguishing agent at a location where ignition can occur. For example, Patent Document 2 discloses an aerosol fire extinguishing agent composition capable of extinguishing a fire by generating an aerosol by combustion.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Even if the flame-retardant heat-insulating sheet described in Patent Document 1 can suppress kindling, it does not have fire extinguishing performance and cannot suppress the outbreak of fire or the generation of high-temperature gas from a power storage unit that has already caused thermal runaway. On the other hand, although Patent Document 2 discloses molding a fire extinguishing agent composition into granules, pellets, tablets, spheres or disks for use, it does not mention measures to be taken to maintain the fire extinguishing performance of the molded body of the fire extinguishing agent composition over a long period of time.

[0005] The fire extinguishing material applied to the secondary battery is required to maintain its fire extinguishing performance over the service life of the secondary battery. According to the study by the present inventors, the molded body described in Patent Document 2 is likely to crack during molding or use, and there is room for improvement in that the stability of the fire extinguishing performance may be impaired by moisture that has penetrated inside through the cracks.

[0006] The present disclosure has been made in view of the above problems, and provides a fire extinguishing material that is less likely to crack and a method for manufacturing the same. Further, the present disclosure provides a composition for a fire extinguishing material that is useful for manufacturing a fire extinguishing material that is less likely to crack.

Means for Solving the Problems

[0007] The fire extinguishing material according to the present disclosure includes a base material and a fire extinguishing agent layer formed on at least one surface of the base material. The fire extinguishing agent layer contains a fire extinguishing agent and a binder resin. The content of the fire extinguishing agent in the fire extinguishing agent layer is 60% by mass or more and 98% by mass or less based on the mass of the fire extinguishing agent layer, and the tensile breaking elongation of the binder resin is 45 mm or more.

[0008] According to the above fire extinguishing material, even if the fire extinguishing agent layer contains a sufficient amount of the fire extinguishing agent, by including the above binder resin, the fire extinguishing agent layer has excellent flexibility and bendability, so that cracks in the fire extinguishing agent layer can be sufficiently suppressed during the manufacture and use of the fire extinguishing material. Since cracks are less likely to occur in the fire extinguishing agent layer, moisture is less likely to penetrate inside the fire extinguishing agent layer, and the fire extinguishing performance can be maintained over a long period. The above fire extinguishing material has excellent bendability with a mandrel diameter of 18 mm or less, for example.

[0009] The composition for a fire extinguishing material according to the present disclosure includes a fire extinguishing agent and a binder resin. The content of the fire extinguishing agent is 60% by mass or more and 98% by mass or less based on the total mass of the solid content of the composition for a fire extinguishing material, and the tensile breaking elongation of the binder is 45 mm or more.

[0010] According to the above fire extinguishing agent composition, even if it contains a sufficient amount of fire extinguishing agent, by including the above binder resin, a fire extinguishing agent layer having excellent flexibility and bendability can be formed. Therefore, it is possible to sufficiently suppress the occurrence of cracks in the fire extinguishing agent layer during the production of the fire extinguishing material provided with the fire extinguishing agent layer and during the use of the fire extinguishing material. When the fire extinguishing agent composition is used as a coating liquid, the fire extinguishing agent composition further contains a liquid medium, and the viscosity of the coating liquid is preferably 1600 mPa·s or more. This viscosity means a value measured using a B-type viscometer at a rotation speed of 12 rpm. The fire extinguishing agent layer obtained by forming the fire extinguishing agent composition into a sheet shape with a thickness of 150 μm has excellent bendability, for example, the mandrel diameter is 18 mm or less.

[0011] The method for manufacturing a fire extinguishing material according to the present disclosure includes: (a) a step of forming a coating film on at least one surface of a base material by a wet coating method using the above fire extinguishing agent composition; and (b) a step of forming a fire extinguishing agent layer on the surface of the base material by drying the coating film. In step (b), the maximum temperature when drying the coating film is 100°C or less, and after the start of step (b), the temperature is raised stepwise or continuously until the maximum temperature is reached. The boiling point of the liquid medium contained in the fire extinguishing agent composition (coating liquid) is preferably 60°C or more and 90°C or less.

[0012] According to the method for manufacturing a fire extinguishing material according to the present disclosure, by setting the maximum temperature in step (b) to 100°C or less and raising the temperature stepwise or continuously until the maximum temperature is reached, a fire extinguishing agent layer having excellent smoothness and sufficiently few defects can be formed. Such a fire extinguishing agent layer is less likely to crack. The wet coating method is preferably a coating method selected from the group consisting of comma coating, gravure coating, curtain coating, and die coating.

Advantages of the Invention

[0013] According to the present disclosure, there are provided a fire extinguishing material in which cracks are less likely to occur and a method for manufacturing the same. Further, according to the present disclosure, there is provided a fire extinguishing agent composition useful for manufacturing a fire extinguishing material in which cracks are less likely to occur.

