Composition for fire extinguishing material, method for producing same, method for selecting binder resin, fire extinguishing material, fire extinguishing material sheet, and device having automatic fire extinguishing function

Abstract

The composition for a fire extinguishing material according to the present disclosure comprises: a fire extinguishing agent comprising at least one of an organic salt and an inorganic salt having deliquescence; and a compound having an acid anhydride group. The fire extinguishing material is formed by the composition for the fire extinguishing material.

Description

Technical Field

[0001] The present disclosure relates to a composition for a fire extinguishing material, a method for producing the same, a method for selecting a binder resin, a fire extinguishing material, a fire extinguishing material sheet, and a device having an automatic fire extinguishing function. Background Art

[0002] In the past, self-extinguishing molded products for extinguishing and suppressing fires were known. For example, the self-extinguishing molded product disclosed in Patent Document 1 includes a fire extinguishing agent composition that extinguishes and suppresses fires by generating aerosols through combustion, and the self-extinguishing function can be activated by generating chemical species with fire extinguishing function by utilizing the heat energy of the fire. The self-extinguishing molded product is formed into a sheet shape, for example. The aerosol fire extinguishing agent composition disclosed in Patent Document 2 can automatically ignite and burn by the heat caused by the fire, generating an aerosol with a fire extinguishing effect. According to these, there is no need to use a fire extinguisher or a fire extinguishing device to extinguish a fire.

[0003] In addition, in recent years, with the advancement of technology, our lives have become more and more comfortable. On the other hand, a large amount of energy is required to create this comfort, and high safety is required in various scenes such as high-density filling, storage, movement, and use of this large amount of energy.

[0004] Taking automobiles as an example, there are potential fire hazards in the mining of fossil fuels represented by gasoline, the refining of fossil fuels into gasoline, and the transportation of electricity. In addition, taking electronic technology as an example, there are potential fire hazards in the movement of electric energy through wires, the adjustment of electric energy in substations or transformers, the use of electric energy in electrical equipment in homes or factories, or the temporary storage in batteries.

[0005] In response to the above-mentioned problems of ignition and fire, Patent Document 3 proposes the use of fire extinguishing liquid and fire extinguishers, Patent Document 4 proposes the use of automatic fire extinguishing devices dropped from helicopters, Patent Document 5 proposes the use of aerosol fire extinguishing devices, and Patent Document 6 proposes the use of fire extinguishing tablets containing fire extinguishing agents.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2018 / 047762

[0009] Patent Document 2: Japanese Patent No. 6443882

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 9-276440

[0011] Patent Document 4: Japanese Patent Application Publication No. 2015-6302

[0012] Patent Document 5: Japanese Patent Application Publication No. 2017-080023

[0013] Patent Document 6: Japanese Patent Application Publication No. 2020-81809 Summary of the invention

[0014] Problems to be solved by the invention

[0015] (First purpose)

[0016] The fire extinguishing agent compositions described in Patent Documents 1 and 2 contain salts such as potassium nitrate and sodium nitrate. Since these salts are deliquescent, there is still room for improvement in maintaining the properties of the self-fire extinguishing molded article stably for a long period of time.

[0017] The present disclosure has been made in view of the above circumstances, and a first object thereof is to provide a fire extinguishing material composition (hereinafter also referred to as a "fire extinguishing agent composition" as the case may be) capable of obtaining a fire extinguishing material having excellent property stability, and a fire extinguishing material formed of the composition.

[0018] (Second Purpose)

[0019] The techniques described in Patent Documents 3 to 6 are all methods of dealing with fires that have occurred after a certain period of time. On the other hand, from the perspective of minimizing the damage caused by the fire, it is preferred to perform some kind of fire extinguishing operation (initial fire extinguishing) at a stage very soon after the fire has started. Therefore, for example, a method can be considered in which the components of the fire extinguishing agent itself are pre-existing near an object that may catch fire. Thus, it is expected that the components of the fire extinguishing agent can be used to extinguish the fire before humans perceive that the object is on fire. However, it is unrealistic to pre-disperse the fire extinguishing agent near the object, and it needs to be pre-set near the object in a shape that is appropriately operable.

[0020] Patent Document 6 proposes a fire extinguishing sheet formed by mixing microcapsules encapsulating a fire extinguishing agent with ink composed of a water-soluble resin and a curing agent, mixing the mixture into fibers, and curing the mixture into a plate-like shape. However, according to the research of the present inventors, in the case of a small fire in the early stage of a fire, the reactivity of the fire extinguishing sheet is insufficient, and the fire extinguishing sheet may not react. In addition, even if the heat from the fire causes rupture in some microcapsules and releases the fire extinguishing agent, the fire will not burn and spread in the sheet, and sufficient fire extinguishing agent will not be released.

[0021] The present disclosure is completed in view of the above situation, and its second purpose is to provide a composition for a fire extinguishing material and a method for manufacturing the same, a fire extinguishing material using the composition for a fire extinguishing material, and a device with an automatic fire extinguishing function equipped with the fire extinguishing material, as well as a method for selecting a binder resin (hereinafter also referred to as a "binder" depending on the situation) that can impart excellent initial fire extinguishing ability to the fire extinguishing material.

[0022] (Third Purpose)

[0023] The self-extinguishing molded product of Patent Document 1 is in the form of a sheet, for example, and can be attached to an adhered object such as a panel of an automobile or a wall of a building. In view of such a usage, it is also conceivable to attach the self-extinguishing molded product to a curved surface, but in Patent Document 1, no research is conducted on the properties required for the curved surface. In this regard, the present inventors conducted research and found that when a test was conducted to bend a fire extinguishing agent composition in the form of a sheet along a curved surface, cracks (breaks) sometimes occurred in the fire extinguishing agent composition because the fire extinguishing agent composition could not completely follow the curved surface.

[0024] Therefore, the third object of the present disclosure is to provide a fire extinguishing material sheet having a fire extinguishing function and in which cracks in the fire extinguishing material layer (hereinafter also referred to as "fire extinguishing agent layer" depending on the situation) are unlikely to occur even when applied to a curved surface, and a fire extinguishing material composition suitable for the fire extinguishing material sheet.

[0025] Means for solving problems

[0026] (First aspect)

[0027] In order to achieve the first objective, the present disclosure provides a fire extinguishing material composition, comprising: a fire extinguishing agent comprising at least one of a deliquescent organic salt and an inorganic salt; and a compound having an acid anhydride group. The fire extinguishing material composition may further comprise a binder resin and / or a liquid medium.

[0028] As a means to solve the problem caused by deliquescent property, the inventors focus on silane coupling agents. That is, it is believed that the film density can be improved by the reaction of the organic functional group of the silane coupling agent with the binder resin contained in the fire extinguishing agent composition, and the contact between the deliquescent salt and water can be suppressed, so as to achieve the above-mentioned purpose. Therefore, the inventors added a specific silane coupling agent to the fire extinguishing agent composition, and the result was as expected to obtain a fire extinguishing material with excellent property stability. Moreover, according to subsequent studies, the silane coupling agent used has an anhydride group, and the anhydride group mainly contributes to the property stability of the fire extinguishing material. As mentioned above, the fire extinguishing material composition can suppress the deliquescence of the salt by containing a compound with anhydride group, and the excellent property stability of the fire extinguishing material composition can be achieved.

[0029] When the mass of the binder resin is set to 100 parts by mass, the fire extinguishing material composition may contain 10 to 250 parts by mass of the compound. By making the content of the compound within the above range, the deliquescence of the salt can be further suppressed, and the excellent property stability of the fire extinguishing material composition can be further achieved.

[0030] From the viewpoint of fire extinguishing performance, the fire extinguishing material composition may contain 70 to 97% by mass of the fire extinguishing agent based on the total amount of the fire extinguishing material composition. The salt may be a potassium salt. The acid anhydride group may be a carboxylic anhydride group. The compound may further have an alkoxysilyl group. The compound may be a silane coupling agent.

[0031] A fire extinguishing material according to one aspect of the present disclosure is formed from the fire extinguishing material composition described above.

[0032] (Second aspect)

[0033] In order to achieve the above-mentioned second purpose, one aspect of the present disclosure provides a composition for fire extinguishing materials, comprising: a fire extinguishing agent containing at least one salt of an organic salt and an inorganic salt, and a binder. The composition for fire extinguishing materials satisfies the following requirements. That is, in a thermogravimetric measurement under an atmospheric atmosphere, when the binder is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight reduction rate of the binder until the temperature reaches 400°C is 30% or more. Such a composition for fire extinguishing materials has excellent fire extinguishing ability at the initial stage of a fire.

[0034] One aspect of the present disclosure relates to a composition for a fire extinguishing material, comprising: a fire extinguishing agent comprising at least one of an organic salt and an inorganic salt, a first binder, and a second binder. The composition for a fire extinguishing material satisfies the following requirements. That is, in a thermogravimetric measurement under an atmospheric atmosphere, when the first binder is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight reduction rate of the first binder until the temperature reaches 400°C is 50% or more. In a thermogravimetric measurement under an atmospheric atmosphere, when the second binder is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight reduction rate of the second binder until the temperature reaches 400°C is 15% or less. When the mass of the first binder is set to 100 parts, the mass of the second binder is 250 parts or less. Such a fire extinguishing material composition has excellent fire extinguishing ability in the initial stage of fire, and can obtain desired properties such as improved substrate adhesion, improved processability, suppressed deliquesce, reduced viscosity, and improved roll-to-roll coating suitability depending on the type of the second binder.

[0035] The second binder may be a compound having an acid anhydride group. The second binder may be a silane coupling agent having a carboxylic anhydride group and an alkoxysilyl group. The fire extinguishing material composition containing such a second binder has excellent fire extinguishing ability at the initial stage of fire and can inhibit deliquescence of salt.

[0036] One aspect of the present disclosure relates to a fire extinguishing material comprising the fire extinguishing material composition. One aspect of the present disclosure relates to a device having an automatic fire extinguishing function, which comprises the fire extinguishing material.

[0037] One aspect of the present invention relates to a method for selecting a binder for a fire extinguishing material composition containing a fire extinguishing agent containing at least one of an organic salt and an inorganic salt and a binder. The method comprises: a step of heating a binder to be evaluated from 30°C to 500°C at a heating rate of 5°C / min in a thermogravimetric measurement under an atmospheric atmosphere, and measuring the weight reduction rate of the binder until the temperature reaches 400°C; and a step of judging that, for a binder resin having a weight reduction rate of 30% or more, a fire extinguishing material composition exhibiting good initial fire extinguishing properties can be prepared.

[0038] One aspect of the present disclosure relates to a method for producing a composition for a fire extinguishing material. The method comprises: a step of preparing a binder, which is determined to be capable of producing a composition for a fire extinguishing material that exhibits good initial fire extinguishing properties in the above-mentioned method for selecting the binder; and a step of preparing the composition for a fire extinguishing material, which contains the binder and a fire extinguishing agent containing at least one of an organic salt and an inorganic salt.

