WO2022186152A1 - Matériau résistant au feu thermo-expansible - Google Patents

Matériau résistant au feu thermo-expansible Download PDF

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Publication number
WO2022186152A1
WO2022186152A1 PCT/JP2022/008347 JP2022008347W WO2022186152A1 WO 2022186152 A1 WO2022186152 A1 WO 2022186152A1 JP 2022008347 W JP2022008347 W JP 2022008347W WO 2022186152 A1 WO2022186152 A1 WO 2022186152A1
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Prior art keywords
refractory material
thermally expandable
mass
component
ratio
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PCT/JP2022/008347
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English (en)
Japanese (ja)
Inventor
健一 大月
美香 辻井
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積水化学工業株式会社
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Publication of WO2022186152A1 publication Critical patent/WO2022186152A1/fr

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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B5/00—Doors, windows, or like closures for special purposes; Border constructions therefor
    • E06B5/10—Doors, windows, or like closures for special purposes; Border constructions therefor for protection against air-raid or other war-like action; for other protective purposes
    • E06B5/16—Fireproof doors or similar closures; Adaptations of fixed constructions therefor

Definitions

  • the present invention relates to a thermally expandable refractory material containing thermally expandable graphite.
  • fireproof materials are used for building materials such as fittings, columns, and wall materials for fire prevention.
  • a thermally expandable refractory material or the like in which thermally expandable graphite is blended with a resin in addition to a flame retardant, an inorganic filler, or 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.
  • thermally expandable refractory material containing thermally expandable graphite in the case of a refractory material that cannot expand sufficiently when heated at a slow heating rate, the surface of the door or window that is not in contact with the flame (non-heated surface) ), it was found that the refractory material strength on the non-heated surface was brittle and sufficient refractoriness was not exhibited.
  • SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a thermally expansible fire-resistant material that can expand sufficiently even when the temperature is raised at a slow heating rate and that has excellent fire resistance.
  • thermally expandable refractory material containing at least one matrix component selected from resins and rubber components and thermally expandable graphite contains a specific It has been found that the above problem can be solved by setting the ratio (II/I) between the expansion ratio (expansion ratio I) and the expansion ratio (expansion ratio II) within a predetermined range.
  • the gist of the present invention is as follows [1] to [10].
  • the thermally expandable refractory material according to any one of [1] to [4], wherein the content of the thermally expandable graphite is 20 to 500 parts by mass with respect to 100 parts by mass of the matrix component.
  • the matrix component is at least one selected from the group consisting of ethylene-vinyl acetate copolymer, polyvinyl acetate resin, styrene-butadiene rubber, acrylonitrile-butadiene rubber, urethane elastomer, chloroprene rubber, and EPDM.
  • the thermally expandable fireproof material according to any one of [1] to [5].
  • the thermally expandable refractory material according to any one of [1] to [6], wherein the rubber component is acrylonitrile-butadiene rubber having a nitrile content of 10 to 35% by mass.
  • the thermally expandable fireproof material according to any one of [1] to [7], wherein the rubber component is an acrylo-nitrile-butadiene rubber having a Mooney viscosity of 30 to 80 at 100°C.
  • the resin is at least one selected from the group consisting of an ethylene-vinyl acetate copolymer containing a high Vac component having a vinyl acetate content of 20% by mass or more, and a polyvinyl acetate resin. ] to [8].
  • the thermally expandable refractory material of the present invention is a thermally expandable refractory material containing a matrix component and thermally expandable graphite, and comprises an expansion ratio (expansion ratio I) when the refractory material is expanded at 300° C.,
  • the ratio (II/I) of the expansion ratio (expansion ratio II) when the refractory material is expanded by increasing the temperature from 20° C. to 300° C. at a heating rate of 5° C./min is 0.5 to 1.0.
  • the thermally expandable fireproof material of the present invention may be simply referred to as fireproof material.
  • the refractory material of the present invention has an expansion ratio (expansion ratio I) when the refractory material is expanded at 300 ° C., and the refractory material is heated from 20 ° C. to 300 ° C. at a heating rate of 5 ° C./min.