Brief Description of the Drawings

[0014]

Figure 1

Figure 2

[0015] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. Note that the present disclosure is not limited to the following embodiments.

[0016] <Fire extinguishing material> The fire extinguishing material of this embodiment includes a fire extinguishing agent layer in which a fire extinguishing material composition is formed into a sheet shape. This fire extinguishing material is used, for example, by being attached to an object that may catch fire. When the object catches fire, chemical species having a fire extinguishing function are released from the fire extinguishing material composition by receiving the thermal energy thereof, and thereby the flame is extinguished. Since it is not necessary to use a fire extinguisher, a fire extinguishing device, etc. for extinguishing the fire, such a fire extinguishing material is expressed as having "self-extinguishing property".

[0017] The object to be extinguished is not particularly limited as long as it may catch fire. Examples of objects that may catch fire include electric wires, switchboards, distribution boards, control panels, storage batteries (such as lithium-ion batteries), building materials such as building wallpapers and ceiling materials, boxes for lithium-ion battery recovery (recycling boxes), trash cans, automobile-related members, outlets, and each member such as an outlet cover.

[0018] The fire extinguishing material 1 shown in FIG. 1 includes a base material 2 and a fire extinguishing agent layer 3 formed on one surface of the base material 2. The mandrel diameter of the fire extinguishing material 1 may be 18 mm or less, 12 mm or less, 6 mm or less, or 3 mm or less. The "mandrel diameter" referred to here means the minimum diameter at which no cracks (fractures) are observed in the base material 2 and the fire extinguishing agent layer 3 when a type 1 mandrel test is carried out on the fire extinguishing material 1 in accordance with JIS K5600-5-1. The minimum diameter possible in the test is 2 mm.

[0019] (Base material) The base material 2 is a film that serves as a support when forming the fire extinguishing agent layer 3 into a sheet shape. In view of the fact that the temperature of a fire is generally about 700°C to 900°C, a resin base material can be selected as the base material 2. For example, as the resin, polyolefin (LLDPE, PP, COP, CPP, etc.), polyester (PET, etc.), fluororesin (PTFE, ETFE, EFEP, PFA, FEP, PCTFE, etc.), PVC, PVA, acrylic resin, epoxy resin, polyamide, polyimide, etc. can be mentioned. With these resins, holes can be formed by heat. Also, by selecting a transparent material, it becomes easier to inspect the appearance of the fire extinguishing material 1 and to confirm the replacement time. Note that the base material 2 preferably has flexibility and bendability superior to those of the fire extinguishing agent layer 3.

[0020] The base material 2 may contain a fire extinguishing agent described later. From the viewpoint of adjusting the water vapor permeability, the base material 2 may be provided with a vapor deposition layer (alumina vapor deposition layer or silica vapor deposition layer) having water vapor barrier properties.

[0021] The thickness, breaking strength, etc. of the base material 2 can be appropriately selected according to the amount of heat, impact, and allowable space at the time of fire outbreak. For example, if it is a thick base material, strength and rigidity can be obtained, a highly planar form can be obtained, and handling becomes easy. Also, if it is a thin base material, a fire extinguishing body can be provided in a narrow space, and since holes are formed in a short time, the fire extinguishing start time can be shortened. The thickness of the base material 2 can be, for example, 4.5 to 100 μm, and may be 12 to 50 μm. The base material 2 may be a laminate of a plurality of base materials. The base material 2 and the object may be adhered by an adhesive layer. Note that it is also possible to form the fire extinguishing agent layer directly on the film for enclosing the fire extinguishing agent without using a base material.

[0022] (Fire extinguishing agent layer) The fire extinguishing agent layer 3 is formed by shaping the fire extinguishing material composition described below into a sheet. The thickness of the fire extinguishing agent layer 3 may be 70 μm to 500 μm, may be 90 μm to 300 μm, or may be 110 μm to 200 μm. The mandrel diameter of the fire extinguishing agent layer 3 may be 18 mm or less, may be 12 mm or less, may be 6 mm or less, or may be 3 mm or less. The "mandrel diameter" mentioned here refers to the minimum diameter at which no cracks (fractures) are observed in the fire extinguishing agent layer 3 when the fire extinguishing agent layer 3 is independently subjected to a type 1 mandrel test in accordance with JIS K5600-5-1. The minimum diameter possible in the test is 2 mm.

[0023] <Fire extinguishing material composition> The fire extinguishing material composition contains a fire extinguishing agent and a binder resin. The content of the fire extinguishing agent in the fire extinguishing agent layer is 60% by mass or more and 98% by mass or less, based on the mass of the dry fire extinguishing agent layer, and may be 80% by mass or more and 90% by mass or less. The content of the binder resin in the fire extinguishing agent layer is 2% by mass or more and 40% by mass or less, based on the mass of the dry fire extinguishing agent layer, and may be 5% by mass or more and 15% by mass or less. The total amount of the fire extinguishing agent and the binder resin in the fire extinguishing agent layer is, for example, 80% by mass or more and 100% by mass or less, based on the mass of the dry fire extinguishing agent layer. Note that the fire extinguishing material composition may contain a curing agent component and a flexibility-imparting material, and may contain arbitrary additives such as a surfactant, a silane coupling agent, and an anti-blocking agent from the viewpoint of property stability.