[0039] (Third aspect)

[0040] In order to achieve the third object, the present disclosure provides a fire extinguishing material sheet comprising a fire extinguishing agent layer including a fire extinguishing agent, a binder resin and an additive, wherein the weight ratio of the solid content of the fire extinguishing agent to the total weight of the solid content of the fire extinguishing agent, the binder resin and the additive is 60 wt % to 98 wt %.

[0041] This fire extinguishing material sheet is unlikely to produce cracks in the fire extinguishing agent layer even when applied to a curved surface, so that the fire extinguishing agent can exert a fire extinguishing function by the heat energy of the fire.

[0042] The fire extinguishing material sheet of the present disclosure may have one or more of the following features.

[0043] The binder resin contains at least one of a polyvinyl acetal-based resin and a polyvinyl alcohol-based resin.

[0044] The additive includes an epoxy compound, and the epoxy compound is difunctional or more.

[0045] The fire extinguishing agent contains potassium salt.

[0046] The thickness of the fire extinguishing agent layer is 70 μm to 500 μm.

[0047] The core diameter of the fire extinguishing agent layer is less than 18mm and can be bent.

[0048] A resin film on which a fire extinguishing agent layer is to be laminated is provided.

[0049] In addition, the present disclosure also provides a fire extinguishing agent composition, comprising a fire extinguishing agent, a binder resin, and an additive, wherein the weight ratio of the solid component of the fire extinguishing agent to the total weight of the solid components of the fire extinguishing agent, the binder resin and the additive is 60 weight % to 98 weight %, and the core shaft diameter when formed into a sheet is less than 18 mm.

[0050] Effects of the Invention

[0051] (First effect)

[0052] According to the first aspect of the present disclosure, a composition for a fire extinguishing material capable of obtaining a fire extinguishing material having excellent property stability can be provided. In addition, according to the first aspect of the present disclosure, a fire extinguishing material formed of the composition can be provided.

[0053] (Second effect)

[0054] According to the second aspect of the present disclosure, there are provided a composition for a fire extinguishing material that can exert excellent fire extinguishing ability in the initial stage of a fire, a method for producing the same, a fire extinguishing material using the composition for a fire extinguishing material, and a device having an automatic fire extinguishing function provided with the fire extinguishing material. In addition, according to the second aspect of the present disclosure, there is provided a method for selecting a binder that can impart excellent initial fire extinguishing ability to a fire extinguishing material.

[0055] (Third Effect)

[0056] According to the third aspect of the present disclosure, a fire extinguishing material sheet having a fire extinguishing function and hardly causing cracks in the fire extinguishing agent layer even when applied to a curved surface can be provided. In addition, according to the third aspect of the present disclosure, a fire extinguishing agent composition suitable for the fire extinguishing material sheet can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] [ Figure 1 ] is a cross-sectional view schematically showing an embodiment of the fire extinguishing material involved in the present disclosure.

[0058] [ Figure 2 ] is a cross-sectional view of the fire extinguishing material sheet involved in the present disclosure.

[0059] [ Figure 3 ] is a cross-sectional view of the fire extinguishing material stack involved in the present disclosure. DETAILED DESCRIPTION

[0060] Hereinafter, embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0061] [Fire extinguishing material composition according to the first aspect]

[0062] The fire extinguishing material composition according to the first aspect comprises: a fire extinguishing agent comprising at least one of a deliquescent organic salt and an inorganic salt; and a compound having an acid anhydride group. The fire extinguishing material composition may further comprise a binder resin and / or a liquid medium.

[0063] (Fire extinguishing agent)

[0064] The fire extinguishing agent includes at least one of a deliquescent organic salt and an inorganic salt, and an oxidant. Examples of deliquescent organic salts include potassium salts, sodium salts, ammonium salts, and the like. Among these, potassium salts are preferably used as organic salts. Examples of organic potassium salts include potassium acetate, potassium citrate (monopotassium citrate, dipotassium citrate, tripotassium citrate), potassium tartrate, potassium lactate, potassium oxalate, potassium maleate, and other carboxylic acid potassium salts. Among these, potassium acetate or potassium citrate is preferably used from the viewpoint of the usefulness of the negative catalytic effect on combustion.

[0065] As inorganic salts having deliquescent properties, for example, potassium salts, sodium salts, etc. can be cited. Among these, potassium salts are preferably used as inorganic salts. As inorganic potassium salts, potassium tetraborate, potassium carbonate, potassium hydrogen carbonate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, etc. can be cited.

[0066] The organic salt and the inorganic salt may be used alone or in combination of two or more.

[0067] The organic salt and the inorganic salt may be in granular form. The average particle size D50 of the organic salt and the inorganic salt may be from 1 μm to 100 μm, or from 3 μm to 40 μm. By making the average particle size D50 greater than the above lower limit, it is easy to disperse in the system; and by making the average particle size D50 less than the above upper limit, the stability as a coating liquid is improved, and thus the smoothness of the coating surface tends to be improved. The average particle size D50 can be calculated by wet measurement using a laser diffraction particle size distribution measuring device.

[0068] Examples of the oxidizing agent include potassium chlorate, potassium nitrate, sodium nitrate, strontium nitrate, ammonium perchlorate, potassium perchlorate, basic copper nitrate, copper (I) oxide, copper (II) oxide, iron (II) oxide, iron (III) oxide, and molybdenum trioxide. Among them, potassium chlorate is preferably used.

[0069] The content of the fire extinguishing agent in the fire extinguishing material composition can be 70-97% by mass, or 85-92% by mass, based on the total amount of the fire extinguishing material composition. By making the content of the fire extinguishing agent below the upper limit, it is easy to suppress the deliquescence of the salt, and the coating adaptability of the fire extinguishing material composition is improved, and film formation is easy; in addition, by making the content of the fire extinguishing agent above the lower limit, it is easy to exert sufficient fire extinguishing performance.

[0070] (Compound having anhydride group)

[0071] The fire extinguishing material composition can maintain the properties of the molded product stably for a long time by including a compound having an acid anhydride group. The reason for this is still unclear, but it is presumed that the acid anhydride group can react with water, and thus prevents the deliquescence of the salt contained in the molded product by capturing water that penetrates through the barrier film. In addition, it is presumed that the compound having an acid anhydride group improves the hydrophobicity by modifying the surface of the salt, thereby inhibiting contact with water.

[0072] As a compound having anhydride groups, there is no particular limitation as long as it is a compound having one or more anhydride groups formed by dehydration condensation of two molecules of oxygen-containing acid in the molecule. As oxygen-containing acids constituting the anhydride groups, for example, carboxylic acids, sulfuric acid, nitric acid, phosphoric acid, etc. can be listed. Among these, the oxygen-containing acid constituting the anhydride groups is preferably carboxylic acid. As compounds having carboxylic acid anhydride groups, for example, monomers of carboxylic acid anhydrides such as phthalic anhydride, succinic anhydride, and maleic anhydride can be listed; or copolymers using carboxylic acid anhydrides having unsaturated bonds such as maleic anhydride as monomers, etc.

[0073] The compound having anhydride groups may further have an alkoxysilyl group in the molecule. The compound having anhydride groups contained in the fire extinguishing material composition may maintain the properties of the molded product more stably for a long time by further having an alkoxysilyl group in the molecule. The reason is still uncertain, but it is speculated that the alkoxysilane undergoes self-reaction after hydrolysis to form siloxane, which improves water resistance and increases film density, thereby inhibiting the contact between deliquescent salts and water. As a compound having anhydride groups and alkoxysilyl groups in the molecule, for example, a silane coupling agent may be used. It should be noted that the silane coupling agent used as a compound having anhydride groups may have the same function as a binder resin in the fire extinguishing material composition.

[0074] The mass of the binder resin contained in the fire extinguishing material composition is set to 100 parts by mass, and the content of the compound having an acid anhydride group contained in the fire extinguishing material composition can be 10 to 250 parts by mass, or 50 to 200 parts by mass. By making the content of the compound having an acid anhydride group below the above upper limit, the coating adaptability of the fire extinguishing material composition is improved, not only is it easy to form a film, but also cracks in the film can be suppressed; in addition, by making the content of the compound having an acid anhydride group above the above lower limit, it is easy to suppress the deliquescence of the salt and it is easy to show sufficient fire extinguishing performance.

[0075] (Binder resin)

[0076] As the binder resin, thermoplastic resins and thermosetting resins can be used. Examples of the thermoplastic resin include polyolefin resins such as polyvinyl alcohol resins, 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, and polyvinyl chloride resins. As thermosetting resins, rubbers such as 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), and urethane rubber (U) can be listed; polyurethane resin, polyisocyanate resin, polyisocyanurate resin, phenolic resin, epoxy resin, etc. Among the above resins, one can be used alone or multiple can be used in combination. Among these, from the viewpoint of coating adaptability, polyurethane resin or polyvinyl alcohol resin is preferably used. It should be noted that the binder resin may also contain a curing agent component.

[0077] The weight average molecular weight of the binder resin may be 10,000 or more, or 20,000 or more, or 150,000 or less, or 100,000 or less. By making the weight average molecular weight above the lower limit, it is easy to ensure the hydrophobicity of the resin; by making the weight average molecular weight below the upper limit, it is easy to ensure appropriate resin flexibility, and it is easy to improve bending resistance and coating adaptability. The weight average molecular weight can be calculated by the GPC method.

[0078] The glass transition temperature of the binder resin may be 55°C or more, 80°C or more, 110°C or less, or 100°C or less. When the glass transition temperature is above the lower limit, the crystallinity becomes large, so it is easy to ensure the hydrophobicity of the resin; and when the glass transition temperature is below the upper limit, it is easy to improve the coating adaptability. The glass transition temperature can be measured by thermal analysis using a differential scanning calorimeter.

[0079] The viscosity of the binder resin at 20° C. may be 500 mPa·s or more, or 1000 mPa·s or less, or 10000 mPa·s or less, or 6000 mPa·s or less. The viscosity can be measured with a B-type rotational viscometer.

[0080] Based on the total amount of the fire extinguishing material composition, the content of the binder resin contained in the fire extinguishing material composition can be 2 to 30% by mass, or 4 to 15% by mass. By making the content of the binder resin below the above upper limit, it is easy to improve the surface smoothness of the coating after drying (easy to suppress the generation of cracks and bubbles in the coating); in addition, by making the content of the binder resin above the above lower limit, it is easy to improve the roll-to-roll coating adaptability when applying the fire extinguishing material composition, and it is easy to improve the substrate adhesion and the coating film cutting processing adaptability.

