Composition for fire-extinguishing material, fire-extinguishing material, and device having automatic fire-extinguishing function

Abstract

This composition for a fire-extinguishing material comprises: a fire-extinguishing agent including a deliquescent organic salt and / or a deliquescent inorganic salt; a first component, which is a compound having an acid anhydride group and an alkoxysilyl group; and a second component, which is a copolymer comprising a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated anhydrous carboxylic acid monomer. When the content of the second component in the composition for a fire-extinguishing material is expressed by B parts by mass and the content of the first component therein is expressed by A parts by mass, then B is greater than A.

Description

Fire extinguishing composition, fire extinguishing material, and device with automatic fire extinguishing function

[0001] The present disclosure relates to a fire-extinguishing composition, a fire-extinguishing material, and an apparatus having an automatic fire-extinguishing function.

[0002] BACKGROUND ART Self-extinguishing molded articles are known, which are prepared by mixing a fire extinguishing composition that generates an aerosol upon combustion with a binder and molding the mixture into a sheet (see, for example, Patent Documents 1 and 2).

[0003] International Publication No. 2018 / 047762 Patent No. 6443882

[0004] The fire extinguishant compositions described in Patent Documents 1 and 2 contain salts such as potassium nitrate and sodium nitrate. Because these salts are deliquescent, there is room for improvement in terms of stably maintaining the properties of the self-extinguishing molded article over a long period of time. Furthermore, according to the inventors' studies, when a small spark is assumed to occur in the early stages of a fire, the reactivity of the self-extinguishing molded article is insufficient, and there is a certain probability that the fire will not be extinguished in the early stages. This leaves room for improvement.

[0005] The present disclosure has been made in consideration of the above circumstances, and provides a fire extinguishing composition having excellent property stability, a fire extinguishing material containing the fire extinguishing composition, and a device having an automatic fire extinguishing function that is equipped with the fire extinguishing material.

[0006] The present inventors have found that adding a compound having an acid anhydride group and an alkoxysilyl group (hereinafter sometimes referred to as the "first component") to a fire extinguishing composition containing at least one salt of a deliquescent organic salt and / or inorganic salt can impart property stability to the fire extinguishing material, although the fire extinguishing performance of the fire extinguishing material is slightly reduced. The present inventors conducted research to further improve the fire extinguishing performance of the fire extinguishing material while maintaining the effect of improving property stability provided by the first component. As a result, they found that adding an appropriate amount of a copolymer (hereinafter sometimes referred to as the "second component") containing structural units derived from vinyl ether monomers and structural units derived from unsaturated carboxylic anhydride monomers to the fire extinguishing composition can compensate for the reduced fire extinguishing performance caused by the first component, while providing a fire extinguishing material composition with excellent property stability. According to the inventors' research, both the first and second components suppress the deliquescence of the salt, i.e., improve the performance stability of the fire extinguishing material. Therefore, both the first and second components can be referred to as deliquescence-suppressing components. The first component has an excellent effect of improving the performance stability of the fire extinguishing material, but the degree of deterioration of the fire extinguishing performance of the fire extinguishing material is greater than that of the second component, whereas the second component has a weaker effect of improving the performance stability of the fire extinguishing material than that of the first component, but can maintain the fire extinguishing performance of the fire extinguishing material without deterioration, or the degree of deterioration is weaker than that of the first component.

[0007] A fire extinguishing material composition according to one aspect of the present disclosure comprises a fire extinguishing agent containing at least one salt of a deliquescent organic salt and an inorganic salt, a first component which is a compound having an acid anhydride group and an alkoxysilyl group, and a second component which is a copolymer containing structural units derived from a vinyl ether monomer and structural units derived from an unsaturated carboxylic acid anhydride monomer, wherein when the content of the second component in the fire extinguishing material composition is B parts by mass and the content of the first component is A parts by mass, the value of B is greater than the value of A. With a fire extinguishing material composition that satisfies this condition, the first and second components impart excellent property stability and enable the fire extinguishing agent to maintain the fire extinguishing performance that it should originally exhibit.

