WO2020241843A1 - バッテリー用熱膨張性耐火材 - Google Patents

バッテリー用熱膨張性耐火材 Download PDF

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WO2020241843A1
WO2020241843A1 PCT/JP2020/021404 JP2020021404W WO2020241843A1 WO 2020241843 A1 WO2020241843 A1 WO 2020241843A1 JP 2020021404 W JP2020021404 W JP 2020021404W WO 2020241843 A1 WO2020241843 A1 WO 2020241843A1
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heat
expandable
resin
refractory material
compound
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PCT/JP2020/021404
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English (en)
French (fr)
Japanese (ja)
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彰人 土肥
健一 大月
倫男 島本
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積水化学工業株式会社
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Priority to JP2020537563A priority Critical patent/JPWO2020241843A1/ja
Publication of WO2020241843A1 publication Critical patent/WO2020241843A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/202—Casings or frames around the primary casing of a single cell or a single battery
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
    • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
    • H01M50/229—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a heat-expandable refractory material for batteries used for various batteries such as lithium batteries.
  • Patent Document 1 discloses a battery cell in which at least a part of the outside is covered with a fire-resistant coating, and the fire-resistant coating is an ablation coating, an expansion coating, or an endothermic coating. It is disclosed that polyurethane-based coatings can be used.
  • Patent Document 1 cannot maintain its shape when ignition occurs, and cannot exhibit sufficient fire resistance and fire-extinguishing performance.
  • the present inventors have achieved high fire resistance and fire extinguishing performance by using a heat-expandable compound for the heat-expandable refractory material for a battery and increasing the expansion coefficient of the refractory material to a certain value or more.
  • the gist of the present invention is the following [1] to [10].
  • the heat-expandable refractory material for a battery according to any one of the above [1] to [9], further comprising a heat absorbing agent having a thermal decomposition start temperature of 800 ° C. or less and an endothermic amount of 300 J / g or more.
  • the present invention it is possible to provide a heat-expandable refractory material for a battery having high fire resistance and fire extinguishing performance against thermal runaway and ignition caused by a temperature rise of the battery.
  • FIG. 5 is a schematic cross-sectional view showing another embodiment of a battery having a square battery cell. It is a schematic sectional drawing which shows one Embodiment of the battery which has a laminated type battery cell. It is the schematic sectional drawing which shows one Embodiment of the battery which has a cylindrical battery cell. It is a schematic cross-sectional view which shows one Embodiment of the battery provided with two battery cells.
  • the heat-expandable refractory material for a battery of the present invention (hereinafter, may be simply referred to as "fire-resistant material”) includes a resin and a heat-expandable compound.
  • the refractory material of the present invention contains a heat-expandable compound, so that when the battery is heated due to thermal runaway or the like, it expands to insulate and suppress ignition or extinguish the fire when ignition occurs. Can be done.
  • the refractory material may be thin at normal times before being heated, it is easy to arrange it around the battery, which has many space restrictions.
  • the refractory material of the present invention has an expansion ratio of 2.5 times or more when heated at 600 ° C. If the expansion ratio of the refractory material is less than 2.5 times, it cannot expand sufficiently even if it is heated to a high temperature due to thermal runaway of the battery, and it becomes difficult to exhibit the ignition suppression effect and the fire extinguishing performance. .. Further, the refractory material of the present invention preferably has an expansion ratio of 5 times or more, preferably 10 times or more, in order to make it easy to sufficiently exert the ignition suppressing effect and the fire extinguishing performance even if the thickness is reduced. More preferably, 20 times or more is further preferable. The expansion ratio of the refractory material is preferably 100 times or less, more preferably 50 times or less.
  • the content of the heat-expandable compound can be adjusted appropriately, and a certain amount of resin can be contained in the refractory material, and the mechanical strength of the refractory material can be easily improved.
  • it is easy to improve the hardness of the expanded residue after expansion and it is easy to improve fire resistance, fire extinguishing property and the like.
  • the expansion ratio as shown in Examples described later, when the refractory material is heated at 600 ° C. for 3 minutes, the thickness of the expansion residue after expansion is divided by the thickness of the refractory material before expansion. It is calculated.
  • thermoplastic resin examples include polyolefin resins, polyester resins such as polyethylene terephthalate, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, polyvinyl acetal resins, polyvinyl alcohol resins, polycarbonate resins, polyphenylene ether resins, acrylic resins, and polyamides.
  • thermosetting resin examples include synthetic resins such as epoxy resin, urethane resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide.
  • acrylonitrile butadiene rubber NBR
  • ethylene-propylene-diene rubber EPDM
  • ethylene-propylene rubber natural rubber
  • polybutadiene rubber polyisoprene rubber
  • styrene-butadiene block copolymer hydrogenated styrene-butadiene block
  • copolymers hydrogenated styrene-butadiene-styrene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-isoprene-styrene block copolymers and the like.
  • one of these resins may be used alone, or two or more thereof may be mixed and used.
  • the resin at least one selected from polyvinyl chloride resin, polyolefin resin, polyvinyl acetal resin, acrylic resin, and epoxy resin is preferable.
  • polyvinyl chloride resin and polyolefin resin are preferable from the viewpoint of ensuring moldability by extrusion molding.
  • polyvinyl acetal resin and acrylic resin from the viewpoint of easily ensuring moldability and mechanical strength such as tensile strength even when a relatively large amount of additives such as heat-expandable compounds are blended. At least one of them is more preferable, and a polyvinyl acetal resin is further preferable.
  • the melt flow rate of a thermoplastic resin such as a polyvinyl chloride resin or a polyolefin resin is preferably 1.0 g / 10 min or more.
  • the melt flow rate is more preferably 2.4 g / 10 min or more, further preferably 10 g / 10 min or more, and even more preferably 20 g / 10 min or more.
  • the melt flow rate of the thermoplastic resin is preferably 40 g / 10 min or less, more preferably 35 g / 10 min or less.
  • the melt flow rate was measured according to JIS K 7210-2: 1999 under the conditions of 190 ° C. and 2.16 kg load.
  • polyolefin resin examples include polypropylene resin, polyethylene resin, poly (1-) butene resin, polypentene resin, ethylene-vinyl acetate copolymer (EVA) resin, and the like. Among these, ethylene-vinyl acetate is used. A polymer (EVA) resin is preferred.
  • the ethylene-vinyl acetate copolymer resin may be a non-crosslinked ethylene-vinyl acetate copolymer resin or a high-temperature crosslinked ethylene-vinyl acetate copolymer resin.
  • an ethylene-vinyl acetate modified resin such as an ethylene-vinyl acetate copolymer saponified product and an ethylene-vinyl acetate hydrolyzate can also be used.
  • the ethylene-vinyl acetate copolymer resin preferably has a vinyl acetate content of 10 to 50% by mass, more preferably 25 to 45% by mass, as measured in accordance with JIS K 6730 “Ethylene-vinyl acetate resin test method”. ..
  • the vinyl acetate content By setting the vinyl acetate content to these lower limit values or more, the adhesiveness to additives such as thermal expansion compounds is improved. Further, by setting the vinyl acetate content to these upper limit values or less, the mechanical strength such as the breaking strength of the refractory resin layer becomes good.
  • the polyvinyl chloride resin may be a vinyl chloride homopolymer or a vinyl chloride-based copolymer.
  • the vinyl chloride-based copolymer is a copolymer of vinyl chloride and a monomer having an unsaturated bond copolymerizable with vinyl chloride, and contains 50% by mass or more of a constituent unit derived from vinyl chloride.
