WO2016182059A1 - 耐火樹脂組成物 - Google Patents

耐火樹脂組成物 Download PDF

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Publication number
WO2016182059A1
WO2016182059A1 PCT/JP2016/064281 JP2016064281W WO2016182059A1 WO 2016182059 A1 WO2016182059 A1 WO 2016182059A1 JP 2016064281 W JP2016064281 W JP 2016064281W WO 2016182059 A1 WO2016182059 A1 WO 2016182059A1
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Prior art keywords
resin composition
weight
refractory
polyphosphate
magnesium
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PCT/JP2016/064281
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English (en)
French (fr)
Japanese (ja)
Inventor
倫男 島本
秀明 矢野
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積水化学工業株式会社
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Priority to JP2016538114A priority Critical patent/JP6244029B2/ja
Publication of WO2016182059A1 publication Critical patent/WO2016182059A1/ja

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/02—Homopolymers or copolymers of monomers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92—Protection against other undesired influences or dangers
    • E04B1/94—Protection against other undesired influences or dangers against fire

Definitions

  • the present invention relates to a refractory resin composition.
  • polyphosphate is very excellent in flame retardancy, but is weak against moisture, and after hydrolysis, a white precipitate is formed on the surface of the thermally expandable sheet (also referred to as bleed out), and the generated precipitate As a result, the appearance of the sheet is impaired, or the polyphosphate is eluted from the blending system, so that the fire resistance is remarkably lowered.
  • An object of the present invention is to provide a refractory resin composition having excellent fire resistance and suppressing generation of precipitates.
  • the present inventors are selected from the group consisting of alkali metals, alkaline earth metals, and magnesium in a resin composition containing a polyphosphate that constitutes a thermally expandable refractory sheet.
  • the inventors have found that by reducing the content of at least one or more, the appearance is not impaired and the fire resistance is remarkably improved, and the present invention has been completed.
  • At least one selected from the group consisting of alkali metals, alkaline earth metals, and magnesium including a matrix component that is a resin, an elastomer, rubber, or a combination thereof, and a polyphosphate.
  • a refractory resin composition having a metal content of 5% by weight or less.
  • a refractory resin composition comprising a matrix component which is a resin, an elastomer, a rubber, or a combination thereof, and a polyphosphate
  • the alkali metal, an alkaline earth metal and magnesium are used.
  • a method for suppressing the generation of precipitates due to hydrolysis of polyphosphate in a refractory resin composition wherein the content of at least one metal selected from the group is 5% by weight or less.
  • the refractory resin composition of the present invention comprises at least one selected from the group consisting of alkali metals, alkaline earth metals, and magnesium, including a matrix component that is a resin, an elastomer, rubber, or a combination thereof, and a polyphosphate.
  • the above metal content is 5% by weight or less.
  • the resin as the matrix component may be a thermoplastic resin or a thermosetting resin.
  • thermoplastic resins include polypropylene resins, polyolefin resins such as polyethylene resins, poly (1-) butene resins, polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene resins, polycarbonate resins, polyphenylene ether resins, (meth) acrylic.
  • examples thereof include a resin, an ethylene vinyl acetate copolymer (EVA) resin, a polyamide resin, a polyamideimide resin, a polybutadiene resin, a polyimide resin, a polyvinyl chloride fat (including a chlorinated vinyl chloride resin), and combinations thereof.
  • EVA ethylene vinyl acetate copolymer
  • polyamide resin a polyamideimide resin
  • polybutadiene resin a polyimide resin
  • polyvinyl chloride fat including a chlorinated vinyl chloride resin
  • thermoplastic resins may be used after being crosslinked or modified as long as the fire resistance performance as a resin composition is not impaired.
  • the crosslinking method of the resin is not particularly limited, and examples thereof include a usual crosslinking method for thermoplastic resins, such as crosslinking using various crosslinking agents and peroxides, and crosslinking by electron beam irradiation.
  • thermosetting resins examples include epoxy resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethanes, thermosetting polyimides, and the like.
  • an epoxy resin is preferable.
  • the epoxy resin used in the present invention is not particularly limited, but is basically obtained by reacting a monomer having an epoxy group with a curing agent.
  • the monomer having an epoxy group include monomers such as a bifunctional glycidyl ether type, a glycidyl ester type, and a polyfunctional glycidyl ether type.
  • These monomers having an epoxy group may be used alone or in combination of two or more.