[0081] (Liquid medium)

[0082] Examples of the liquid medium include organic solvents. Examples of the organic solvent include water-soluble solvents, such as alcohols such as methanol, ethanol, isopropanol, and n-propanol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and diethylene glycol; glycol ethers such as N-methylpyrrolidone, tetrahydrofuran, and butyl cellosolve. From the perspective of use with a deliquescent salt, the liquid medium may be an alcohol solvent, specifically, a mixed solvent of ethanol and isopropanol.

[0083] The amount of the liquid medium can be appropriately adjusted according to the method of use of the fire extinguishing material composition, and can be set to 40 to 95% by mass based on the total amount of the fire extinguishing material composition. The fire extinguishing material composition containing the liquid medium can be referred to as a fire extinguishing material coating liquid.

[0084] (Other ingredients)

[0085] In addition to the above, other ingredients can be added to the fire extinguishing material composition. As other ingredients, colorants, antioxidants, flame retardants, inorganic fillers, fluidity imparting agents, moisture-proofing agents, dispersants, UV absorbers, catalysts, etc. can be listed. These other ingredients can be appropriately selected according to the types of salts, compounds with anhydride groups, binder resins, or liquid media. Based on the total amount of the fire extinguishing material composition, the content of other ingredients contained in the fire extinguishing material composition is, for example, 10% by mass or less.

[0086] <Fire extinguishing materials involved in the first aspect>

[0087] The fire extinguishing material according to the first aspect may be formed from the fire extinguishing material composition according to the first aspect. A method for forming the fire extinguishing material (manufacturing method) is exemplified below.

[0088] The fire extinguishing material can be formed on the object by applying a fire extinguishing material coating liquid on the treated surface of the object and drying it. The material of the object can include metal, resin, wood, ceramic, glass, etc. The object can be non-porous or porous.

[0089] The coating can be performed by a wet coating method, which includes gravure coating, comma coating, spray coating, dip coating, curtain coating, spin coating, sponge roll coating, die coating, and coating with a brush.

[0090] Regarding the viscosity of the coating liquid for fire extinguishing materials, for example, if it is a gravure coating method, it is preferably set to 1 to 2000 mPa·s; if it is a comma coating method, it is preferably set to 500 to 100000 mPa·s; if it is a spray coating method, it is preferably set to 0.1 to 4000 mPa·s. In order to make the viscosity of the coating liquid within the desired range, the amount of the above-mentioned liquid medium can be appropriately adjusted. The viscosity can be measured by a coaxial double cylinder rotation viscometer.

[0091] When the object is porous, the fire extinguishing material coating liquid can be immersed in the object. In this case, the fire extinguishing material can also be formed on the object by impregnating the object with the fire extinguishing material coating liquid and drying it.

[0092] The fire extinguishing material can also be obtained by shaping the fire extinguishing material composition. The shape of the fire extinguishing material can be selected according to its use, and the fire extinguishing material can be a granular fire extinguishing material, a plate-shaped fire extinguishing material, a columnar fire extinguishing material, etc.

[0093] [Fire extinguishing material composition according to the second aspect]

[0094] <First Embodiment>

[0095] The fire extinguishing material composition involved in the second aspect contains: a fire extinguishing agent including at least one salt selected from an organic salt and an inorganic salt, and a binder. In a thermogravimetric measurement under an atmospheric atmosphere, when the binder is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight reduction rate of the binder until the temperature reaches 400°C is 30% or more.

[0096] (Fire extinguishing agent)

[0097] The fire extinguishing agent contains at least one of an organic salt and an inorganic salt, and an oxidant. As the organic salt and the inorganic salt, the same organic salt and the inorganic salt as those used in the fire extinguishing material composition according to the first aspect can be used.

[0098] Examples of the oxidizing agent include potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, magnesium chlorate, potassium nitrate, sodium nitrate, strontium nitrate, ammonium perchlorate, potassium perchlorate, basic copper nitrate, copper (I) oxide, copper (II) oxide, iron (II) oxide, iron (III) oxide, molybdenum trioxide, etc. Among them, potassium chlorate is preferably used.

[0099] The content of the fire extinguishing agent in the fire extinguishing material composition can be 70-97% by mass, or 85-92% by mass, based on the total amount of the fire extinguishing material composition. By making the content of the fire extinguishing agent below the upper limit, it is easy to suppress the deliquescence of the salt, and the coating adaptability of the fire extinguishing material composition is improved, and it is easy to form a film; in addition, by making the content of the fire extinguishing agent above the lower limit, it is easy to exert sufficient fire extinguishing ability.

[0100] (Binder)

[0101] The binder preferably easily loses weight due to heat. That is, in a thermogravimetric measurement under an atmospheric atmosphere, when the binder is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight reduction rate of the binder until the temperature reaches 400°C is 30% or more. The above-mentioned weight reduction rate can be 32% or more. By making the weight reduction rate within the above-mentioned range, the fire extinguishing ability of the obtained fire extinguishing material composition in the initial stage of fire is excellent. It should be noted that, in the presence of multiple binders, the weight reduction rate of the binder refers to the weight reduction rate of the mixture. The upper limit of this value can be, for example, 88%, or 46% or 32%.

[0102] In order to select a binder suitable for a composition for a fire extinguishing material, the following selection method can be implemented. That is, the method for selecting a binder includes: in a thermogravimetric measurement under an atmospheric atmosphere, heating the binder to be evaluated from 30°C to 500°C at a heating rate of 5°C / min, and measuring the weight reduction rate of the binder until the temperature reaches 400°C; and for a binder with a weight reduction rate of 30% or more, judging that a composition for a fire extinguishing material that exhibits good initial fire extinguishing properties can be prepared. The benchmark for the weight reduction rate can be set to 32% or more.

[0103] As the resin used as the binder, the same resin as the binder resin described in the fire extinguishing material composition according to the first aspect can be used.

[0104] The weight average molecular weight of the binder can be 5000 or more, or 20000 or more, or 150000 or less, or 100000 or less. By making the weight average molecular weight above the lower limit, it is easy to ensure the hydrophobicity of the resin; by making the weight average molecular weight below the upper limit, it is easy to ensure the appropriate flexibility of the resin, and it is easy to improve the bending resistance and coating adaptability. The weight average molecular weight can be calculated by the GPC method.

[0105] The glass transition temperature of the binder is not particularly limited, and may be above -40°C, above 55°C, or above 80°C, or below 110°C or below 100°C. By making the glass transition temperature above the lower limit, the crystallinity becomes larger, so it is easy to ensure the hydrophobicity of the resin; and by making the glass transition temperature below the upper limit, it is easy to improve the coating adaptability. The glass transition temperature can be measured by thermal analysis using a differential scanning calorimeter.

[0106] The viscosity of the adhesive at 20° C. may be 500 mPa·s or more, or 1000 mPa·s or less, or 10000 mPa·s or less, or 6000 mPa·s or less. The viscosity can be measured by a B-type rotational viscometer.

[0107] Based on the total amount of the fire extinguishing material composition, the content of the binder contained in the fire extinguishing material composition can be 2 to 30% by mass, or 4 to 15% by mass. By making the content of the binder below the above upper limit, it is easy to improve the surface smoothness of the coating after drying (easy to suppress the generation of cracks and bubbles in the coating); in addition, by making the content of the binder above the above lower limit, it is easy to improve the roll-to-roll coating adaptability when applying the fire extinguishing material composition, and it is easy to improve the substrate adhesion and the coating film cutting processing adaptability.

[0108] (Liquid medium)

[0109] The fire extinguishing material composition may further contain a liquid medium. As the solvent used as the liquid medium, the same liquid medium as described in the fire extinguishing material composition according to the first aspect can be used.

[0110] The amount of the liquid medium may be appropriately adjusted according to the method of use of the fire extinguishing material composition, and may be 30 to 70% by mass based on the total amount of the fire extinguishing material composition. The fire extinguishing material composition containing the liquid medium may be referred to as a fire extinguishing material coating liquid.

[0111] (Other ingredients)

[0112] In the fire extinguishing material composition, other ingredients can be matched in addition to the above. As other ingredients, surfactants, silane coupling agents, anti-adhesion agents, colorants, antioxidants, flame retardants, inorganic fillers, fluidity imparting agents, moisture-proofing agents, dispersants, UV absorbers, flexibility imparting agents, catalysts, etc. can be listed. These other ingredients can be appropriately selected according to the types of fire extinguishing agents, binders, or liquid media. Based on the total amount of the fire extinguishing material composition, the content of other ingredients contained in the fire extinguishing material composition is, for example, less than 10% by mass.

[0113] [Method for producing the fire extinguishing material composition according to the second aspect]

[0114] The fire extinguishing material composition according to the second aspect can be produced by mixing a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, a binder, and other components used as needed. The binder used can be any binder that is judged to be capable of preparing a fire extinguishing material composition that exhibits good initial fire extinguishing properties in the above-mentioned binder selection method.

[0115] <Second Embodiment>

[0116] The fire extinguishing material composition of the second embodiment involved in the second aspect contains: a fire extinguishing agent containing at least one salt of an organic salt and an inorganic salt, a first binder, and a second binder. In a thermogravimetric measurement under an atmospheric atmosphere, when the first binder is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight reduction rate of the first binder until the temperature reaches 400°C is 50% or more. In a thermogravimetric measurement under an atmospheric atmosphere, when the second binder is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight reduction rate of the second binder until the temperature reaches 400°C is 15% or less. When the mass of the first binder is set to 100 parts, the mass of the second binder is 250 parts or less.

[0117] As the fire extinguishing agent and the first adhesive of the second embodiment according to the second aspect, the same fire extinguishing agent and the adhesive as those described in the first embodiment can be used, respectively.

[0118] Since the second binder is used together with the first binder that is easy to lose weight due to heat, it can also be a binder that is difficult to lose weight due to heat. That is, in the thermogravimetric measurement carried out under the above conditions, as described above, the weight loss rate of the second binder can be 15% or less, or 13% or less, or 12% or less. The lower limit of this value can be, for example, 0%, or 3% or 7%.

[0119] As described above, the mass of the first binder is set to 100 parts, and the content of the second binder contained in the fire extinguishing material composition is 250 parts or less, or 200 parts or less, 150 parts or less, or 100 parts or less. By making the content of the second binder within the above range, the desired physical properties corresponding to the type of the second binder can be obtained while maintaining the fire extinguishing ability of the obtained fire extinguishing material composition in the initial stage of fire in practical use. The lower limit of this value is, for example, 10 parts, or 50 parts.

[0120] It should be noted that the first binder used in combination with the second binder may also be a binder that is more easily reduced in weight by heat. That is, in the thermogravimetric measurement performed under the above conditions, the weight reduction rate of the first binder is preferably 50% or more, 52% or more, 54% or more, or 60% or more.