[0008] The fire extinguishing composition preferably further contains a binder resin that is a component different from the second component. When the total mass of the first and second components and the binder resin is taken as 100 parts by mass, the amount of the first component is preferably 10 parts by mass or more but less than 25 parts by mass, the amount of the second component is preferably 25 parts by mass or more but less than 90 parts by mass, and the amount of the binder resin is preferably 3 parts by mass or more but less than 40 parts by mass. The binder resin serves to bind the fire extinguishing agent and the first and second components. When the total mass of the first and second components and the binder resin is taken as 100 parts by mass, the amount of the binder resin is preferably 10 parts by mass or more. Having an amount of binder resin of 10 parts by mass or more makes it easy to prepare a sheet-shaped fire extinguishing material from the fire extinguishing composition, and the fire extinguishing material has the advantages of excellent cuttability and resistance to cracking.

[0009] The vinyl ether monomer may be methyl vinyl ether, and the unsaturated carboxylic anhydride monomer may be maleic anhydride. The acid anhydride group may be a carboxylic anhydride group, and the first component may be a silane coupling agent. The salt may be a potassium salt. The fire extinguishing material composition may further contain a liquid medium. From the viewpoint of coating suitability and / or cutting suitability of the sheet-shaped fire extinguishing material, the binder resin may be at least one resin selected from the group consisting of polyurethane-based resins, polyvinyl alcohol-based resins, polyvinyl acetal-based resins, and acrylic-based resins.

[0010] One aspect of the present disclosure relates to a fire extinguishing material including the fire extinguishing composition. Another aspect of the present disclosure relates to a device having an automatic fire extinguishing function and including the fire extinguishing material.

[0011] According to the present disclosure, there are provided a fire extinguishing composition having excellent property stability, a fire extinguishing material containing the fire extinguishing composition, and a device having an automatic fire extinguishing function that is equipped with the fire extinguishing material.

[0012] Fig. 1 is a cross-sectional view schematically showing one embodiment of a fire extinguishing material according to the present disclosure. Fig. 2 is a cross-sectional view schematically showing one embodiment of a device having a fire extinguishing function according to the present disclosure. Fig. 3 is a cross-sectional view schematically showing one embodiment of a fire extinguishing material package (a sheet-shaped fire extinguishing material contained in a packaging bag) according to the present disclosure.

[0013] Hereinafter, embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

[0014] <Fire Extinguishing Material Composition> The fire extinguishing material composition according to this embodiment includes a fire extinguishing agent containing at least one salt selected from the group consisting of an organic salt and an inorganic salt having deliquescent properties, and a deliquescent inhibitor. The deliquescent inhibitor includes a first component that is a compound having an acid anhydride group and an alkoxysilyl group, and a second component that is a copolymer containing structural units derived from a vinyl ether monomer and structural units derived from an unsaturated carboxylic acid anhydride monomer. When the content of the second component in the fire extinguishing material composition is B parts by mass and the content of the first component is A parts by mass, the value of B is greater than the value of A. From the viewpoint of the balance between the property stability and fire extinguishing performance of the fire extinguishing material, the value of B / A is preferably 1.5 to 10.0, more preferably 1.7 to 6.0, and more preferably 2.0 to 4.6.

[0015] It is preferable that the fire extinguishing composition further contains a binder resin that is a component different from the second component. When the total amount of the first and second components and the binder resin component in the fire extinguishing composition is 100 parts by mass, the content of the first component is, for example, 10 parts by mass or more and less than 25 parts by mass. The lower limit of the content may be 13 parts by mass or may be 15 parts by mass. When the content is equal to or greater than the lower limit, deliquescence of the salt is easily suppressed. Furthermore, the upper limit of the content may be 23 parts by mass, 20 parts by mass, or 18 parts by mass. When the content is equal to or less than the upper limit, sufficient fire extinguishing performance is easily exhibited.

[0016] When the total amount of the first and second components and the binder resin in the fire extinguishing composition is 100 parts by mass, the content of the second component is, for example, 25 parts by mass or more and less than 90 parts by mass. The lower limit of the content may be 30 parts by mass, or may be 40 parts by mass, 50 parts by mass, 55 parts by mass, or 59 parts by mass. When the content is equal to or greater than the lower limit, deliquescence of salt is easily suppressed. Furthermore, the upper limit of the content may be 89 parts by mass, 81 parts by mass, or 75 parts by mass. When the content is equal to or less than the upper limit, not only is deliquescence of salt easily suppressed, but also it becomes possible to add a sufficient amount of binder resin to the fire extinguishing composition, which improves the coating suitability of the fire extinguishing composition, facilitates film formation, and suppresses film cracking.