  • a polyaddition type or a catalyst type is used as the curing agent.
  • the polyaddition type curing agent include polyamine, acid anhydride, polyphenol, and polymercaptan.
  • the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes.
  • the curing method of the epoxy resin is not particularly limited, and can be performed by a known method.
  • elastomers examples include olefin elastomers, styrene elastomers, ester elastomers, amide elastomers, vinyl chloride elastomers, combinations thereof, and the like.
  • Examples of rubber include natural rubber, silicone rubber, styrene / butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, acrylonitrile / butadiene rubber, nitrile butadiene rubber, butyl rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, Examples thereof include urethane rubber, silicone rubber, fluororubber, and combinations thereof. Of these, butyl rubber is preferred.
  • Polyphosphate functions as a flame retardant, and examples include ammonium polyphosphate and melamine polyphosphate.
  • ammonium polyphosphate examples include “AP422” and “AP462” manufactured by Clariant, “Sumisafe P” manufactured by Sumitomo Chemical Co., Ltd., and “Terrage C60” manufactured by Chisso.
  • a preferred ammonium polyphosphate is a surface-coated ammonium polyphosphate (also referred to as a coated ammonium polyphosphate).
  • a coated ammonium polyphosphate also referred to as a coated ammonium polyphosphate.
  • melamine-coated ammonium polyphosphate surface-coated with melamine is disclosed in JP-A-9-286875.
  • JP-A-2000-63562 describes a silane-coated ammonium polyphosphate surface-coated with silane.
  • the melamine-coated ammonium polyphosphate is composed of (a) melamine-coated ammonium polyphosphate obtained by adding and / or adhering melamine to the surface of powdered ammonium polyphosphate particles, and (b) melamine molecules present in the coating layer of the melamine-coated ammonium polyphosphate particles. And / or (c) powdered ammonium polyphosphate or the melamine in which the particle surface is crosslinked with an active hydrogen possessed by an amino group therein and a compound having a functional group capable of reacting with the active hydrogen This is a coated ammonium polyphosphate in which the surface of the coated ammonium polyphosphate particles is coated with a thermosetting resin.
  • Examples of commercially available melamine-coated ammonium polyphosphate particles include “AP462” manufactured by Clariant, “FR CROS 484”, “FR CROS 487” manufactured by Budenheim Iberica, and the like.
  • Examples of commercially available silane-coated ammonium polyphosphate particles include “FR CROS 486” manufactured by Budenheim Iberica.
  • the average particle size of the coated ammonium polyphosphate is preferably 15 to 35 ⁇ m.
  • the average particle diameter of the coated ammonium polyphosphate can be measured by laser diffraction particle size distribution measurement.
  • the content of the polyphosphate is not particularly limited, but is preferably 5 to 30% by weight, more preferably 10 to 25% by weight, and more preferably 15 to 23% by weight in the refractory resin composition. Further preferred.
  • the fireproof resin composition of the present invention contains at least one metal selected from the group consisting of alkali metals, alkaline earth metals, and magnesium, and the content of such metals is 5% by weight or less.
  • alkali metal examples include lithium, sodium, potassium, rubidium, and cesium.
  • Alkaline earth metals include calcium, strontium, barium and radium.
  • Alkali metals, alkaline earth metals, and magnesium may be included in any form such as metal salts, metal oxides, metal hydroxides, or metal ions.
  • At least one or more metals selected from the group consisting of alkali metals, alkaline earth metals, and magnesium contained in raw materials and reaction reagents may be mixed unintentionally.
  • alkali metal or alkaline earth metal is mixed during the neutralization treatment of the thermally expandable graphite described later.
  • “alkali metal”, “alkaline earth metal”, and “magnesium” in the refractory resin composition of the present invention include unintentionally mixed alkali metal, alkaline earth metal, and magnesium. Further, it refers to alkali metals, alkaline earth metals, and magnesium contained in the refractory resin composition.
  • the content of at least one metal selected from the group consisting of alkali metals, alkaline earth metals and magnesium in the refractory resin composition (total amount of alkali metals, alkaline earth metals and magnesium) is 5% by weight or less.
  • the fireproof resin composition retains excellent water resistance.
  • the alkali metal concentration is 1% by weight or less, more preferably 0.2% by weight or less (2000 ppm or less).
  • the alkaline earth metal concentration is 2% by weight or less.