[0024] (Fire extinguishing agent) As the fire extinguishing agent, organic salts and inorganic salts can be used alone or in combination. Examples of the organic salts include potassium salts, sodium salts, ammonium salts, etc. Potassium salts can be used as the organic salts. Examples of the organic potassium salts include carboxylic acid potassium salts such as potassium acetate, potassium citrate (monopotassium citrate, dipotassium citrate, tripotassium citrate), potassium tartrate, potassium lactate, potassium oxalate, and potassium maleate. Among these, potassium citrate can be preferably used from the viewpoint of its usefulness for the negative catalytic effect of combustion.

[0025] Examples of the inorganic salts include potassium salts and sodium salts. Potassium salts can be used as the inorganic salts. Examples of the inorganic potassium salts include potassium tetraborate, potassium carbonate, potassium hydrogen carbonate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, etc. Further, the fire extinguishing agent may contain a compound having an oxidizing action. Examples of the compound having an oxidizing action include chlorates such as potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, and magnesium chlorate. These can generate an aerosol from each potassium salt by receiving the thermal energy of a fire.

[0026] (Binder resin) As the binder resin, a thermoplastic resin and a thermosetting resin can be used. Examples of the thermoplastic resin include polyolefin resins such as polypropylene-based resins, polyethylene-based resins, poly(1-)butene-based resins, polypentene-based resins, etc., polystyrene-based resins, acrylonitrile-butadiene-styrene-based resins, methyl methacrylate-butadiene-styrene resins, ethylene-vinyl acetate resins, ethylene-propylene resins, polycarbonate-based resins, polyphenylene ether-based resins, acrylic resins, polyamide-based resins, polyvinyl chloride-based resins, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), etc. Examples of the thermosetting resin 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), polysulfide rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), urethane rubber (U), etc., polyurethane resins, phenol resins, epoxy resins, polyvinyl ether (PMVE)-maleic anhydride resins, etc.

[0027] By using a resin having elasticity as the binder resin, it is possible to suppress cracking of the fire extinguishing agent layer during formation and use of the fire extinguishing agent layer. Specifically, the tensile elongation at break of the binder resin is 45 mm or more, and for example, it may be 50 mm to 500 mm or 100 mm to 500 mm. This tensile elongation at break means the elongation at break when a film having a thickness of 90 μm made of the binder resin is produced and a tensile test conforming to JIS K 7127 is performed under the following conditions. The above film is obtained, for example, by recovering the binder resin recovered from the fire extinguishing material composition or the fire extinguishing agent layer and forming it into a film with a thickness of 90 μm. <Test Conditions> Test piece type: 2 Sample width: 25 mm Sample chucking distance: 10 cm Tensile speed: 50 mm / min

[0028] The binder resin may contain a compound having an acid anhydride group and an alkoxysilyl group. By including this compound in the fire extinguishing agent layer, the properties of the fire extinguishing agent layer can be stably maintained over a long period. The reason for this is not clear, but since the acid anhydride group can react with water, even if water enters the fire extinguishing agent layer, this compound traps the water and prevents deliquescence of the fire extinguishing agent, and / or after the alkoxysilane is hydrolyzed, self-reaction occurs to form siloxane, which is presumed to affect the improvement of water resistance and film density and the suppression of contact between the deliquescent salt and water.

[0029] When the fire extinguishing composition is used as a coating liquid, the fire extinguishing composition further includes a liquid medium. Hereinafter, the fire extinguishing composition containing a liquid medium may be referred to as a "coating liquid" in some cases. The coating liquid used for coating needs to have fluidity. However, if the fluidity of the coating liquid is too high, that is, if the viscosity of the coating liquid is too low, the coating liquid may flow locally before forming the fire extinguishing agent layer, and there may be a risk of local cracks in the fire extinguishing agent layer or non-uniformity in the in-plane thickness. From the viewpoint of forming a fire extinguishing agent layer with a sufficiently smooth and uniform thickness, the viscosity of the coating liquid is preferably 1600 mPa·s or more. This viscosity means the value measured at a rotation speed of 12 rpm using a B-type viscometer (spindle BL type No. 3). The lower limit value of the viscosity may be 2000 mPa·s or 3000 mPa·s. The upper limit value of the viscosity may be 7000 mPa·s or 5000 mPa·s.