[0017] When the total amount of the first and second components and the binder resin in the fire extinguishing composition is 100 parts by mass, the content of the binder resin is, for example, 3 parts by mass or more and less than 40 parts by mass. The lower limit of the content may be 10 parts by mass, 20 parts by mass, or 25 parts by mass. When the content is equal to or greater than the lower limit, the binder resin can function as a binding agent, improving the coating suitability of the fire extinguishing composition and facilitating film formation, as well as suppressing film cracking. In particular, from the viewpoint of cut suitability, the content is preferably 10 parts by mass or more. The upper limit of the content may be 33 parts by mass or 30 parts by mass. When the content is equal to or less than the upper limit, it becomes possible to add sufficient amounts of the first and second components to the fire extinguishing composition, making it easier to achieve both property stability and fire extinguishing performance in the early stages of ignition.

[0018] (Fire Extinguishing Agent) The fire extinguishing agent contains at least one of a deliquescent organic salt and an inorganic salt, and an oxidizing agent. Examples of the organic salt include potassium salt, sodium salt, and ammonium salt. Of these, it is preferable to use potassium salt as the organic salt. Examples of the organic potassium salt include potassium carboxylate salts such as potassium acetate, potassium citrate (monopotassium citrate, dipotassium citrate, tripotassium citrate), potassium tartrate, potassium lactate, potassium oxalate, and potassium maleate. Among these, it is preferable to use potassium acetate or potassium citrate from the viewpoint of usefulness in the negative catalytic effect of combustion.

[0019] Examples of inorganic salts include potassium salts and sodium salts. Of these, potassium salts are preferred as the inorganic salt. Examples of inorganic potassium salts include potassium tetraborate, potassium carbonate, potassium hydrogen carbonate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate.

[0020] The organic salt and inorganic salt may be used alone or in combination of two or more. The organic salt and inorganic salt may be granular. The average particle diameter D50 of the organic salt and inorganic salt may be 1 μm or more and 100 μm or less, or 3 μm or more and 40 μm or less. When the average particle diameter D50 is equal to or greater than the lower limit, the salt is easily dispersed in the system. Furthermore, when the average particle diameter D50 is equal to or less than the upper limit, the stability of the coating liquid is improved, and the smoothness of the coated surface tends to be improved. The average particle diameter D50 can be calculated by wet measurement using a laser diffraction particle size distribution analyzer.

[0021] 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 these, potassium chlorate is preferably used.

[0022] The content of the fire extinguishing agent in the fire extinguishing composition may be 70% by mass or more and 97% by mass or less, or 85% by mass or more and 92% by mass or less, based on the total amount (solid content) of the fire extinguishing composition. When the content of the fire extinguishing agent is equal to or less than the upper limit, deliquescence of the salt is easily suppressed, and the coating suitability of the fire extinguishing composition is improved, facilitating film formation. Furthermore, when the content of the fire extinguishing agent is equal to or more than the lower limit, sufficient fire extinguishing performance is easily exhibited.

[0023] (First component: compound having an acid anhydride group and an alkoxysilyl group) The fire extinguishing material composition contains the first component, which allows the properties of the molded article to be stably maintained for a long period of time. Although the reason for this is unclear, it is presumed that this is because the acid anhydride group can react with water, trapping water that penetrates through the barrier film used to package the fire extinguishing material and preventing deliquescence of the salt contained in the molded article, and / or because the alkoxysilane is hydrolyzed and then self-reacts to form siloxane, which improves water resistance and film density and suppresses contact between the deliquescent salt and water.

[0024] The first component is preferably less susceptible to weight loss due to heat than the second component and the binder resin. That is, when the first component is heated from 30°C to 500°C at a temperature increase rate of 5°C / min in an atmospheric thermogravimetric measurement, the weight loss rate of the first component until the temperature reaches 400°C is, for example, less than 50%. The upper limit of the weight loss rate may be 40%, or may be 30%, 20%, or 15%. When the weight loss rate is within the above range, the resulting fire extinguishing composition has excellent property stability. Note that, when there are multiple first components, the weight loss rate of the first component refers to the weight loss rate of the mixture. The lower limit of the weight loss rate may be, for example, 0%, 3%, or 7%.