  • Examples of the monomer having an unsaturated bond copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate, and acrylic acid esters such as acrylic acid, methacrylic acid, methyl acrylate, and ethyl acrylate.
  • the polyvinyl chloride resin may be a polyvinyl chloride vinyl chloride resin obtained by chlorinating a vinyl chloride homopolymer, a vinyl chloride-based copolymer or the like.
  • the polyvinyl chloride resin one type may be used alone from the above-mentioned ones, or two or more types may be used in combination.
  • the polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde, but a polyvinyl butyral resin is preferable.
  • a polyvinyl butyral resin By using polyvinyl butyral, it is possible to increase the mechanical strength even when the amount of resin in the refractory material is relatively small. Therefore, even if the thickness of the refractory material is reduced, a certain level of mechanical strength can be ensured.
  • the amount of hydroxyl groups in the polyvinyl acetal resin is preferably 20 to 40 mol%.
  • the amount of hydroxyl groups By setting the amount of hydroxyl groups to 20 mol% or more, the polarity of the polyvinyl acetal resin becomes high, the adhesive strength to heat-expandable compounds, solid flame retardants, adsorbents, etc. becomes strong, and the mechanical strength of the fireproof material can be easily improved. Become. Further, by setting the amount of hydroxyl groups to 40 mol% or less, it is possible to prevent the refractory material from becoming too hard and lowering mechanical strength such as tensile strength.
  • the amount of the hydroxyl group is more preferably 22 mol% or more.
  • the amount of the hydroxyl group is more preferably 37 mol% or less, still more preferably 35 mol% or less, still more preferably 33 mol% or less.
  • the degree of acetalization of the polyvinyl acetal resin is preferably 40 to 80 mol%. By setting the degree of acetalization within the above range, the above-mentioned amount of hydroxyl groups is set within the desired range, and the mechanical strength of the refractory material can be easily improved.
  • the degree of acetalization is more preferably 55 mol% or more, further preferably 65 mol% or more, still more preferably 67 mol% or more, and even more preferably 76 mol% or less.
  • the amount of acetyl groups in the polyvinyl acetal resin is preferably 0.1 to 30 mol%.
  • the amount of acetyl groups is more preferably 0.2 mol% or more, further preferably 0.5 mol% or more, still more preferably 15 mol% or less, still more preferably 7 mol% or less.
  • the degree of acetalization, the amount of hydroxyl groups, and the amount of acetyl groups can be measured and calculated by, for example, a method based on JIS K6728 "Polyvinyl butyral test method".
  • the degree of polymerization of the polyvinyl acetal resin is preferably 200 to 3000. By setting the degree of polymerization within these ranges, it is possible to appropriately disperse the heat-expandable compound, the solid flame retardant, the adsorbent and the like in the refractory material.
  • the degree of polymerization is more preferably 250 or more, still more preferably 300 or more. When the degree of polymerization of the polyvinyl acetal resin is lowered, the viscosity is also lowered, and it becomes easier to disperse a heat-expandable compound, a solid flame retardant, an adsorbent, etc. in the fire-resistant material, and the mechanical strength of the fire-resistant material is improved.
  • the degree of polymerization of the polyvinyl acetal resin is more preferably 1500 or less, still more preferably 1000 or less, still more preferably 900 or less.
  • the degree of polymerization of the polyvinyl acetal resin refers to the degree of viscosity average polymerization measured based on the method described in JIS K6728.
  • the viscosity of 10% by mass ethanol / toluene of the polyvinyl acetal resin is preferably 5 mPa ⁇ s or more, more preferably 10 mPa ⁇ s or more, and further preferably 15 mPa ⁇ s or more.
  • the viscosity of 10% by mass ethanol / toluene is preferably 500 mPa ⁇ s or less, more preferably 300 mPa ⁇ s or less, and further preferably 200 mPa ⁇ s or less.
  • the 10% by mass ethanol / toluene viscosity of the polyvinyl acetal resin is a value measured as follows. 150 ml of an ethanol / toluene (weight ratio 1: 1) mixed solvent is placed in an Erlenmeyer flask, a weighed sample is added thereto, the resin concentration is adjusted to 10 wt%, and the mixture is shaken and dissolved in a thermostatic chamber at 20 ° C. The solution can be held at 20 ° C. and the viscosity can be measured using a BM type viscometer to determine the viscosity of 10% by mass ethanol / toluene.
  • the above aldehyde is not particularly limited, but in general, an aldehyde having 1 to 10 carbon atoms is preferably used.
  • the aldehyde having 1 to 10 carbon atoms is not particularly limited, and for example, n-butyraldehyde, isobutylaldehyde, n-barrelaldehyde, 2-ethylbutylaldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde are not particularly limited. , N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like.
  • n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and n-butyraldehyde is more preferable.
  • These aldehydes may be used alone or in combination of two or more.
  • the acrylic resin is, for example, a polymer obtained by polymerizing a monomer component containing a (meth) acrylic acid alkyl ester-based monomer.
  • (meth) acrylic acid alkyl ester means "acrylic acid alkyl ester, or methacrylic acid alkyl ester”. The same is true for other similar terms.
  • the (meth) acrylic acid alkyl ester-based monomer in the present invention is an ester of (meth) acrylic acid and an aliphatic alcohol, and the alkyl group of the aliphatic alcohol has, for example, 1 to 18, preferably 1. It is ⁇ 14, more preferably 1 to 10, and even more preferably 1 to 8.
  • (meth) acrylic acid alkyl ester-based monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate.
  • Examples thereof include (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and tetradecyl (meth) acrylate.
  • the (meth) acrylic acid alkyl ester-based monomer may be used alone or in combination of two or more.
  • a polar group-containing monomer may be contained in addition to the above-mentioned (meth) acrylic acid alkyl ester-based monomer.
  • the polar group-containing monomer include (meth) acrylic acid, a vinyl group-containing carboxylic acid such as itaconic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl.
  • Vinyl monomers having hydroxyl groups such as (meth) acrylate, caprolactone-modified (meth) acrylate, polyoxyethylene (meth) acrylate, and polyoxypropylene (meth) acrylate, (meth) acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam. , N-vinyllaurilolactam, (meth) acryloylmorpholine, (meth) acrylamide, dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and dimethylaminomethyl (meth) acrylate.
  • nitrogen-containing vinyl monomer Such as nitrogen-containing vinyl monomer.
  • the glass transition temperature (Tg) of the acrylic resin is preferably 5 to 80 ° C. By setting the glass transition temperature (Tg) within these ranges, it is possible to impart a certain mechanical strength to the refractory material while improving moldability, flexibility and the like. From these viewpoints, the glass transition temperature (Tg) of the acrylic resin is preferably 15 to 70 ° C, more preferably 25 to 60 ° C. The glass transition temperature (Tg) of the acrylic resin can be adjusted by appropriately selecting the type and amount of the monomer components used. The glass transition temperature (Tg) of the acrylic resin can be measured by, for example, a differential thermal scanning calorimeter (DSC).
  • DSC differential thermal scanning calorimeter
  • a polymer of a (meth) acrylic acid alkyl ester-based monomer is preferable. Specifically, a polymer of a (meth) acrylic acid alkyl ester-based monomer having an alkyl group having 1 to 14 carbon atoms is preferable, and a (meth) acrylic acid alkyl ester-based monomer having an alkyl group having 1 to 10 carbon atoms is preferable. A polymer of a monomer is more preferable, and a polymer of a (meth) acrylic acid alkyl ester-based monomer having an alkyl group having 1 to 8 carbon atoms is further preferable.
  • the acrylic resin may be a homopolymer of a (meth) acrylic acid alkyl ester-based monomer, or may be a copolymer of two or more kinds of (meth) acrylic acid alkyl ester-based monomers.
