WO2025197927A1 - Composition d'agent d'extinction d'incendie, feuille d'agent d'extinction d'incendie et procédé de production de feuille d'agent d'extinction d'incendie - Google Patents

Composition d'agent d'extinction d'incendie, feuille d'agent d'extinction d'incendie et procédé de production de feuille d'agent d'extinction d'incendie

Info

Publication number
WO2025197927A1
WO2025197927A1 PCT/JP2025/010529 JP2025010529W WO2025197927A1 WO 2025197927 A1 WO2025197927 A1 WO 2025197927A1 JP 2025010529 W JP2025010529 W JP 2025010529W WO 2025197927 A1 WO2025197927 A1 WO 2025197927A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
fire
mass
fire extinguishing
sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/010529
Other languages
English (en)
Japanese (ja)
Inventor
健一 稲葉
大理 久保
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Publication of WO2025197927A1 publication Critical patent/WO2025197927A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0007—Solid extinguishing substances

Definitions

  • the present invention relates to a fire extinguishing composition, a fire extinguishing sheet, and a method for producing a fire extinguishing sheet.
  • secondary batteries such as lithium secondary batteries have been widely used not only in small devices such as portable electronic devices but also in medium- to large-sized devices such as automobiles and power storage devices.
  • secondary batteries have advantages such as high operating voltage and excellent energy density, they also pose a major safety issue due to the risk of internal short circuits and fires caused by overheating.
  • a technology has been proposed that places a fire extinguishing agent around the secondary battery.
  • Patent Document 1 discloses an electrochemical energy storage device having a housing and at least one electrochemical cell provided in the housing, in which at least one wall of the housing is coated with a fire extinguishing agent or a fire extinguishing agent additive, or is supplied with a fire extinguishing agent or a fire extinguishing agent additive, at least in a region thereof.
  • a secondary battery that has caught fire may not be easily extinguished.
  • the temperature may rise further and spread to the surrounding area, causing a chain reaction of fires that makes it difficult to extinguish the fire.
  • Patent Document 2 also discloses a fire-extinguishing sheet containing a fire-extinguishing agent that thermally decomposes when it reaches a certain temperature, generating a fire-extinguishing component in the form of an aerosol. Patent Document 2 also describes that the sheet can be used by placing it in contact with or adjacent to a lithium-ion battery.
  • Patent Document 3 discloses a method for producing a fire-extinguishing film, which includes the steps of obtaining a kneaded mixture of a fire-extinguishing composition by kneading a thermoplastic resin with a slurry or powder containing a fire-extinguishing agent component that generates an aerosol upon combustion, and molding the kneaded mixture.
  • Patent Document 4 discloses a flame-resistant fiber sheet comprising a flame-resistant fiber sheet substrate and a fire-extinguishing agent component that generates an aerosol (radicals) by thermal energy generated by combustion. Patent Document 4 also discloses a secondary battery cell or a secondary battery cell unit in which individual battery cells and/or assemblies of multiple battery cells are covered with a flame-resistant fiber sheet.
  • the fire extinguishing performance was still insufficient, and improving the fire extinguishing performance increased the affinity with water, causing problems with storage stability, making it difficult to apply these materials to large-capacity secondary batteries.
  • the object of the present disclosure is to provide a fire extinguishing composition that has sufficient fire extinguishing performance and excellent storage stability.
  • a fire extinguisher composition comprises a component (A) a cellulose derivative, a component (B) an inorganic oxidizing agent, and a component (C) an organic acid alkali metal salt,
  • the content of the component (A) in the total amount of the component (A), the component (B), and the component (C) is 0.5% by mass or more and 18.5% by mass or less.
  • This disclosure makes it possible to provide a fire extinguishing composition that has sufficient fire extinguishing performance and excellent storage stability.
  • the fire extinguisher composition of this embodiment contains a cellulose derivative as component (A), an inorganic oxidizing agent as component (B), and an organic acid alkali metal salt as component (C), and is characterized in that the content of component (A) in the total amount of components (A), (B), and (C) is within a specific range.
  • the fire extinguisher composition of the present embodiment relates to a fire extinguisher composition that uses an aerosol-like fire-extinguishing component to enable efficient fire extinguishing, and more specifically, to a fire extinguisher composition that uses metal radicals and is particularly effective in the early stage of extinguishing a heat-generating fire caused by a secondary battery or the like.