[0030] (Liquid medium) Examples of the liquid medium include organic solvents. Examples of the organic solvent include water-soluble solvents, such as alcohols such as methanol (boiling point: 64.7 °C), ethanol (boiling point: 78.3 °C), isopropyl alcohol (IPA, boiling point: 82.4 °C), and n-propyl alcohol; esters such as ethyl acetate (boiling point: 77.1 °C); ketones such as acetone (boiling point: 56 °C) and methyl ethyl ketone (boiling point: 79.6 °C); glycols such as ethylene glycol (boiling point: 197.3 °C) and diethylene glycol (boiling point: 244.3 °C); glycol ethers such as N-methylpyrrolidone (NMP, boiling point: 202 °C), tetrahydrofuran (boiling point: 66 °C), and butyl cellosolve (boiling point: 171.2 °C). From the viewpoint of being used together with a hygroscopic fire extinguishing agent, the liquid medium may be an alcohol-based solvent, and specifically, a mixed solvent of ethanol and isopropyl alcohol may be used. As the liquid medium, a mixed solvent of ethanol and ethyl acetate may be used.

[0031] The amount of the liquid medium may be appropriately adjusted according to the coating method, but it can be 40 to 95% by mass based on the total amount of the coating liquid.

[0032] <Method for manufacturing fire extinguishing material> The fire extinguishing material 1 shown in Fig. 1 is manufactured through the following steps. (a) A step of forming a coating film on at least one surface of the base material 2 by a wet coating method (b) A step of forming a fire extinguishing agent layer 3 on the surface of the base material 2 by drying the coating film In step (b), when drying the coating film, the maximum temperature is 100°C or lower, and after the start of step (b), the temperature is raised stepwise or continuously until the maximum temperature is reached. To dry the coating film at a maximum temperature of 100°C or lower, the boiling point of the liquid medium is preferably 90°C or lower, more preferably 80°C or lower. The boiling point of the liquid medium is preferably 60°C or higher, more preferably 70°C or higher. The maximum temperature is preferably 100°C, more preferably 90°C, and even more preferably 80°C.

[0033] Examples of the wet coating method include comma coating, gravure coating, curtain coating, and die coating. From the perspective of controlling the film thickness of a thick fire extinguishing agent layer, comma coating and die coating are preferred among these coating methods. These methods apply the coating liquid in an arbitrary shape or on one surface of the base material, and then, by applying hot air or the like in a drying furnace, the liquid medium is evaporated to form a fire extinguishing agent layer. At this time, if high-temperature drying is performed in a state where a large amount of the liquid medium remains, only the outermost layer of the coating film is rapidly dried, causing skinning, inhibiting the evaporation of the liquid medium in the film, resulting in poor film formation, and reducing the strength and flexibility of the fire extinguishing agent layer. Therefore, the maximum temperature during drying is preferably 100°C or lower as described above.

[0034] In step (b), when performing a first heat treatment at a preheating temperature lower than the maximum temperature and then a second heat treatment at the maximum temperature, the preheating temperature is preferably lower than the boiling point of the liquid medium, for example, preferably 50 to 60°C. After heating the entire coating film at the preheating temperature over a period of 1 to 3 minutes, it is preferable to perform the second heat treatment. From the perspective of sufficiently volatilizing the liquid medium, the second heat treatment is preferably performed over a longer time than the first heat treatment, for example, preferably over 4 to 6 minutes.

[0035] As described above in detail with respect to the embodiments of the present disclosure, the present invention is not limited to the above embodiments. In the above embodiments, the mode in which the fire extinguishing agent layer 3 is formed on one surface of the base material 2 is exemplified, but both surfaces of the fire extinguishing agent layer 3 may be covered with resin layers. For example, the fire extinguishing material 10 shown in FIG. 2 includes resin layers 4, 4 so as to cover the fire extinguishing agent layer 3 from both sides thereof, and further includes water vapor barrier layers 6, 6 via adhesive layers 5, 5 from both sides thereof. Further, an adhesive layer 7 is provided on one of the water vapor barrier layers 6, and a release film 8 is laminated thereon. The release film 8 is peeled off when the fire extinguishing material 10 is attached to a desired location, and may be made of resin or paper. The mandrel diameter of the fire extinguishing material 10 may be 18 mm or less, 12 mm or less, 6 mm or less, or 3 mm or less.

[0036] As the material of the resin layers 4, 4, polyolefins (such as PE, PP, COP, etc.), polyesters (such as PET, etc.), fluororesins (such as PTFE, ETFE, EFEP, PFA, FEP, PCTFE, etc.), vinyl resins (such as PVC, PVA, etc.), acrylic resins, epoxy resins, polyamides, polyimides, etc. can be mentioned. The resin layers 4, 4 may have heat meltability (heat fusibility). Examples of the resin having heat meltability include polyolefin resins. That is, the resin layers 4, 4 may contain polyolefin resins. Examples of polyolefin resins include polyolefin resins such as low-density polyethylene resin (LDPE), linear low-density polyethylene resin (LLDPE), medium-density polyethylene resin (MDPE), unoriented polypropylene resin (CPP), etc., polyethylene resins such as ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, etc., and polypropylene resins such as propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-α-olefin copolymer, etc. Among these, from the viewpoints of excellent heat sealability, low water vapor permeability, and easy suppression of the deterioration of the fire extinguishing agent, the polyolefin resin may contain low-density polyethylene resin (LDPE), linear low-density polyethylene resin (LLDPE), or unoriented polypropylene resin (CPP). These resins have transparency, and the appearance inspection of the fire extinguishing agent is easy. Therefore, it becomes easy to confirm the replacement time of the fire extinguishing material laminate, etc.