  • Specific suitable acrylic resins include homopolymers of isobutyl methacrylate, copolymers of isobutyl methacrylate and methyl methacrylate, and the like.
  • the acrylic resin may be used alone or in combination of two or more.
  • the weight average molecular weight of the acrylic resin is 10,000 to 300, from the viewpoint of improving the mechanical strength of the refractory material by appropriately dispersing the heat-expandable compound, solid flame retardant, adsorbent, etc. in the refractory material. 000 is preferable. From these viewpoints, the weight average molecular weight of the acrylic resin is more preferably 30,000 to 250,000 and further preferably 60,000 to 200,000.
  • the weight average molecular weight of the acrylic resin is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC). Examples of the column for measuring the weight average molecular weight by the GPC method include Shodex LF-804 (manufactured by Showa Denko KK) and the like.
  • the epoxy resin used in the present invention is not particularly limited, and examples thereof include an epoxy compound alone, or an epoxy compound as a main agent and a curing agent.
  • the epoxy compound is a compound having an epoxy group, and specific examples thereof include a glycidyl ether type and a glycidyl ester type.
  • the glycisyl ether type may be bifunctional or may be trifunctional or higher. The same applies to the glycidyl ester type.
  • the epoxy compound may contain a monofunctional one in order to adjust the degree of cross-linking or the like. Of these, the bifunctional glycidyl ether type is preferable.
  • bifunctional glycidyl ether type epoxy compound examples include aliphatic glycol types such as polyethylene glycol type and polypropylene glycol type, neopentyl glycol type, 1,6-hexanediol type, and hydrogenated bisphenol A type.
  • Epoxy compounds are exemplified.
  • aromatic epoxy compounds containing an aromatic ring such as bisphenol A type, bisphenol F type, bisphenol AD type, ethylene oxide-bisphenol A type, and propylene oxide-bisphenol A type can be mentioned.
  • aromatic epoxy compounds such as bisphenol A type and bisphenol F type are preferable.
  • Examples of the glycidyl ester type epoxy compound include hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, p-oxybenzoic acid type and other epoxy compounds.
  • Examples of the trifunctional or higher functional glycidyl ether type epoxy compound include phenol novolac type, orthocresol novolak type, DPP novolak type, dicyclopentadiene phenol type and the like. These epoxy compounds may be used alone or in combination of two or more.
  • a heavy addition type or a catalytic type is used as the curing agent.
  • the heavy addition type curing agent include polyamine-based curing agents, acid anhydride-based curing agents, polyphenol-based curing agents, and polymercaptans.
  • the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes. These curing agents may be used alone or in combination of two or more.
  • the content of the resin in the refractory material is, for example, 5 to 90% by mass, preferably 10 to 85% by mass, more preferably 30 to 75% by mass, still more preferably 40 to 65% by mass, based on the total amount of the refractory material. Most preferably, it is 45 to 60% by mass.
  • the dispersibility of the refractory material such as a heat-expandable compound, a solid flame retardant, and an endothermic agent is improved, and the mechanical strength and moldability of the refractory material such as tensile strength are likely to be increased.
  • the fire resistance and fire extinguishing performance of the refractory material are likely to be improved.
  • the thermally expandable compound used in the present invention is a compound that expands to a certain degree or more by being heated so that the expansion ratio of the refractory material becomes the above-mentioned predetermined value or more.
  • the degree of expansion of the heat-expandable compound is preferably 5 ml / g or more. By setting it to 5 ml / g or more, it is possible to set the expansion coefficient of the refractory material to the above-mentioned predetermined value or more by using an appropriate amount of the heat-expandable compound.
  • the degree of expansion of the heat-expandable compound is more preferably 20 ml / g or more, further preferably 100 ml / g or more, still more preferably 150 ml / g or more.
  • the degree of expansion of the thermally expandable compound is preferably 400 ml / g or less, more preferably 300 ml / g or less, still more preferably 250 ml / g or less.
  • the thermal expansion compound used in the present invention preferably has an expansion start temperature of 95 ° C. or higher.
  • the expansion start temperature of the thermally expandable compound is more preferably 105 ° C. or higher, still more preferably 115 ° C. or higher.
  • the expansion start temperature of the thermally expandable compound is preferably less than 600 ° C., preferably 450 ° C. or lower so that the refractory material can expand at 600 ° C. By setting the temperature to 450 ° C.
  • the battery can be rapidly expanded when the battery ignites or when thermal runaway occurs, and the fire resistance and fire extinguishing performance can be improved.
  • the expansion start temperature is more preferably 200 ° C. or lower, still more preferably 140 ° C. or lower.
  • the expansion start temperature of the heat-expandable compound expands to 1.1 times or more the volume before the start of temperature rise when the temperature of the heat-expandable compound is raised from 25 ° C. to 5 ° C./min. It is the temperature when it is used.
  • the temperature interval for measuring the volume of the heat-expandable graphite is not particularly limited, and for example, the volume may be measured every time the temperature rises by 5 ° C.
  • the degree of expansion is the volume (ml) per unit mass (g) after the thermally expandable compound is held at 1000 ° C. for 10 seconds.
  • the heat-expandable compound used in the present invention is preferably at least one selected from a heat-expandable layered inorganic substance, a heat-expandable solid phosphorus-based compound, and a heat-expandable microcapsule.
  • at least one selected from a heat-expandable layered inorganic substance and a heat-expandable solid phosphorus-based compound is more preferable, and at least a heat-expandable layered inorganic substance is further preferably used.
  • the heat-expandable layered inorganic substance is a conventionally known substance that expands when heated, and examples thereof include vermiculite and heat-expandable graphite. Among them, heat-expandable graphite is preferable.
  • As the heat-expandable layered inorganic substance particulate or flaky ones may be used.
  • the heat-expandable layered inorganic substance, particularly the heat-expandable graphite can have a high degree of expansion (for example, 100 ml / g or more, further 150 ml / g or more) as described above, and has a large capacity of voids during heat expansion. Can be formed.
  • the expansion start temperature can be lowered (for example, 200 ° C. or lower, further 140 ° C. or lower, etc.). Therefore, the fire resistance and fire extinguishing performance of the refractory material can be improved.
  • Thermally expandable graphite is obtained by treating powders such as natural scaly graphite, pyrolytic graphite, and kiss graphite with an inorganic acid and a strong oxidizing agent to form a graphite interlayer compound, and maintains a layered structure of carbon. It is a kind of crystalline compound as it is.
  • the inorganic acid include concentrated sulfuric acid, nitric acid and selenic acid.
  • the strong oxidizing agent include concentrated nitric acid, persulfate, perchloric acid, perchlorate, permanganate, dichromate, dichromate, hydrogen peroxide and the like.
  • the heat-expandable graphite obtained by the acid treatment as described above may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound or the like.
  • the particle size of the heat-expandable graphite is preferably 20 to 200 mesh. When the particle size of the heat-expandable graphite is within the above range, it expands easily to form a large-capacity void, and thus the fire resistance is improved. In addition, the dispersibility in the resin is also improved.
  • the average aspect ratio of the heat-expandable graphite is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more.
  • the upper limit of the average aspect ratio of the heat-expandable graphite is not particularly limited, but is preferably 1,000 or less from the viewpoint of preventing cracking of the heat-expandable graphite.
  • the average aspect ratio of the heat-expandable graphite When the average aspect ratio of the heat-expandable graphite is 2 or more, it expands and easily forms a large-capacity void, so that flame retardancy is improved.