[0121] As the second binder, for example, a compound having an anhydride group can be used. The fire extinguishing material composition can stably maintain the properties of the molded product for a long time by including a compound having an anhydride group. The reason is still uncertain, but it is speculated that the anhydride group can react with water, so the deliquescence of the salt contained in the molded product is prevented by capturing the infiltrated water. In addition, it is speculated that the compound having anhydride group improves the hydrophobicity by modifying the surface of the salt, thereby inhibiting contact with water.

[0122] As a compound having anhydride groups, there is no particular restriction as long as it is a compound having one or more anhydride groups formed by dehydration condensation of two molecules of oxygen-containing acid in the molecule. As oxygen-containing acids constituting the anhydride groups, for example, carboxylic acids, sulfuric acid, nitric acid, phosphoric acid, etc. can be listed. Among these, the oxygen-containing acid constituting the anhydride groups is preferably carboxylic acid. As compounds having carboxylic acid anhydride groups, for example, monomers of carboxylic acid anhydrides such as phthalic anhydride, succinic anhydride, and maleic anhydride can be listed; or copolymers with carboxylic acid anhydrides having unsaturated bonds such as maleic anhydride as monomers, etc. It should be noted that compounds having anhydride groups can also be used as the first binder.

[0123] The compound having anhydride groups may further have an alkoxysilyl group in the molecule. The compound having anhydride groups contained in the fire extinguishing material composition may maintain the properties of the molded product more stably for a long time by further having an alkoxysilyl group in the molecule. The reason is still uncertain, but it is speculated that the alkoxysilane undergoes self-reaction after hydrolysis to form siloxane, which improves water resistance and increases film density, thereby inhibiting the contact between deliquescent salts and water. As a compound having anhydride groups and alkoxysilyl groups in the molecule, for example, a silane coupling agent may be used. It should be noted that the silane coupling agent used as a compound having anhydride groups may have the same function as a binder resin in the fire extinguishing material composition.

[0124] As the second binder, for example, thermoplastic resins and thermosetting resins can be used. In addition, from the viewpoint of easy formation of a coating film and stabilization of the properties after film formation, surfactants, silane coupling agents, anti-adhesion agents, antioxidants, flame retardants, fluidity imparting agents, moisture-proofing agents, dispersants, UV absorbers, flexibility imparting agents, etc. can also be used. By appropriately using the second binder separately or in combination, the composition for fire extinguishing materials can be given desired properties such as improved adhesion to the substrate, improved processability, reduced viscosity, and improved roll-to-roll coating adaptability. Among them, as the second binder, a compound having an anhydride group is preferred, and a silane coupling agent having a carboxylic anhydride group and an alkoxysilyl group is particularly preferred.

[0125] The fire extinguishing material composition of the second embodiment of the second aspect may further include the same liquid medium or other components as the fire extinguishing material composition of the first embodiment. The amount of the liquid medium can be appropriately adjusted according to the method of use of the fire extinguishing material composition, and can be set to 30 to 70% by mass based on the total amount of the fire extinguishing material composition. The content of other components contained in the fire extinguishing material composition is, for example, 10% by mass or less based on the total amount of the fire extinguishing material composition.

[0126] [Fire extinguishing materials involved in the second aspect]

[0127] The fire extinguishing material according to the second aspect may be formed from the composition for fire extinguishing material according to the second aspect. Figure 1 1 is a cross-sectional view schematically showing an embodiment of a fire extinguishing material. The fire extinguishing material 1 includes a substrate 2 and a fire extinguishing material layer 3 provided on one surface of the substrate 2. The fire extinguishing material 1 can be manufactured by applying a fire extinguishing material coating liquid on one surface of the substrate 2 and drying the applied layer to form the fire extinguishing material layer 3. The material of the substrate 2 is, for example, metal, resin, wood, ceramic, or glass, and may be non-porous or porous.

[0128] The coating can be performed by a wet coating method, which includes gravure coating, comma coating, spray coating, dip coating, curtain coating, spin coating, sponge roll coating, die coating, and coating with a brush.

[0129] Regarding the viscosity of the coating liquid for fire extinguishing materials, for example, if it is a gravure coating method, it is preferably set to 1 to 2000 mPa·s; if it is a comma coating method, it is preferably set to 500 to 100000 mPa·s; if it is a spray coating method, it is preferably set to 0.1 to 4000 mPa·s. In order to make the viscosity of the coating liquid within the desired range, the amount of the above-mentioned liquid medium can be appropriately adjusted. The viscosity can be measured by a coaxial double cylinder rotation viscometer.

[0130] When the substrate 2 is porous, the fire extinguishing material coating liquid can penetrate into the substrate 2. In this case, a part of the fire extinguishing material layer 3 can penetrate into the inside of the substrate 2, and the remaining part can be laminated on the surface of the substrate 2.

[0131] The fire extinguishing material can also be obtained by forming the fire extinguishing material composition into a predetermined shape. The shape of the fire extinguishing material can be selected according to its use, and the fire extinguishing material can be a granular fire extinguishing material, a plate-shaped fire extinguishing material, a columnar fire extinguishing material, etc.

[0132] [Device with automatic fire extinguishing function]

[0133] Devices with automatic fire extinguishing functions are equipped with fire extinguishing materials. As devices with automatic fire extinguishing functions, electrical system equipment equipped with electrical wiring or cables, transformers or circuits, etc. can be listed. Specifically, distribution boards, distribution boards, storage batteries (lithium-ion batteries, etc.), batteries (mobile batteries, tool batteries, EV batteries for cars, etc.), and storage systems equipped with the above can be listed. In addition, places with the risk of accidental fire can be listed, such as battery recycling boxes, garbage bins, socket covers, etc.

[0134] [Fire extinguishing material sheet involved in the third aspect]

[0135] The fire extinguishing material sheet involved in the third aspect is formed by forming a fire extinguishing agent composition into a sheet. The fire extinguishing material sheet is pasted on a flammable object for use. Then, when the object catches fire, it is subjected to its heat energy, and chemical species with fire extinguishing function are released from the fire extinguishing agent composition, thereby extinguishing the flame. Since it is not necessary to use a fire extinguisher or fire extinguishing device to extinguish the fire, such a fire extinguishing material sheet exhibits "self-extinguishing properties".

[0136] As the fire extinguishing object, there is no particular limitation as long as it is a material that may catch fire. As the material that may catch fire, for example, wires, switchboards, distribution boards, control panels, batteries (lithium-ion batteries, etc.), building materials such as wallpaper for building materials, ceiling materials, boxes for recycling lithium-ion batteries (recycling boxes), trash cans, automobile-related parts, sockets, socket covers and other parts can be listed. In particular, the fire extinguishing material sheet of this embodiment has high followability to curved surfaces, and is therefore suitable for application to curved surfaces.

[0137] like Figure 2 As shown, the fire extinguishing material sheet 11 according to the third aspect comprises a resin film 12 and a fire extinguishing agent layer 13 laminated on the resin film 12. The fire extinguishing agent layer 13 is formed by forming a fire extinguishing agent composition into a sheet. The thickness of the fire extinguishing agent layer 13 may be 70 μm to 500 μm, 90 μm to 300 μm, or 110 μm to 200 μm.

[0138] The mandrel diameter of the fire extinguishing agent layer 13 may be 18 mm or less, 12 mm or less, 6 mm or less, or 3 mm or less. Here, the "mandrel diameter" refers to the minimum diameter at which no cracks (ruptures) are observed when the fire extinguishing agent layer 13 is subjected to a mandrel test of type 1 according to JIS K5600-5-1 alone. The minimum diameter possible in the test is 2 mm.

[0139] The resin film 12 is a film as a support when the fire extinguishing agent layer 13 is formed into a sheet. There is no particular restriction on the material, and for example, a polyethylene terephthalate film is preferred. In addition, in consideration of the situation of using the fire extinguishing agent layer 13 alone, it is preferred that the surface of the resin film 12 on the side in contact with the fire extinguishing agent layer 13 is subjected to an anti-adhesion treatment.

[0140] [Fire extinguishing agent composition according to the third aspect]

[0141] The fire extinguishing agent composition according to the third aspect includes at least a fire extinguishing agent, a binder resin, and an additive. The fire extinguishing agent composition is a composition obtained by uniformly mixing these.

[0142] (Fire extinguishing agent)

[0143] As the fire extinguishing agent, various organic salts or inorganic salts can be used alone or in combination. As the organic salt and inorganic salt, the same organic salt and inorganic salt as those described in the fire extinguishing material composition according to the first aspect can be used.

[0144] In addition, the fire extinguishing agent may also contain a compound having an oxidizing effect. Examples of the compound having an oxidizing effect include chlorates such as potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, and magnesium chlorate. These can generate aerosols from the potassium salts when they are exposed to the heat energy of the fire.

[0145] The amount of fire extinguishing agent can be appropriately selected according to the shape of the object, the fire power at the time of fire, the fire extinguishing time, the allowed space, etc. The more the amount of fire extinguishing agent, the higher the fire extinguishing ability and the shorter the fire extinguishing time, but sometimes the volume will also increase, so the place where the fire extinguisher can be placed is limited. The amount of fire extinguishing agent can be set to 0.01 to 1.0 g / cm 2 , can be 0.02~0.2g / cm 2 .

[0146] Regarding the content of the fire extinguishing agent in the fire extinguishing agent composition, the ratio of the weight of the solid content of the fire extinguishing agent to the total weight of the solid content of the fire extinguishing agent, the binder resin and the additive (hereinafter referred to as the "fire extinguishing agent solid content ratio") is 60% to 98% by weight. By making this ratio above 60% by weight, it can have a sufficient fire extinguishing function; by making it below 98% by weight, when the fire extinguishing agent composition is formed into a sheet, the bending followability can be fully exerted. The fire extinguishing agent solid content ratio can be 70% to 97% by weight, or 75% to 96% by weight, or 80% to 95% by weight, or 85% to 94% by weight.

[0147] (Binder resin)

[0148] The binder resin (hereinafter also referred to as "binder") uniformly disperses the fire extinguishing agent and connects the particles of the fire extinguishing agent together. In addition, the binder resin also acts as a fuel for releasing chemical species with fire extinguishing function from the fire extinguishing agent composition, thereby improving the coating adaptability when forming the fire extinguishing agent layer. In addition, when a deliquescent salt is included as a fire extinguishing agent component, the binder resin can inhibit its deliquescence.

[0149] As the binder resin, thermoplastic resins and thermosetting resins can be used. As thermoplastic resins, polyolefin resins such as polypropylene resins, polyethylene resins, poly(1-)butene resins, and polypentene resins can be listed; 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, etc. As thermosetting resins, the same resins as those described in the composition for fire extinguishing materials according to the first aspect can be used.

