WO2016117702A1 - 耐火性樹脂組成物 - Google Patents

耐火性樹脂組成物 Download PDF

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Publication number
WO2016117702A1
WO2016117702A1 PCT/JP2016/051929 JP2016051929W WO2016117702A1 WO 2016117702 A1 WO2016117702 A1 WO 2016117702A1 JP 2016051929 W JP2016051929 W JP 2016051929W WO 2016117702 A1 WO2016117702 A1 WO 2016117702A1
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Prior art keywords
resin composition
weight
phosphate
parts
composition according
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PCT/JP2016/051929
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English (en)
French (fr)
Japanese (ja)
Inventor
倫男 島本
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積水化学工業株式会社
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Priority to JP2016508512A priority Critical patent/JP6139018B2/ja
Publication of WO2016117702A1 publication Critical patent/WO2016117702A1/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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • 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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • 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
    • 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
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • Patent Document 1 includes a thermoplastic resin containing a phosphorus compound, neutralized thermally expandable graphite, and an inorganic filler, and each content is based on 100 parts by weight of the thermoplastic resin.
  • the total amount of the phosphorus compound and neutralized thermally expandable graphite is 20 to 200 parts by weight
  • the inorganic filler is 50 to 500 parts by weight
  • the weight ratio of neutralized thermally expandable graphite: phosphorus compound is 9: 1 to 1: 100
  • the inorganic filler is a metal salt or oxide of a metal belonging to Group II or Group III of the Periodic Table. Yes.
  • the fire-resistant resin composition of Patent Document 1 contains many inorganic fillers that do not burn in order to impart fire resistance. For this reason, even if the fire resistance performance is good, the inorganic filler is in the form of a powder, so the bondability of the fire resistance resin composition containing the filler is impaired, and the sheet moldability or wrapping property of the fire resistance resin composition, etc. Workability is reduced. For example, if the refractory resin composition contains a large amount of powdered inorganic filler, it may be difficult to wind or crack when formed into a long sheet, Since it is easy to be cracked, wrinkled or marked, it may interfere with the installation work to building materials such as sashes.
  • An object of the present invention is to provide a fire resistant resin composition that improves workability and maintains fire resistance.
  • the present inventors have reduced the blending amount of the inorganic filler in the refractory resin composition and contained a phosphorus compound such as a phosphorus plasticizer, thereby achieving excellent fire resistance and work.
  • the inventors have found that both sexes can be obtained, and have completed the present invention.
  • a matrix that is a thermoplastic resin, an elastomer, a rubber, or a combination thereof contains a phosphorus compound and thermally expandable graphite, and the respective contents are the matrix 100.
  • a refractory resin composition characterized in that the total amount of the phosphorus compound and the thermally expandable graphite is 250 parts by weight or more with respect to parts by weight, and the inorganic filler is 0 to 50 parts by weight.
  • the molded product of the fire resistant resin composition exhibits excellent performance.
  • Excellent fire resistance can be given by covering or sticking to a building or the like.
  • the fireproof resin composition of the present invention contains a thermoplastic resin, elastomer, rubber, or a combination thereof (hereinafter referred to as “matrix”), a phosphorus compound, and thermally expandable graphite.
  • the thermoplastic resin is not particularly limited, and examples thereof include polyolefin resins such as polypropylene resins and polyethylene resins, poly (1-) butene resins, polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene resins, Examples include polycarbonate resins, polyphenylene ether resins, acrylic resins, polyamide resins, polyamideimide resins, polybutadiene resins, polyimide resins, polyvinyl chloride resins, polyvinyl acetate resins, and combinations thereof. . Of these, polyolefin resins, polyvinyl chloride resins, ethylene-polyvinyl acetate resins, and combinations thereof are preferable.
  • the polyolefin resin is preferably a polyethylene resin.
  • thermoplastic resins may be used after being crosslinked or modified as long as the fire resistance of the 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.
  • elastomer examples include olefin elastomers, styrene elastomers, ester elastomers, amide elastomers, vinyl chloride elastomers, and combinations thereof.
  • Examples of rubbers 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 (EPDM). , Urethane rubber, silicone rubber, fluororubber, and combinations thereof.
  • the matrix is a thermoplastic resin, preferably a polyethylene resin, polyvinyl chloride resin, ethylene-polyvinyl acetate resin (EVA), polystyrene, EPDM, or combinations thereof.
  • the matrix is a thermoplastic resin, preferably a polyethylene resin, a polyvinyl chloride resin, an ethylene-polyvinyl acetate resin, or a combination thereof. In this case, a fire resistant resin composition excellent in workability such as sheet formability or winding property is obtained.
