WO2023145907A1 - Matériau réfractaire thermiquement expansible - Google Patents

Matériau réfractaire thermiquement expansible Download PDF

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WO2023145907A1
WO2023145907A1 PCT/JP2023/002747 JP2023002747W WO2023145907A1 WO 2023145907 A1 WO2023145907 A1 WO 2023145907A1 JP 2023002747 W JP2023002747 W JP 2023002747W WO 2023145907 A1 WO2023145907 A1 WO 2023145907A1
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refractory material
thermally expandable
rubber
resin
phosphate
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PCT/JP2023/002747
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English (en)
Japanese (ja)
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泰輝 松本
健一 大月
聡 與口
建彦 牛見
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積水化学工業株式会社
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62C—FIRE-FIGHTING
    • A62C2/00—Fire prevention or containment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials

Definitions

  • the present invention relates to a thermally expandable fireproof material.
  • fireproof materials are used for building materials such as fittings, columns, and wall materials for fire prevention.
  • a thermally expandable refractory material in which thermally expandable graphite is blended with a resin in addition to a flame retardant, an inorganic filler, and the like is used (see, for example, Patent Document 1).
  • Such a thermally expandable refractory material expands when heated, and the combustion residue forms a refractory and heat insulating layer, thereby exhibiting refractory and heat insulating performance.
  • the thermally expandable refractory material containing thermally expandable graphite is provided, for example, in the gap between fittings such as doors and windows provided in openings of buildings and frames such as door frames and window frames surrounding these.
  • the sheet expands in the thickness direction to block the gap between the fitting and the frame material, thereby preventing the spread of the fire.
  • an object of the present invention is to provide a thermally expandable fireproof material that expands sufficiently in the plane direction.
  • the present inventors have found that a matrix component consisting of at least one selected from the group consisting of rubbers and resins (both of which are solid at 23°C), thermally expandable graphite, and a flexibility-imparting agent.
  • a thermally expandable refractory material with a certain or higher closed expansion ratio, the above problems were solved, and the present invention was completed.
  • the present invention provides the following [1] to [7].
  • a thermally expandable refractory material which, when heated, has a closed expansion ratio of 4.0 times or more obtained by dividing the area of the thermally expandable refractory material viewed in the thickness direction by the area before heating.
  • the thermally expandable fireproof material according to [1] which further contains a flame retardant.
  • the plasticizer is a non-phthalate plasticizer.
  • thermally expandable refractory material according to any one of [1] to [5], wherein the thermally expandable refractory material has a Mooney viscosity of 80 or less at 100°C.
  • thermoly expandable fireproof material that expands sufficiently in the plane direction.
  • the thermally expandable refractory material of the present invention (hereinafter sometimes referred to as "refractory material”) has a closed expansion ratio of 4.0 times or more. If the occlusion expansion ratio is less than 4.0 times, the expansion in the surface direction becomes insufficient, and when the refractory material is arranged in a narrow space in the thickness direction, the performance of the refractory material cannot be sufficiently exhibited. . From this point of view, the occlusion expansion ratio is preferably 4.5 times or more, more preferably 5.0 times or more. On the other hand, the upper limit of the occlusion expansion ratio is not particularly limited, but practically it is, for example, 15 times or less, preferably 10 times or less.
  • the closed expansion ratio can be increased by incorporating a matrix component, thermally expandable graphite, and a flexibility imparting agent into the refractory material.
  • a flexibility-imparting agent when contained, the refractory material is likely to thermally expand, and the occlusion expansion ratio is likely to be increased.
  • the occlusion expansion ratio can be obtained by the following method. First, a refractory material is cut into a rectangular parallelepiped of 25 mm ⁇ 25 mm ⁇ 2 mm, and the cut refractory material is arranged in a space of 6 mm in the thickness direction.
  • the thickness of the refractory material is less than 2 mm, two or more refractory materials may be superimposed so as to have a thickness of 2 mm and integrated by press molding or the like to form a measurement sample. More specifically, as shown in FIG. 1, it is preferable to arrange the refractory material 10 in a space 12 having a height h of 6 mm in the jig 11 . After that, when the refractory material 10 is heated at 400° C. for 15 minutes, the area of the refractory material 10 viewed from the thickness direction shown in the right diagram of FIG.
  • the space 12 is formed between the two metal plates 13 by arranging the two metal plates 13 (material: SUS) via a spacer with a thickness of 6 mm and fixing the two metal plates with a fixing member 14. It is a space that
  • the thermally expandable refractory material of the present invention contains a matrix component, thermally expandable graphite, and a flexibility imparting agent. Each component will be described in detail below.
  • the refractory material of the present invention contains a matrix component consisting of at least one selected from rubber and resin. Both rubbers and resins are solids at 23°C.
  • the rubber component is preferably a thermosetting rubber containing no halogen in its molecular structure.
  • a thermosetting rubber is a rubber having a thermosetting property even in a heat-expandable refractory material, and examples thereof include rubbers having a double bond in the main chain, such as conjugated diene rubbers.
  • thermosetting rubbers containing no halogen in the molecular structure include natural rubber, isoprene rubber, butyl rubber (IIR), butadiene rubber (BR), 1,2-polybutadiene rubber, styrene-butadiene rubber (SBR), and acrylonitrile.
  • Conjugated diene rubber such as rubber-butadiene rubber (NBR), ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM), acrylic rubber, polyvulcanized rubber, unvulcanized rubber, silicone rubber, urethane elastomer and the like.
  • acrylonitrile-butadiene rubber is more preferable from the viewpoint that the area of the thermally expandable refractory material after heating can be easily adjusted to the desired range.
  • the nitrile content of the acrylonitrile-butadiene rubber is preferably 8 to 40% by mass, more preferably 10 to 35% by mass, even more preferably 15 to 25% by mass.