[0037] The area of the resin layers 4, 4 is wider than that of the fire extinguishing agent layer 3, and the fire extinguishing agent layer 3 can be sealed by heat-sealing (heat sealing) the portions where the resin layers 4, 4 are in contact with each other. In FIG. 2, the fire extinguishing agent layer 3 is used in a state where the base material 2 is peeled off from the fire extinguishing material 1, but the fire extinguishing material 1 itself may be sealed by the resin layers 4, 4 without peeling off the base material 2. The thickness of the resin layers 4, 4 can be 25 μm to 150 μm alone, and may be 30 μm to 100 μm.

[0038] As the adhesive constituting the adhesive layer 5,5, acrylic adhesives, epoxy adhesives, silicone adhesives, polyolefin adhesives, urethane adhesives, polyvinyl ether adhesives, or their synthetic adhesives, etc. can be mentioned. Among these, from the viewpoint of achieving both adhesion to the resin layers 4,4 at 85°C - 85%RH high temperature and high humidity and low cost, an epoxy-urethane synthetic adhesive can be preferably used as the adhesive.

[0039] The water vapor barrier layers 6,6 can easily maintain a water vapor barrier property to such an extent that the properties of the fire extinguishing agent do not change significantly regardless of the installation location and usage environment of the fire extinguishing material 10. The water vapor permeability of the water vapor barrier layers 6,6 (under the conditions of 40°C / 90%RH in accordance with JIS K 7129) is not particularly limited because it can be designed according to the type of fire extinguishing agent, but it can be 10 g / m 2 / day or less, and can be 1 g / m 2 / day or less. From the viewpoint of adjusting the water vapor permeability, examples of the water vapor barrier layers 6,6 include polyester resin layers (such as PET layers) provided with metal oxide vapor deposition layers such as alumina vapor deposition layers and silica vapor deposition layers, and metal foils such as aluminum foils. When the water vapor barrier layer is provided with a metal oxide vapor deposition layer, the metal oxide vapor deposition layer may face the fire extinguishing agent side. The thickness of the water vapor barrier layers 6,6 can be 4.5 μm to 25 μm alone, and can also be 7 μm to 12 μm.

[0040] As the adhesive layer 7, known ones can be appropriately used. When the base material 2 is sealed together with the fire extinguishing agent layer 3, the adhesive layer 7 is provided on the side where the base material 2 exists. By the adhesive layer 7, the fire extinguishing material 10 can be attached to the object. When the object to which the fire extinguishing material 10 is attached catches fire, the heat energy causes the water vapor barrier layer 6, the adhesive layer 5, and the resin layer 4 to melt, and chemical species having a fire extinguishing function are released from the fire extinguishing agent layer 3, thereby extinguishing the flame.

[0041] From the viewpoint of ensuring the property stability of the fire extinguishing agent layer, the fire extinguishing agent layer may be encapsulated in a packaging film. Any resin film can be used as the packaging film. For example, polyolefin resin, polyester resin, fluororesin, vinyl resin, acrylic resin, epoxy resin, polyamide, polyimide, urethane resin, styrene resin, polycarbonate, ketone resin, sulfone resin, cellulose resin, etc. The packaging film desirably has a water vapor barrier property, and the water vapor permeability (under the conditions of 40°C / 90%RH in accordance with JIS K 7129) can be 2 / m 2 / day or less, and may be 1×10 2 g / m 2 / day or less. From the viewpoint of adjusting the water vapor permeability, examples of the film having a water vapor barrier property include a polyester resin layer (for example, a PET layer) provided with an inorganic metal oxide vapor deposition layer such as an alumina vapor deposition layer or a silica vapor deposition layer, and a metal foil such as an aluminum foil. When the water vapor barrier layer includes a metal oxide vapor deposition layer, the metal oxide vapor deposition layer may face the fire extinguishing agent layer side.