[0150] As the binder resin, it is preferred to include at least one of polyvinyl acetal resin and polyvinyl alcohol resin. Both polyvinyl acetal resin and polyvinyl alcohol resin are hydroxyl-containing resins. The greater the degree of acetalization of the polyvinyl acetal resin, the higher the hydrophobicity of the resin, and thus it is easy to suppress the moisture absorption caused by salt (salt used as a fire extinguishing agent). Since the polyvinyl alcohol resin is not acetalized, it has more hydroxyl numbers than the polyvinyl acetal resin, but it is believed that there are also more reaction points with other resin components other than the above-mentioned resins. Therefore, from the viewpoint of binder design, the polyvinyl alcohol resin has a high degree of design freedom and is easy to handle.

[0151] The polyvinyl alcohol resin is obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers. Examples of other monomers include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamides having an ammonium group.

[0152] The saponification degree of the polyvinyl alcohol resin is not particularly limited, and may be 80 mol% or more, or 95 mol% or more. When the polyvinyl alcohol resin has an appropriate saponification degree, the adhesion with the salt is easily improved, and the moisture absorption caused by the salt is easily suppressed.

[0153] The polyvinyl alcohol resin may be modified. Examples of the modification include acetoacetyl modification, carboxylic acid modification, carbonyl modification, sulfonic acid modification, hydrazide modification, thiol modification, alkyl modification, silyl modification, polyethylene glycol modification, oxirane modification, modification of a group having a carbamate bond, and phosphate modification. By modifying the polyvinyl alcohol resin, it is easy to improve the adhesion with salt, thereby easily suppressing the moisture absorption caused by the salt.

[0154] The polyvinyl acetal resin is obtained by acetalizing a polyvinyl alcohol resin.

[0155] The saponification degree of the polyvinyl alcohol-based resin used to obtain the polyvinyl acetal-based resin is not particularly limited, and may be 80 mol % or more, or 95 mol % or more.

[0156] The aldehyde used for acetalization is not particularly limited, and examples thereof include aldehydes having an aliphatic group or an aromatic group having 1 to 10 carbon atoms. Examples of aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, n-hexanal, 2-ethylbutyraldehyde, 2-ethylhexanal, n-heptylaldehyde, n-octanal, n-nonanal, n-decanal, and valeraldehyde; and aromatic aldehydes such as benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, and β-phenylpropionaldehyde. These aldehydes may be used alone or in combination of two or more. Among these, from the viewpoint of excellent acetalization reactivity, the aldehyde may be butyraldehyde, 2-ethylhexanal, or n-nonanal, or may be butyraldehyde.

[0157] The ketone used for acetalization is not particularly limited, and examples thereof include acetone, ethyl methyl ketone, diethyl ketone, tert-butyl ketone, dipropyl ketone, allyl ethyl ketone, acetophenone, p-methylacetophenone, 4'-aminoacetophenone, p-chloroacetophenone, 4'-methoxyacetophenone, 2'-hydroxyacetophenone, 3'-nitroacetophenone, p-(1-piperidyl)acetophenone, benzylideneacetophenone, propiophenone, benzophenone, 4-nitrobenzophenone, 2-methylbenzophenone, p-bromobenzophenone, cyclohexyl(phenyl)methyl ketone, 2-butylnaphthone, 1-acetophenone, 2-hydroxy-1-acetophenone, and 8'-hydroxy-1-benzonaphthone.

[0158] The amount of aldehyde and ketone used can be appropriately set according to the degree of acetalization. For example, the total amount of aldehyde and ketone can be set to 0.30 to 0.45 hydroxyl equivalents relative to the hydroxyl group of the polyvinyl alcohol-based resin before the reaction.

[0159] The hydroxyl amount (residual hydroxyl value) of the polyvinyl acetal resin can be 10 to 40 mol%, or 15 to 25 mol%. When the hydroxyl amount is within the above range, hydrophobicity is obtained by the aliphatic group or aromatic group of the aldehyde and ketone, and the moisture absorption rate tends to be easily deactivated. The hydroxyl amount is the ratio (mol%) of the amount of ethylene bonded with hydroxyl groups relative to the total amount of ethylene in the main chain. The amount of ethylene bonded with hydroxyl groups can be calculated, for example, by the method according to JIS K6728 "Testing methods for polyvinyl butyral".

[0160] The polyvinyl acetal resin and the polyvinyl alcohol resin may be used alone or in combination of two or more.

[0161] The weight average molecular weight Mw of the polyvinyl acetal resin and the polyvinyl alcohol resin can be 10000 or more, or 20000 or more, or 150000 or less, or 100000 or less. By making the weight average molecular weight Mw above the above lower limit, it is easy to ensure the hydrophobicity of the resin; by making the weight average molecular weight Mw below the above upper limit, it is easy to ensure appropriate resin flexibility, and it is easy to improve bending resistance and coating adaptability. The weight average molecular weight Mw can be calculated by the GPC method.

[0162] The glass transition temperature Tg of the polyvinyl acetal resin and the polyvinyl alcohol resin may be 55°C or more, or 80°C or more, or 110°C or less, or 100°C or less. By making the glass transition temperature Tg above the lower limit, the crystallinity becomes large, so it is easy to ensure the hydrophobicity of the resin; and by making the glass transition temperature Tg below the upper limit, it is easy to improve the coating adaptability. The glass transition temperature Tg can be measured by thermal analysis using a differential scanning calorimeter.

[0163] From the viewpoint of fully expressing the characteristics of the resins, the content of the polyvinyl acetal resin and the polyvinyl alcohol resin contained in the binder can be set to 40% by weight or more, 70% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total amount of the binder.

[0164] From the viewpoint of suppressing the hygroscopicity of salts with the improvement of hydrophobicity, the binder may contain other components in addition to the above-mentioned resins. As other components, silane coupling agents etc. can be listed. The content of other components contained in the binder is, for example, 60% by mass or less.

[0165] (additive)

[0166] The additive in this embodiment is used to make the fire extinguishing agent composition soft to improve the formability, and to improve the followability of the sheet forming body to the curved surface. As the additive, an epoxy compound is particularly preferred. Among the epoxy compounds, a difunctional or higher epoxy compound is preferred, and a compound represented by the chemical formula (1) shown below is particularly preferred.

[0167] [Chemical formula 1]

[0168]

[0169] In the chemical formula (1), m is an integer of 1 to 6, and n is an integer of 1 to 30. m may be an integer of 1 to 4, or an integer of 1 to 3. n may be an integer of 1 to 20, or an integer of 1 to 15. In particular, when m is 1, n may be an integer of 1 to 25. In addition, in particular, when m is 2 or 3, n may be an integer of 5 to 15, or an integer of 8 to 12. It should be noted that due to the deviation in chain length generated during the synthesis of the compound, n as a value representing its average is not necessarily an integer. For example, the above-mentioned "n is an integer of 5 to 15" can also be understood as "n is an arbitrary number in the range of 5 to 15".

[0170] Regarding the content of the additive in the fire extinguishing agent composition, from the perspective of serving as a flexibility-imparting agent for the fire extinguishing agent composition, the ratio of the weight of the solid content of the additive to the total weight of the solid content of the fire extinguishing agent, the binder resin and the additive can be 0.2% by weight to 12.0% by weight, 0.4% by weight to 8.0% by weight, or 1.0% by weight to 4.0% by weight.

[0171] When the compound added as an additive is a resin, the resin is not treated as a binder resin but as an additive. The resin used as an additive is a resin that does not form a film when the resin is used alone as a binder resin. That is, it is a resin that can be coated on a substrate, but after drying, the film breaks and peels off from the substrate.

[0172] [The method for manufacturing the fire extinguishing material sheet according to the third aspect]

[0173] The fire extinguishing material sheet 11 can be manufactured by preparing a coating liquid (composition liquid for forming a fire extinguishing agent layer) containing a fire extinguishing agent, a binder resin, and an additive, applying it on a resin film, and drying it. Here, as a method for preparing the coating liquid, a fire extinguishing agent liquid containing a fire extinguishing agent and a binder resin liquid containing a binder resin can also be prepared separately, and the coating liquid can be prepared by mixing them with the additive.

[0174] As the solvent used in the preparation of the fire extinguishing agent liquid and the binder resin liquid, an organic solvent is preferred. As the organic solvent, water-soluble solvents can be listed, for example, alcohols such as methanol, ethanol, isopropanol, and n-propanol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and diethylene glycol; glycol ethers such as N-methylpyrrolidone (NMP), tetrahydrofuran, and butyl cellosolve, etc. In the case of using a hygroscopic fire extinguishing agent, the organic solvent can be an alcohol solvent, specifically, a mixed solvent of ethanol and isopropanol.

[0175] When preparing a fire extinguishing agent liquid, the ratio of the weight of the fire extinguishing agent to the weight of the solvent can be 30:70 to 70:30, or 40:60 to 60:40, or 45:55 to 55:45. When preparing a binder resin liquid, the ratio of the weight of the binder resin to the weight of the solvent can be 2:98 to 30:70, or 5:95 to 25:75, or 10:90 to 20:80. In order to maintain the coating adaptability of the coating liquid, the amount of solvent is preferably within these lower limits. In addition, in order to ensure the thickness required for one coating, the amount of solvent is preferably within these upper limits. In addition, from the viewpoint of having little residual solvent after drying and being able to dry sufficiently without causing film rupture or bubbles after drying, the amount of solvent is preferably within these upper limits.

[0176] As a method for applying the coating liquid on the resin film, a wet coating method can be cited. As the wet coating method, a gravure coating method, a comma coating method, a spray coating method, a dip coating method, a curtain coating method, a spin coating method, a sponge roller method, a die coating method, and coating using a brush can be cited. Drying after coating can be performed using an oven.

[0177] <Effect>

[0178] The fire extinguishing material sheet 11 constructed as described above can be pasted on a flammable object for use. The fire extinguishing material sheet 11 is not only adaptable to pasting to compact and narrow places, but also can be bent or rolled without cracking or peeling of the fire extinguishing agent layer 13 even when pasted to a curved place with a fire hazard (such as the inside of a battery shell or the battery itself) or a place with bumps (such as the corner of the shell). In addition, due to its favorable characteristics, it is suitable for roll-to-roll processing. Moreover, when the object after pasting catches fire, the fire extinguishing agent layer 13 releases chemical species with fire extinguishing function (for example, in the form of aerosol) due to its heat energy, thereby extinguishing the flame.

[0179] <Fire Extinguishing Material Laminate>

[0180] As another embodiment of the present disclosure, a fire extinguishing agent composition formed into a sheet may be laminated with a resin layer or a water vapor barrier layer. Here, it is referred to as a "fire extinguishing material laminate" as a type of fire extinguishing material sheet. Figure 3 As shown, the fire extinguishing material stack 100 includes resin layers 14, 14 so as to cover the fire extinguishing agent layer 13 from both sides thereof, and includes water vapor barrier layers 16, 16 from both sides thereof via adhesive layers 15, 15. In addition, an adhesive layer 17 is further provided on one side of the water vapor barrier layer 16, and a release film 18 is laminated thereon. The release film 18 is peeled off when the fire extinguishing material stack 100 is attached to a desired location, and may be made of resin or paper.