  • Acrylonitrile-butadiene rubber having a nitrile content within the above range can easily increase the expansion pressure of the refractory material and can easily adjust the closed expansion ratio to a certain level or higher.
  • Mooney viscosity ML(1+4) at 100° C. of acrylonitrile-butadiene rubber is preferably 20-90, more preferably 30-80, and even more preferably 40-70.
  • An acrylonitrile-butadiene rubber having a Mooney viscosity ML(1+4) at 100° C. within the above range can easily increase the expansion pressure of the refractory material and easily adjust the closed expansion ratio above a certain level.
  • Styrene-butadiene rubber includes random copolymers of styrene and butadiene.
  • the styrene content of the styrene-butadiene rubber is preferably 20 to 60% by mass, more preferably 25 to 50% by mass, even more preferably 30 to 45% by mass.
  • a styrene-butadiene rubber having a styrene content within the above range can easily increase the expansion pressure of the refractory material, and can easily adjust the closed expansion ratio to a certain level or more.
  • the Mooney viscosity ML(1+4) at 100° C. of the styrene-butadiene rubber is preferably 20-60, more preferably 30-55, even more preferably 40-50.
  • a styrene-butadiene rubber having a Mooney viscosity ML(1+4) at 100° C. within the above range can easily increase the expansion pressure of the refractory material and easily adjust the closed expansion ratio to a certain level or higher.
  • the Mooney viscosity ML(1+4) is measured according to JIS K6300.
  • the resin may be a thermoplastic resin or a thermosetting resin.
  • the thermoplastic resin include, for example, polypropylene resin, polyethylene resin, poly(1-)butene resin, polyolefin resin such as polypentene resin, polyester resin such as polyethylene terephthalate, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, Ethylene-vinyl acetate copolymer resin (EVA), polycarbonate resin, polyphenylene ether resin, (meth)acrylic resin such as polymethyl methacrylate resin (PMMA), polyamide resin, polyvinyl chloride resin (PVC), novolak resin , polyurethane resin, polyisobutylene, and the like.
  • thermoplastic resins from the viewpoint of improving the fire resistance of the refractory material, at least one selected from polyvinyl chloride resins, ethylene-vinyl acetate copolymer resins, and (meth)acrylic resins is preferable. Vinyl chloride resins and ethylene-vinyl acetate copolymer resins are more preferred, and polyvinyl chloride resins are even more preferred.
  • Polyvinyl chloride resins include homopolymers of vinyl chloride monomers, copolymers of vinyl chloride monomers and monomers having unsaturated bonds copolymerizable with vinyl chloride monomers, and polymers other than vinyl chloride monomers.
  • a graft copolymer obtained by graft-copolymerizing a vinyl chloride monomer to a copolymer may be mentioned, and these may be used alone or in combination of two or more.
  • chlorinated polyvinyl chloride-based resins which are chlorinated polyvinyl chloride-based resins, are also included in polyvinyl chloride-based resins.
  • the degree of polymerization of the polyvinyl chloride resin is preferably 500-2000, more preferably 800-1500.
  • 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. good too.
  • ethylene-vinyl acetate copolymer resin ethylene-vinyl acetate modified resins such as ethylene-vinyl acetate copolymer saponification products and ethylene-vinyl acetate hydrolysates can also be used.
  • the ethylene-vinyl acetate copolymer resin preferably has a vinyl acetate content of 5 to 90% by mass, more preferably 8 to 50% by mass, as measured according to JIS K 6730 "Ethylene-vinyl acetate resin test method". More preferably, it is 12 to 35% by mass.
  • the melt flow rate (MFR) of the ethylene-vinyl acetate copolymer resin at 190° C. is preferably 0.5 to 15 g/10 min, more preferably 1 to 8 g/10 min.
  • the melt flow rate of the ethylene-vinyl acetate copolymer at 190° C. is a value measured under a load of 2.16 kg, and is measured according to JIS K7210:1999.
  • thermosetting resin is not particularly limited, and examples thereof include epoxy resins, polyurethane resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, and thermosetting polyimides. Epoxy resins are preferred from the viewpoint of improving the properties.
  • Epoxy compounds are compounds having an epoxy group, and specific examples thereof include glycidyl ether type and glycidyl ester type. Glydisyl ether type may be bifunctional or polyfunctional such as trifunctional or more. 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. Among these, a bifunctional glycidyl ether type is preferred.
  • bifunctional glycidyl ether type epoxy compound examples include, for example, polyethylene glycol type, polypropylene glycol type alkylene glycol type, neopentyl glycol type, 1,6-hexanediol type, hydrogenated bisphenol A type aliphatic Epoxy compounds are exemplified. Furthermore, 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 are listed. Among these, aromatic epoxy compounds such as bisphenol A type and bisphenol F type are preferred.
  • Examples of the glycidyl ester type epoxy compounds include hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type and p-oxybenzoic acid type epoxy compounds.
  • Examples of tri- or more functional glycidyl ether type epoxy compounds include phenol novolak type, ortho-cresol 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.
  • the epoxy resin may be an epoxy resin having an aromatic ring or an epoxy resin not having an aromatic ring, but an epoxy resin having an aromatic ring is preferable from the viewpoint of enhancing nonflammability.
  • a polyaddition type or a catalyst type is used as the curing agent.
  • polyaddition type curing agents include polyamines, acid anhydrides, polyphenols, and polymercaptans.
  • catalytic curing agents 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 curing agent is preferably in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the epoxy resin compound. When the amount is 50 parts by mass or more, the epoxy resin compound is easily cured, and when the amount is 150 parts by mass or less, an effect corresponding to the blending amount of the curing agent can be obtained.
  • the above matrix components may be used singly or in combination of two or more.