[0042] The packaging film may have an adhesive layer for sealing the fire extinguishing material. The adhesive layer can be formed of materials such as, for example, a heat-sealing material, an adhesive, a pressure-sensitive adhesive, etc. Further, the fire extinguishing material may be provided with a sealing portion, and by joining the packaging films at the peripheries of the fire extinguishing agent layer to each other with the sealing portion, the fire extinguishing agent layer is prevented from coming into contact with air, and deterioration of the property stability can be suppressed. When the sealing portion has heat-sealability, it may be formed by heat fusion. The adhesion strength between the base materials in the sealing portion may be 5 N / 15 mm or more, may be 7 N / 15 mm or more, and may be 10 N / 15 mm or more from the viewpoint of stably enclosing the fire extinguishing agent layer. The adhesion strength can be varied by adjusting the resin layer, adjusting the adhesive, adjusting the heat-sealing conditions (heat-sealing temperature, pressure, time), etc. Note that the adhesion strength between the base materials is measured as follows. That is, a sample in which the resin layers of the base materials are heat-fused or bonded by an adhesive is prepared. The heat-fused portion or the bonded portion of this sample is cut out to a width of 15 mm, and in accordance with JIS K6854-3, the average strength from the start of peeling until the heat-fused portion or the bonded portion separates when T-peel is performed at a peeling speed of 300 mm / min with a tensile tester placed in an environment at room temperature of 23°C is taken as the adhesion strength between the base materials.

Example

[0043] Hereinafter, the present disclosure will be described more specifically with reference to examples and comparative examples. Note that the present invention is not limited to the following examples.

[0044] <Example 1> Potassium chlorate (KClO 3 ) and tripotassium citrate were pulverized in an agate mortar so that the average particle diameter D50 was 12 μm or less to prepare a fire extinguishing agent. A fire extinguishing material composition was obtained by mixing this fire extinguishing agent with various materials at the following mixing ratios. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 50.1 parts by mass (2-2) EX-991L (epoxy resin, Nagase ChemteX, solid content ratio 100%) 4.7 parts by mass (2-3) X-12-1287A (silane coupling agent having an acid anhydride group and an alkoxysilyl group, Shin-Etsu Chemical Co., Ltd., solid content ratio 100%) 2.8 parts by mass (3) Liquid medium (ethanol) 87 parts by mass

[0045] On one surface of a polyethylene terephthalate (PET) substrate (product name: E7002, manufactured by Toyobo Co., Ltd., thickness 50 μm), the fire extinguishing agent composition was applied using an applicator so that the thickness of the dried fire extinguishing agent layer was 150 μm. After heating the coating film at a preheating temperature of 55 °C for 2 minutes, the coating film was dried at 75 °C (maximum temperature) for 5 minutes to obtain a fire extinguishing material.

[0046] <Example 2> A fire extinguishing material was produced in the same manner as in Example 1, except that the coating film was heated at a preheating temperature of 60 °C for 2 minutes and then dried at 90 °C (maximum temperature) for 5 minutes.

[0047] <Example 3> A fire extinguishing material was produced in the same manner as in Example 1, except that a fire extinguishing agent composition having the following composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 84.4 parts by mass (2-2) EX-991L (epoxy resin, Nagase ChemteX, solid content ratio 100%) 3.7 parts by mass (3) Liquid medium (ethanol) 87 parts by mass

[0048] <Example 4> A fire extinguishing agent was produced in the same manner as in Example 1, except that the composition for a fire extinguishing agent having the following composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 107.4 parts by mass (2-2) EX-991L (epoxy resin, Nagase ChemteX, solid content ratio 100%) 1.2 parts by mass (3) Liquid medium (ethanol) 87 parts by mass

[0049] <Example 5> A fire extinguishing agent was produced in the same manner as in Example 1, except that the composition for a fire extinguishing agent having the following composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 107.4 parts by mass (2-2) EX-861 (epoxy resin, Nagase ChemteX, solid content ratio 100%) 1.2 parts by mass (3) Liquid medium (ethanol) 87 parts by mass

[0050] <Example 6> A fire extinguishing agent was produced in the same manner as in Example 1, except that the composition for a fire extinguishing agent having the following composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin (2-1) AD-393 (modified urethane resin, Toyo Morton, solid content ratio 50%) 22.14 parts by mass (2-2) CAT-EP1 (isocyanate curing agent, Toyo Morton, solid content ratio 100%) 1.46 parts by mass (3) Liquid medium (3-1) Ethanol 87 parts by mass (3-2) 1.46 parts by mass of IPA

[0051] <Example 7> A fire extinguishing agent was prepared in the same manner as in Example 1, except that a fire extinguishing composition having the following composition was used. (1) 87 parts by mass of fire extinguishing agent (potassium chlorate, tripotassium citrate) (2) Binder resin Takelac TE5899 (urethane resin, Mitsui Chemicals, solid content ratio 30%) 41.77 parts by mass (3) Liquid medium (3-1) 87 parts by mass of ethanol (3-2) 10.44 parts by mass of ethyl acetate

[0052] <Example 8> A fire extinguishing agent was prepared in the same manner as in Example 1, except that a fire extinguishing composition having the following composition was used. (1) 87 parts by mass of fire extinguishing agent (potassium chlorate, tripotassium citrate) (2) Binder resin Ether-based polyurethane resin solution (a solution prepared by dissolving 100 parts by mass of ether-based polyurethane resin in 210 parts by mass of isopropyl alcohol) 40.3 parts by mass (3) Liquid medium (ethanol) 87 parts by mass