  • the matrix used in the present invention contains a phosphorus compound and thermally expandable graphite.
  • the fire resistance performance of the fire resistant resin composition of the present invention is manifested by these two components exhibiting their respective properties.
  • the heat-expandable graphite forms an expanded heat insulating layer during heating to prevent heat transfer.
  • the phosphorus compound has shape retention ability in the expanded heat insulating layer and the filler.
  • the phosphorus compound is not particularly limited. For example, red phosphorus; various phosphate esters (excluding phosphate plasticizers); ammonium polyphosphates; melamine polyphosphates; metal phosphates; And a phosphoric acid plasticizer.
  • R1 and R3 each represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • R2 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 It represents 6 to 16 aryloxy groups.
  • red phosphorus commercially available red phosphorus can be used, but from the viewpoint of safety such as moisture resistance and not spontaneously igniting during kneading, it is preferable that the surface of the red phosphorus particles is coated with a resin.
  • the phosphate ester that is not a phosphate plasticizer is not particularly limited, but includes a phosphate ester in a liquid state when the resin composition is melt-kneaded.
  • ammonium polyphosphates include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and the like, and ammonium polyphosphate is preferred from the viewpoint of handleability.
  • Commercially available products include “AP422” and “AP462” manufactured by Hoechst, “Sumisafe P” manufactured by Sumitomo Chemical Co., Ltd., and “Terrage C60” manufactured by Chisso.
  • the content of ammonium polyphosphates is not particularly limited, but is preferably 30 to 200 parts by weight, and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the matrix.
  • the content of melamine polyphosphate is not particularly limited, but is preferably 30 to 200 parts by weight, and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the matrix.
  • metal phosphate examples include sodium phosphate, potassium phosphate, and magnesium phosphate.
  • Examples of the compound represented by the general formula (1) include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid.
  • Phosphate plasticizer is added to adjust the melt viscosity of a matrix such as a thermoplastic resin.
  • phosphoric acid series plasticizers include phosphate ester compounds such as tricresyl phosphate (TCP), cresyl diphenyl phosphate, trixylenyl phosphate, 2-ethylhexyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl phosphate, Aryl esters such as triphenyl phosphate; alkyl esters such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tris 2-ethylhexyl phosphate; resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate Bisphenol aromatic condensed phosphate esters such as bisphenol A bis-diphenyl phosphate; and combinations
  • the content of the phosphoric acid plasticizer is not particularly limited, but the total amount of the phosphoric acid plasticizer is preferably more than 0 and 200 parts by weight or less with respect to 100 parts by weight of the matrix, 25 to 150 parts by weight. It is more preferable that
  • the phosphorus compound includes at least one selected from the group consisting of ammonium polyphosphates; melamine polyphosphate; and a phosphate plasticizer.
  • the phosphorus compound is 30-200 parts by weight ammonium polyphosphates relative to 100 parts by weight of the matrix; 30-200 parts by weight melamine polyphosphate; and greater than 0 and less than or equal to 200 parts by weight.
  • a phosphate plasticizer at least one selected from the group consisting of;
  • the phosphate plasticizer is trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, aromatic condensed phosphate ester, tricresyl phosphate, triethyl phosphate, tributyl phosphate, Including tri-2-ethylhexyl phosphate, or combinations thereof.
  • An aromatic condensed phosphate is, for example, resorcinol bis-diphenyl phosphate. In this case, a fire resistant resin composition excellent in fire resistance, sheet formability, and workability can be obtained. *
  • the phosphorus compound includes only ammonium polyphosphates. In another embodiment, the phosphorus compound comprises ammonium polyphosphates that are 30 to 200 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the matrix.
  • the phosphorus compound includes ammonium polyphosphates and at least one selected from the group consisting of melamine polyphosphate and a phosphate plasticizer.
  • the phosphorous compound comprises 30 to 200 parts by weight of ammonium polyphosphates, 30 to 200 parts by weight of melamine polyphosphate and 100 to 200 parts by weight of polyphosphate.
  • a phosphate plasticizer at least one selected from the group consisting of:
  • the phosphate plasticizer is trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, aromatic condensed phosphate (eg resorcinol bis-diphenyl phosphate), tricresyl phosphate , Triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, or combinations thereof.
  • a fire resistant resin composition excellent in fire resistance, sheet formability, and workability can be obtained.
  • the phosphorus compound comprises ammonium polyphosphates and trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, condensed aromatic phosphate ester, tricresyl phosphate, or combinations thereof .