  • the average aspect ratio of the heat-expandable graphite was measured for each of the 10 heat-expandable graphites in the maximum dimension (major axis) and the minimum dimension (minor axis), and the maximum dimension (major axis) was divided by the minimum dimension (minor axis). Let the average value be the average aspect ratio.
  • the major axis and minor axis of the heat-expandable graphite can be measured using, for example, a field emission scanning electron microscope (FE-SEM).
  • the thermally expandable solid phosphorus-based compound is a compound that is solid at room temperature (25 ° C.) and normal pressure (1 atm), has a phosphorus atom, and has an expansion degree of 5 ml / g or more.
  • the degree of expansion of the thermally expandable solid phosphorus compound is preferably 20 ml / g or more.
  • the degree of expansion of the heat-expandable solid phosphorus-based compound may be not more than the above upper limit value, but is usually lower than that of the heat-expandable layered inorganic substance, and is typically 100 ml / g or less.
  • the heat-expandable solid phosphorus-based compound has a flame retardancy due to having a phosphorus atom, and tends to improve fire extinguishing performance and fire resistance. Further, as will be described later, when used in combination with a thermally expandable layered inorganic substance, it becomes easy to keep the expansion residue in a mesh-like state, and it is easy to improve fire extinguishing performance and fire resistance.
  • Examples of the heat-expandable solid phosphorus-based compound include those which are metal salts of lower phosphoric acids and have a degree of expansion of 5 ml / g or more as described above.
  • “Lower phosphoric acids” refers to non-condensed, that is, non-polymerized inorganic phosphoric acids among the inorganic phosphoric acids. That is, inorganic phosphoric acids have one phosphorus atom in the molecule.
  • Examples of lower phosphoric acids include primary phosphoric acid, secondary phosphoric acid, tertiary phosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid and the like.
  • the metal used for the metal salt may be any of alkali metal, alkaline earth metal, periodic table 3B metal, transition metal and the like.
  • a typical example is a metal salt of phosphorous acid, and a specific compound is aluminum phosphate.
  • Aluminum phosphite has a high degree of expansion, and it becomes easy to improve fire resistance and fire extinguishing property.
  • the heat-expandable compound may be used alone or in combination of two or more.
  • a heat-expandable microcapsule contains a volatile substance such as a low boiling point solvent inside the outer shell resin.
  • the outer shell resin is softened by heating, and the contained volatile substance volatilizes or expands. The pressure causes the outer shell to expand and the particle size to increase.
  • the outer shell of the heat-expandable microcapsules is preferably formed of a thermoplastic resin.
  • Thermoplastic resins are made from vinyl polymers such as ethylene, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, butadiene, and chloroprene, copolymers thereof, polyamides such as nylon 6, nylon 66, and polyesters such as polyethylene terephthalate.
  • vinyl polymers such as ethylene, styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, butadiene, and chloroprene, copolymers thereof, polyamides such as nylon 6, nylon 66, and polyesters such as polyethylene terephthalate.
  • acrylonitrile copolymer is preferable because the contained volatile substances are difficult to permeate.
  • Volatile substances contained inside the heat-expandable microcapsules include hydrocarbons having 3 to 7 carbon atoms such as propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normal pentane, hexane, and heptane, and chloride.
  • One or 2 selected from methane halides such as methyl and methylene chloride, chlorofluorocarbons such as CCl 3 F and CCl 2 F 2 , tetraalkylsilanes such as tetramethylsilane and trimethylethylsilane, and petroleum ethers.
  • methane halides such as methyl and methylene chloride
  • chlorofluorocarbons such as CCl 3 F and CCl 2 F 2
  • tetraalkylsilanes such as tetramethylsilane and trimethylethylsilane
  • petroleum ethers
  • the heat-expandable microcapsules include microcapsules in which a copolymer of acrylonitrile and vinylidene chloride is used as an outer shell resin and a hydrocarbon having 3 to 7 carbon atoms such as isobutane is contained.
  • a copolymer of acrylonitrile and vinylidene chloride is used as an outer shell resin and a hydrocarbon having 3 to 7 carbon atoms such as isobutane is contained.
  • the heat-expandable microcapsules it is particularly preferable to use them in combination with at least one selected from the above-mentioned heat-expandable solid phosphorus compound and the solid flame retardant described later.
  • the heat-expandable microcapsules are maintained in an expanded state even at a high temperature, and a high expansion coefficient can be achieved when heated to 600 ° C.
  • both a heat-expandable layered inorganic substance and a heat-expandable solid phosphorus-based compound it is more preferable to use both a heat-expandable layered inorganic substance and a heat-expandable solid phosphorus-based compound.
  • both of these compounds are used as the heat-expandable compound, it becomes easy to keep the expansion residue in a mesh-like state, and it is possible to insulate while dissipating flammable gas and flame to the outside, and it is fire-extinguishing and fire-resistant. Excellent for.
  • the content of the heat-expandable compound is preferably 10 to 1500 parts by mass with respect to 100 parts by mass of the resin.
  • the expansion ratio of the refractory material can be set to a predetermined value or more.
  • the content of the heat-expandable compound is more preferably 20 parts by mass or more, further preferably 40 parts by mass or more, further preferably 50 parts by mass or more, still more preferably 1000 parts by mass or less, and more preferably 500 parts by mass. It is more preferably parts or less, more preferably 250 parts by mass or less, still more preferably 130 parts by mass or less.
  • both a heat-expandable layered inorganic substance and a heat-expandable solid phosphorus-based compound it is preferable to use both a heat-expandable layered inorganic substance and a heat-expandable solid phosphorus-based compound, but when both are used, the total amount thereof contains the above.
  • the amount 40 parts by mass or more is more preferable, 50 parts by mass or more is further preferable, and 80 parts by mass or more is further preferable.
  • 500 parts by mass or less is more preferable, 250 parts by mass or less is further preferable, and 130 parts by mass or less is further preferable.
  • the mass ratio of these contents is preferably 2/8 to 8/2, more preferably 3/7 to 7/3, and 4/6. ⁇ 6/4 is more preferable. Within these ranges, the hardness of the expanded residue in the form of a mesh is maintained high, and the fire resistance and fire extinguishing property can be further improved.
  • the refractory material of the present invention preferably contains a solid flame retardant other than the above-mentioned heat-expandable compound.
  • the solid flame retardant is a flame retardant that is solid at room temperature and normal pressure.
  • Examples of the solid flame retardant include low melting point glass, phosphorus compounds other than the heat-expandable solid phosphorus compound, melamine compounds, and nitrogen-containing flame retardants such as cyclic urea compounds.
  • the solid flame retardant one type selected from these may be used, or two or more types may be used in combination.
  • the refractory material of the present invention contains a solid flame retardant in addition to the above-mentioned heat-expandable compound, the expansion residue is easily held in a mesh-like state, and while dissipating flammable gas and flame to the outside. It can be insulated and has good fire extinguishing and fire resistance.
  • the low melting point glass used as a solid flame retardant softens when heated and becomes a molten state, acts as an inorganic binder, and has the effect of improving the mechanical strength of the refractory material.
  • the low melting point glass specifically means a glass that softens or melts at a temperature of 1000 ° C. or lower, and the softening temperature of the low melting point glass is preferably 200 to 900 ° C., more preferably 300 to 800 ° C., still more preferably 300. It is ⁇ 600 ° C.
  • the softening temperature is, for example, a value measured from the inflection point of DTA.
  • low melting point glass examples include silicon, aluminum, boron, phosphorus, zinc, iron, copper, titanium, vanadium, zirconium, tungsten, molybdenum, thallium, antimony, tin, cadmium, arsenic, lead, alkali metal, and alkaline earth metal.