[0181] Here, the material of the resin layers 14, 14 can include: polyolefins (PE, PP, COP, etc.), polyesters (PET, etc.), fluororesins (PTFE, ETFE, EFEP, PFA, FEP, PCTFE, etc.), vinyl resins (PVC, PVA, etc.), acrylic resins, epoxy resins, polyamides, polyimides, etc.

[0182] The resin layers 14, 14 may have thermal melting properties (thermal fusion properties). As resins having thermal melting properties, polyolefin resins may be cited. That is, the resin layers 14, 14 may include polyolefin resins. As polyolefin resins, polyolefin resins such as low-density polyethylene resin (LDPE), linear low-density polyethylene resin (LLDPE), medium-density polyethylene resin (MDPE), and unstretched polypropylene resin (CPP) may be cited; polyethylene resins such as ethylene-vinyl acetate copolymers and ethylene-α-olefin copolymers; polypropylene resins such as propylene-ethylene random copolymers, propylene-ethylene block copolymers, and propylene-α-olefin copolymers. Among these, from the perspective of excellent heat sealing properties, low water vapor permeability, and easy suppression of deterioration of the fire extinguishing agent, the polyolefin resin may include low-density polyethylene resin (LDPE), linear low-density polyethylene resin (LLDPE), or unstretched polypropylene resin (CPP). These resins are transparent and it is easy to perform an appearance inspection of the fire extinguishing agent. Therefore, it is easy to confirm the replacement period of the fire extinguishing material stack.

[0183] The resin layers 14, 14 have a larger area than the fire extinguishing agent layer 13, and the fire extinguishing agent layer 13 can be sealed by heat-sealing the portions where the resin layers 14, 14 contact each other. Figure 3 In the embodiment, the fire extinguishing agent layer 13 is used in a state where the resin film 12 is peeled off from the fire extinguishing material sheet 10, but the fire extinguishing material sheet 10 itself may be sealed with the resin layers 14, 14 without peeling off the resin film 12. The thickness of the resin layers 14, 14 may be set to 25 μm to 150 μm, or 30 μm to 100 μm.

[0184] As the adhesive constituting the adhesive layers 15, 15, there can be cited acrylic adhesives, epoxy adhesives, silicone adhesives, polyolefin adhesives, urethane adhesives, polyvinyl ether adhesives, or synthetic adhesives thereof, etc. Among these, epoxy-urethane synthetic adhesives can be preferably used as the adhesive from the viewpoint of both adhesion with the resin layers 14, 14 at high temperature and high humidity of 85°C-85%RH and low cost.

[0185] The water vapor barrier layers 16, 16 are independent of the installation location and usage environment of the fire extinguishing material stack 100, and it is easy to maintain the water vapor barrier properties to the extent that the properties of the fire extinguishing agent do not change significantly. The water vapor permeability of the water vapor barrier layers 16, 16 (according to JIS K 7129, under the conditions of 40°C / 90%RH) can be designed according to the type of fire extinguishing agent, so there is no particular limitation, and it can be set to 10 g / m 2 / day or less, or 1g / m 2 / day or less. From the viewpoint of adjusting the water vapor permeability, as the water vapor barrier layers 16, 16, polyester resin layers (such as PET layers) having metal oxide vapor deposited layers such as aluminum oxide vapor deposited layers and silicon dioxide vapor deposited layers; metal foils such as aluminum foil. In the case where the water vapor barrier layer has a metal oxide vapor deposited layer, the metal oxide vapor deposited layer may face the fire extinguishing agent side. The thickness of the water vapor barrier layers 16, 16 may be individually set to 4.5μm to 25μm, or may be 7μm to 12μm.

[0186] A known adhesive layer can be used as appropriate as the adhesive layer 17. When the resin film 12 is sealed together with the fire extinguishing agent layer 13, the adhesive layer 17 is provided on the side where the resin film 12 exists. The adhesive layer 17 allows the fire extinguishing material laminate to be attached to an object.

[0187] When a fire occurs in an object to which the fire extinguishing material laminate is attached, the water vapor barrier layer 16, the adhesive layer 15 and the resin layer 14 melt due to the heat energy, and chemical species having a fire extinguishing function are released from the fire extinguishing agent composition, thereby extinguishing the flame.

[0188] The preferred embodiments of the third aspect are described above, but the embodiments of the third aspect are not limited by the above embodiments. For example, in the above embodiments, a method of preparing a coating liquid containing a fire extinguishing agent, a binder resin, and an additive and applying it on a resin film to form a fire extinguishing agent layer is shown, but the resin film is not necessary. Instead of applying the coating liquid on the resin film, a method of directly forming a fire extinguishing agent layer on the object by applying the coating liquid on the treated surface of the object and drying it can also be adopted. Examples of the material of the object include metals, resins, wood, ceramics, glass, etc., and the object can be non-porous or porous.

[0189] Example

[0190] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to the following examples.

[0191] [Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3]

[0192] <Formation of fire extinguishing materials>

[0193] (Example 1-1)

[0194] The following components were mixed to prepare a composition for a fire extinguishing material.

[0195] Fire extinguishing agent: mixture of potassium citrate and potassium chlorate (87 parts by mass)

[0196] Binder resin: ether urethane resin (6 parts by mass)

[0197] Compound having anhydride group: silane coupling agent (3 parts by mass)

[0198] Liquid medium: ethanol (87 parts by mass)

[0199] Liquid medium: isopropyl alcohol (14 parts by mass)

[0200] A mixture of potassium citrate and potassium chlorate was ground in an agate mortar and filtered through a No. 800 mesh to adjust the particle size D50 to 8 to 12 μm. X-12-1287A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent. This silane coupling agent has an acid anhydride group and an alkoxysilyl group.

[0201] The obtained fire extinguishing material composition was applied onto a polyethylene terephthalate (PET) film (trade name: E7002, manufactured by Toyobo Co., Ltd., thickness 50 μm) using an applicator (gap 450 μm), and dried in an oven at 75° C. for 7 minutes. Thus, a laminated body having a fire extinguishing material with a thickness of 200 μm formed on the PET film was obtained.

[0202] (Example 1-2)

[0203] A fire extinguishing material composition was prepared in the same manner as in Example 1-1 except that the amount of the silane coupling agent was changed to 6 parts by mass, thereby obtaining the above-mentioned laminate.

[0204] (Example 1-3)

[0205] A fire extinguishing material composition was prepared in the same manner as in Example 1-1, except that the amount of the silane coupling agent was changed to 12 parts by mass, thereby obtaining the above-mentioned laminate.

[0206] (Examples 1-4)

[0207] The following components were mixed to prepare a composition for a fire extinguishing material.

[0208] Fire extinguishing agent: mixture of potassium citrate and potassium chlorate (87 parts by mass)

[0209] Binder resin: polyvinyl butyral resin (6 parts by mass)

[0210] Compound having anhydride group: silane coupling agent (6 parts by mass)

[0211] Liquid medium: ethanol (130 parts by mass)

[0212] Liquid medium: isopropyl alcohol (5 parts by mass)

[0213] A mixture of potassium citrate and potassium chlorate was ground in an agate mortar and filtered through a No. 800 mesh to adjust the particle size D50 to 8 to 12 μm. X-12-1287A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent. This silane coupling agent has an acid anhydride group and an alkoxysilyl group.

[0214] The obtained fire extinguishing material composition was applied onto a PET film using an applicator (gap 750 μm), and dried in an oven at 75° C. for 7 minutes. Thus, a laminated body in which the fire extinguishing material was formed on the PET film to a thickness of 200 μm was obtained.

[0215] (Examples 1-5)

[0216] The following components were mixed to prepare a composition for a fire extinguishing material.

[0217] Fire extinguishing agent: mixture of potassium citrate and potassium chlorate (87 parts by mass)

[0218] Binder resin: ether urethane resin (5 parts by mass)

[0219] Compound having anhydride group: polymethyl vinyl ether / maleic anhydride copolymer (8 parts by mass)

[0220] Liquid medium: ethanol (87 parts by mass)

[0221] Liquid medium: isopropyl alcohol (14 parts by mass)

[0222] A mixture of potassium citrate and potassium chlorate was ground in an agate mortar and filtered through a No. 800 mesh to adjust the particle size to D50 = 8 to 12 μm. Gantrez AN-119 (manufactured by Ashland Japan Ltd.) was used as a compound having an anhydride group. This compound is a polymethyl vinyl ether / maleic anhydride copolymer having an anhydride group but no alkoxysilyl group in the polymer skeleton.

[0223] The obtained fire extinguishing material composition was applied onto a polyethylene terephthalate (PET) film using an applicator (gap 450 μm) and dried in an oven at 75° C. for 7 minutes. Thus, a laminate having a fire extinguishing material formed on the PET film with a thickness of 200 μm was obtained.

[0224] (Comparative Example 1-1)

[0225] The following components were mixed to prepare a composition for a fire extinguishing material.

[0226] Fire extinguishing agent: mixture of potassium citrate and potassium chlorate (87 parts by mass)

[0227] Binder resin: ether urethane resin (5 parts by mass)

[0228] Compounds with anhydride groups: None

[0229] Liquid medium: ethanol (87 parts by mass)

[0230] Liquid medium: isopropyl alcohol (14 parts by mass)

[0231] Other ingredients: silane coupling agent (8 parts by mass)

[0232] A mixture of potassium citrate and potassium chlorate was ground in an agate mortar and filtered through a No. 800 mesh to adjust the particle size D50 to 8 to 12 μm. X-12-1281A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a silane coupling agent. This silane coupling agent has an alkoxysilyl group but no acid anhydride group.

[0233] The obtained fire extinguishing material composition was applied onto a polyethylene terephthalate (PET) film using an applicator (gap 450 μm) and dried in an oven at 75° C. for 7 minutes. Thus, a laminate having a fire extinguishing material formed on the PET film with a thickness of 200 μm was obtained.

[0234] (Comparative Example 1-2)

[0235] The following components were mixed to prepare a composition for a fire extinguishing material.

[0236] Fire extinguishing agent: mixture of potassium citrate and potassium chlorate (87 parts by mass)

[0237] Binder resin: ether urethane resin (13 parts by mass)

[0238] Compounds with anhydride groups: None

[0239] Liquid medium: ethanol (87 parts by mass)

[0240] Liquid medium: isopropyl alcohol (14 parts by mass)

[0241] A mixture of potassium citrate and potassium chlorate was ground in an agate mortar and then filtered through a No. 800 mesh to adjust the particle size to D50 = 8 to 12 μm.