  • the matrix component it is preferable to use rubber from the viewpoint of ensuring that the residual strength of the refractory material after thermal expansion is above a certain level and exhibiting excellent fire resistance, and thermosetting rubber that does not contain halogen in its molecular structure. More preferably, NBR is used.
  • the content of the matrix component is preferably 15% by mass or more, more preferably 18% by mass or more, still more preferably 20% by mass or more, and preferably 40% by mass, based on the total amount of the refractory material. Below, more preferably 35% by mass or less, still more preferably 30% by mass or less.
  • the shape retention of the refractory material is improved.
  • the content of the matrix component is at most these upper limits, the content of the thermally expandable graphite described later can be adjusted to a large amount, so the fire resistance is improved.
  • Thermally expandable graphite is a conventionally known substance that expands when heated, and is produced by acid-treating a raw material powder such as natural flake graphite, pyrolytic graphite, or Kish graphite with a strong oxidizing agent to form a graphite intercalation compound.
  • strong oxidizing agents include inorganic acids such as concentrated sulfuric acid, nitric acid and selenic acid, concentrated nitric acid, perchloric acid, perchlorates, permanganates, bichromates, and hydrogen peroxide.
  • Thermally expandable graphite is a crystalline compound that maintains the layered structure of carbon.
  • Thermally expandable graphite may be neutralized. That is, the thermally expandable graphite obtained by treatment with a strong oxidizing agent or the like 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 content of thermally expandable graphite in the refractory material of the present invention is preferably 50 to 500 parts by mass, more preferably 70 to 250 parts by mass, and still more preferably 100 parts by mass with respect to 100 parts by mass of the matrix component. ⁇ 200 parts by mass.
  • the content of the thermally expandable graphite is at least these lower limits, it becomes easier to increase the expansion pressure of the thermally expandable refractory material and to adjust the closing expansion ratio to a certain level or more.
  • the content of the thermally expandable graphite is not more than these upper limits, the shape retainability, workability, etc. are improved.
  • the thermally expandable graphite in the present invention preferably has an average aspect ratio of 15 or more, more preferably 20 or more, and usually 1000 or less.
  • the aspect ratio of thermally expandable graphite is obtained by measuring the maximum dimension (major axis) and the minimum dimension (minor axis) of 10 or more (for example, 50) thermally expandable graphite, and calculating the ratio (maximum dimension / minimum dimension).
  • the average particle size of the thermally expandable graphite is preferably 50 to 500 ⁇ m, more preferably 100 to 400 ⁇ m, from the viewpoint of achieving a desired expansion pressure.
  • the average particle size of the thermally expandable graphite is determined as the average value of the maximum dimensions of 10 or more (for example, 50) thermally expandable graphites.
  • the minimum and maximum dimensions of the thermally expandable graphite described above can be measured using, for example, a field emission scanning electron microscope (FE-SEM).
  • the refractory material of the present invention contains a flexibility imparting agent.
  • flexibility-imparting agent flexibility is imparted to the refractory material, the viscosity of the components of the refractory material is lowered, and the thermally expandable graphite is less likely to be crushed during the production of the refractory material.
  • the closing expansion ratio can be set to a certain value or higher, and expansion according to the shape of the space in which the refractory material is arranged can be achieved.
  • the shape of the refractory material can be stably maintained.
  • the refractory material can be made excellent in workability.
  • the flexibility imparting agent is preferably at least one selected from plasticizers, rubber processing oils, liquid rubbers, and liquid resins, and is preferably selected from plasticizers, rubber processing oils, and liquid rubbers. is preferably at least one.
  • the plasticizer is preferably a non-phthalate plasticizer.
  • Environmental load can be reduced because the plasticizer is a non-phthalate plasticizer.
  • a non-phthalate plasticizer is a plasticizer other than a phthalate plasticizer composed of a derivative of phthalic acid (orthophthalic acid).
  • Non-phthalate plasticizers include trimellitic acid plasticizers, phosphate ester plasticizers, adipic acid plasticizers, sulfonic acid plasticizers, citric acid plasticizers, soybean oil plasticizers, cyclohexanedicarboxy rate-based plasticizers, terephthalic acid-based plasticizers, and the like. These plasticizers are usually liquid at 23°C.
  • Phosphate plasticizers include, for example, triphenyl phosphate, tricresyl phosphate, benzyldiphenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, propylphenyl diphenyl phosphate, dipropylphenyl phenyl phosphate, ethylphenyl diphenyl phosphate, Triaryl phosphates such as diethyl phenyl phosphate, triethyl phenyl phosphate, tripropyl phenyl phosphate, butyl phenyl diphenyl phosphate, dibutyl phenyl phosphate, tributyl phenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, trihexyl phosphate, tri(2-ethylhexyl) phosphate, tridecyl phosphat
  • adipic acid plasticizers examples include di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate, and adipic acid ether esters such as dibutoxyethoxyethyl adipate.
  • Sulfonic acid-based plasticizers include benzenesulfonbutyramide, o-toluenesulfonamide, p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, o-tolueneethylsulfonamide, p-tolueneethylsulfonamide, N -cyclohexyl-p-toluenesulfonamide, phenol and cresol alkylsulfonate, sulfonamide-formamide, alkylsulfonate and the like.
  • the rubber processing oil is not particularly limited, but those commonly used as lubricants can be used. By including the rubber processing oil, the fluidity of the matrix component is improved, and the thermally expandable graphite is appropriately dispersed in the composition. Therefore, the thermal expansibility and residue strength of the refractory material are improved, and the fire resistance of the refractory material is improved.
  • the rubber processing oil used in the present invention is not particularly limited, but includes, for example, process oil.