  • the low melting point glass is preferably in the form of particles such as glass frit.
  • low melting point glass examples include Nippon Ryu Glazed Co., Ltd., trade name "4020” (aluminum phosphate salt-based low melting point glass, softening temperature: 380 ° C.), Nippon Ryu Glazing Co., Ltd., trade name "4706” (borosilicate).
  • Low melting point glass, softening temperature: 610 ° C.), manufactured by Asahi Techno Glass Co., Ltd., trade name "FF209” (lithium borate low melting point glass, softening temperature: 450 ° C.), etc. are commercially available.
  • the phosphorus-based compound used as a solid flame retardant is a compound having a phosphorus atom, and examples thereof include a polyphosphoric acid compound.
  • examples of the polyphosphoric acid compound include ammonium polyphosphate, polyphosphoric acid amide, and the like, and among these, ammonium polyphosphate is preferable. Further, it may be a metal salt of lower phosphoric acids having a degree of expansion of less than 5 ml / g.
  • the nitrogen-containing flame retardant is a flame retardant having a nitrogen atom, and examples thereof include melamine compounds and cyclic urea compounds. As described later, the nitrogen-containing flame retardant may further contain a phosphorus atom as long as it has a basic skeleton containing a nitrogen atom such as a melamine skeleton or cyclic urea. Examples of the melamine-based compound include compounds having a melamine skeleton, a melamine derivative skeleton such as melam, and melem.
  • examples thereof include cyanurate and melamine borate.
  • Cyclic urea compounds include ethylene urea (2-imidazolidinone), propylene urea (tetrahydro-2-pyrimidineone), hydantoin (2,5-imidazolidinedione), and cyanuric acid [1,3,5-triazine-2, 4,6 (1H, 3H, 5H) -trione], biolic acid [5- (hydroxyimimino) pyrimidin-2,4,6 (1H, 3H, 5H) -trione] and the like.
  • the solid flame retardant is preferably at least one selected from low melting point glass, polyphosphoric acid compound, melamine compound, and cyclic urea compound, and more preferably selected from low melting point glass and polyphosphoric acid compound. At least one kind to be done. By using these, it becomes easy to hold the expansion residue in a mesh shape and increase the hardness of the expansion residue to improve fire extinguishing property and fire resistance.
  • Specific suitable compounds of the solid flame retardant are low melting point glass, ammonium polyphosphate, polyphosphate amide, melamine pyrophosphate, melamine orthophosphate, melamine polyphosphate, melamine melem compound salt, melamine polymethaphosphate, melamine sulfate.
  • the content of the solid flame retardant in the refractory material is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the resin.
  • the amount is 10 parts by mass or more, the expansion residue of the refractory material is easily held in a mesh shape, and flammable gas, flame, etc. are dissipated to the outside to improve fire resistance and fire extinguishing property.
  • the amount is 1000 parts by mass or less, the mechanical strength and moldability of the refractory material tend to be improved.
  • the content within the above range, the hardness of the expansion residue can be increased, and the fire extinguishing property and the fire resistance can be easily improved.
  • the content of the solid flame retardant is more preferably 20 parts by mass or more, further preferably 40 parts by mass or more, further preferably 500 parts by mass or less, further preferably 150 parts by mass or less, and further preferably 100 parts by mass. The following is even more preferable.
  • the mass ratio of the content of the solid flame retardant to the heat-expandable compound is preferably, for example, 1/20 to 20/1, and 2/8 to 8/2. Preferably, 3/7 to 7/3 is more preferable, and 4/6 to 6/4 is even more preferable. Within these ranges, the mechanical strength of the expanded residue in the form of a mesh becomes good, and the fire resistance and fire extinguishing property can be further improved.
  • the heat-expandable compound may contain both a heat-expandable layered inorganic substance and a heat-expandable solid phosphorus-based compound, but the heat-expandable layered inorganic substance and Sufficient fire resistance and fire extinguishing performance can be obtained by containing only one of the thermally expandable solid phosphorus compounds.
  • a particularly preferred combination when the fire retardant contains a solid flame retardant is to use thermally expandable graphite as the thermally expandable compound and at least one selected from polyphosphate compounds and low melting point glass as the solid flame retardant. To do. Further, lower phosphoric acids such as aluminum phosphite are used as the expandable compound, and at least one selected from polyphosphoric acid compounds is used as the solid flame retardant.
  • the total amount of the heat-expandable compound and the solid flame-retardant in the fire-resistant material is preferably 20 to 1500 parts by mass and 50 to 1000 parts by mass with respect to 100 parts by mass of the resin. Parts by mass are more preferable, parts by mass of 80 to 300 are even more preferable, and parts by mass of 80 to 130 are even more preferable.
  • the total amount of the heat-expandable compound and the solid flame retardant is at least the above lower limit value, it is easy to improve the fire extinguishing property and the fire resistance of the refractory material. Further, when it is not more than the above upper limit value, it is easy to improve the mechanical strength and moldability of the refractory material.
  • the refractory material of the present invention may further contain an endothermic agent.
  • the endothermic agent include an endothermic agent having a thermal decomposition start temperature of 800 ° C. or less and an endothermic amount of 300 J / g or more.
  • the thermal decomposition start temperature or the amount of heat absorption is within the above range, the heat absorbing agent can quickly extinguish the fire when the battery or the like ignites, and the fire extinguishing property can be further improved.
  • the thermal decomposition start temperature of the endothermic agent is preferably 500 ° C. or lower, more preferably 400 ° C. or lower, and even more preferably 300 ° C. or lower. By setting the thermal decomposition start temperature of the endothermic agent to these upper limit values or less, the endothermic agent is rapidly decomposed at the time of ignition, and the fire can be extinguished quickly.
  • the thermal decomposition start temperature of the endothermic agent is, for example, 50 ° C. or higher, preferably 100 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 180 ° C. or higher.
  • the thermal decomposition start temperature can be measured by a thermogravimetric differential thermal analyzer (TG-DTA), and specifically, can be measured by the method described in Examples.
  • TG-DTA thermogravimetric differential thermal analyzer
  • the endothermic amount of the endothermic agent is preferably 500 J / g or more, more preferably 600 J / g or more, still more preferably 900 J / g or more.
  • the endothermic amount of the endothermic agent is usually 4000 J / g or less, preferably 3000 J / g or less, and more preferably 2000 J / g or less.
  • the amount of heat absorbed can be measured using a thermogravimetric differential thermal analyzer (TG-DTA), and specifically, it can be measured by the method described in Examples.
  • the endothermic agent preferably has an average particle size of 0.1 to 90 ⁇ m.
  • the average particle size of the endothermic agent is more preferably 0.5 to 60 ⁇ m, further preferably 0.8 to 40 ⁇ m, and even more preferably 0.8 to 10 ⁇ m.
  • the average particle size of the endothermic agent is within the above range, the dispersibility of the endothermic agent in the refractory material is improved, the endothermic agent is uniformly dispersed in the resin, and the amount of the endothermic agent blended with the resin is increased. be able to.
  • the heat absorbing agent is not particularly limited as long as it satisfies the above-mentioned thermal decomposition start temperature and heat absorbing amount, but a hydrated metal compound can be preferably used.
  • the hydrated metal compound is a compound having an effect of absorbing heat and extinguishing a fire by decomposing by heating to generate water vapor.
  • Examples of the hydrated metal compound include metal hydroxides and hydrates of metal salts, and among them, metal hydroxides are preferable. Further, a combination of a metal hydroxide compound and a hydrate of a metal salt is also preferable. By using a metal hydroxide compound, it becomes easy to improve the fire extinguishing performance.