[0242] The obtained fire extinguishing material composition was applied onto a polyethylene terephthalate (PET) film using an applicator (gap 500 μm) and dried in an oven at 75° C. for 7 minutes. Thus, a laminate having a fire extinguishing material formed on the PET film with a thickness of 200 μm was obtained.

[0243] <Sealing of Laminated Body>

[0244] A barrier film having a sealant layer (L-LDPE (linear low-density polyethylene) resin, 30 μm thick) and a substrate layer (PET resin with a silica vapor-deposited film, 12 μm thick) was prepared. The water vapor permeability of the barrier film is 0.2 to 0.6 g / m 2 / day (under 40°C / 90%RH conditions). Use two sheets of the barrier film to cover the laminate of the PET film and the fire extinguishing material, and seal the laminate by heat-sealing the four sides of the barrier film. The heat-sealing conditions are set to 140°C and 2 seconds. This is used as an evaluation sample.

[0245] <Evaluation of property stability>

[0246] The total light transmittance of the evaluation sample obtained was measured using a haze meter (BYK-Gardner Haze-Guard Plus manufactured by BYK) according to the method of JIS K 7361-1. The measurement was performed before (before the test) and 136 hours after (after the test) exposure to a constant temperature and humidity chamber (under conditions of 85°C / 85% RH). The total light transmittance of the barrier film is 95%. The measurement site was changed for 3 measurements, and the change in the total light transmittance of each site before and after the test was calculated according to the following formula. The average value of the change is shown in Tables 1 and 2. Since the transparency increases when the fire extinguishing material absorbs moisture (deliquesces), the stability of the properties is evaluated by confirming the change.

[0247] Change Δ = measured value after the test - measured value before the test

[0248] [Table 1]

[0249]

[0250] [Table 2]

[0251]

[0252] [Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-2]

[0253] <Formation of fire extinguishing materials>

[0254] (Example 2-1)

[0255] The following components were mixed to prepare a composition for a fire extinguishing material.

[0256] Fire extinguishing agent: mixture of potassium citrate and potassium chlorate (87.4 parts by mass)

[0257] First binder: ether urethane resin (12.6 parts by mass)

[0258] Liquid medium: ethanol (87 parts by mass)

[0259] Liquid medium: isopropyl alcohol (27 parts by mass)

[0260] A mixture of potassium citrate and potassium chlorate was ground in an agate mortar and then filtered through a No. 800 mesh to adjust the particle size to D50 = 8 to 12 μm.

[0261] The fire extinguishing material composition was applied to one surface of a polyethylene terephthalate (PET) substrate (trade name: E7002, manufactured by Toyobo Co., Ltd.) not subjected to a release treatment using an applicator so that the coating thickness after drying was 150 μm, and then dried in an oven at 75° C. for 7 minutes. Thus, a sheet of fire extinguishing material was prepared on the surface of the substrate.

[0262] (Example 2-2)

[0263] A fire extinguishing material composition was prepared in the same manner as in Example 2-1, and a fire extinguishing material was produced using the fire extinguishing material composition, except that 12.6 parts by mass of acrylic resin was used instead of 12.6 parts by mass of ether-based urethane resin and 23 parts by mass of ethyl acetate was used instead of 27 parts by mass of isopropyl alcohol as the liquid medium.

[0264] (Example 2-3)

[0265] A fire extinguishing material composition was prepared in the same manner as in Example 2-1, and a fire extinguishing material was produced using the fire extinguishing material composition, except that 12.6 parts by mass of polyvinyl butyral (PVB) resin was used instead of 12.6 parts by mass of ether-based urethane resin, and the amount of ethanol as the liquid medium was set to 179 parts by mass and the amount of isopropyl alcohol was set to 10 parts by mass.

[0266] (Example 2-4)

[0267] A composition for a fire extinguishing material was prepared in the same manner as in Example 2-1, and a fire extinguishing material was produced using the composition for a fire extinguishing material, except that 8.4 parts by mass of a PVB resin was used instead of 12.6 parts by mass of an ether-based urethane resin, 4.2 parts by mass of X-12-1287A (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a second binder, and the amount of ethanol as a liquid medium was set to 148 parts by mass and the amount of isopropyl alcohol was set to 7 parts by mass.

[0268] (Example 2-5)

[0269] A fire extinguishing material composition was prepared in the same manner as in Example 2-1, and a fire extinguishing material was prepared using the fire extinguishing material composition, except that 12.6 parts by mass of a polymethyl vinyl ether (PMVE) / maleic anhydride copolymer (Gantrez AN-139 (manufactured by Ashland Japan Ltd.) was used instead of 12.6 parts by mass of the ether-based urethane resin, the amount of ethanol was changed to 150 parts by mass, and the amount of isopropyl alcohol was changed to 0 parts by mass.

[0270] (Example 2-6)

[0271] A fire extinguishing material composition was prepared in the same manner as in Example 2-1 except that the amount of 12.6 parts by mass of the ether-based urethane resin was changed to 4.2 parts by mass and 8.4 parts by mass of X-12-1287A was used as the second binder, and a fire extinguishing material was produced using the fire extinguishing material composition.

[0272] (Comparative Example 2-1)

[0273] A fire extinguishing material composition was prepared in the same manner as in Example 2-1 except that the amount of the ether urethane resin was changed from 12.6 parts by mass to 3.2 parts by mass and 9.4 parts by mass of X-12-1287A was used as the second binder, and a fire extinguishing material was produced using the fire extinguishing material composition.

[0274] (Comparative Example 2-2)

[0275] A fire extinguishing material composition was prepared in the same manner as in Example 2-1, except that 12.6 parts by mass of X-12-1287A was used instead of 12.6 parts by mass of the ether-based urethane resin, and a fire extinguishing material was produced using the fire extinguishing material composition.

[0276] <Measurement of weight change rate>

[0277] For the first and second binders used in each embodiment and comparative example, the weight change rate when the temperature is increased from 30°C to 500°C at a heating rate of 5°C / min in an atmospheric atmosphere until the temperature is increased to 400°C was measured using a differential thermogravimetric measuring device "STA7200RV" manufactured by Hitachi High-Tech Corporation. The sampling period at this time is set to 1 second. The measurement results are shown in Tables 3 and 4. The "weight reduction rate of the mixture" in the table refers to the weight reduction rate of the mixture of the first and second binders (Examples 2-4, 2-6 and Comparative Example 2-1).

[0278] <Sealing of fire extinguishing materials>

[0279] A barrier film having a sealant layer (L-LDPE (linear low-density polyethylene) resin, 30 μm thick) and a substrate layer (PET resin with a silica vapor-deposited film, 12 μm thick) was prepared. The water vapor permeability of the barrier film is 0.2 to 0.6 g / m 2 / day (under 40°C / 90%RH conditions). Two sheets of the barrier film were used to cover the fire extinguishing material in sheet form, and the fire extinguishing material was sealed by heat sealing the four sides of the barrier film. The heat sealing conditions were set to 140°C and 2 seconds. This was used as an evaluation sample.

[0280] <Fire extinguishing test>

[0281] An iron container with a length of 20 cm, a width of 30 cm, and a height of 40 cm was prepared. In order to prevent the solid fuel from extinguishing due to suffocation after the fire, five circular vents with a diameter of 8.5 mm were set on the sides of the container at the heights of 5, 12.5, 20.0, 27.5, and 35.0 cm from the top surface. A fire extinguishing material with an area of ​​50 mm × 50 mm was attached to the center of the top surface of the container using double-sided tape. 1.5 g of solid fuel (solid fuel flame block igniter manufactured by CAPTAIN STAG) with a length of 15 mm, a width of 15 mm, and a height of 10 mm was placed in the center of the bottom surface of the container.

[0282] When solid fuel is ignited, whether the fire extinguishing material can extinguish the fire within 180 seconds after the solid fuel is ignited is evaluated while adjusting the distance between the solid fuel and the fire extinguishing material. The evaluation is performed based on the following criteria.

[0283] A: Able to extinguish fire at a distance of 20cm from the fire extinguishing material to the fire source.

[0284] B: Able to extinguish fire at a distance of 10 cm from the fire extinguishing material to the fire source.

[0285] C: Fire cannot be extinguished within 10cm from the fire extinguishing material to the fire source.

[0286] <Evaluation of deliquescent properties>

[0287] 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 the method of JIS K 7361-1. The total light transmittance was measured before being placed in a constant temperature and humidity chamber (under 85°C / 85% RH conditions) (initial total light transmittance) and 24 hours after being placed (total light transmittance after storage), and the change Δ in the total light transmittance before and after storage was calculated according to the following formula. The transparency of the fire extinguishing material increases when moisture absorption (deliquesce) occurs, so the degree of deliquesce is evaluated by confirming the change Δ. The evaluation is based on the following criteria.

[0288] Change Δ = Total light transmittance value after saving - Initial total light transmittance value

[0289] A: The amount of change Δ is 35 or less.

[0290] B: The change amount Δ exceeds 35.

[0291] [Table 3]

[0292]

[0293] [Table 4]

[0294]

[0295] [Examples 3-1 to 3-12 and Comparative Examples 3-1 to 3-2] (Example 3-1)

[0296] <Preparation of Fire Extinguishing Liquid>

[0297] A mixture of potassium citrate and potassium chlorate as a fire extinguishing agent was mixed with an equal weight of ethanol to obtain a fire extinguishing agent liquid.

[0298] <Preparation of Binder Resin Liquid>

[0299] Polyvinyl butyral as a binder resin was mixed into a mixed solution of ethanol and isopropyl alcohol to obtain a binder resin solution.

[0300] <Preparation of coating solution>

[0301] The fire extinguishing agent liquid, the binder resin liquid, and the following epoxy compound A as an additive prepared above were mixed. The mixing ratio was calculated so that the weight of the solid content of the fire extinguishing agent relative to the total weight of the solid content of the fire extinguishing agent, the binder resin, and the additive (hereinafter referred to as "fire extinguishing agent solid content ratio") was 90% by weight with respect to the weight of the solid content after drying. In this way, a coating liquid was obtained.

[0302] [Chemical formula 2]

[0303]

[0304] A terephthalate (PET) film treated with silicone anti-adhesive was prepared. The coating solution obtained above was applied to the PET film using an applicator with a gap set to 650 μm. The film was dried in an oven set to 75°C for 7 minutes. Then, a fire extinguishing agent layer was obtained by peeling off the coating formed on the surface of the film. The thickness of the fire extinguishing agent layer was measured using "DIGIMICRO MU-501A" and "DIGIMICRO STAND MS-3G" manufactured by NIKON CORPORATION, and the result was 150 μm.