  • the process oil is not particularly limited, and examples thereof include paraffinic process oil, naphthenic process oil, and olefinic process oil. Among these, it is preferable to contain a naphthenic process oil.
  • the kinematic viscosity of the rubber processing oil at 40° C. is preferably 5 to 500 cSt, more preferably 10 to 450 cSt, even more preferably 20 to 400 cSt.
  • the kinematic viscosity can be measured according to JIS K 2283.
  • Liquid rubber is rubber that becomes liquid at 23°C.
  • Liquid rubbers include liquid polyisoprene rubber, carboxy-modified liquid polyisoprene rubber, liquid polybutadiene rubber, carboxy-modified liquid polybutadiene rubber, hydroxyl group-modified liquid polybutadiene rubber, liquid acrylonitrile-butadiene copolymer rubber, liquid styrene-butadiene copolymer rubber, and liquid styrene-isoprene.
  • Copolymer rubber and the like can be mentioned.
  • the number average molecular weight (Mn) of the liquid rubber is preferably 1,000 to 150,000, more preferably 10,000 to 100,000.
  • the number average molecular weight (Mn) of the liquid rubber is a measured value obtained by conversion with standard polystyrene using a gel permeation chromatography measuring device.
  • the viscosity of the liquid rubber at 38° C. is preferably 5 to 1000 Pa ⁇ s, more preferably 50 to 800 Pa ⁇ s, even more preferably 100 to 500 Pa ⁇ s.
  • liquid resin A liquid resin is a resin that becomes liquid at 23°C.
  • Liquid resins include polyvinyl acetate (PVAc) resins, silicone resins, modified silicone (MS) resins, polyisobutylene (PIB) resins, polysulfide resins, modified polysulfide resins, polyurethane resins, and polyacrylic resins. Examples include resins and polyacrylic urethane resins. Among these, polyvinyl acetate resins are preferred.
  • the flexibility-imparting agent may be used alone or in combination of two or more.
  • a plasticizer among those mentioned above.
  • the use of a plasticizer can also inhibit bleeding of the flexibilizer onto the refractory surface.
  • the plasticizers at least one selected from phosphate ester plasticizers, adipic acid plasticizers, and sulfonic acid plasticizers is preferable, and it is more preferable to use sulfonic acid plasticizers. It is even more preferred to use esters.
  • the content of the flexibility imparting agent is preferably 20 to 120 parts by mass, more preferably 25 to 110 parts by mass, still more preferably 30 to 80 parts by mass, and 45 to 80 parts by mass with respect to 100 parts by mass of the matrix component. More preferably, when the content of the flexibility-imparting agent is at least the above lower limit, the occlusion expansion ratio can be kept at a certain level or higher, and the refractory material can easily expand in the event of a fire. Further, when the content of the flexibility-imparting agent is equal to or less than the above upper limit, the residual strength of the refractory material can be increased to a certain level or more, and the refractory material can be formed with excellent shape retention.
  • the refractory material of the present invention preferably contains a flame retardant.
  • a flame retardant By containing a flame retardant, the flame retardancy of the refractory material can be enhanced, and the performance of the refractory material can be exhibited more effectively.
  • the flame retardant used in the present invention is preferably solid at normal temperature (23° C.) and normal pressure (1 atm). Specifically, phosphorus solid flame retardant, red phosphorus flame retardant, boron Including flame retardants, brominated flame retardants, antimony-containing flame retardants, metal hydroxides, low-melting glass, needle-like fillers, and the like.
  • the phosphorus-based solid flame retardant is solid at normal temperature (23° C.) and normal pressure (1 atm), and is other than the red phosphorus-based flame retardant described later.
  • Specific examples include phosphates, phosphazene compounds, phosphate ester compounds, and metal phosphinates.
  • phosphates include monophosphates and polyphosphates.
  • the phosphate referred to here is a concept that includes not only orthophosphate but also phosphite, hypophosphite, and the like. The same is true for polyphosphate.
  • Monophosphates include, for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, sodium Sodium salts such as disodium phosphate and sodium hypophosphite, potassium such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite and potassium hypophosphite salts, lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite, barium dihydrogen phosphate, barium hydrogen phosphate, Barium salts such as tribarium phosphate and barium hypophosphite, magnesium monohydrogen
  • Polyphosphates include, for example, ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, and aluminum polyphosphate, among which ammonium polyphosphate is preferred.
  • Intumescent flame retardants can also be used as phosphates.
  • Intumescent flame retardants include, for example, phosphates containing phosphorus-based components that promote carbonization and nitrogen-based components that promote fire extinguishing and foaming.
  • intumescent flame retardants start burning and heat up, bubbles blow out on the surface of the material, creating a foam-like adiabatic expansion layer that prevents heat from being transferred to the interior of the material and cuts off the supply of oxygen. By suppressing thermal decomposition and oxidation reaction, it can play a role as a flame retardant.
  • Examples of phosphorus-based components that make up intumescent flame retardants include polyphosphoric acids such as pyrophosphoric acid and triphosphoric acid, and monophosphoric acids such as orthophosphoric acid (orthophosphoric acid).
  • Nitrogen-based components constituting intumescent flame retardants include, for example, N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-propanediamine, 1, aliphatic diamines such as 3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane and 1,10-diaminodecane; Piperazine ring-containing amine compounds such as piperaz
  • the phosphorus-based component that constitutes the intumescent flame retardant preferably contains polyphosphoric acid from the viewpoint of obtaining higher flame retardancy.
  • the intumescent flame retardant is at least one compound selected from the group consisting of melamine orthophosphate, melamine pyrophosphate, melamine polyphosphate, piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate.
  • melamine salts selected from the group consisting of melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate, and selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate
  • a mixture with a piperazine salt is more preferred.