  • the phosphorus compound comprises 30 to 200 parts by weight of ammonium polyphosphates and 30 to 200 parts by weight of trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl phosphate with respect to 100 parts by weight of the matrix. Diphenyl, aromatic condensed phosphate, tricresyl phosphate, or combinations thereof. In this case, it is possible to obtain a fire-resistant resin composition that is excellent in fire resistance in terms of both expansion ratio and residual hardness and excellent in workability such as sheet formability or winding property.
  • the phosphorus compound includes an aryl ester. In another embodiment, 50 to 300 parts by weight of the aryl ester is included per 100 parts by weight of the matrix.
  • the aryl ester is tricresyl phosphate.
  • the refractory resin composition containing such aryl ester may contain ammonium polyphosphates, in which case the amount of ammonium polyphosphates is, for example, 30 to 200 parts by weight with respect to 100 parts by weight of the matrix.
  • the sheet formability includes the appearance of the sheet obtained in the coating process. Winding property is bent to the refractory resin composition of the present invention, including the presence or absence of folds, cracks, cracks and / or chips when the refractory resin composition of the present invention is wound or pasted on a curved surface. It refers to the ease of winding when the power is applied.
  • the heat-expandable graphite used in the present invention 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, and perchloric acid.
  • inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid, concentrated nitric acid, and perchloric acid.
  • a graphite intercalation compound produced by treatment with a strong oxidant such as perchlorate, permanganate, dichromate, hydrogen peroxide, etc., while maintaining the layered structure of carbon It is.
  • 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 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. If the particle size is finer than 200 mesh, the degree of expansion of graphite is small, the desired fireproof heat insulating layer cannot be obtained, and if the particle size is larger than 20 mesh, there is an effect in that the degree of swelling is large, but when kneading with the resin, Dispersibility is poor and physical properties are unavoidable.
  • the total amount of phosphorus compound and thermally expandable graphite is 250 parts by weight or more with respect to 100 parts by weight of the matrix.
  • the total amount of the phosphorus compound and the thermally expandable graphite is 250 parts by weight or more, sufficient fire resistance can be obtained.
  • the upper limit of the total amount of a phosphorus compound and thermally expansible graphite is not specifically limited, For example, it is 500 weight part or less. When the total amount of the phosphorus compound and the thermally expandable graphite is 500 parts by weight or less, sufficient mechanical properties are maintained.
  • thermally expandable graphite by combining thermally expandable graphite and a phosphorus compound, the dispersion of thermally expandable graphite at the time of combustion is suppressed and the shape is maintained. If there is too much thermally expandable graphite, the graphite expanded at the time of combustion However, it is preferable that the heat-expandable graphite and the phosphorous are not sufficiently obtained at the time of heating.
  • the range of thermally expandable graphite: phosphorus compound 5: 1 to 1:80 is excellent. Even if the composition itself is flame retardant, if the shape retentivity is insufficient, the brittle residue collapses and penetrates the flame, so depending on whether the shape retentivity is sufficient, the fire resistant composition The application forms are greatly different. More preferably, the heat-expandable graphite: phosphorus compound is in the range of 5: 1 to 1:50, particularly preferably 2: 1 to 1:20.
  • the fireproof resin composition of the present invention contains 0 to 50 parts by weight of an inorganic filler.
  • the thermally expandable graphite forms an expanded heat insulating layer during heating to prevent heat transfer, but the inorganic filler increases the heat capacity at that time.
  • Examples of the inorganic filler used in the present invention include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, Aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawn night, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite , Activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various Metal powder, potassium titanate, magnesium sulfate “MOS”, lead zirconate titanate, aluminum borate, molybdenum s
  • the inorganic filler functions as an aggregate, it is considered that it contributes to an improvement in residual strength and an increase in heat capacity.
  • the said inorganic filler may be used independently and 2 or more types may be used together.
  • the particle size of the inorganic filler is preferably 0.5 to 100 ⁇ m, more preferably 1 to 50 ⁇ m.
  • the inorganic filler having a small particle size is preferable because the dispersibility greatly affects the performance when the addition amount is small. However, if it is less than 0.5 ⁇ m, secondary aggregation occurs and the dispersibility is deteriorated.
  • the amount of the inorganic filler added is large, the viscosity of the resin composition increases and the moldability decreases as the high filling proceeds, but the viscosity of the resin composition can be decreased by increasing the particle size.
  • a particle having a large particle size is preferable in the above range. When the particle size exceeds 100 ⁇ m, the surface properties of the molded body and the mechanical properties of the resin composition are lowered.