  • the magnesium concentration is 2% by weight or less.
  • the content of at least one metal selected from the group consisting of alkali metals, alkaline earth metals and magnesium in the refractory resin composition of the present invention is 0% by weight.
  • the content of at least one or more metals selected from the group consisting of alkali metals, alkaline earth metals and magnesium in the refractory resin composition of the present invention is greater than 0% by weight.
  • the refractory resin composition of the present invention contains at least one metal selected from the group consisting of alkali metals, alkaline earth metals, and magnesium only as an unintentionally mixed impurity.
  • the refractory resin composition of the present invention contains at least one metal selected from the group consisting of alkali metals, alkaline earth metals and magnesium as the metal contained in the constituent components.
  • the refractory resin composition of the present invention contains such a metal (specifically, a calcium salt or the like) as an inorganic filler described later.
  • the fireproof resin composition of the present invention may further contain a plasticizer.
  • the plasticizer is added particularly for adjusting the melt viscosity of the thermoplastic resin.
  • one or more plasticizers exemplified below may be used in combination: Di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or a higher or mixed alcohol having about 10 to 13 carbon atoms
  • Phthalate plasticizers such as phthalates Aliphatic dibasic acids such as di-2-ethylhexyl adipate, di-n-octyl adipate, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-e
  • the refractory resin composition of the present invention may further contain thermally expandable graphite.
  • the refractory resin composition contains thermally expandable graphite, the refractory resin composition becomes a thermally expandable refractory resin composition that expands by heating.
  • Thermally expandable graphite is a conventionally known substance, and powders such as natural scaly graphite, pyrolytic graphite, and quiche graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, concentrated nitric acid, perchloric acid, and perchlorate.
  • a graphite intercalation compound is produced by treatment with a strong oxidant such as permanganate, dichromate, hydrogen peroxide, etc., and is a crystalline compound that maintains a carbon layered structure.
  • the thermally expandable graphite may optionally be neutralized. That is, the thermally expandable graphite obtained by acid treatment as described above is further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.
  • the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine.
  • the alkali metal compound and alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium, and magnesium, oxides, carbonates, sulfates, and organic acid salts.
  • Specific examples of the heat-expandable graphite subjected to the neutralization treatment include “CA-60S” manufactured by Nippon Kasei Co., Ltd. and “GREP-EG” manufactured by Tosoh Corporation.
  • the particle size of the thermally expandable graphite used in the present invention is preferably 20 to 200 mesh.
  • the particle size is larger than 200 mesh, the degree of expansion of graphite is large and a desired fireproof heat insulating layer is obtained.
  • the particle size is smaller than 20 mesh, the dispersibility when kneading with the resin is good.
  • the refractory resin composition of the present invention may further contain an inorganic filler.
  • the inorganic filler increases the heat capacity and suppresses heat transfer, and works as an aggregate to improve the strength of the expanded heat insulating layer.
  • the inorganic filler is not particularly limited, and examples thereof include metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; calcium hydroxide, magnesium hydroxide And water-containing inorganic substances such as aluminum hydroxide and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate.
  • inorganic fillers include calcium salts such as calcium sulfate, gypsum fiber, calcium silicate; silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite.
  • calcium salts such as calcium sulfate, gypsum fiber, calcium silicate; silica, diatomaceous earth, dosonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite.
  • These inorganic fillers may be used alone or in combination of two or more.
  • the particle size of the inorganic filler is preferably 0.5 to 100 ⁇ m, more preferably 1 to 50 ⁇ m.
  • the addition amount of the inorganic filler is small, the dispersibility largely affects the performance, so that the particle size is preferably small. However, when it is less than 0.5 ⁇ m, secondary aggregation occurs and the dispersibility deteriorates.
  • the addition amount is large, the viscosity of the resin composition increases and moldability decreases as the high filling progresses, but the viscosity of the resin composition can be decreased by increasing the particle size. A thing with a large diameter is preferable.
  • the particle size exceeds 100 ⁇ m, the surface properties of the molded body and the mechanical properties of the resin composition are lowered.
  • the inorganic filler is selected from metal oxides, hydrous minerals, metal carbonates, silica, and combinations thereof.
  • the hydrous inorganic substance contains an alkaline earth metal hydroxide.