  • the melamine salt is more preferably melamine pyrophosphate from the viewpoint of flame retardancy
  • the piperazine salt is more preferably piperazine pyrophosphate from the viewpoint of flame retardancy.
  • a phosphazene compound is an organic compound in which phosphorus atoms and nitrogen atoms are alternately bonded.
  • the phosphazene compound includes, for example, a cyclic phosphazene compound, a chain phosphazene compound, a crosslinked phosphazene compound crosslinked with a crosslinking group, and the like.
  • Specific examples of phosphazene compounds include those containing structural units represented by the following general formula (1).
  • X is each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. Any of 12 substituted or unsubstituted aryloxy groups, amino groups and halogen atoms.
  • substituents in the aryl group include alkyl groups, amino groups, and halogen atoms.
  • Each X is preferably a phenyl group, a substituted phenyl group, a phenyloxy group, or a substituted phenyl group, more preferably a phenyl group or a phenyloxy group.
  • the phosphate ester compound is not particularly limited as long as it is solid at room temperature (23° C.), and examples thereof include monophosphate esters and condensed phosphate esters. These phosphate ester compounds may be commercially available products. Monophosphates include triphenyl phosphate and tris(tribromoneopentyl) phosphate. Monophosphate esters include commercially available products such as "TPP", "CR-900", and "DAIGUARD-1000" (manufactured by Daihachi Chemical Industry Co., Ltd.). The condensed phosphate may be a halogen-containing condensed phosphate, or may be a halogen-free condensed phosphate.
  • alkyl-substituted aromatic condensed phosphates such as 1,3-phenylenebis(di-2,6-xylenylphosphate).
  • commercially available products can also be used as condensed phosphates.
  • Specific examples include non-halogen condensed phosphate esters such as "DAIGUARD-850" and “PX200” (manufactured by Daihachi Chemical Industry Co., Ltd.).
  • a phosphinate metal salt is a metal salt of an organic phosphinic acid.
  • metal phosphinates include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, Titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, and titanium tetrakisdiphenylphosphinate.
  • the phosphorus concentration in the phosphorus-based solid flame retardant is preferably 10% by mass or more, more preferably 12% by mass or more, based on the total amount of the phosphorus-based solid flame retardant, from the viewpoint of sufficiently improving the flame retardancy of the refractory material. % by mass or more is more preferable.
  • the red phosphorus-based flame retardant may be composed of red phosphorus alone, or may be red phosphorus coated with resin, metal hydroxide, metal oxide, or the like, or may be red phosphorus coated with resin, metal hydroxide, metal A mixture of oxides or the like may also be used.
  • Resins coated with red phosphorus or mixed with red phosphorus are not particularly limited, but include thermosetting resins such as phenol resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. be done. From the viewpoint of flame retardancy, metal hydroxides are preferable as the film or compound to be mixed. It is preferable to appropriately select and use the metal hydroxide described later.
  • Boron-containing flame retardants for use in the present invention include borax, boron oxide, boric acid, borates, and the like.
  • boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
  • borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12 and 13 of the periodic table, and ammonium.
  • alkali metal borate salts such as lithium borate, sodium borate, potassium borate and cesium borate
  • alkaline earth metal borate salts such as magnesium borate, calcium borate and barium borate
  • Zirconium borate, zinc borate, aluminum borate, ammonium borate and the like are examples of alkali metal borate salts such as lithium borate, sodium borate, potassium borate and cesium borate
  • alkaline earth metal borate salts such as magnesium borate, calcium borate and barium borate
  • the brominated flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is solid at normal temperature and pressure.
  • Examples include aromatic compounds containing brominated aromatic rings.
  • Brominated aromatic ring-containing aromatic compounds include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromphenoxy)ethane, ethylenebis( pentabromophenyl), ethylenebis(tetrabromophthalimide), tetrabromobisphenol A and other monomeric organic bromine compounds.
  • the brominated aromatic ring-containing aromatic compound may be a brominated compound polymer.
  • a polycarbonate oligomer produced using brominated bisphenol A as a starting material a brominated polycarbonate such as a copolymer of this polycarbonate oligomer and bisphenol A, and a diepoxy compound produced by reacting brominated bisphenol A with epichlorohydrin. etc.
  • brominated epoxy compounds such as monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenols of brominated polyphenylene ether, brominated bisphenol A and cyanuric chloride brominated polystyrene such as brominated (polystyrene), poly(brominated styrene), crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(-methylstyrene), and the like.
  • Compounds other than the brominated aromatic ring-containing aromatic compound such as hexabromocyclododecane may also be used.
  • Antimony-containing flame retardants include, for example, antimony oxide, antimonate, pyroantimonate, and the like.
  • antimony oxide include antimony trioxide and antimony pentoxide.
  • antimonates include sodium antimonate and potassium antimonate.
  • pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.
  • metal hydroxide examples include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide and the like.
  • low-melting-point glass used as a solid flame retardant is softened and becomes a molten state when heated, acts as an inorganic binder, and has the effect of improving the mechanical strength of the refractory material.
  • Low-melting glass specifically means glass that softens or melts at a temperature of 1000° C. or lower. ⁇ 600°C.
  • the softening temperature is, for example, a value measured from the inflection point of DTA.
  • Examples of the low-melting glass include silicon, aluminum, boron, phosphorus, zinc, iron, copper, titanium, vanadium, zirconium, tungsten, molybdenum, thallium, antimony, tin, cadmium, arsenic, lead, alkali metals, and alkaline earth metals. , halogen, chalcogen and at least one element selected from the group consisting of oxygen.
  • the low-melting-point glass is preferably in the form of particles such as glass frit.
  • Nippon Enamel Glaze Co., Ltd. trade name "4020” (aluminum phosphate salt-based low-melting glass, softening temperature: 380 ° C.), Nippon Enamel Glaze 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 salt low melting point glass, softening temperature: 450° C.), etc. are commercially available.