  • the ratio (II/I) of the expansion ratio (expansion ratio II) when the material is expanded (hereinafter referred to as “ratio (II/I)”) is 0.5 to 1.0. If the ratio (II/I) is less than the above lower limit, the refractory material will not expand sufficiently when the temperature of the refractory material is gradually increased, and the fire resistance will be impaired. From this point of view, the ratio (II/I) is preferably 0.6 or more, more preferably 0.7 or more. The ratio (II/I) can be adjusted by appropriately selecting matrix components.
  • the expansion ratio II in the refractory material of the present invention is 7 from the viewpoint that the refractory material expands sufficiently even when the temperature of the refractory material is gradually increased, and the ratio (II/I) can be easily adjusted to the desired range. It is preferably at least 15 times, more preferably at least 30 times, even more preferably at least 30 times. On the other hand, although the upper limit of the expansion ratio II is not particularly limited, it is preferably 55 times or less, more preferably 50 times or less, and still more preferably from the viewpoint of maintaining a certain level or more of the residue residual rate and residue hardness. 45 times or less.
  • the expansion ratio I in the refractory material of the present invention is not particularly limited as long as the ratio (II/I) satisfies the above range. From the viewpoint of security, it is preferably 8 times or more, more preferably 17 times or more, still more preferably 33 times or more, and preferably 70 times or less, more preferably 60 times or less, further preferably 50 times or less.
  • the refractory material of the present invention contains at least one matrix component selected from rubber components and resins.
  • the matrix component is preferably a rubber component.
  • Rubber components include natural rubber, isoprene rubber, butyl rubber, butadiene rubber (BR), 1,2-polybutadiene rubber, styrene-butadiene rubber (SBR), chloroprene rubber, acrylonitrile rubber-butadiene rubber (NBR), ethylene- Propylene rubber, ethylene-propylene-diene rubber (EPDM), chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, urethane elastomer and the like.
  • natural rubber isoprene rubber, butyl rubber, butadiene rubber (BR), 1,2-polybutadiene rubber, styrene-butadiene rubber (SBR), chloroprene rubber, acrylonitrile rubber-butadiene rubber (NBR), ethylene- Propylene rubber, ethylene-propylene-diene rubber (EPDM), chlorosulfon
  • At least one selected from the group consisting of acrylonitrile-butadiene rubber, chloroprene rubber, and styrene-butadiene rubber is more preferable from the viewpoint of easily adjusting the ratio (II/I) to a desired range, acrylonitrile-butadiene rubber, At least one selected from the group consisting of chloroprene rubber is more preferred, and acrylonitrile-butadiene rubber is particularly preferred.
  • Acrylonitrile-butadiene rubber has a stable structure even when the temperature of the refractory material is gradually raised, so it can maintain an appropriate viscosity when a fire occurs, and the ratio (II/I) can be adjusted to the desired range. It is easy to improve fire resistance.
  • 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.
  • An 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 ratio (II/I) within the desired range.
  • 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 ratio (II/I) within the desired range.
  • chloroprene rubber can reduce the content of carbon in the refractory material, it is also preferable to use chloroprene rubber as the rubber contained in the refractory material from the viewpoint of enhancing fire resistance.
  • chloroprene rubber a sulfur-modified type (G type), a non-sulfur-modified type (W type), and the like can also be used.
  • the Mooney viscosity ML(1+4) at 100° C. of the chloroprene rubber is preferably 60-120, more preferably 70-90.
  • a chloroprene 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 can easily adjust the ratio (II/I) within the desired range.
  • Mooney viscosity is measured based on JISK6300 in this specification.
  • the refractory material preferably contains a plasticizer, which will be described later.
  • a plasticizer which will be described later.
  • aliphatic ester plasticizers are preferred, among them, aliphatic ester plasticizers having ether bonds are more preferred, and dibutoxyethoxyethyl adipate is even more preferred.
  • Commercial products of dibutoxyethoxyethyl adipate include, for example, Adekasizer RS-107 manufactured by ADEKA Co., Ltd., which is called an adipic acid ether ester. The amount of the plasticizer to be used for the resin will be described later.
  • 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 ratio (II/I) within the desired range.
  • 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 can easily adjust the ratio (II/I) within the desired range.
  • the resin may be a thermosetting resin or a thermoplastic resin, preferably a thermoplastic resin.