  • the inorganic filler for example, for aluminum hydroxide, “Hijilite H-31” (manufactured by Showa Denko) having a particle size of 18 ⁇ m, “B325” (manufactured by ALCOA) having a particle size of 25 ⁇ m, Examples include 1.8 ⁇ m “Whiteon SB Red” (manufactured by Bihoku Powdered Industries Co., Ltd.), “BF300” (manufactured by Bihoku Powdered Industries Co., Ltd.) having a particle size of 8 ⁇ m, and the like.
  • the content of the inorganic filler is not particularly limited, but is preferably 30 to 500 parts by weight with respect to 100 parts by weight of the matrix component. When the content is 30 parts by weight or more, sufficient fireproof performance is obtained, and when it is 500 parts by weight or less, the mechanical strength is maintained.
  • the content of the inorganic filler is more preferably 40 to 350 parts by weight.
  • R 1 and R 3 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 carbon. Represents an aryloxy group of formula 6-16.
  • red phosphorus commercially available red phosphorus can be used, but from the viewpoint of safety such as moisture resistance and spontaneous ignition during kneading, a material in which the surface of red phosphorus particles is coated with a resin is preferably used.
  • the compound represented by the chemical formula (1) is not particularly limited.
  • methylphosphonic acid dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 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, phenylphosphine Acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid and the like.
  • t-butylphosphonic acid is expensive but preferable in terms of high fire
  • phosphate esters such as triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate.
  • TCP tricresyl phosphate
  • the phosphate ester functions as a plasticizer and can improve water resistance and fire resistance.
  • the content of the phosphorus compound is not particularly limited, but is preferably 30 to 300 parts by weight with respect to 100 parts by weight of the matrix component. When the blending amount is 30 parts by weight or more, the effect of improving the strength of the expanded heat insulating layer is sufficient, and when it is 300 parts by weight or less, the mechanical strength is maintained.
  • the content of the phosphorus compound is more preferably 40 to 250 parts by weight.
  • a heat stabilizer a lubricant, a processing aid, a pyrolytic foaming agent, an antioxidant, an antistatic agent, a pigment, and the like are added to the fireproof resin composition of the present invention as long as the physical properties are not impaired. Also good.
  • heat stabilizer examples include lead heat stabilizers such as tribasic lead sulfate, tribasic lead sulfite, dibasic lead phosphite, lead stearate, dibasic lead stearate; organotin mercapto, organic Organotin heat stabilizers such as tin malate, organotin laurate, dibutyltin malate; metal soap heat stabilizers such as zinc stearate and calcium stearate; these may be used alone or in combination of two or more You may use together.
  • lead heat stabilizers such as tribasic lead sulfate, tribasic lead sulfite, dibasic lead phosphite, lead stearate, dibasic lead stearate
  • organotin mercapto organic Organotin heat stabilizers such as tin malate, organotin laurate, dibutyltin malate
  • metal soap heat stabilizers such as zinc stearate and calcium ste
  • lubricant examples include waxes such as polyethylene, paraffin, and montanic acid; various ester waxes; organic acids such as stearic acid and ricinoleic acid; organic alcohols such as stearyl alcohol; and amide compounds such as dimethylbisamide. These may be used alone or in combination of two or more.
  • processing aids include chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, and high molecular weight polymethyl methacrylate.
  • pyrolytic foaming agent examples include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), p, p-oxybisbenzenesulfonylhydrazide (OBSH), azobisisobutyronitrile (AIBN), and the like. Can be mentioned.
  • ADCA azodicarbonamide
  • DPT dinitrosopentamethylenetetramine
  • OBSH p-oxybisbenzenesulfonylhydrazide
  • AIBN azobisisobutyronitrile
  • the refractory resin composition of the present invention can be obtained by subjecting the refractory resin composition of the present invention to melt extrusion with an extruder such as a single screw extruder or a twin screw extruder according to a conventional method.
  • the melting temperature varies depending on the matrix component and is not particularly limited. For example, in the case of a polyvinyl chloride resin, it is 130 to 170 ° C.
  • the fire-resistant resin composition or fire-resistant resin molded article of the present invention is used to impart fire resistance to structures such as windows, shojis, doors (that is, doors), doors, brans, and bams; ships; and structures such as elevators. Can be used. Since the refractory resin composition of the present invention has excellent moldability, it is possible to easily obtain a modified molded body adapted to the complex shape of the structure.
  • FIG. 1 is an example in which a fireproof resin molded body 4 of the present invention is applied to a sash frame of a window 1 as a fitting.