  • needle-shaped filler examples include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, xonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, and graphite fibers. , metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, stainless steel fibers, and the like.
  • the mechanical properties of the refractory material can be effectively improved.
  • One or more of these needle-like fillers can be used.
  • the aspect ratio (length/diameter) of the needle-like filler used in the present invention is preferably in the range of 5-50, more preferably in the range of 10-40.
  • the aspect ratio can be obtained by observing the needle-like filler with a scanning electron microscope and measuring its length and width.
  • These flame retardants may be used alone or in combination of two or more.
  • the flame retardant used in the present invention is preferably a phosphorus-based solid flame retardant, more preferably a phosphate, and even more preferably aluminum phosphite, from the viewpoint of sufficiently effectively imparting flame retardancy to a refractory material.
  • a phosphorus-based solid flame retardant more preferably a phosphate, and even more preferably aluminum phosphite
  • the content of the phosphorus-containing compound is preferably 1 part by mass or less with respect to 100 parts by mass of the matrix component, and more preferably the refractory material does not contain the phosphorus-containing compound.
  • phosphorus-containing compound as used herein is a general term for compounds containing phosphorus, and includes the above-described phosphorus-based solid flame retardants, red phosphorus-based flame retardants, phosphorus-containing low-melting-point glass, and the like.
  • the content of the flame retardant in the present invention is not particularly limited, it is preferably 20 to 100 parts by mass, more preferably 30 to 90 parts by mass, and even more preferably 40 to 80 parts by mass, based on 100 parts by mass of the matrix component.
  • the content of the flame retardant is equal to or higher than the above lower limit, flame retardancy can be effectively imparted to the refractory material.
  • the content of the flame retardant is equal to or less than the above upper limit, the proportion of other components in the refractory material can be kept at a certain level or higher, and the closing expansion ratio can be kept at a certain level or higher.
  • Inorganic fillers other than the solid flame retardants described above may also be used.
  • examples of such inorganic fillers include alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic Magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, Aluminum nitride, boron nitride, silicon nitride, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, and the like can be used as appropriate.
  • inorganic fillers may be used individually by 1 type, and may use 2 or more types together.
  • the inorganic filler it is preferable to use calcium carbonate among those mentioned above.
  • its content is not particularly limited, but it is preferably 1 to 200 parts by mass, more preferably 10 to 100 parts by mass, and further 15 to 60 parts by mass with respect to 100 parts by mass of the matrix component. preferable.
  • the refractory material of the present invention may contain a cross-linking agent. Especially when acrylonitrile-butadiene rubber is used as the rubber component, the combined use of the cross-linking agent can increase the expansion pressure and improve the fire resistance. do. When the refractory material contains a cross-linking agent, it is believed that the heat generated during a fire promotes cross-linking of the matrix component such as the rubber component, increasing the viscosity and increasing the expansion pressure.
  • any known cross-linking agent can be used without limitation, and examples thereof include sulfur-based cross-linking agents, organic peroxides, and azo compounds.
  • the sulfur-based cross-linking agent may be an inorganic cross-linking agent such as sulfur, insoluble sulfur, precipitated sulfur, sulfur chloride, sulfur monochloride, sulfur dichloride, or a sulfur-containing organic cross-linking agent.
  • sulfur-containing organic cross-linking agents examples include morpholine disulfide, alkylphenol disulfide, N,N'-dithio-bis(hexahydro-2H-azepinone-2), thiuram polysulfide, 2-(4'-morpholino-dithio)benzothiazole and the like. be done.
  • organic peroxides examples include 2,5-dimethylhexane, 2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 3-di-t -butyl peroxide, t-dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, dicumyl peroxide, ⁇ , ⁇ '-bis(t-butylperoxyisopropyl ) benzene, n-butyl-4,4-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)cyclohexane, 1 ,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, t-butylperoxybenzoate; benzoyl peroxide; t-but
  • cross-linking agents when producing a refractory material, a cross-linking reaction is unlikely to occur at the temperature (for example, 70 ° C. to 150 ° C.) at which each component is kneaded, and acrylonitrile-butadiene rubber etc. It is preferable that the cross-linking reaction of the rubber component easily occurs.
  • a sulfur-based cross-linking agent is preferred, and among these, an inorganic cross-linking agent is preferred from the viewpoint of cross-linkability, and sulfur is more preferred.
  • the content of the cross-linking agent is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, with respect to 100 parts by mass of the matrix component. Yes, more preferably 0.5 to 3 parts by mass.
  • the refractory material of the present invention may contain a cross-linking accelerator in addition to the cross-linking agent.
  • cross-linking accelerators include metal oxides.
  • metal oxides include zinc oxide and magnesium oxide. When using metal oxides in the present invention, it is preferred to use zinc oxide.
  • These metal oxides are more preferably used in combination with a long-chain aliphatic carboxylic acid having 12 to 24 carbon atoms, preferably 16 to 20 carbon atoms, such as stearic acid.
  • the long-chain aliphatic carboxylic acid used in combination with the metal oxide is also referred to as a cross-linking accelerator.
  • cross-linking accelerators examples include, in addition to those described above, thiazole-based compounds, sulfenamide-based compounds, thiuram-based compounds, dithiocarbamate-based compounds, and guanidine-based compounds.
  • Thiazole compounds include bis(benzothiazol-2-ylthio)zinc.
  • a crosslinking accelerator may be used individually by 1 type, and may use 2 or more types together.
  • the cross-linking accelerator at least one selected from metal oxides and thiazole-based compounds is preferable, and a mode in which these are used in combination is also preferable. At this time, the metal oxide may be used in combination with a long-chain aliphatic carboxylic acid having 16 to 20 carbon atoms such as stearic acid.