[0053] <Comparative Example 1> A fire extinguishing agent was prepared in the same manner as in Example 1, except that a fire extinguishing composition having the following composition was used. (1) 87 parts by mass of fire extinguishing agent (potassium chlorate, tripotassium citrate) (2) Binder resin (2-1) Maxceleb M-100 (epoxy resin, Mitsubishi Gas Chemical, solid content ratio 100%) 2.76 parts by mass (2-2) Maxceleb C-97 (amine-based curing agent, Mitsubishi Gas Chemical, solid content ratio 65%) 13.64 parts by mass (3) Liquid medium (3-1) 91.7 parts by mass of ethanol (3-2) 3.1 parts by mass of ethyl acetate

[0054] <Comparative Example 2> A fire extinguishing material was produced in the same manner as in Example 1, except that the composition for a fire extinguishing material having the following composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 84.4 parts by mass (2-2) X-12-1287A (a silane coupling agent having an acid anhydride group and an alkoxysilyl group, Shin-Etsu Chemical, solid content ratio 100%) 3.7 parts by mass (3) Liquid medium (ethanol) 87 parts by mass

[0055] <Comparative Example 3> A fire extinguishing material was produced in the same manner as in Example 1, except that the composition for a fire extinguishing material having the following composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 107.4 parts by mass (2-2) X-12-1267B (a silane coupling agent having an acid anhydride group and an alkoxysilyl group, Shin-Etsu Chemical, solid content ratio 100%) 1.2 parts by mass (3) Liquid medium (ethanol) 87 parts by mass

[0056] <Reference Example 4> A fire extinguishing material was produced in the same manner as in Example 1, except that the composition for a fire extinguishing material having the following composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin Ether-based polyurethane resin solution (a solution prepared by dissolving 100 parts by mass of ether-based polyurethane resin in 210 parts by mass of isopropyl alcohol) 40.3 parts by mass (3) Liquid medium (ethanol) 174 parts by mass

[0057] <Reference Example 5> A fire extinguishing material was produced in the same manner as in Example 1, except that the composition for a fire extinguishing material having the following composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 87 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 50.1 parts by mass (2-2) EX-991L (epoxy resin Nagase ChemteX solid content rate 100%) 4.7 parts by mass (2-3) X-12-1287A (silane coupling agent having an acid anhydride group and an alkoxysilyl group Shin-Etsu Chemical Co., Ltd. solid content rate 100%) 2.8 parts by mass (3) Liquid medium (ethanol) 174 parts by mass

[0058] <Reference Example 6> A fire extinguishing material was produced in the same manner as in Example 1, except that the coating film was heated at a preheating temperature of 90°C for 2 minutes and then dried at 110°C (maximum temperature) for 5 minutes.

[0059] <Reference Example 7> A fire extinguishing material was produced in the same manner as in Example 1, except that the coating film was dried at 90°C (maximum temperature) for 7 minutes.

[0060] <Reference Example 8> A composition for a fire extinguishing material with a low content of the fire extinguishing agent was prepared, and a fire extinguishing material was produced using this composition. That is, a fire extinguishing material was produced in the same manner as in Example 1, except that the following composition for a fire extinguishing material was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 50 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 192.6 parts by mass (2-2) EX-991L (Epoxy resin, Nagase ChemteX, solid content rate 100%) 18.2 parts by mass (2-3) X-12-1287A (Silane coupling agent having an acid anhydride group and an alkoxysilyl group, Shin-Etsu Chemical Co., Ltd., solid content rate 100%) 10.6 parts by mass (3) Liquid medium (ethanol) 50 parts by mass

[0061] <Reference Example 9> A fire extinguishing agent composition with a low binder resin content was prepared, and a fire extinguishing agent was produced using this. That is, a fire extinguishing agent was produced in the same manner as in Example 1 except that the following fire extinguishing agent composition was used. (1) Fire extinguishing agent (potassium chlorate, tripotassium citrate) 99 parts by mass (2) Binder resin (2-1) Polyvinyl butyral resin solution (a solution prepared by dissolving 11 parts by mass of polyvinyl butyral resin in 80 parts by mass of ethanol and 9 parts by mass of isopropyl alcohol) 3.9 parts by mass (2-2) EX-991L (Epoxy resin, Nagase ChemteX, solid content rate 100%) 0.4 parts by mass (2-3) X-12-1287A (Silane coupling agent having an acid anhydride group and an alkoxysilyl group, Shin-Etsu Chemical Co., Ltd., solid content rate 100%) 0.2 parts by mass (3) Liquid medium (ethanol) 99 parts by mass

[0062] <Presence or absence of coating film cracks and coating film non-uniformity> After forming a coating film on the surface of the substrate, the presence or absence of coating film cracks and coating film non-uniformity was visually confirmed during the process of drying the coating film.