[0025] The first component is not particularly limited as long as it has one or more acid anhydride groups in the molecule formed by dehydration condensation of two oxo acid molecules, and further has one or more alkoxysilyl groups in the molecule. Examples of oxo acids that form the acid anhydride groups include carboxylic acids, sulfuric acid, nitric acid, and phosphoric acid. Of these, the oxo acid that forms the acid anhydride group is preferably a carboxylic acid. Examples of compounds having a carboxylic acid anhydride group include simple carboxylic acid anhydrides such as phthalic anhydride, succinic anhydride, and maleic anhydride, and copolymers in which a carboxylic acid anhydride having an unsaturated bond, such as maleic anhydride, is used as a monomer.

[0026] The first component may be, for example, a silane coupling agent. The silane coupling agent used as the first component may have the same function as a binder resin in the fire extinguishing composition.

[0027] (Second component: copolymer containing structural units derived from vinyl ether monomers and structural units derived from unsaturated carboxylic anhydride monomers) By including the second component, the fire extinguishing composition can stably maintain the properties of the molded article over a long period of time and can achieve initial fire extinguishing with a sufficiently high probability. Although the reason for this is unclear, it is presumed that the structural units derived from vinyl ether monomers contribute to improved fire extinguishing performance, and the structural units derived from unsaturated carboxylic anhydride monomers contribute to improved property stability. The second component may have the same function as a binder resin in the fire extinguishing composition, but is distinguished from a binder resin in that it is a copolymer containing structural units derived from vinyl ether monomers and structural units derived from unsaturated carboxylic anhydride monomers.

[0028] The second component is preferably one that easily loses weight due to heat. That is, when the second component is heated from 30°C to 500°C at a temperature increase rate of 5°C / min in an atmospheric thermogravimetric measurement, the weight loss rate of the second component until the temperature reaches 400°C is, for example, 50% or more. The lower limit of the weight loss rate may be 55%. When the weight loss rate is within the above range, the resulting fire extinguishing composition has excellent fire extinguishing performance in the early stages of ignition. Note that, when there are multiple second components, the weight loss rate of the second component refers to the weight loss rate of the mixture. The upper limit of the weight loss rate may be, for example, 80%, 70%, or 60%.

[0029] The second component can be obtained, for example, by copolymerizing a vinyl ether monomer and an unsaturated carboxylic acid anhydride monomer. Examples of the vinyl ether monomer include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether. Of these, the vinyl ether monomer is preferably methyl vinyl ether. Examples of the unsaturated carboxylic acid anhydride monomer include maleic anhydride and citraconic anhydride. Of these, the unsaturated carboxylic acid anhydride monomer is preferably maleic anhydride.

[0030] (Binder Resin) Thermoplastic resins and thermosetting resins can be used as the binder resin. Examples of the thermoplastic resin include polyolefin resins such as polyvinyl alcohol resins, polyvinyl acetal 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. Examples of thermosetting resins include 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), multi-vulcanized rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), and urethane rubber (U), as well as polyurethane resins, polyisocyanate resins, polyisocyanurate resins, phenolic resins, and epoxy resins. Of the above resins, one type may be used alone, or two or more types may be used in combination. Among these, according to the findings of the present inventors, it is preferable to use polyurethane resins, polyvinyl alcohol resins, and polyvinyl acetal resins from the viewpoint of coating suitability, and it is preferable to use polyurethane resins and acrylic resins from the viewpoint of cutting suitability of the sheet-shaped fire extinguishing material. The binder resin may contain a curing agent component.

[0031] The binder resin is preferably one that easily loses weight due to heat. That is, when the binder resin is heated from 30°C to 500°C at a temperature increase rate of 5°C / min in an atmospheric thermogravimetric measurement, the weight loss rate of the binder resin until the temperature reaches 400°C is, for example, 50% or more. The lower limit of the weight loss rate may be 60%. When the weight loss rate is within the above range, the resulting fire extinguishing composition has excellent fire extinguishing performance in the early stages of ignition. Note that, when multiple binder resins are used, the weight loss rate of the binder resin refers to the weight loss rate of the mixture. The upper limit of the weight loss rate may be, for example, 88%, 80%, or 70%.