  • the thermoplastic resin is not particularly limited, but examples include polypropylene resin, polyethylene resin, polyolefin resin such as ethylene-vinyl acetate copolymer, polyvinyl acetate resin, polyvinyl chloride resin, fluororesin such as polytetrafluoroethylene, Urethane resins such as phenol resins, polycarbonate resins, polyacrylonitrile resins, and urethane elastomers can be used.
  • thermoplastic resins ethylene-vinyl acetate copolymers and polyvinyl acetate resins are preferable from the viewpoint of increasing the ratio (II/I) to improve fire resistance.
  • a thermoplastic resin having a high vinyl acetate content is preferred.
  • the thermoplastic resin is at least one selected from an ethylene-vinyl acetate copolymer containing a high Vac component having a vinyl acetate content of 20% by mass or more, and a polyvinyl acetate resin.
  • Polyvinyl acetate resin is preferred, and polyvinyl acetate resin is more preferred.
  • the high Vac component having a vinyl acetate content of 20% by mass or more means an ethylene-vinyl acetate copolymer component having a vinyl acetate content of 20% by mass or more.
  • Ethylene-vinyl acetate copolymers and polyvinyl acetate resins are non-chlorinated resins, so dioxins are less likely to occur, and they are kneaded with thermally expandable graphite at relatively low temperatures without containing plasticizers. It is preferable to use it as a resin contained in the refractory material because it can be used and the moldability of the refractory material is improved.
  • the vinyl acetate content of the high-Vac component is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably from the viewpoint of easily adjusting the ratio (II/I) to a desired range. is 50% by mass or more, more preferably 70% by mass or more.
  • the ethylene-vinyl acetate copolymer may contain an ethylene-vinyl acetate copolymer component (low Vac component) with a vinyl acetate content of less than 20% by mass to the extent that the effects of the present invention are not impaired.
  • the content of the high Vac component is preferably 50% by mass or more based on the total amount of the ethylene-vinyl acetate copolymer, and more It is preferably 70% by mass or more, more preferably 100% by mass.
  • the ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer having a melt flow rate (MFR) at 190°C of 8.0 g/10 min or less from the viewpoint of increasing the expansion pressure of the refractory material and improving the moldability. It preferably contains a polymer component (hereinafter also referred to as a low MFR component).
  • the melt flow rate (MFR) of the low MFR component at 190° C. is more preferably 6.0 g/10 min or less, still more preferably 1.0 g/10 min or less.
  • 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.
  • the content of the low-MFR component is preferably 70% by mass or more, more preferably 90% by mass or more, based on the total amount of the ethylene-vinyl acetate copolymer.
  • MFR and vinyl acetate content are separate parameters representing the structure of the ethylene-vinyl acetate copolymer, there are also components that correspond to low MFR components and high Vac components.
  • the high Vac component when using a high Vac component having a vinyl acetate content of 20% by mass or more and less than 50% by mass, the high Vac component is used from the viewpoint of increasing the expansion pressure and improving fire resistance.
  • the MFR (190° C.) of the high-Vac component is preferably 8.0 g/10 min or less, more preferably 6.0 g/10 min or less, even more preferably 1.0 g/10 min or less, and preferably 0 05 g/10 min or more, more preferably 0.1 g/10 min or more, and still more preferably 0.3 g/10 min or more.
  • the Mooney viscosity ML(1+4) at 100° C. of the high-Vac component is preferably 10-50, more preferably 20-40.
  • Polyvinyl acetate resin is a homopolymer of vinyl acetate, and by using this as a resin contained in a fireproof material, the ratio (II/I) can be easily adjusted to the desired range, and fire resistance can be effectively improved. do.
  • the weight average molecular weight of the polyvinyl acetate resin is preferably 100,000 to 1,000,000, more preferably 200,000 to 600,000, and still more preferably from the viewpoint of increasing the expansion pressure while improving the moldability of the refractory material. is 300,000 to 500,000.
  • the weight average molecular weight is a standard polystyrene conversion value obtained by measuring by gel permeation chromatography (GPC).