  • the amount of the cross-linking accelerator when it is used in the refractory material of the present invention is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 100 parts by mass of the matrix component. is 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass.
  • the refractory material of the present invention can contain various additive components as necessary within a range that does not impair the object of the present invention.
  • the type of additive component is not particularly limited, and various additives can be used.
  • Such additives include, for example, shrinkage inhibitors, crystal nucleating agents, coloring agents (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, anti-aging agents, dispersants, gelation accelerators, fillers, reinforcing agents, agents, flame retardant aids, antistatic agents, surfactants, and surface treatment agents.
  • the amount of the additive to be added can be appropriately selected within a range that does not impair the moldability and the like. Additives may be used alone or in combination of two or more.
  • the refractory material of the present invention preferably has a Mooney viscosity of 80 or less at 100°C.
  • the Mooney viscosity of the refractory material is 80 or less, the expansion ratio of the refractory material to blockage can be kept at a certain level or more, and the refractory material easily expands in the plane direction when a fire occurs. From this point of view, the Mooney viscosity is more preferably 75 or less, and even more preferably 70 or less.
  • the lower limit of the Mooney viscosity is not particularly limited, but is preferably 5 or more, more preferably 20 or more, and 35 or more from the viewpoint of ensuring the shape retention of the refractory material to some extent. is more preferred.
  • the Mooney viscosity of the refractory material is a numerical value measured before the refractory material thermally expands, and the measurement method is based on JIS K6300 in the same manner as rubber.
  • the refractory material of the present invention preferably has a residual strength of 2N or more after thermal expansion, more preferably 5N or more, and even more preferably 7N or more.
  • the residual strength after thermal expansion is 5 N or more, the refractory material can sufficiently exhibit the effect of blocking the flame and preventing the spread of the fire when a fire breaks out.
  • the upper limit of the residual strength after thermal expansion is not particularly limited, but is, for example, 20 N or less, preferably 15 N or less from a practical viewpoint.
  • the refractory material of the present invention is preferably in the form of a sheet, and its thickness is not particularly limited. preferable.
  • the refractory material of the present invention can be produced, for example, as follows. First, a matrix component, thermally expandable graphite, a resin, a plasticizer, a flame retardant to be blended as necessary, a cross-linking agent, and other components are mixed with a mixer such as a kneading roll to form a fire-resistant resin composition. get Next, the resulting refractory resin composition can be formed into a sheet by a known molding method such as press molding, calendar molding, extrusion molding, etc., to obtain a refractory material. Also, the fire-resistant resin composition may be applied to a support substrate such as a release sheet or a resin film to form a sheet.
  • the support substrate may be appropriately peeled off from the refractory material obtained in the form of a sheet.
  • the refractory resin composition may be appropriately heated after being molded into a sheet or while being molded into a sheet, and when a thermosetting resin is used, the refractory resin composition is Let things harden.
  • the temperature for mixing and the temperature for forming into a sheet are preferably lower than the expansion initiation temperature of the thermally expandable graphite. Therefore, the kneading temperature is preferably 70 to 150°C, more preferably 90 to 140°C.
  • the temperature for forming into a sheet is preferably 80 to 130°C, more preferably 90 to 120°C.
  • the refractory material of the present invention may be laminated with another sheet member or adhesive layer to form a laminated sheet.
  • a laminated sheet includes, for example, a base material and a fireproof material laminated on one side or both sides of the base material. Substrates are typically woven or non-woven. Fibers used for woven fabrics or non-woven fabrics are not particularly limited, but nonflammable or quasi-flammable materials are preferred, such as glass fibers, ceramic fibers, cellulose fibers, polyester fibers, carbon fibers, graphite fibers, thermosetting A flexible resin fiber or the like is preferable.
  • the laminated sheet can be obtained, for example, by molding the fire-resistant resin composition into a sheet on a base material.
  • the laminated sheet may include a refractory material and an adhesive layer.
  • the adhesive layer may be laminated on one side or both sides of the refractory material, for example.
  • the laminated sheet may comprise a refractory material, a substrate, and an adhesive layer.
  • Such a laminated sheet may have a refractory material on one side of the substrate and an adhesive layer on the other side, or a refractory material and an adhesive layer on one side of the substrate. They may be provided in order.
  • the pressure-sensitive adhesive layer can be formed, for example, by transferring the pressure-sensitive adhesive applied to the release paper to the laminated sheet.
  • the refractory material of the present invention, and the laminated sheet using the same are specifically used for various fittings such as detached houses, collective housing, high-rise housing, high-rise buildings, commercial facilities, public facilities, automobiles, trains, etc. It can be used for various vehicles, ships, aircraft, etc. Among these, it is preferably used for fittings.
  • fixtures concretely, it can be used for walls, beams, pillars, floors, bricks, roofs, board materials, windows, shoji screens, doors, doors, doors, fusuma, transoms, wiring, piping, and the like.
  • refractory material of the present invention and the laminated sheet using the same are particularly applied to the gaps of fittings such as windows, doors, and doors to prevent flames from penetrating through the gaps in the event of a fire or the like. can be prevented.
  • Table 1 shows the evaluation results for each item.
  • ⁇ Occluded expansion ratio> A rectangular parallelepiped of 25 mm ⁇ 25 mm ⁇ 2 mm was cut from the refractory material produced in each example and comparative example. After that, as shown in FIG. 1, the refractory material 10 was placed in a space 12 with a height h of 6 mm in a jig 11 made of a SUS plate with a vertical dimension of 100 mm ⁇ 100 mm. Then, the refractory material 10 together with the jig 11 was put into an oven preheated to 400° C., and the refractory material 10 was heated for 15 minutes. After the heating, the closed expansion ratio was calculated by the following formula based on the area of the refractory material viewed from the thickness direction.