[0032] The weight average molecular weight of the binder resin may be 5,000 or more, 20,000 or more, or 150,000 or less, or 100,000 or less. When the weight average molecular weight is equal to or greater than the lower limit, the hydrophobicity of the resin is easily ensured. When the weight average molecular weight is equal to or less than the upper limit, appropriate resin flexibility is easily ensured, and bending resistance and coatability are easily improved. The weight average molecular weight can be calculated by GPC.

[0033] The glass transition temperature of the binder resin is not particularly limited, but may be -40°C or higher, 55°C or higher, or 80°C or higher, or 110°C or lower, or 100°C or lower. When the glass transition temperature is above the lower limit, the crystallinity increases, making it easier to ensure the hydrophobicity of the resin. When the glass transition temperature is below the upper limit, it makes it easier to improve the coating suitability. The glass transition temperature can be measured by thermal analysis using a differential scanning calorimeter.

[0034] The viscosity of the resin solution obtained by dissolving the binder resin in the liquid medium at 20°C may be 500 mPa·s or more, or 1000 mPa·s or more, or 10000 mPa·s or less, or 6000 mPa·s or less. The viscosity can be measured using a B-type rotational viscometer.

[0035] (Liquid Medium) The fire extinguishing composition may further contain a liquid medium. Examples of the liquid medium include organic solvents. Examples of the organic solvent include water-soluble solvents, such as alcohols such as methanol, ethanol, isopropyl alcohol, and n-propyl alcohol; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and diethylene glycol; and glycol ethers such as N-methylpyrrolidone, tetrahydrofuran, and butyl cellosolve. From the viewpoint of being used together with a salt, the liquid medium may be an alcohol-based solvent.

[0036] The amount of the liquid medium may be adjusted appropriately depending on the method of use of the fire extinguishing composition, but may be 30% by mass or more and 70% by mass or less based on the total amount of the fire extinguishing composition (including the liquid medium). A fire extinguishing composition containing a liquid medium can be called a fire extinguishing coating liquid.

[0037] (Other Components) The fire extinguishing composition may contain other components in addition to those described above. Examples of other components include surfactants, antiblocking agents, colorants, antioxidants, flame retardants, inorganic fillers, fluidity imparting agents, moisture-proofing agents, dispersants, UV absorbers, flexibility imparting agents, catalysts, etc. These other components can be appropriately selected depending on the type of fire extinguishing agent, the first and second components, and the binder resin or the liquid medium, etc. The content of other components contained in the fire extinguishing composition can be 10 mass% or less based on the total amount of the fire extinguishing composition.

[0038] The fire extinguishing composition can be produced by mixing a fire extinguishing agent containing at least one of an organic salt and an inorganic salt having deliquescent properties, the first and second components, the binder resin, and other components used as needed.

[0039] <Fire Extinguishing Material> A fire extinguishing material can be formed from a fire extinguishing material composition. FIG. 1 is a cross-sectional view schematically showing one 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 produced by applying a fire extinguishing material coating liquid to 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, ceramics, or glass, and may be non-porous or porous.

[0040] The application can be carried out by a wet coating method, such as gravure coating, comma coating, spray coating, dip coating, curtain coating, spin coating, sponge roll coating, die coating, or brush coating.

[0041] The viscosity of the fire-extinguishing material coating liquid is preferably 1 to 2,000 mPa·s if the gravure coating method is used, 500 to 100,000 mPa·s if the comma coating method is used, and 0.1 to 4,000 mPa·s if the spray coating method is used. The amount of the liquid medium may be adjusted appropriately so that the coating liquid viscosity falls within the desired range. The viscosity can be measured using a coaxial double cylinder rotational viscometer.

[0042] 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 may soak into the interior of the substrate 2, and the remainder may be laminated on the surface of the substrate 2.

[0043] The fire extinguishing material can also be obtained by molding the fire extinguishing material composition into a predetermined shape. The shape of the fire extinguishing material may be selected depending on the application, and the fire extinguishing material may be a granular fire extinguishing material, a plate-shaped fire extinguishing material, a columnar fire extinguishing material, or the like.

[0044] <Devices with Automatic Fire-Extinguishing Function> Devices with automatic fire-extinguishing function are equipped with fire-extinguishing material. Examples of devices with automatic fire-extinguishing function include electrical system equipment equipped with electrical wiring and cables, transformers, electrical circuits, etc. Specific examples include distribution boards, power distribution panels, storage batteries (lithium ion batteries, etc.), batteries (mobile batteries, tool batteries, automotive EV batteries, etc.), and power storage systems equipped with the above. Further examples include places where there is a risk of unintended fire, such as collection boxes for storage batteries, trash cans, and outlet covers.