  • (A) Cellulose derivatives are cellulose derivatives synthesized by modifying some of the hydroxy groups of ⁇ -glucose molecules linearly linked by glycosidic bonds, making them water-soluble.
  • the cellulose derivatives may be compounds in which some of the hydroxy groups have been modified with one or more groups selected from methoxy groups, carboxymethoxy groups, and hydroxy(C2-C3)alkoxy groups.
  • the hydroxy(C2-C3)alkoxy groups are specifically hydroxyethoxy groups and hydroxypropoxy groups.
  • CMC carboxymethyl cellulose
  • methyl cellulose cellulose derivatives substituted with methoxy groups
  • hydroxyethyl cellulose hydroxyethyl cellulose
  • hydroxypropyl cellulose Cellulose derivatives substituted with hydroxypropyl cellulose.
  • the hydroxy groups in cellulose may be substituted with multiple types of substituents.
  • hydroxyethyl methylcellulose in which the hydroxy groups in cellulose are substituted with methoxy groups and hydroxyethoxy groups at a certain ratio
  • Metolose registered trademark
  • SE-SEB hydroxyethyl methylcellulose
  • SNB manufactured by Shin-Etsu Chemical Co., Ltd.
  • hydroxypropyl methylcellulose in which the hydroxy groups in cellulose are substituted with methoxy groups and hydroxypropoxy groups at a certain ratio, is available on the market as Metolose (registered trademark) SH-60SH, 65SH, and 90SH (manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in combination.
  • the inorganic oxidizing agent (B) can promote the generation of radicals from the organic acid alkali metal salt (C) by the thermal energy of combustion.
  • the inorganic oxidizing agent (B) is not particularly limited as long as it is an inorganic compound, but examples thereof include nitrates (potassium nitrate, calcium nitrate, strontium nitrate, sodium nitrate, barium nitrate, lithium nitrate, aluminum nitrate, iron nitrate, etc.), nitrites (sodium nitrite, potassium nitrite, etc.), chlorates (potassium chlorate, sodium chlorate, etc.), perchlorates (potassium perchlorate, sodium perchlorate, etc.), chlorites (potassium chlorite, sodium chlorite, etc.), hypochlorites (potassium hypochlorite, sodium hypochlorite, etc.), sodium, etc.), bromates (potassium nitrate, calcium nit
  • component (B) may be at least one inorganic oxidizing agent selected from halogen acid salts, nitrates, nitrites, carbonates, hydrogen carbonates, borates, ferrates, ferrites, manganates, permanganates, and the like.
  • component (B) preferably used in the fire extinguisher composition of the present embodiment may be at least one inorganic oxidizing agent selected from halogen salts such as chlorate, perchlorate, chlorite, hypochlorite, bromate, perbromate, bromite, and hypobromite.
  • Component (B) may more preferably be at least one inorganic oxidizing agent selected from chlorate, perchlorate, chlorite, and hypochlorite.
  • Component (B) may further preferably be at least one inorganic oxidizing agent selected from potassium chlorate and potassium perchlorate, and particularly preferably potassium chlorate.
  • the alkali metal in the organic acid alkali metal salt may be one or more selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). Potassium and sodium are preferred as the alkali metal, with potassium being particularly preferred. Therefore, component (C) organic acid alkali metal salt may be an organic acid potassium salt.
  • an organic acid potassium salt as component (C) organic acid alkali metal salt, the fire extinguishing performance of the fire extinguisher composition can be effectively improved due to the fire extinguishing performance provided by potassium radicals.
  • the content of component (A) is 0.5% by mass or more and 18.5% by mass or less of the total amount of components (A), (B), and (C).
  • the content of the binder component needs to be at least a certain amount from the viewpoint of moldability, as described in Patent Document 3, for example. However, if the content is too high, there is a concern that it may affect fire extinguishing performance. Therefore, the binder and its content must be determined appropriately through trial and error.
  • a cellulose derivative was found to be optimal as a binder, and the invention was completed using a cellulose derivative as component (A). In this case, the optimal content of component (A) is as described above.
  • More preferred amounts (content ratios) of component (A) are, in order of preference, 18.0 mass%, 16.0 mass%, 14.0 mass%, 12.0 mass%, 10.0 mass%, 9.0 mass%, 8.0 mass%, 7.0 mass%, and 6.0 mass%, with 5.0 mass% being particularly preferred, and lower limits are, in order of preference, 0.8 mass%, 1.0 mass%, 1.2 mass%, 1.5 mass%, and 1.8 mass%, with 2.0 mass% being particularly preferred.