  • the refractory material of the present invention has a viscosity A of the matrix component at 250 ° C. when heated at a temperature increase rate of 40 ° C./min at 100 ° C. to 300 ° C. at 5 ° C./min at 100 ° C. to 300 ° C.
  • the ratio (B/A) of the viscosity B of the matrix component at 250° C. when the temperature is raised (hereinafter referred to as “ratio (B/A)”) is preferably 2.0 or less. When the ratio (B/A) is 2.0 or less, it is possible to prevent the viscosity of the matrix component from excessively increasing even when the temperature of the refractory material is gradually increased.
  • the refractory material expands easily, the ratio of the expansion ratio can also satisfy a predetermined range, and the fire resistance is improved. Moreover, in the process of manufacturing the refractory material, the fluidity of the resin composition can be ensured to some extent, and excellent moldability can be obtained, making it possible to provide a high-quality refractory material. Based on these points of view, 1.8 or less is more preferable, and 1.6 or less is even more preferable.
  • the lower limit of the ratio (B/A) is not particularly limited. From the viewpoint of obtaining moldability, it is preferably 0.7 or more, more preferably 0.8 or more, and still more preferably 1.0 or more.
  • the ratio (B/A) can be appropriately adjusted depending on the type, viscosity, molecular weight, etc. of the matrix component.
  • the viscosity B of the matrix component in the present invention is preferably 7500 Pa s or less from the viewpoint of making the refractory material sufficiently expand easily and obtaining excellent moldability even when the temperature of the refractory material is gradually increased. , 5000 Pa ⁇ s or less, and more preferably 3000 Pa ⁇ s or less.
  • the lower limit of the viscosity B of the matrix component is not particularly limited, but from the viewpoint of improving moldability, it is preferably 1000 Pa ⁇ s or more, more preferably 1200 Pa ⁇ s or more, and still more preferably 1300 Pa ⁇ s. s or more.
  • the viscosity A of the matrix component in the present invention is not particularly limited as long as the ratio (B/A) satisfies the above range. From the viewpoints of sufficient expansion and excellent moldability, the viscosity is preferably 6000 Pa ⁇ s or less, more preferably 4500 Pa ⁇ s or less, and even more preferably 2500 Pa ⁇ s or less.
  • the lower limit of the viscosity B of the matrix component is not particularly limited, but from the viewpoint of obtaining the minimum moldability, it is preferably 800 Pa ⁇ s or more, more preferably 900 Pa ⁇ s or more, and still more preferably 1100 Pa. - s or more.
  • 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 20 to 500 parts by mass, more preferably 30 to 250 parts by mass, and still more preferably 70 parts by mass with respect to 100 parts by mass of the matrix component. ⁇ 150 parts by mass.
  • the content of thermally expandable graphite is at least these lower limits, it becomes easier to increase the expansion pressure of the thermally expandable refractory material, and it becomes easier to adjust the expansion ratio ratio (II/I) within a desired range.
  • 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 preferably contains a flame retardant. Fire resistance improves by containing a flame retardant.
  • flame retardants include various phosphoric acid esters such as triphenyl phosphate (triphenyl phosphate), tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl phosphate, sodium phosphate, phosphorus phosphites such as sodium phosphite, potassium phosphite, magnesium phosphite, aluminum phosphite and the like, ammonium polyphosphate, red phosphorus, and the like. be done.
  • flame retardants include compounds represented by the following general formula (1).
  • R 1 and R 3 are the same or different and represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • R 2 is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or a carbon number Represents 6-16 aryloxy groups.
  • Specific examples of the compound represented by the general formula (1) include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, n-propylphosphonic acid, n-butylphosphonic acid and 2-methylpropylphosphonic acid.
  • t-butylphosphonic acid 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid , phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid and the like.
  • the flame retardants may be used alone or in combination of two or more.
  • Zinc borate etc. are mentioned as a boron-type compound.
  • metal hydroxides include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, hydrotalcite, and the like. When a metal hydroxide is used, water is produced by heat generated by ignition, and the fire can be quickly extinguished.
  • red phosphorus, phosphoric acid esters such as triphenyl phosphate (triphenyl phosphate), aluminum phosphite, ammonium polyphosphate, and zinc borate are preferable from the viewpoint of safety and cost.
  • aluminum phosphite and ammonium polyphosphate are more preferable.