[0063] <Measurement of tensile elongation at break of binder resin> Solutions of each binder resin were applied onto a release-treated PET film using an applicator. The coating amount was adjusted so that the film thickness after drying would be 90 μm. After drying the coating film, the binder resin film was recovered. From this film, samples of test piece type 2 (sample width 25 mm) in JIS K 7127 were obtained. For this sample, using an autograph testing machine AGS-X (Shimadzu Corporation), with the sample held such that the chuck width was 10 cm, it was pulled at a speed of 50 mm / min, and the elongation at break was measured.

[0064] <Measurement of the viscosity of the coating solution> A spindle BL type No. 3 was set on a B-type viscometer BL type (Tokki Sangyo), and the viscosity of the coating solution at a rotation speed of 12 rpm was measured.

[0065] <Mandrel test> The fire extinguishing material cut to 100 mm × 50 mm was bent in a type 1 mandrel test in accordance with JIS K5600-5-1. When the fire extinguishing agent layer bent without cracking at a diameter of 18 mm, it was marked as "〇", and when it cracked, it was marked as "×".

[0066] <Fire extinguishing test> A 1 cm square solid fuel was ignited. With the fire extinguishing agent layer facing the burning solid fuel, the fire extinguishing material was placed at a position 8 cm above the solid fuel, and it was confirmed whether it could extinguish the fire. When it could extinguish the fire, it was marked as "○", and when it could not extinguish the fire, it was marked as "×".

[0067] The results are shown in Tables 1 to 4. The "-" in the tables means that it was not measured or could not be evaluated.

[0068]

Table 1

[0069]

Table 2

[0070]

Table 3

[0071]

Table 4

[0072] Good results were obtained in Examples 1 to 8. It is presumed that this is because the tensile elongation at break of the binder resin was 45 mm or more, the viscosity of the coating liquid was adjusted to 1600 mPa·s or more, heat treatment was performed in two steps, and the maximum temperature of the heat treatment was 100°C or less.

[0073] In Comparative Examples 1, 2, and 3, cracks occurred at 18 mm bending in the mandrel test because the tensile elongation at break of the binder resin was less than 45 mm. In Reference Examples 4 and 5, cracks and non-uniformity due to high fluidity occurred in the coating film because the viscosity of the coating liquid was low. In Reference Examples 6 and 7, film cracking occurred due to rapid drying. In Reference Example 8, the fire extinguishing ability decreased because the content of the fire extinguishing agent was small. In Reference Example 9, a coating film could not be formed because the content of the binder resin was small.

Description of Reference Numerals

[0074] 1, 10... fire extinguishing material, 2... base material, 3... fire extinguishing agent layer, 4... resin layer, 5... adhesive layer, 6... water vapor barrier layer, 7... adhesive layer, 8... release film

Claims

1. a base material, a fire extinguishing agent layer formed on at least one surface of the base material, comprising: the fire extinguishing agent layer contains a fire extinguishing agent and a binder resin, the content of the fire extinguishing agent in the fire extinguishing agent layer is 60% by mass or more and 98% by mass or less based on the mass of the fire extinguishing agent layer, a fire extinguishing material, wherein the tensile breaking elongation of the binder resin is 45 mm or more.

2. The fire extinguishing material according to claim 1, wherein the mandrel diameter is 18 mm or less.

3. A composition for a fire extinguishing material containing a fire extinguishing agent and a binder resin, wherein the content of the fire extinguishing agent is 60% by mass or more and 98% by mass or less based on the total mass of the solid content of the composition for a fire extinguishing material, a composition for a fire extinguishing material, wherein the tensile breaking elongation of the binder is 45 mm or more.

4. further comprising a liquid medium, The composition for a fire extinguishing material according to claim 3, wherein the viscosity measured at a rotation speed of 12 rpm using a B-type viscometer is 1600 mPa·s or more.

5. The composition for a fire extinguishing material according to claim 4, wherein the boiling point of the liquid medium is 60°C or more and 90°C or less.

6. (a) A step of forming a coating film by wet coating the composition for a fire extinguishing material according to claim 5 on at least one surface of a base material, (b) A step of forming a fire extinguishing agent layer on the surface of the base material by drying the coating film, comprising: in step (b), the maximum temperature when drying the coating film is 100°C or less, A method for manufacturing a fire extinguishing material, wherein the temperature is gradually increased until the maximum temperature is reached after the start of step (b).

7. (a) A step of forming a coating film by wet coating the composition for a fire extinguishing material according to claim 5 on at least one surface of a base material, (b) A step of forming a fire extinguishing agent layer on the surface of the base material by drying the coating film, comprising: in step (b), the maximum temperature when drying the coating film is 100°C or less, A method for manufacturing a fire extinguishing material, wherein the temperature is continuously increased until the maximum temperature is reached after the start of step (b).

8. The method for manufacturing a fire extinguishing material according to claim 6 or 7, wherein the wet coating method is a coating method selected from the group consisting of comma coating, gravure coating, curtain coating, and die coating.

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