  • the content of component (A) in the total amount of components (A), (B), and (C) may be 0.8% by mass or more and 18.0% by mass or less, 1.0% by mass or more and 16.0% by mass or less, 1.2% by mass or more and 14.0% by mass or less, 1.5% by mass or more and 12.0% by mass or less, 1.8% by mass or more and 10.0% by mass or less, 1.8% by mass or more and 9.0% by mass or less, 1.8% by mass or more and 8.0% by mass or less, 1.8% by mass or more and 7.0% by mass or less, or 1.8% by mass or more and 6.0% by mass or less.
  • the most preferable content of component (A) in the total amount of components (A), (B), and (C) is 2.0% by mass or more and 5.0% by mass or less.
  • the content of component (D) relative to the total amount of components (A), (B), (C), and (D) may be 0.3% by mass or more and 5.0% by mass or less, 0.5% by mass or more and 4.0% by mass or less, or 0.8% by mass or more and 3.0% by mass or less.
  • the most preferred content of component (D) relative to the total amount of components (A), (B), (C), and (D) is 1.0% by mass or more and 2.0% by mass or less.
  • the fire extinguisher composition of the present embodiment may contain other components such as catalysts, colorants, antioxidants, flame retardants, inorganic fillers, and fuels, as long as the effects of the composition are not impaired.
  • the catalyst that may be contained in the fire extinguisher composition of the present embodiment is not particularly limited, but examples thereof include catalysts that promote combustion to make the generation of alkali metal radicals more efficient and that more effectively suppress the combustion of hydrogen that has leaked into the air.
  • catalysts include lithium oxide, beryllium oxide, sodium oxide, magnesium oxide, aluminum oxide, silicon oxide, potassium oxide, calcium oxide, scandium (III) oxide, titanium (IV) oxide, vanadium (V) oxide, chromium (III) oxide, chromium (IV) oxide, manganese (IV) oxide, nickel (II) oxide, nickel (III) oxide, copper (I) oxide, copper (II), zinc oxide, gallium (III), molybdenum (VI), zirconium oxide, hafnium (IV), cerium (IV), copper, rubidium, rhodium, palladium, silver, iridium, platinum, and gold.
  • One or more catalysts selected from the above-listed candidates can be used.
  • a colorant may be added to the fire extinguisher composition of the present embodiment, mainly for the purpose of design.
  • colorants include direct dyes, basic dyes, acid dyes, reactive dyes, solvent dyes, disperse dyes, leather dyes, natural dyes, sulfur dyes, vat dyes, synthetic pigments, and natural pigments.
  • the colorant one or more types selected from the above-listed candidates can be used.
  • the antioxidant that may be contained in the fire extinguisher composition of the present embodiment is not particularly limited, and examples thereof include butylated hydroxytoluene, butylated hydroxyanisole, tertiary butylhydroquinone, gallate, 2-phenyl-2-propanol, 1-(2,4,5-trihydroxyphenyl)-1-butanone, bisphenolmethane derivatives, 2,2-methylenebis(4-methyl-6-t-butylphenol), etc.
  • the antioxidant one or more types selected from the above-listed candidates can be used.
  • the flame retardant that may be contained in the fire extinguisher composition of the present embodiment is not particularly limited, and examples thereof include phosphates, halogenated aromatic compounds, fluorinated iodocarbons, fluorinated bromocarbons, etc.
  • the flame retardant one or more types selected from the above-listed candidates can be used.
  • the inorganic filler that may be contained in the fire extinguisher composition of the present embodiment is not particularly limited, and examples thereof include fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., and preferably fused silica, crystalline silica, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, etc., and more preferably fused silica, crystalline
  • the fire extinguisher composition of the present embodiment can be produced by thoroughly mixing and kneading components (A) to (C), and optionally component (D) and other components at room temperature.
  • an organic solvent may be added during production. That is, the method for producing a fire extinguisher composition of this embodiment may include a kneading step of kneading raw materials.
  • the raw materials include component (A), component (B), and component (C), and may further include component (D) and other components as necessary.
  • each component can be weighed and kneaded so that the content of component (A) in the total amount of component (A), component (B), and component (C) falls within a predetermined range. Whether the mixture has been sufficiently kneaded can be confirmed by visually checking for the presence or absence of aggregates.
  • LLDPE low-density polyethylene
  • PP polypropylene
  • COP cycloolefin polymer
  • CPP non-oriented polypropylene
  • PET polyethylene terephthalate.
  • PTFE means polytetrafluoroethylene
  • ETFE means a copolymer of tetrafluoroethylene and ethylene
  • EFEP means a copolymer of tetrafluoroethylene, ethylene and hexafluoropropylene