  • the sash frame has two inner frames 2 and one outer frame 3 surrounding the inner frame 2, and the inner frame 2 and the outer frame 3 along each side of the frame main body 2.
  • the fireproof resin molding 3 is attached to the inside of the outer frame 3.
  • fire resistance can be imparted to the window 1 by providing the fireproof resin molded body 3 of the present invention.
  • the present invention is at least selected from the group consisting of alkali metals, alkaline earth metals and magnesium in a refractory resin composition comprising a matrix component which is a resin, an elastomer, rubber, or a combination thereof, and a polyphosphate. Also included is a method for suppressing the generation of precipitates due to hydrolysis of polyphosphate in a refractory resin composition, wherein the content of one or more metals is 5% by weight or less. Each component in the refractory resin composition is as described above for the refractory resin composition.
  • DOP D-2-ethylhexyl phthalate
  • TCP tricresyl phosphate
  • ammonium polyphosphate “AP422” manufactured by Clariant was used.
  • silane-coated ammonium polyphosphate silane-coated APP
  • FR CROS 486 manufactured by Budenheim Iberica was used.
  • calcium carbonate “Whiteon BF-300” manufactured by Bihoku Flour Chemical Co., Ltd. was used.
  • Example 11 Comparative Example 2
  • bisphenol F type epoxy monomer (“E807” manufactured by Yuka Shell Co., Ltd.) amine curing agent (“FL079” manufactured by Yuka Shell Inc.), heat, Expandable graphite (“GREP-EG” manufactured by Tosoh Corporation), ammonium polyphosphate (Sumisafe P, manufactured by Sumitomo Chemical Co., Ltd.), and silica in Example 11
  • GREP-EG Expandable graphite
  • ammonium polyphosphate Sudisafe P, manufactured by Sumitomo Chemical Co., Ltd.
  • silica in Example 11 were further kneaded with a kneading roll to obtain a refractory resin composition.
  • the obtained fire-resistant resin composition was applied to a 0.5 mm-thick zinc iron plate and cured by pressing at 150 ° C. for 15 minutes to obtain a fire-resistant sheet having a predetermined thickness used for fire resistance evaluation and water resistance evaluation.
  • the fireproof sheets of Examples 1 to 15 were excellent in water resistance, and the generation of white precipitates on the fireproof sheet surface was suppressed. 5.
  • the sample after immersion was dried at 50 ° C. for 3 days, and the dissolution rate was calculated from the weight difference before and after immersion.
  • the thickness of the test piece after drying is measured, supplied to an electric furnace, heated at 600 ° C. for 30 minutes, then the thickness of the test piece is measured, and (thickness of the test piece after heating) / (heating The thickness of the previous test piece) was calculated as the expansion ratio.
  • a refractory resin composition having 5% by weight or less.
  • the refractory resin composition according to [1] further containing thermally expandable graphite.
  • the phosphorus compound is at least one selected from the group consisting of triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl phosphate
  • TCP tricresyl phosphate
  • TCP trixylenyl phosphate
  • cresyl diphenyl phosphate cresyl diphenyl phosphate
  • xylenyl diphenyl phosphate xylenyl diphenyl phosphate
  • a fire resistant resin molded article comprising the fire resistant resin composition according to any one of [1] to [15].
  • a joinery comprising the fireproof resin molded product according to [16].

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PCT/JP2016/064281 2015-05-14 2016-05-13 耐火樹脂組成物 WO2016182059A1 (ja)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018109137A (ja) * 2017-07-06 2018-07-12 株式会社レグルス 熱膨張性塩化ビニル系樹脂材料及び熱膨張性塩化ビニル系樹脂材料の製造方法
JP2018109091A (ja) * 2016-12-28 2018-07-12 株式会社レグルス 熱膨張性塩化ビニル系樹脂材料及び熱膨張性塩化ビニル系樹脂材料の製造方法
WO2018139494A1 (ja) * 2017-01-25 2018-08-02 積水化学工業株式会社 熱膨張性耐火シート
WO2018198706A1 (ja) * 2017-04-24 2018-11-01 パナソニックＩｐマネジメント株式会社 熱膨張性耐火シート用樹脂組成物、これを用いた熱膨張性耐火シート及びその製造方法
JP2019127509A (ja) * 2018-01-23 2019-08-01 古河電気工業株式会社 耐火性樹脂成形体
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