[0305] <Flexibility Evaluation>

[0306] After the fire extinguishing agent layer is obtained, it is placed under normal environment at room temperature for more than one night. Then, under normal environment at room temperature, a mandrel test of type 1 is implemented according to JIS K5600-5-1. The test is started from the mandrel with a large diameter, and the fire extinguishing agent layer after the test is visually confirmed to confirm whether the fire extinguishing agent layer has cracks (ruptures). As a result, no cracks are observed even in the test with a diameter of 2 mm.

[0307] <Evaluation of fire-fighting capability>

[0308] Two laminates were made by using LLDPE film as the resin layer and pasting a silica vapor-deposited film as a water vapor barrier layer thereon with an adhesive. Next, the fire extinguishing agent layer was cut into a size of 10 mm x 10 mm. The fire extinguishing agent layer was sandwiched between two laminates with the resin layers facing each other. Temporary bonding was performed by full-surface heat lamination, and then four-sided sealing was performed with a heat seal strip. Furthermore, a release film having a urethane adhesive layer was pasted on one side of the laminate. In this way, a Figure 3 The fire extinguishing material stack shown.

[0309] A metal container with a glass bottom plate and a volume of 139×109×30 mm was prepared. A ventilation hole was set on a part of the side of the container. The fire extinguishing material laminated body prepared above was peeled off the anti-adhesive film and pasted on the center of the glass plate. 1.0 mL of heptane was placed in a Φ30 mm crucible and ignited. The above container was covered and the flame was observed to see whether it was extinguished by the action of the fire extinguishing material laminated body. As a result, the fire was extinguished within 30 seconds.

[0310] (Example 3-2)

[0311] The coating liquid was prepared in the same manner as in Example 3-1 except that the following epoxy compound B was used as an additive, and the fire extinguishing agent layer was obtained and the bendability was evaluated. It should be noted that since the epoxy compound B is solid at room temperature, the coating liquid was prepared after heating in an oven set at 75° C. for 10 minutes to form a liquid.

[0312] [Chemical formula 3]

[0313]

[0314] As a result, no cracks were observed even in the test with a diameter of 2 mm.

[0315] <Example 3-3>

[0316] A coating liquid was prepared in the same manner as in Example 3-1 except that the following epoxy compound C was used as an additive to obtain a fire extinguishing agent layer, and the bendability was evaluated.

[0317] [Chemical formula 4]

[0318]

[0319] As a result, no cracks were observed even in the test with a diameter of 2 mm.

[0320] <Examples 3-4 to 3-6>

[0321] In Examples 3-1 to 3-3, the amount of epoxy compound added was doubled to prepare a coating solution, and a fire extinguishing agent layer was obtained, and the bendability was evaluated. These tests were respectively set as Examples 3-4 to 3-6. In Examples 3-4 to 3-6, the fire extinguishing agent solid content ratio was 86.4% by weight.

[0322] In the bendability evaluation, no cracks were observed in Examples 3-4 to 3-6 even in the test with a diameter of 2 mm.

[0323] <Examples 3-7 to 3-9>

[0324] In Examples 3-1 to 3-3, the amount of epoxy compound added was set to 0.5 times to prepare a coating solution, obtain a fire extinguishing agent layer, and evaluate the flexibility. These tests were respectively set as Examples 3-7 to 3-9. In Examples 3-7 to 3-9, the fire extinguishing agent solid content ratio was 91.9% by weight.

[0325] In the bendability evaluation, no cracks were observed in Examples 3-7 to 3-9 even in the test with a diameter of 2 mm.

[0326] <Examples 3-10 to 3-12>

[0327] In Examples 3-1 to 3-3, the amount of epoxy compound added was set to 0.1 times to prepare a coating solution, obtain a fire extinguishing agent layer, and evaluate the flexibility. These tests are respectively set as Examples 3-10 to 3-12. In Examples 3-10 to 3-12, the fire extinguishing agent solid content ratio is 93.4% by weight.

[0328] In the bendability evaluation, no cracks were observed in Examples 3-10 to 3-12 even in the test with a diameter of 2 mm.

[0329] <Comparative Example 3-1>

[0330] The coating liquid was prepared in the same manner as in Example 3-1 except that the mixing amount of the fire extinguishing agent liquid was increased so that the fire extinguishing agent solid content ratio was 99 wt %. The fire extinguishing agent layer was obtained and the bendability was evaluated. In addition, the fire extinguishing ability was also evaluated.

[0331] As a result, in the bendability evaluation, cracks were observed in the test with a diameter of 32 mm. In the fire extinguishing ability evaluation, the flame was extinguished within 30 seconds.

[0332] <Comparative Example 3-2>

[0333] In the preparation of the coating liquid, except that the mixing amount of the fire extinguishing agent liquid was reduced so that the solid content ratio of the fire extinguishing agent was 50% by weight, the coating liquid was prepared in the same manner as in Example 3-1, and the fire extinguishing agent layer was obtained and the bendability was evaluated. In addition, the fire extinguishing ability was also evaluated.

[0334] As a result, in the bendability evaluation, no cracks were observed even in the test with a diameter of 2 mm. In the fire extinguishing ability evaluation, the flame did not extinguish even after 3 minutes.

[0335] Industrial Applicability

[0336] The fire extinguishing material sheet of the present disclosure can be particularly suitably used for parts used in industrial materials such as building materials, automobile parts, aircraft parts, and electronic parts.

[0337] Explanation of symbols

[0338] 1...fire extinguishing material, 2...base material, 3...fire extinguishing material layer, 11...fire extinguishing material sheet, 12...resin film, 13...fire extinguishing agent layer, 14...resin layer, 15...adhesive layer, 16...water vapor barrier layer, 17...adhesive layer, 18...anti-sticking film, 100...fire extinguishing material laminate (fire extinguishing material sheet).

Claims

1. A composition for fire extinguishing material, comprising: a fire extinguishing agent comprising at least one of an organic salt and an inorganic salt having deliquescent properties; and A compound having an acid anhydride group.

2. The fire extinguishing material composition according to claim 1, further comprising a binder resin.

3. The fire extinguishing material composition according to claim 2, wherein: When the mass of the binder resin is 100 parts by mass, the compound is contained in an amount of 10 to 250 parts by mass.

4. The fire extinguishing material composition according to any one of claims 1 to 3, wherein The fire extinguishing agent is contained in an amount of 70 to 97% by mass based on the total amount of the fire extinguishing material composition.

5. The fire extinguishing material composition according to any one of claims 1 to 4, wherein The acid anhydride group is a carboxylic acid anhydride group.

6. The fire extinguishing material composition according to any one of claims 1 to 5, wherein The compound further has an alkoxysilyl group.

7. The fire extinguishing material composition according to any one of claims 1 to 6, wherein The compound is a silane coupling agent.

8. The fire extinguishing material composition according to any one of claims 1 to 7, wherein The salt is a potassium salt. 9 . The fire extinguishing material composition according to claim 1 , further comprising a liquid medium.

10. A composition for a fire extinguishing material, comprising: a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, and a binder resin, In a thermogravimetric measurement under an air atmosphere, when the binder resin is heated from 30° C. to 500° C. at a temperature increase rate of 5° C. / min, the weight reduction rate of the binder resin until the temperature reaches 400° C. is 30% or more.

11. A composition for a fire extinguishing material, comprising: a fire extinguishing agent containing at least one of an organic salt and an inorganic salt, a first binder resin, and a second binder resin, In a thermogravimetric measurement under an atmospheric atmosphere, when the first binder resin is heated from 30° C. to 500° C. at a heating rate of 5° C. / min, the weight reduction rate of the first binder resin until the temperature reaches 400° C. is 50% or more, In a thermogravimetric measurement under an atmospheric atmosphere, when the second binder resin is heated from 30° C. to 500° C. at a heating rate of 5° C. / min, the weight loss rate of the second binder resin until the temperature reaches 400° C. is 15% or less, When the mass of the first binder resin is 100 parts, the mass of the second binder resin is 250 parts or less.

12. The fire extinguishing material composition according to claim 11, wherein The second binder resin is a compound having an acid anhydride group.

13. The fire extinguishing material composition according to claim 11 or 12, wherein: The second binder resin is a silane coupling agent having a carboxylic anhydride group and an alkoxysilyl group.

14. A composition for fire extinguishing material, comprising: a fire extinguishing agent, a binder resin, and an additive, The weight ratio of the solid content of the fire extinguishing agent to the total weight of the solid content of the fire extinguishing agent, the binder resin and the additive is 60% by weight to 98% by weight. The mandrel diameter when forming into a sheet shape is 18 mm or less.

15. A method for selecting a binder resin for a fire extinguishing material composition containing a fire extinguishing agent containing at least one of an organic salt and an inorganic salt and the binder resin, the method comprising: A step of heating a binder resin to be evaluated from 30°C to 500°C at a temperature increase rate of 5°C / min in a thermogravimetric measurement under an atmospheric atmosphere, and measuring the weight loss rate of the binder resin until the temperature reaches 400°C; as well as The binder resin having a weight reduction rate of 30% or more is judged to be a step capable of preparing a fire extinguishing material composition exhibiting good initial fire extinguishing properties.

16. A method for producing a composition for fire extinguishing material, comprising: A step of preparing a binder resin, the binder resin being determined to be capable of preparing a fire extinguishing material composition exhibiting good initial fire extinguishing properties in the method for selecting a binder resin according to claim 15; as well as A step of preparing a fire extinguishing material composition, the fire extinguishing material composition containing the binder resin and a fire extinguishing agent containing at least one salt selected from an organic salt and an inorganic salt.

17. A fire extinguishing material comprising the fire extinguishing material composition according to any one of claims 1 to 13.

18. A device with automatic fire extinguishing function, comprising the fire extinguishing material according to claim 17.

19. A fire extinguishing material sheet comprising a fire extinguishing material layer comprising a fire extinguishing agent, a binder resin and an additive, The ratio of the weight of the solid content of the fire extinguishing agent to the total weight of the solid content of the fire extinguishing agent, the binder resin, and the additive is 60% by weight to 98% by weight.

20. The fire extinguishing material sheet according to claim 19, wherein: The binder resin includes at least one of a polyvinyl acetal resin and a polyvinyl alcohol resin.

21. The fire extinguishing material sheet according to claim 19 or 20, wherein: The additive comprises an epoxy compound, The epoxy compound is difunctional or more.

22. The fire extinguishing material sheet according to any one of claims 19 to 21, wherein: The fire extinguishing agent comprises a potassium salt.

23. The fire extinguishing material sheet according to any one of claims 19 to 22, wherein: The thickness of the fire extinguishing material layer is 70 μm to 500 μm.

24. The fire extinguishing material sheet according to any one of claims 19 to 23, wherein: The core shaft diameter of the fire extinguishing material layer is less than 18 mm. 25 . The fire extinguishing material sheet according to claim 19 , further comprising a resin film on which the fire extinguishing material layer is laminated.

Images