  • the metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, hydrotalcite and the like.
  • a hydrate of metal salt for example, 2ZnO ⁇ 3B 2 O 5 ⁇ 3.5H hydrate of zinc borate represented by 2 O, hydrate of calcium sulfate (e.g., dihydrate), sulfate Examples thereof include hydrates of metal sulfates such as magnesium hydrate (for example, heptahydrate).
  • kaolinite, dosonite, boehmite and the like can be mentioned.
  • the endothermic agent may be calcium aluminates, talc or the like.
  • heat absorbing agent examples include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, hydrate of zinc borate, hydrate of calcium sulfate (for example, dihydrate), and hydration of magnesium sulfate. (For example, heptahydrate) is preferable, and among these, aluminum hydroxide and magnesium hydroxide are more preferable.
  • the content of the endothermic agent is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the resin.
  • the content of the endothermic agent is more preferably 40 parts by mass or more, more preferably 80 parts by mass or more, still more preferably 400 parts by mass or less, still more preferably 200 parts by mass or less.
  • the content of the heat absorbing agent has a mass ratio (total amount of the heat absorbing agent / heat expanding compound and the solid flame retardant) to the total amount of the heat-expandable compound and the solid flame retardant, for example, 1/9 to 9/1. This is preferable, 2/8 to 8/2 is preferable, 3/7 to 7/3 is more preferable, and 4/6 to 6/4 is further preferable. Within these ranges, it is possible to achieve a good balance between maintaining the mechanical strength of the refractory material and improving the fire extinguishing performance by the endothermic agent.
  • the refractory material of the present invention may further contain an inorganic filler other than the above-mentioned heat-expandable compound, solid flame retardant, and endothermic agent.
  • an inorganic filler is not particularly limited, and for example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide and ferrite, and water such as calcium carbonate.
  • the average particle size of the inorganic filler is preferably 0.5 to 100 ⁇ m, more preferably 1 to 50 ⁇ m.
  • the particle size is preferably small from the viewpoint of improving dispersibility, and when the content is high, the viscosity of the refractory resin composition increases and the moldability becomes higher as the filling progresses. It is preferable that the particle size is large because it decreases.
  • the refractory material of the present invention contains the above-mentioned inorganic filler, the content thereof is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the resin. When the content of the inorganic filler is within the above range, the mechanical properties and moldability of the refractory material can be improved.
  • the refractory material of the present invention may further contain a plasticizer.
  • a plasticizer may be contained from the viewpoint of improving moldability and the like.
  • the plasticizer is not particularly limited as long as it is a plasticizer generally used in combination with a polyvinyl chloride resin or a polyvinyl acetal resin.
  • phthalate ester plasticizers such as di-2-ethylhexylphthalate (DOP), dibutylphthalate (DBP), diheptylphthalate (DHP), and diisodecylphthalate (DIDP), di-2-ethylhexyl adipate ( DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA) and other fatty acid ester plasticizers, epoxidized soybean oil and other epoxidized ester plasticizers, adipate ester, adipate polyester and other adipate plasticizers, tree 2 -Examples include trimellitic acid ester plasticizers such as ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM), and process oils such as mineral oil.
  • DOP di-2-ethylhexylphthalate
  • DBP dibutylphthalate
  • DHP dihept
  • the plasticizer may be used alone or in combination of two or more.
  • the content of the plasticizer is preferably 1 to 60 parts by mass, more preferably 5 to 50 parts by mass, and 10 to 40 parts by mass with respect to 100 parts by mass of the resin. More preferred.
  • the content of the plasticizer is within the above range, the moldability tends to be improved, and it is possible to prevent the refractory resin layer from becoming too soft.
  • the refractory material of the present invention may contain additive components other than the above, if necessary, as long as the object of the present invention is not impaired.
  • the type of this additive component is not particularly limited, and various additives can be used. Examples of such additives include lubricants, shrinkage agents, crystal nucleating agents, colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, antioxidants, flame retardants, antistatic agents, and surfactants. Activators, vulcanizers, dispersants, surface treatment agents and the like can be mentioned.
  • the amount of the additive added can be appropriately selected within a range that does not impair the moldability and the like, and the additive may be used alone or in combination of two or more.
  • the refractory material is typically in the form of a sheet, and the thickness of the refractory material is, for example, 2 to 5000 ⁇ m, preferably 10 to 2000 ⁇ m, more preferably 20 to 1000 ⁇ m, and even more preferably 35 to 600 ⁇ m.
  • the "thickness" of the refractory material in the present specification refers to the average thickness of three points in the width direction of the refractory material.
  • the refractory material of the present invention can be produced by preparing a refractory resin composition and molding the refractory resin composition into a sheet or the like.
  • the fire-resistant resin composition contains a resin, a heat-expandable compound, and optional components such as a solid flame retardant, a heat absorbing agent, an inorganic filler, and a plasticizer, which are blended as necessary, in a Banbury mixer, a kneader mixer, a kneading roll, and a Raikai machine. , Obtained by mixing using a known mixing device such as a planetary stirrer.
  • the method for molding the fire-resistant resin composition into a fire-resistant material include extrusion molding, press molding, and injection molding. Among them, extrusion molding is preferable, and a single-screw extruder, a twin-screw extruder, and injection molding are preferable. It can be molded using a machine or the like. When a thermosetting resin is used as the resin, it is preferable to cure the resin component after molding the refractory resin composition into a sheet or the like.
  • the refractory material can also be suitably produced by a method of molding by applying a diluted solution of the refractory resin composition on a mold release sheet or the like and drying it.
  • the resin used in this production method may be appropriately selected from the above-mentioned resins, but is preferably at least one selected from polyvinyl acetal resins and acrylic resins.
  • the solvent used when diluting the refractory resin composition is not particularly limited, but is an aliphatic hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, cyclohexane, and an aromatic hydrocarbon solvent such as toluene.
  • Examples thereof include a solvent, an ester solvent such as ethyl acetate and n-butyl acetate, a ketone solvent such as acetone and methyl ethyl ketone (MEK), and an alcohol solvent such as ethanol, isopropyl alcohol and butanol.
  • the resin is usually dissolved by a solvent, and a heat-expandable compound, a solid flame retardant, a heat absorbing agent, and an inorganic filler to be blended as necessary are dispersed in the solvent to form a slurry. ..
  • a slurry for example, first, powders or particles of a heat-expandable compound, a solid flame retardant, a heat absorbing agent, an inorganic filler, etc., which are optionally blended, are stirred and dispersed in a solvent by a dispersion mixer such as a bead mill. Make a liquid. At this time, the solvent may be mixed with a dispersant in advance. Then, a resin solution dissolved in a solvent in advance and other components used as necessary are added to the dispersion, and the mixture is further stirred by the dispersion mixer to prepare a diluted solution of the refractory resin composition. Good.
  • a dispersion mixer such as a bead mill.
  • the solid content concentration in the diluted solution of the refractory resin composition is, for example, 30 to 70% by mass, preferably 35 to 65% by mass, and more preferably 40 to 60% by mass.
  • the refractory material can be efficiently molded.
  • the resin can be easily dissolved in the solvent and the endothermic agent can be easily dispersed in the solvent.
  • the refractory material of the present invention may be used as a single refractory material, or layers other than the refractory material may be laminated to form a refractory laminate.
  • the refractory laminate may include, for example, an adhesive material as a layer other than the refractory material.
  • the refractory laminate may include, for example, the refractory material and an adhesive material provided on at least one surface of the refractory material.
  • the refractory laminate provided by the adhesive material can be attached to the battery via the adhesive material.