[0045] FIG. 2 is a perspective view schematically illustrating electrical equipment according to this embodiment. FIG. 2 shows a switchboard as an example of electrical equipment. The electrical equipment 100 mainly comprises a housing 101 having a storage section 101a and an opening / closing door 101b for storing electrical equipment, a circuit breaker 103 as electrical equipment, and wiring 104. Some of the wiring 104 is housed together in a wiring cover 102. The electrical equipment 100 comprises fire extinguishing materials 10a, 10b, 10c, and 10d in the following areas: Fire extinguishing material 10a: Area of ​​the opening / closing door 101b facing the electrical equipment Fire extinguishing material 10b: Area on the top surface of the storage section 101a facing the electrical equipment Fire extinguishing material 10c: Area on the bottom surface of the wiring cover 102 facing the electrical equipment Fire extinguishing material 10d: Area on the back surface of the storage section 101a facing the electrical equipment, i.e., the area behind the electrical equipment

[0046] The position where the fire extinguishing material is disposed is not limited to the embodiment shown in FIG. 2, and the position can be adjusted appropriately depending on the location of electrical equipment or the like which is at risk of ignition.

[0047] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to the following examples.

[0048] The following materials were used in the examples and comparative examples. (1) Fire extinguishing agent: organic potassium salt: tripotassium citrate; Oxidizing agent: potassium chlorate (KClO ３) Tripotassium citrate is a deliquescent salt. (2) First component: Compound having an acid anhydride group and an alkoxysilyl group Silane coupling agent having an acid anhydride group and an alkoxysilyl group (Shin-Etsu Chemical Co., Ltd., trade name: X-12-1287A) (weight loss rate: 11.8%) (3) Second component: Copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid anhydride monomer Polymethyl vinyl ether (PMVE) / maleic anhydride copolymer (Ashland Japan Co., Ltd., trade name: Gantrez AN-119) (weight loss rate: 60.0%) (4) Binder resin (4-1) Ether-based polyurethane resin (weight loss rate: 88.0%) (4-2) Acrylic resin (weight loss rate: 76.3%) (4-3) Polyvinyl butyral resin (PVB resin) (weight loss rate: 54.1%) When preparing the fire extinguishing material composition, a solution of the above binder resin was used. (4-1) An ether-based polyurethane resin solution obtained by dissolving 100 parts by mass of the ether-based polyurethane resin in 210 parts by mass of isopropyl alcohol. (4-2) A solution containing the acrylic resin (manufactured by Saiden Chemical Co., Ltd., trade name: Saivinol TPO-3183). (4-3) A PVB resin solution obtained by dissolving 100 parts by mass of the PVB resin in 910 parts by mass of a mixture of ethanol and isopropyl alcohol. (5) Liquid medium: Ethanol. (6) Resin substrate: Polyethylene terephthalate (PET) substrate (manufactured by Toyobo Co., Ltd., trade name: E7002, thickness 50 μm).

[0049] <Measurement of Weight Change Rate> The weight change rates of the first and second components and the binder resin were measured when the temperature was increased from 30° C. to 500° C. at a rate of 5° C. / min in an air atmosphere and then increased to 400° C. using a differential thermal thermogravimetry analyzer "STA7200RV" manufactured by Hitachi High-Tech Science Corp. The sampling period was 1 second.

[0050] <Preparation of Fire Extinguishing Composition> (Example 1) Tripotassium citrate and KClO ３The mixture was ground in an agate mortar to an average particle size D50 of 12 μm or less. A fire extinguishing composition was obtained containing 87.4 parts by mass of the ground mixture and 12.6 parts by mass of the total solid content of the first and second components and binder resin solution. When the solid content of the first and second components and binder resin was taken as 100 parts by mass, the contents of these components were as shown in Table 1. In preparing the fire extinguishing composition, 87 parts by mass of ethanol was used per 100 parts by mass of the solid content. In the table, the notation in parentheses next to "second component" refers to the ratio (B / A) of the content of the second component (B parts by mass) to the content of the first component (A parts by mass).