  • PFA means a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene
  • FEP means a copolymer of tetrafluoroethylene and hexafluoropropylene
  • PCTFE means trifluorochloroethylene.
  • the fire extinguishing agent sheet of this embodiment may be stored in a bag made of a material with low moisture permeability for the purpose of long-term storage, and an item having such a structure is also referred to as a fire extinguishing agent sheet in this specification.
  • the fire extinguishant sheet obtained by any of the above (i) to (iii) and housed in an aluminum pack still functions as a fire extinguishant sheet. Therefore, the fire extinguishant sheet of this embodiment may include an aluminum pack processed into a bag shape by lamination or the like, and a molded product of the fire extinguishant composition of this embodiment housed in the aluminum pack.
  • the aluminum pack refers to a laminate film in which aluminum foil and a resin film are laminated together.
  • the fire extinguishing sheet of this embodiment can be used for the purpose of imparting fire-extinguishing capabilities to secondary batteries by being laminated on one or both sides of secondary battery cells such as lithium-ion secondary batteries, nickel-metal hydride batteries, lithium-sulfur batteries, nickel-cadmium batteries, nickel-iron batteries, nickel-zinc batteries, sodium-sulfur batteries, lead-acid batteries, air batteries, all-solid-state batteries, and all-resin batteries.
  • the fire extinguisher composition and fire extinguisher sheet of the present embodiment have excellent fire extinguishing properties and also have excellent long-term storage stability, and therefore contribute to the realization of secondary batteries that are stable for long periods and safe.
  • a fire extinguisher composition and a fire extinguisher sheet were produced.
  • the moisture content was measured using a heating moisture meter (MX-50) manufactured by A&D Co., Ltd. After removing from the dryer, the sample was allowed to cool at room temperature in a desiccator for 10 to 15 minutes, and then ground in a mortar to measure the moisture content. 1.2 g of the sample was then crushed in a mortar.
  • ⁇ Fire extinguishing test> A commercially available candle was lit, and 0.20 g of the fire extinguisher composition obtained as described above was picked up with tweezers and placed in the candle flame to observe whether it could extinguish the fire. Evaluation was carried out according to the following criteria, and the results are shown in Table 1.
  • the evaluation of ⁇ means that the fire extinguishing performance is the best, and the fire extinguishing performance decreases in the order of ⁇ and ⁇ .
  • the evaluation of ⁇ means that the fire extinguisher composition has excellent fire extinguishing performance.
  • ⁇ It took more than 3 seconds for the fire to be completely extinguished.
  • ⁇ The fire was not completely extinguished.
  • PL-2KP low-temperature constant-temperature and constant-humidity chamber
  • Table 1 The terms in Table 1 have the following meanings: Metrolose (registered trademark): Metrolose 90SH-100000 (manufactured by Shin-Etsu Chemical Co., Ltd.) PVP: Polyvinylpyrrolidone CMC-Na: Sodium methyl cellulose carboxylate
  • Examples 1 to 11 of the present invention exhibited good fire extinguishing performance in the fire extinguishing test.
  • Comparative Example 1 which contained 18.8% by mass of component (A), was confirmed to have poor fire extinguishing performance.
  • the moisture absorption rate after 8 hours was 60% or less in all Examples, confirming excellent storage stability.
  • Example 2 which used Metolose, in which the hydroxy groups in the cellulose were substituted with methoxy groups and hydroxypropoxy groups at a certain ratio, had a lower moisture absorption rate than Example 10, which used the same amount of CMC-Na.
  • a fire extinguishing composition and a fire extinguishing sheet that have sufficient fire extinguishing performance and excellent storage stability, and therefore a secondary battery in which the composition and sheet are stacked can ensure safety over a long period of time.
  • aspects of the embodiments of the present disclosure are, for example, as follows.
  • the composition contains a component (A) a cellulose derivative, a component (B) an inorganic oxidizing agent, and a component (C) an organic acid alkali metal salt, A fire extinguisher composition, wherein the content of the component (A) is 0.5 mass% or more and 18.5 mass% or less based on the total amount of the component (A), the component (B), and the component (C).
  • a fire extinguisher composition wherein the content of the component (A) is 0.5 mass% or more and 18.5 mass% or less based on the total amount of the component (A), the component (B), and the component (C).
  • the component (B) is at least one inorganic oxidizing agent selected from chlorates, perchlorates, chlorites, hypochlorites, bromates, perbromates, bromites, and hypobromites.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)