  • the adhesive material may be provided on one surface of the refractory material, or may be provided on both sides of the refractory material. By providing the adhesive material on both sides of the refractory material, for example, when the refractory material is arranged between two battery cells, the refractory material can be attached to both battery cells.
  • the adhesive material is a member capable of pressure-sensitive adhesion of a refractory material to another member, and may be composed of an adhesive layer or a double-sided adhesive tape having adhesive layers provided on both surfaces of a base material. However, it is preferably composed of an adhesive layer.
  • the double-sided adhesive tape is laminated to form an adhesive material by adhering one of the adhesive layers to the refractory material.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include, but are not limited to, acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and rubber-based pressure-sensitive adhesives.
  • the thickness of the adhesive material is not particularly limited, but is, for example, 3 to 500 ⁇ m, preferably 10 to 200 ⁇ m.
  • the base material used for the double-sided adhesive tape it is preferable to use a known base material used for the double-sided adhesive tape, such as a resin film or a non-woven fabric.
  • the refractory laminate of the present invention may be a laminate having a base material and a refractory material provided on at least one surface of the base material.
  • the refractory material may be provided on only one side of the base material or on both sides.
  • the refractory material may be directly laminated on the base material, or the base material may be laminated directly on the base material via a primer layer, an adhesive layer or the like formed on the surface of the base material as long as the effect of the present invention is not impaired.
  • it may be laminated on, it is preferable that it is directly laminated.
  • the base material may be a flammable layer, a semi-incombustible layer, or a non-combustible layer.
  • the thickness of the base material is not particularly limited, but is, for example, 5 ⁇ m to 1 mm.
  • the base material is formed of a resin, a metal, an inorganic material other than metal, or a composite thereof.
  • the form of the base material may be a film, a foil or the like, or a cloth, a mesh or the like. Therefore, for example, a resin film, a graphite sheet, a metal foil, a metal cloth, a metal mesh, an organic fiber cloth, a cloth made of an inorganic material other than metal (inorganic fiber cloth), and the like can be mentioned.
  • the refractory laminate having the above-mentioned base material and refractory material can be produced by forming a refractory material on one surface or both sides of the base material by extrusion molding or the like of a refractory resin composition. Further, in the refractory laminate, a diluted solution of the refractory resin composition diluted with a solvent is applied to one or both sides of the base material and dried to form a refractory material on one or both sides of the base material. It may be manufactured by forming.
  • the type of solvent used for dilution, the solid content concentration in the diluent, etc. are as described above.
  • the refractory laminate may be manufactured by laminating a preformed refractory material on one side or both sides of the base material by pressure bonding or the like.
  • the refractory material may be formed on both sides at the same time, or the refractory material may be sequentially formed on each side.
  • an adhesive material may be further provided on at least one surface of the refractory laminate.
  • the adhesive material may be provided on the other surface of the base material, or may be provided on the refractory material, but may be provided on the refractory material. Is preferable.
  • the refractory laminate is arranged in the order of the refractory material and the base material from the battery side when the fireproof laminate is attached to the battery via the adhesive material. With such an arrangement, the fire extinguishing performance can be easily improved.
  • the adhesive material may be provided on one refractory material or both refractory materials, but on both refractory materials. It is preferable to be provided.
  • the adhesive material By providing the adhesive material on both refractory materials, for example, when the refractory laminate is arranged between two battery cells, the refractory laminate can be attached to both battery cells.
  • the specific configuration of the adhesive material is as described above.
  • the refractory material of the present invention is a heat-expandable refractory material for a battery used for a battery.
  • a battery usually has at least one battery cell, and a refractory material or a refractory laminate may be attached to the surface of the battery cell.
  • the refractory material or refractory laminate is usually placed on the surface of the battery cell.
  • the battery may have one battery cell or two or more batteries.
  • the battery cell refers to a constituent unit of a battery in which a positive electrode material, a negative electrode material, a separator, a positive electrode terminal, a negative electrode terminal, and the like are housed in an exterior member. Further, the battery cell is classified into a cylindrical type, a square type, and a laminated type according to the shape of the cell. When the battery cell has a cylindrical shape, it refers to a constituent unit of a battery in which a positive electrode material, a negative electrode material, a separator, a positive electrode terminal, a negative electrode terminal, an insulating material, a safety valve, a gasket, a positive electrode cap, and the like are housed in an outer can.
  • the battery cell when the battery cell is square, it refers to a constituent unit of a battery in which a positive electrode material, a negative electrode material, a separator, a positive electrode terminal, a negative electrode terminal, an insulating material, a safety valve, and the like are housed in an outer can.
  • the battery cell when the battery cell is a laminated type, it refers to a constituent unit of a battery in which a positive electrode material, a negative electrode material, a separator, a positive electrode terminal, a negative electrode terminal, and the like are housed in an exterior film.
  • a positive electrode material between two exterior films, or one exterior film is folded in half, for example, and between the folded exterior films, a positive electrode material, a negative electrode material, a separator, a positive electrode terminal, And the negative electrode terminal and the like are arranged, and the outer edge portion of the exterior film is crimped by heat sealing.
  • the battery cells are lithium ion battery, lithium ion polymer battery, nickel / hydrogen battery, lithium / sulfur battery, nickel / cadmium battery, nickel / iron battery, nickel / zinc battery, sodium / sulfur battery, lead storage battery, and air battery. Etc., and among these, a lithium ion battery is preferable. Batteries are used, for example, in small electronic devices such as mobile phones and smartphones, notebook computers, automobiles, and the like, but are not limited thereto.
  • the refractory material or the refractory laminate may be provided on any surface of the battery cell, in which case the refractory material is at least 50%, more preferably 70% or more of the surface area of the battery cell. ) Is preferably covered. Since the refractory material covers most of the surface of the battery cell, it becomes easy to extinguish the fire quickly against the ignition of the battery cell. Further, the battery cell often has a safety valve, but in the battery cell having the safety valve, it is preferable that the battery cell is provided so as to cover the safety valve with the refractory material regardless of whether the refractory material or the fireproof laminate is used. At this time, the refractory material may be covered so as not to seal the safety valve in order to ensure the function of the safety valve.
  • the heat seal portion to be crimped by the heat seal is covered with a refractory material. Since the battery cell often ignites from the safety valve or the heat seal portion, covering these with a refractory material makes it easier to extinguish the ignition of the battery cell more effectively. Further, when the refractory material covers most of the surface of the battery cell and the battery cell has a safety valve or a heat seal portion, it is more preferable that the refractory material is arranged so as to cover the safety valve or the heat seal portion as well. For example, the refractory material or the refractory laminate may be arranged so as to be wound around the battery cell.
  • the refractory material 12 is arranged so that the outer peripheral surface of the battery cell 11 can be wound around, and for example, the main surfaces 11A and 11B and the end surfaces 11C and 11D thereof. It is preferably placed on top of it.
  • the main surfaces 11A and 11B are both sides having the largest area in the square battery cell 11, and the end surfaces 11C and 11D are end surfaces connecting the main surfaces 11A and 11B.
  • a safety valve (not shown) is generally provided on either of the end faces 11C and 11D. Therefore, even in the configuration of FIG. 1, the refractory material 11 covers the safety valve of the battery cell 11.
  • the refractory material 12 may be provided only on both the main surfaces 11A and 11B. Further, it may be provided on only one of the main surfaces 11A and 11B.