  • the flame retardants listed above may be used alone or in combination of two or more, but it is preferable to use one alone, and phosphorous acid More preferably, aluminum is used. Since aluminum phosphite has expansive properties, the expansion pressure of the refractory material containing the aluminum phosphite tends to increase, and the fire resistance tends to be improved more effectively.
  • the average particle size of the flame retardant is preferably 1-200 ⁇ m, more preferably 1-60 ⁇ m, still more preferably 3-40 ⁇ m, and even more preferably 5-20 ⁇ m.
  • the average particle size of the flame retardant is within the above range, the dispersibility of the flame retardant in the refractory material is improved, the flame retardant is uniformly dispersed in the resin, and the amount of the flame retardant compounded in the resin is increased. be able to.
  • the average particle size is outside the above range, the flame retardant will be difficult to disperse in the resin, making it difficult to uniformly disperse the flame retardant in the resin or to mix a large amount of the flame retardant.
  • the average particle size of the flame retardant is the value of the median size (D50) measured with a laser diffraction/scattering particle size distribution analyzer.
  • the content of the flame retardant in the refractory material of the present invention is preferably 15 to 1000 parts by mass, more preferably 20 to 300 parts by mass, and even more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the matrix component. .
  • the content of the flame retardant is at least these lower limit values, the fire resistance of the fire resistant material is improved.
  • the content of the flame retardant is not more than these upper limits, it becomes easier to uniformly disperse in the resin, and moldability and the like are excellent.
  • 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. When the refractory material contains a cross-linking agent, it is believed that the heat generated during a fire promotes the 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 preferably contains 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 may contain a plasticizer.
  • a plasticizer By using a plasticizer, moldability tends to be improved.
  • the content of the plasticizer is not particularly limited, but is preferably 10 to 200 parts by mass, more preferably 20 to 60 parts by mass, based on 100 parts by mass of the matrix component. If the content of the plasticizer is at least these lower limits, the moldability of the refractory material will be improved. When the content of the plasticizer is below these upper limits, it becomes easier to adjust the ratio (II/I) within the desired range, and the expansion pressure also increases, making it easier to improve the fire resistance.
  • plasticizers include di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or those having 10 to 10 carbon atoms.
  • Phthalic acid ester plasticizers such as phthalic acid esters of higher alcohols or mixed alcohols of about 13, di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), di-n-octyl adipate, Aliphatic ester plasticizers such as di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, dibutoxyethoxyethyl adipate, tri-2-ethylhexyl Trimellitate ester plasticizers such as trimellitate (TOTM), tri-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, and di-n-octyl-n-decy
  • the refractory material of the present invention may further contain an inorganic filler other than the flame retardant and thermally expandable graphite.
  • Inorganic fillers other than flame retardants and thermally expandable graphite are not particularly limited, and examples include metal carbonates such as alumina, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate, and silica.
  • diatomaceous earth dawsonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, Graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, and dehydrated sludge.
  • These inorganic fillers may be used alone or in combination of two or more.
  • the average particle size of the inorganic filler is preferably 0.5-100 ⁇ m, more preferably 1-50 ⁇ m.
  • the particle size of the inorganic filler is small from the viewpoint of improving dispersibility. Therefore, those having a large particle size are preferable.
  • the refractory material of the present invention contains an inorganic filler other than a flame retardant and thermally expandable graphite
  • the content thereof is preferably 10 to 300 parts by mass, more preferably 10 to 200 parts by mass, based on 100 parts by mass of the resin. part by mass.
  • the content of the inorganic filler is within the above range, the mechanical properties of the refractory material can be improved.
  • 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, lubricants, anti-shrinking agents, crystal nucleating agents, coloring agents (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, anti-aging agents, dispersants, gelation accelerators, fillers, , reinforcing agents, flame retardant aids, antistatic agents, surfactants, vulcanizing agents, 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 residual hardness of 0.10 kgf/cm 2 or more, more preferably 0.13 kgf/cm 2 or more, and still more preferably 0.13 kgf/cm 2 or more after thermal expansion. It is 17 kgf/cm 2 or more, more preferably 0.22 kgf/cm 2 or more.