Abstract

Cette composition d'agent d'extinction d'incendie contient : un composant (A) qui est un dérivé de cellulose ; un composant (B) qui est un agent oxydant inorganique ; et un composant (C) qui est un sel de métal alcalin d'un acide organique. Dans la quantité totale du composant (A), du composant (B) et du composant (C), la teneur en composant (A) est de 0,5 à 18,5% en masse.
PCT/JP2025/010529 2024-03-19 2025-03-18 Composition d'agent d'extinction d'incendie, feuille d'agent d'extinction d'incendie et procédé de production de feuille d'agent d'extinction d'incendie Pending WO2025197927A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024-043271 2024-03-19
JP2024043271 2024-03-19

Publications (1)

Publication Number Publication Date
WO2025197927A1 true WO2025197927A1 (fr) 2025-09-25

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ID=97139277

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/010529 Pending WO2025197927A1 (fr) 2024-03-19 2025-03-18 Composition d'agent d'extinction d'incendie, feuille d'agent d'extinction d'incendie et procédé de production de feuille d'agent d'extinction d'incendie

Country Status (1)

Country Link
WO (1) WO2025197927A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007535977A (ja) * 2004-04-30 2007-12-13 グッドリッチ コーポレイション 改善された火炎抑制エアロゾル発生剤
WO2017134703A1 (fr) * 2016-02-02 2017-08-10 ヤマトプロテック株式会社 Composition d'agent extincteur
JP2023133405A (ja) * 2016-09-12 2023-09-22 ヤマトプロテック株式会社 自己消化性成形品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007535977A (ja) * 2004-04-30 2007-12-13 グッドリッチ コーポレイション 改善された火炎抑制エアロゾル発生剤
WO2017134703A1 (fr) * 2016-02-02 2017-08-10 ヤマトプロテック株式会社 Composition d'agent extincteur
JP2023133405A (ja) * 2016-09-12 2023-09-22 ヤマトプロテック株式会社 自己消化性成形品

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