  • the refractory material 12 may be provided so as to cover both sides 11X and 11Y of the battery cell 11, for example. At this time, the refractory material 12 may be arranged so as to cover the heat seal portion 11Z as well. Even in the laminated type, the refractory material 12 may be provided so as to cover only one surface 11X. Further, also in the laminated type, the refractory material 12 may be arranged so as to wind around the outer peripheral surface of the battery cell 11. Further, as shown in FIG. 4, when the battery cell 11 is cylindrical, the refractory material 12 may be arranged so as to be wound around the outer peripheral surface of the battery cell 11. Further, as shown in FIG.
  • the refractory material 12 can be arranged between the battery cells 11 and 11. According to such a configuration, even if one battery cell 11 ignites due to thermal runaway, the fireproof material 12 effectively extinguishes the fire, so that the adjacent battery cells 11 continuously ignite. Can be prevented.
  • the battery shown in FIG. 5 schematically shows only two battery cells 11, but three or more battery cells may be provided. In that case, the refractory material 12 may be arranged between the battery cells 11 and 11, respectively.
  • a refractory laminate may be used instead of the refractory material.
  • a refractory laminate having an adhesive material provided on one surface of the refractory material and the refractory material.
  • the refractory laminate is connected to the battery cell 11 via the adhesive material. It should be glued.
  • a refractory laminate having a refractory material and adhesive materials provided on both sides of the refractory material.
  • the refractory laminate is made of the refractory laminate by each adhesive material. Stick both sides to the battery.
  • the refractory laminate may be a refractory laminate including a refractory material and a base material, and even in that case, the refractory laminate may be arranged instead of the refractory material in the configurations of FIGS. 1 to 5. Further, the refractory laminate may be appropriately bonded to the battery cell via an adhesive material.
  • the configurations shown in FIGS. 1 to 5 are merely examples of the arrangement positions of the refractory material or the refractory laminate, and may be arranged at positions other than these.
  • the measurement method and evaluation method of each physical property are as follows. ⁇ Expansion ratio of refractory material> Using a cutter, cut the refractory material to a length of 100 mm and a width of 100 mm, install it on the bottom of a stainless steel holder (101 mm square, height 80 mm), supply the refractory material to the electric furnace, and heat it at 600 ° C for 3 minutes. Heated. It was calculated by dividing the thickness of the expansion residue after heating by the thickness of the refractory material before heating. The thickness of the expansion residue and the thickness of the refractory material before heating were measured at three points using a caliper, and an average value was calculated.
  • ⁇ Battery nail piercing test> Around a battery cell made of a laminated lithium-ion battery used in a smartphone, the fireproof material produced in Examples and Comparative Examples is arranged so as to be wrapped around it, and a nail having a diameter of 5 mm is used, and a piercing speed of 10 mm / s is required. I did a nail piercing test on the battery. The case where the fire did not come out even if the nail was pierced was evaluated as "AA”. The case where the time from when the fire was confirmed by piercing the nail to when the fire was extinguished was within 30 seconds was evaluated as "A".
  • Tensile elastic modulus is less than 1 MPa
  • ⁇ Measurement method of thermal decomposition start temperature of endothermic agent> The measurement was performed using a thermogravimetric differential thermal analyzer (TG-DTA). The measurement conditions were from room temperature to 1000 ° C., a heating rate of 4 ° C./min, and an endothermic agent weight of 10 mg. The temperature at which the weight began to decrease from the obtained TG curve was defined as the thermal decomposition start temperature of the endothermic agent.
  • ⁇ Measuring method of endothermic amount of endothermic agent> The measurement was performed using a thermogravimetric differential thermal analyzer (TG-DTA). The measurement conditions were from room temperature to 1000 ° C., a heating rate of 4 ° C./min, and an endothermic agent weight of 10 mg.
  • the amount of heat absorption was calculated from the obtained DTA curve.
  • ⁇ Measuring method of average particle size The average particle size of each component was measured by laser diffraction. Specifically, the average particle size was defined as the particle size at an integrated value of 50% in the particle size distribution obtained by a particle size distribution meter such as a laser diffraction / scattering type particle size distribution meter.
  • PVB1 Polyvinyl butyral resin, degree of polymerization 800, degree of acetalization 69 mol%, amount of acetyl group 1 mol%, amount of hydroxyl group 30 mol%, 10 mass% ethanol / toluene viscosity 142 mPa ⁇ s PVB2: Polyvinyl butyral resin, degree of polymerization 320, degree of acetalization 75 mol%, acetyl group amount 3 mol%, hydroxyl group amount 22 mol%, 10 mass% ethanol / toluene viscosity 21 mPa ⁇ s PVB3: Polyvinyl butyral resin, degree of polymerization 1,100, degree of acetalization 64 mol%, amount of acetyl group 1 mol%, amount of hydroxyl group 35 mol%, 10% by mass ethanol / toluene viscosity 280 mPa
  • PVC Product name "TK-1000", Shin-Etsu Chemical Co., Ltd.
  • Epoxy resin 1 Product name "FL-079", Mitsubishi Chemical Corporation, Hardener
  • Epoxy resin 2 Product name "E-807”, Mitsubishi Chemical Made by Co., Ltd., main agent
  • Thermally expandable graphite (1) Expansion start temperature 120 ° C., expansion degree 200 ml / g, product name "EXP-50S120N", Fuji Kokuen Industry Co., Ltd.
  • Thermal expansion graphite (2) Expansion start temperature 160 ° C., degree of expansion 200 ml / g, product name "EXP-50S160”, manufactured by Fuji Kokuen Industry Co., Ltd.
  • Aluminum phosphite expansion start temperature 400 ° C, expansion degree 40 ml / g, product name "APA100", manufactured by Taihei Chemical Industry Co., Ltd.
  • Examples 1 to 24, 26 to 30, Comparative Examples 1 to 3 In accordance with the formulation shown in Table 1, components other than the resin were added to a mixed solvent of ethanol and toluene (mass ratio 1: 1), and each component was dispersed in the solvent to obtain a dispersion. Further, according to the formulation shown in Table 1, a resin dissolved in a mixed solvent of ethanol and toluene (mass ratio 1: 1) was added to the above dispersion to prepare a diluted product of a fire-resistant resin composition having a solid content concentration of 10% by mass. Obtained. A diluted solution of the obtained refractory resin composition was applied to one side of a release sheet (PET film manufactured by Lintec Corporation) and dried at 120 ° C.
  • a release sheet PET film manufactured by Lintec Corporation
  • the refractory material was peeled off from the release sheet to obtain a single refractory material.
  • the thickness of the refractory sheet was 500 ⁇ m.
  • Example 25> The refractory resin composition obtained by supplying each component shown in Table 1 to a uniaxial extruder and kneading it was extruded at 120 ° C. to obtain a sheet-shaped refractory material having a thickness of 500 ⁇ m.
  • Example 31> The refractory resin composition obtained by supplying each component shown in Table 1 to a uniaxial extruder and kneading it was extruded at 120 ° C. to obtain a sheet-shaped refractory material having a thickness of 500 ⁇ m.
  • Example 32> Each component shown in Table 1 was supplied to a planetary stirrer (“ARE500” manufactured by Shinky Co., Ltd.) and kneaded at 700 rpm for 3 minutes at room temperature to obtain a refractory resin composition. Then, the refractory resin composition was applied onto the PET film, and press molding was carried out at 20 ° C. at 10 MPa to obtain a sheet-shaped molded product having a thickness of 500 ⁇ m. Then, the molded product was placed in a constant temperature bath at 90 ° C. for 10 hours and cured to obtain a sheet-shaped refractory material.
  • ARE500 manufactured by Shinky Co., Ltd.
  • the refractory material contains a heat-expandable compound and the expansion coefficient is set to a predetermined value or more, so that the fire resistance and fire extinguishing performance are improved.

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