  • water-containing inorganic substances such as magnesium hydroxide and aluminum hydroxide are endothermic due to the water generated by the dehydration reaction during heating, and the temperature rise is reduced and high heat resistance is obtained. And, an oxide remains as a heating residue, and this is particularly preferable in that the residue strength is improved by acting as an aggregate.
  • Magnesium hydroxide and aluminum hydroxide differ in the temperature range where the dehydration effect is exerted. Therefore, when used together, the temperature range where the dehydration effect is exhibited widens, and a more effective temperature rise suppressing effect can be obtained. preferable.
  • the particle size of the hydrated inorganic material When the particle size of the hydrated inorganic material is small, it becomes bulky and it is difficult to achieve high filling. Therefore, a large particle size is preferable for high filling in order to enhance the dehydration effect. Specifically, it is known that when the particle size is 18 ⁇ m, the filling limit amount is improved by about 1.5 times compared to the particle size of 1.5 ⁇ m. Further, by combining a large particle size and a small particle size, higher packing can be achieved.
  • inorganic fillers include, for example, as aluminum hydroxide, “H-42M” (made by Showa Denko) having a particle size of 1 ⁇ m, “H-31” (made by Showa Denko) having a particle size of 18 ⁇ m; calcium carbonate Examples thereof include “Whiteon SB red” (manufactured by Shiraishi Calcium Co., Ltd.) having a particle diameter of 1.8 ⁇ m, “BF300” (manufactured by Shiraishi Calcium Co., Ltd.) having a particle diameter of 8 ⁇ m, and the like.
  • the water-containing inorganic substance as the inorganic filler is advantageous in improving heat resistance because it has the property of dehydrating and absorbing heat when heated.
  • Specific examples include calcium hydroxide, magnesium hydroxide, and aluminum hydroxide. These may be used alone or in admixture of two or more.
  • the total amount of the phosphorus compound and the thermally expandable graphite is 250 parts by weight or more and the inorganic filler is 50 parts by weight or less with respect to 100 parts by weight of the matrix. If it exists, workability
  • the refractory resin composition of the present invention may further contain a phthalate ester plasticizer.
  • a phthalate ester plasticizer 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), phthalate esters of higher alcohols or mixed alcohols having about 10 to 13 carbon atoms, or combinations thereof.
  • DOP di-2-ethylhexyl phthalate
  • DINP di-n-octyl phthalate
  • DINP diisononyl phthalate
  • DIDP Diisodecyl phthalate
  • DUP diundecyl phthalate
  • the content of the phthalate ester plasticizer is not particularly limited, but is preferably 30 to 200 parts by weight, and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the matrix.
  • workability such as sheet formability or winding property of the refractory resin composition is improved.
  • antioxidants such as phenols, amines, and sulfurs, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, Lubricants, softeners, pigments and the like may be added.
  • the fire-resistant resin composition of the present invention can be obtained by kneading, coating, and if necessary, drying and curing processes.
  • a kneading apparatus such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, or a roll is used.
  • the fireproof resin composition of the present invention can be laminated on a substrate such as a nonwoven fabric.
  • the fire-resistant resin composition of the present invention can be used for imparting fire resistance to building materials.
  • windows including sliding windows, open windows, raising / lowering windows, etc.
  • shojis including sliding windows, open windows, raising / lowering windows, etc.
  • doors ie doors
  • doors ie doors
  • brans ie doors
  • balustrades fire-penetrating parts
  • joints By disposing a functional resin composition, it is possible to reduce or prevent fire and smoke intrusion.
  • this invention can also take the following structures.
  • a matrix that is a thermoplastic resin, an elastomer, rubber, or a combination thereof contains a phosphorus compound and thermally expandable graphite, and each content is phosphorus with respect to 100 parts by weight of the matrix.
  • the refractory resin composition according to (1), wherein the matrix preferably includes the thermoplastic resin that is a polyethylene resin, a polyvinyl chloride resin, an ethylene-polyvinyl acetate resin, polystyrene, EPDM, or a combination thereof. .
  • the fire resistant resin composition according to (1), wherein the matrix includes the thermoplastic resin which is a polyethylene resin, a polyvinyl chloride resin, an ethylene-polyvinyl acetate resin, or a combination thereof.
  • the phosphorus compound includes at least one selected from the group consisting of ammonium polyphosphates; melamine polyphosphate; and a phosphate plasticizer. object.
  • the refractory resin composition according to (5), wherein the content of ammonium polyphosphates is 30 to 200 parts by weight with respect to 100 parts by weight of the matrix.
  • the phosphorus compound includes a phosphoric acid plasticizer that is greater than 0 and less than or equal to 200 parts by weight with respect to 100 parts by weight of the matrix.