  • the residual hardness is preferably 1.00 kgf/cm 2 or less, more preferably 0.95 kgf/cm 2 or less, and even more preferably, from the viewpoint of ensuring fire resistance by making the refractory material expand easily. is 0.85 kgf/cm 2 or less.
  • the refractory material of the present invention preferably exhibits residual hardness within the above range even after being immersed in water at 60° C. for one week. If the swelling residue is within the above range after being immersed in water for a long period of time, the water resistance is also good.
  • the hardness of the residue can be obtained by measuring the hardness of the expanded residue after heating and expanding the refractory material.
  • 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 predetermined amount of thermally expandable graphite, a resin, a plasticizer, a flame retardant, a cross-linking agent, an inorganic filler, and other components blended as necessary are kneaded with a kneader such as a kneading roll to obtain a refractory product. to obtain a flexible resin composition. 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.
  • a kneader such as a kneading roll
  • the temperature during kneading 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.
  • expansion ratio I The refractory materials of each example and comparative example were made to have a predetermined size (thickness 1.8 mm, width 25 mm, length 25 mm). A refractory material of a predetermined size is placed on the bottom surface of a stainless steel plate (98 mm square, thickness 0.3 mm), and the refractory material is placed in an electric furnace that has been set to 300 ° C in advance. heated for a minute. The expansion ratio I was obtained by dividing the thickness of the refractory material after heating by the thickness of the refractory material before heating.
  • Viscosity A of matrix component Among the formulations shown in Table 1, the matrix component was hot-pressed at 100° C. to prepare a circular test piece with a thickness of 1 mm and a diameter of 2 cm. After that, using "MCR 302" (manufactured by Anton Paar), the viscosity was evaluated while heating from 100 ° C. to 300 ° C. at a temperature increase rate of 40 ° C./min at an angular frequency of 63 rad / s. Viscosity was measured.
  • Viscosity B of matrix component The viscosity of the matrix component at 250° C. was measured when the temperature was gradually raised in the same manner as in the measurement of (3) except that the temperature was raised at a rate of 5° C./min.
  • Residual hardness Put the refractory material in an electric furnace preliminarily heated to 600 ° C. and heat the test piece for 30 minutes. It was compressed with an indenter of 0.25 cm 2 at a rate of 0.1 cm/sec, and the stress at break was measured.
  • a door member for fire-resistant time evaluation was prepared, which consisted of a door made of a calcium silicate plate (manufactured by Nippon Insulation Co., Ltd.) and a door frame. A gap of 1 cm was provided between the side surface of the door member for fire resistance time evaluation and the door frame. A refractory material (thickness: 1.8 mm, width: 25 mm, length: 1000 mm) of each example and comparative example having a predetermined size was attached to the side of the door. Then, in a refractory furnace, it was heated according to the standard heating curve of ISO834, and the time until the refractory material peeled off was measured.
  • the evaluation criteria of the fire resistance time are as follows. A: Time until peeling off 90 minutes or more B: Time until peeling off 75 minutes or more and less than 90 minutes C: Time until peeling off 60 minutes or more and less than 75 minutes D: Time until peeling off less than 60 minutes
  • Formability When kneading with rolls, if the material is too hard to flow, or too soft to flow easily and the shape cannot be maintained, the yield will deteriorate.
  • the formability was determined by the yield of the material that was taken out in the form of a sheet after kneading, out of the charged materials, as follows. A: 90% or more B: 70% or more and less than 90% C: 50% or more and less than 70% D: less than 50%
  • (matrix component) Rubber component/NBR (1) “Nipol DN401L” manufactured by Nippon Zeon Co., Ltd. Mooney viscosity ML (1+4): 70, nitrile content 18% by mass ⁇ NBR (2) “Nipol 1052J” manufactured by Nippon Zeon Co., Ltd. Mooney viscosity ML (1+4): 46, nitrile content 33.5% by mass ⁇ NBR (3) “Nipol DN101L” manufactured by Nippon Zeon Co., Ltd.