  • the occlusion expansion ratio was evaluated based on the occlusion expansion ratio calculated by the above method. Evaluation criteria are as follows. AA: 8 times or more A: 4.0 times or more and less than 8 times C: less than 4.0 times
  • the residual strength of the refractory material was measured according to the procedures (1) to (3) below.
  • (1) The refractory material produced in each example and comparative example was cut into rectangular parallelepipeds of 20 mm x 100 mm x 2 mm.
  • Rubber/Rubber A NBR “DN401L” manufactured by Nippon Zeon Co., Ltd. Nitrile content: 18% ⁇ Rubber B: BR JSR “BR-01” ⁇ Rubber C: SBR JSR "SBR1502” ⁇ Rubber D: "BUTYL065" manufactured by IIR JSR ⁇ Rubber E: EPDM “EPT X-4010M” manufactured by Mitsui Chemicals, Inc.
  • Resin/Resin A EVA “EV170” manufactured by Mitsui Dow Polychemicals
  • Resin B PVC "TK1000” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Resin D PMMA "Acrypet VH” manufactured by Mitsubishi Chemical Corporation
  • Lubricant A Naphthenic process oil 1 "Sansen 410” manufactured by Japan Sun Oil Co., Ltd., kinematic viscosity 20.8 cSt
  • Lubricant B Naphthenic process oil 2 “Sansen 4240” manufactured by Japan Sun Oil Co., Ltd., kinematic viscosity 374 cSt
  • Liquid rubber > ⁇ Liquid rubber A: Liquid NBR “Nipol 1312” manufactured by Nippon Zeon Co., Ltd. ⁇ Liquid rubber B: Liquid BR “TD3000” manufactured by Nippon Soda Co., Ltd. ⁇ Liquid resin> ⁇ Liquid resin A: PVAc Kanto Chemical Co., Ltd. “Vinyl acetate (polymer) solution”
  • Examples 1-18, 20-23, Comparative Examples 1-2 A matrix component, thermally expandable graphite, a flame retardant, and a flexibility-imparting agent were put into a roll and kneaded at 120° C. for 5 minutes to obtain a fire-resistant resin composition. The resulting refractory resin composition was press-molded at 100° C. for 3 minutes to obtain a sheet-like refractory material with a thickness of 1.8 mm. The evaluation results are shown in Table 1.
  • Example 19 A matrix component, thermally expandable graphite, a flame retardant, and a flexibility-imparting agent were supplied to a planetary stirrer according to the formulation shown in Table 1, and kneaded at room temperature at 1000 rpm for 1 minute to obtain a refractory resin composition. got stuff After that, the fire-resistant resin composition was applied onto the PET film, and press molding was performed at 20° C. and 10 MPa to obtain a sheet-like molding with a thickness of 500 ⁇ m. After that, the molded product was placed in a constant temperature bath at 90° C. for 10 hours and cured to obtain a sheet-like refractory material. The evaluation results are shown in Table 1.
  • the thermally expandable refractory material satisfying the requirements of the present invention expanded sufficiently in the plane direction even in a narrow space in the thickness direction.
  • the heat-expandable refractory material prepared in the comparative example expanded sufficiently in the plane direction when the refractory material was placed in a narrow space in the thickness direction.

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Abstract

La présente invention concerne un matériau réfractaire thermiquement expansible contenant : au moins un composant de matrice choisi dans le groupe constitué par un caoutchouc et une résine ; du graphite thermiquement expansible ; et un agent conférant de la flexibilité, le caoutchouc et la résine étant tous deux solides à 23 °C. Lorsque le matériau réfractaire thermiquement expansible est coupé en une taille de 25 mm × 25 mm × 2 mm et placé dans un espace de 6 mm dans la direction de l'épaisseur, puis chauffé à 400 °C pendant 15 minutes dans chaque espace, le rapport d'expansion fermé du matériau réfractaire thermiquement expansible est d'au moins 4,0 tel qu'obtenu en divisant la zone du matériau réfractaire thermiquement expansible vu dans la direction de l'épaisseur par la zone avant le chauffage.
PCT/JP2023/002747 2022-01-27 2023-01-27 Matériau réfractaire thermiquement expansible WO2023145907A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7511041B1 (ja) 2023-02-28 2024-07-04 デンカ株式会社 パテ状耐火組成物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003119926A (ja) * 2001-10-10 2003-04-23 Sekisui Chem Co Ltd 防火換気部構造
JP2007315007A (ja) * 2006-05-25 2007-12-06 Sekisui Chem Co Ltd 防火措置構造
JP2017034824A (ja) * 2015-07-31 2017-02-09 積水化学工業株式会社 電力ケーブル用バスダクト
JP2020006185A (ja) * 2019-08-20 2020-01-16 積水化学工業株式会社 熱膨張性耐火材、開口枠体、および建具
JP2020139058A (ja) * 2019-02-28 2020-09-03 積水化学工業株式会社 耐火材

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003119926A (ja) * 2001-10-10 2003-04-23 Sekisui Chem Co Ltd 防火換気部構造
JP2007315007A (ja) * 2006-05-25 2007-12-06 Sekisui Chem Co Ltd 防火措置構造
JP2017034824A (ja) * 2015-07-31 2017-02-09 積水化学工業株式会社 電力ケーブル用バスダクト
JP2020139058A (ja) * 2019-02-28 2020-09-03 積水化学工業株式会社 耐火材
JP2020006185A (ja) * 2019-08-20 2020-01-16 積水化学工業株式会社 熱膨張性耐火材、開口枠体、および建具

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7511041B1 (ja) 2023-02-28 2024-07-04 デンカ株式会社 パテ状耐火組成物

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