  • Phosphate plasticizers include trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, aromatic condensed phosphate ester, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2 phosphate
  • the fire resistant resin composition according to any one of (7) and (8), comprising ethylhexyl or a combination thereof.
  • the phosphate plasticizer includes trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, aromatic condensed phosphate ester, tricresyl phosphate, or combinations thereof (7) or (8 ).
  • the fireproof resin composition according to any one of the above.
  • the phosphorus compound includes ammonium polyphosphates in an amount of 30 to 200 parts by weight based on 100 parts by weight of the matrix; melamine polyphosphate in an amount of 30 to 200 parts by weight;
  • the fire-resistant resin composition according to any one of (1) to (11), which comprises at least one selected from the group consisting of acid plasticizers.
  • the phosphorus compound comprises 30 to 200 parts by weight of ammonium polyphosphates, 30 to 200 parts by weight of melamine polyphosphate, and phosphorus greater than 0 and less than or equal to 200 parts by weight with respect to 100 parts by weight of the matrix.
  • the phosphate plasticizer is 30 to 200 parts by weight of trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, aromatic condensed phosphate ester, tricresyl phosphate with respect to 100 parts by weight of the matrix.
  • the fireproof resin composition according to (15) which is a combination thereof.
  • the refractory resin composition according to any one of (1) to (22), wherein the weight ratio of the thermally expandable graphite to the phosphorus compound is 2: 1 to 1:20. .
  • VLDPE2 Very low density polyethylene
  • VLDPE3 Very low density polyethylene
  • MI 3.0 ultra low density polyethylene
  • VLDPE3 VLDPE3
  • density 0.910
  • neutralized thermally expandable graphite GREP-EG, manufactured by Tosoh Corporation
  • ammonium polyphosphate Sumisafe P, manufactured by Sumitomo Chemical Co., Ltd.
  • tricresyl phosphate (Sunsosizer TCP) New Nippon Rika Co., Ltd.)
  • magnesium hydroxide Karl-methyl methacrylate
  • the obtained resin composition was pressed at 140 ° C. to produce a molded body sheet used for fire resistance evaluation and workability evaluation.
  • Fire resistance evaluation expansion magnification
  • a test piece (length 100 mm, width 100 mm, thickness 2.0 mm) prepared from the obtained molded body was supplied to an electric furnace and heated at 600 ° C. for 30 minutes, and then the thickness of the test piece was measured ( The thickness of the test piece after heating) / (thickness of the test piece before heating) was calculated as the expansion ratio.
  • the heated test piece whose expansion ratio was measured was supplied to a compression tester (“Finger Filling Tester” manufactured by Kato Tech Co., Ltd.), compressed at a speed of 0.1 cm / sec with a 0.25 cm 2 indenter, and fractured. Point stress was measured.
  • the fire resistance was evaluated as follows.
  • Workability evaluation ⁇ Sheet formability> The appearance of the obtained sheet was visually observed and evaluated as follows.
  • Vinyl chloride resin manufactured by Tokuyama Sekisui Industry Co., Ltd.
  • DOP and DIDP manufactured by JPLUS
  • calcium carbonate BF300, manufactured by Shiraishi Calcium Co., Ltd.
  • melamine polyphosphate MPP-A, Tsubame Sanwa Chemical Co., Ltd.
  • aluminum hydroxide B703S, Nippon Light Metal Co., Ltd.
  • aromatic condensed phosphate ester resorcinol bis-diphenyl phosphate (CR-733S, Daihachi Chemical Industry Co., Ltd.) was used. Commercially available products were also used for other compounds.
  • DOP represents bis (2-ethylhexyl) phthalate
  • DIDP represents diisodecyl phthalate

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
PCT/JP2016/051929 2015-01-22 2016-01-22 耐火性樹脂組成物 WO2016117702A1 (ja)

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Cited By (11)

* Cited by examiner, † Cited by third party
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JP2018100410A (ja) * 2016-12-21 2018-06-28 積水化学工業株式会社 耐火性樹脂組成物
WO2018212337A1 (ja) * 2017-05-18 2018-11-22 積水化学工業株式会社 熱膨張性樹脂組成物及び建材用多層耐火成形体
JP2018199814A (ja) * 2016-12-19 2018-12-20 積水化学工業株式会社 耐火樹脂組成物及び耐火樹脂成形体
JP2019119859A (ja) * 2017-12-28 2019-07-22 積水化学工業株式会社 熱膨張性シート
JP2019167541A (ja) * 2016-10-24 2019-10-03 積水化学工業株式会社 熱膨張性耐火性シート
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