  • Mooney viscosity ML (1+4) 60, nitrile content 42.5% by mass ⁇ NBR (4) “Nipol DN401” manufactured by Nippon Zeon Co., Ltd. Mooney viscosity ML (1+4): 77.5, nitrile content 18% by mass ⁇ NBR (5) “Nipol DN101LL” manufactured by Nippon Zeon Co., Ltd. Mooney viscosity ML (1+4): 32, nitrile content 18% by mass ⁇ SBR (1) “Nipol 1502” manufactured by Nippon Zeon Co., Ltd.
  • Mooney viscosity ML (1+4) 52, styrene content 23.5% by mass ⁇ SBR (2) “Nipol 1739” manufactured by Nippon Zeon Co., Ltd. Mooney viscosity ML (1+4): 49, styrene content 40% by mass ⁇ Chloroprene rubber (1) “Skyprene TSR-56” manufactured by Tosoh Corporation Mooney viscosity ML(1+4) at 100°C: 70 ⁇ Chloroprene rubber (2) “Skyprene 640” manufactured by Tosoh Corporation Mooney viscosity ML(1+4) at 100°C: 85
  • Polyvinyl acetate resin/Polyvinyl acetate (1) “VINNAPAS 4FS” manufactured by Tomoe Chemical Industry Co., Ltd. Weight average molecular weight: 300,000 g/mol ⁇ Polyvinyl acetate (2) “VINNAPAS 25FS” manufactured by Tomoe Chemical Industry Co., Ltd. Weight average molecular weight: 500,000 g/mol
  • EVM Ethylene-Vinyl Acetate Copolymer
  • EVM Ethylene-Vinyl Acetate Copolymer
  • Thermal expandable graphite (Thermal expandable graphite) ⁇ Thermal expandable graphite “ADT351” manufactured by ADT Average aspect ratio: 21.3
  • Examples 1 to 17, Comparative Examples 1 to 3 A matrix component, thermally expandable graphite, a flame retardant, a cross-linking agent, and a plasticizer 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.
  • the refractory material of the present invention containing a matrix component and thermally expandable graphite and having an expansion ratio within a predetermined range was found to have a long fire resistance time and excellent fire resistance. rice field.
  • the refractory materials of each comparative example having expansion ratios outside the predetermined range had a short fire resistance time and poor fire resistance.

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Abstract

La présente invention concerne un matériau résistant au feu thermo-expansible contenant du graphite thermo-expansible et au moins un type de composant de matrice choisi dans le groupe constitué d'un composant de caoutchouc et d'une résine, et ayant un rapport (II /I) de 0,5 à 1,0 d'un facteur d'expansion (facteur d'expansion II) lorsque le matériau résistant au feu se dilate tout en étant chauffé de 20 °C à 300 °C à une vitesse de 5 °C/min à un facteur d'expansion (facteur d'expansion I) lorsque le matériau résistant au feu se dilate à 300° C.
PCT/JP2022/008347 2021-03-02 2022-02-28 Matériau résistant au feu thermo-expansible WO2022186152A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018150391A (ja) * 2017-03-09 2018-09-27 旭化成建材株式会社 熱膨張性耐火組成物
JP2019116606A (ja) * 2017-12-26 2019-07-18 清典 藏田 熱膨張性耐火断熱塗料およびこれを用いたケーブル用耐火断熱シート
JP2020128089A (ja) * 2018-02-20 2020-08-27 積水化学工業株式会社 耐火積層体及びバッテリー
JP2020139058A (ja) * 2019-02-28 2020-09-03 積水化学工業株式会社 耐火材
JP2021187974A (ja) * 2020-06-01 2021-12-13 積水化学工業株式会社 耐火性樹脂組成物、耐火シート及び建具

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018150391A (ja) * 2017-03-09 2018-09-27 旭化成建材株式会社 熱膨張性耐火組成物
JP2019116606A (ja) * 2017-12-26 2019-07-18 清典 藏田 熱膨張性耐火断熱塗料およびこれを用いたケーブル用耐火断熱シート
JP2020128089A (ja) * 2018-02-20 2020-08-27 積水化学工業株式会社 耐火積層体及びバッテリー
JP2020139058A (ja) * 2019-02-28 2020-09-03 積水化学工業株式会社 耐火材
JP2021187974A (ja) * 2020-06-01 2021-12-13 積水化学工業株式会社 耐火性樹脂組成物、耐火シート及び建具

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