[0051] (Examples 2 to 9 and Comparative Examples 1 to 7) Fire extinguishing compositions were obtained in the same manner as in Example 1, except that the contents of the first and second components and the binder resin were changed to the amounts shown in Table 1. The contents shown in Table 1 refer to the contents of each component when the total mass of the first and second components and the binder resin is taken as 100 parts by mass.

[0052] (Examples 10 to 12) Fire extinguishing compositions were obtained in the same manner as in Example 1, except that an acrylic resin was used as the binder resin instead of the ether-based polyurethane resin, and the contents of the first and second components and the binder resin were set as shown in Table 2. In preparing the fire extinguishing compositions, the amount of ethanol used per 100 parts by mass of solids was appropriately adjusted.

[0053] (Examples 13 to 15) Fire extinguishing compositions were obtained in the same manner as in Example 10, except that a PVB resin was used as the binder resin instead of an acrylic resin, and the contents of the first and second components and the binder resin were set as shown in Table 3. In preparing the fire extinguishing compositions, the amount of ethanol used per 100 parts by mass of solids was appropriately adjusted.

[0054] <Preparation of Fire Extinguishing Material> The fire extinguishing material composition obtained in each example was applied to a PET substrate using an applicator, and then dried in an oven at 75°C for 7 minutes to obtain a laminate in which a sheet-like fire extinguishing material having a thickness of 150 µm was formed on the PET substrate.

[0055] <Various Tests> A barrier film (water vapor permeability: 0.2 to 0.6 g / (m)) comprising a sealant layer 5 (L-LDPE (linear low-density polyethylene) resin, thickness: 30 μm) and a substrate layer 6 (PET resin with a silica vapor deposition film, thickness: 12 μm) ２ 1 day), in accordance with JIS K 7129 (under conditions of 40°C / 90% RH), was prepared. Two sheets of this barrier film were used to cover a sheet-shaped fire extinguishing material (50 mm x 50 mm), and the four sides of the barrier film were heat-sealed to enclose the sheet-shaped fire extinguishing material. The heat-sealing conditions were 140°C and 2 seconds. The heat-seal width on each side was 10 mm. As a result, a fire extinguishing material package 20 (sheet-shaped fire extinguishing material 10 contained in a packaging bag 4) with outer dimensions of 70 mm x 70 mm as shown in Figure 3 was obtained. This was used as an evaluation sample. The evaluation samples obtained from each example were tested as follows. The results are shown in Tables 1 to 3.

[0056] <Property Stability Test> The total light transmittance of the evaluation sample was measured using a haze meter (BYK-Gardner Haze-Guard Plus, manufactured by BYK Corporation) according to a method in accordance with JIS K 7361-1. The measurement was performed 168 hours after placing the sample in a constant temperature and humidity chamber (under conditions of 85°C / 85% RH). This procedure was performed three times at different measurement locations, and the average value was recorded. As the deliquescence of the salt progresses, the transparency of the fire-extinguishing material increases and the total light transmittance value rises, so the degree of deliquescence was evaluated by measuring the total light transmittance. The results are shown in Tables 1 to 3. It can be said that the lower the total light transmittance value, the higher the property stability of the fire-extinguishing material. The total light transmittance of the barrier film was 85%.

[0057] <Fire Extinguishing Performance Test> An iron container measuring 20 cm in length, 30 cm in width, and 40 cm in height was prepared. To prevent the ignited solid fuel from suffocating, five circular vents with a diameter of 8.5 mm were provided on each side of the container at heights of 5.0 cm, 12.5 cm, 20.0 cm, 27.5 cm, and 35.0 cm from the top. A fire extinguishing material package (evaluation sample) was attached to the center of the top of the container with double-sided tape. 1.5 g of solid fuel (Captain Stag Co., Ltd. Solid Fuel Fire Block Ignition Agent) measuring 15 mm in length, 15 mm in width, and 10 mm in height was placed in the center of the bottom of the container. The distance between the solid fuel and the evaluation sample was adjusted to 20 cm, and a test was conducted to determine whether the evaluation sample could extinguish the fire within 180 seconds after ignition of the solid fuel. The above test was repeated multiple times, and the success rate of fire extinguishing was recorded. The results are shown in Tables 1 to 3. In the table, the notation in parentheses for the probability of successful fire extinguishing means (number of successful fire extinguishing attempts / number of trials).

[0058] <Cutting Suitability Evaluation Test> The laminate on which the fire extinguishing material was formed was cut with a cutter from the surface side of the fire extinguishing material, and the presence or absence of chipping of the fire extinguishing material coating film and peeling from the substrate was visually confirmed. The evaluation was performed based on the following criteria. The results are shown in Tables 1 to 3.

[0059] A: No chipping of the coating film or peeling from the substrate is observed. B: Chipping of the coating film and peeling from the substrate occurs in some areas. C: Chipping of the coating film and peeling from the substrate occurs over the entire area.

[0060]

[0061]

[0062]

[0063] 1...fire extinguishing material, 2...substrate, 3...fire extinguishing material layer, 4...packaging bag, 5...sealant layer, 6...substrate layer, 10, 10a, 10b, 10c, 10d...fire extinguishing material, 20...fire extinguishing material package, 100...electrical equipment, 103...breaker, 104...wiring.

Claims

1. A fire extinguishing composition comprising: a fire extinguishing agent containing at least one salt of an organic salt and an inorganic salt having deliquescent properties; a first component which is a compound having an acid anhydride group and an alkoxysilyl group; and a second component which is a copolymer containing a structural unit derived from a vinyl ether monomer and a structural unit derived from an unsaturated carboxylic acid anhydride monomer, wherein when the content of the second component in the fire extinguishing composition is B parts by mass and the content of the first component is A parts by mass, the value of B is greater than the value of A.

2. The fire extinguishing composition according to claim 1, wherein the first and second components suppress deliquescence of the salt.

3. The fire extinguishing composition according to claim 1 or 2, further comprising a binder resin which is a component different from the second component.

4. A fire extinguishing composition as described in claim 3, wherein, when the total mass of the first and second components and the binder resin is 100 parts by mass, the amount of the first component is 10 parts by mass or more and less than 25 parts by mass, the amount of the second component is 25 parts by mass or more and less than 90 parts by mass, and the amount of the binder resin is 3 parts by mass or more and less than 40 parts by mass.

5. A fire extinguishing composition according to claim 3 or 4, wherein the amount of the binder resin is 10 parts by mass or more when the total mass of the first and second components and the binder resin is 100 parts by mass.

6. A fire extinguishing composition according to any one of claims 1 to 5, wherein the content of the fire extinguishing agent is 70 mass% or more and 97 mass% or less based on the total solid content of the fire extinguishing composition.

7. The fire extinguishing composition according to any one of claims 1 to 6, wherein the vinyl ether monomer is methyl vinyl ether.

8. The fire extinguishing composition according to any one of claims 1 to 7, wherein the unsaturated carboxylic anhydride monomer is maleic anhydride.

9. The fire extinguishing composition according to any one of claims 1 to 8, wherein the acid anhydride group is a carboxylic acid anhydride group.

10. The fire extinguishing composition according to any one of claims 1 to 9, wherein the first component is a silane coupling agent.

11. A fire extinguishing composition according to any one of claims 1 to 10, wherein the salt is a potassium salt.

12. The fire extinguishing composition according to any one of claims 3 to 5, wherein the binder resin is at least one resin selected from the group consisting of polyurethane resins, polyvinyl alcohol resins, polyvinyl acetal resins, and acrylic resins.

13. The fire extinguishing composition according to any one of claims 1 to 12, further comprising a liquid medium.

14. A fire-extinguishing composition according to any one of claims 1 to 13, wherein, when the first component is heated from 30°C to 500°C at a heating rate of 5°C / min in an atmospheric thermogravimetry, the weight loss rate of the first component until the temperature reaches 400°C is less than 50%.

15. A fire-extinguishing composition according to any one of claims 1 to 14, wherein, when the second component is heated from 30°C to 500°C at a heating rate of 5°C / min in an atmospheric thermogravimetry, the weight loss rate of the second component until the temperature reaches 400°C is 50% or more.

16. A fire extinguishing composition according to any one of claims 3 to 5, wherein, in thermogravimetry under atmospheric conditions, when the binder resin is heated from 30°C to 500°C at a heating rate of 5°C / min, the weight loss rate of the binder resin is 50% or more by the time the temperature reaches 400°C.

17. A fire extinguishing material comprising the fire extinguishing composition according to any one of claims 1 to 16.

18. An apparatus having an automatic fire extinguishing function, comprising the fire extinguishing material according to claim 17.

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