EP3594424B1 - Matériau de moulage d'article moulé multicolore ayant une excellente rigidité et une excellente résistance au feu - Google Patents
Matériau de moulage d'article moulé multicolore ayant une excellente rigidité et une excellente résistance au feu Download PDFInfo
- Publication number
- EP3594424B1 EP3594424B1 EP18763284.9A EP18763284A EP3594424B1 EP 3594424 B1 EP3594424 B1 EP 3594424B1 EP 18763284 A EP18763284 A EP 18763284A EP 3594424 B1 EP3594424 B1 EP 3594424B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fire
- molding material
- resin
- rubber
- resistant molding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920006285 olefinic elastomer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C2/00—Fire prevention or containment
- A62C2/06—Physical fire-barriers
- A62C2/065—Physical fire-barriers having as the main closure device materials, whose characteristics undergo an irreversible change under high temperatures, e.g. intumescent
-
- 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 fire-resistant molding material.
- Fireproof performance is one of the performances required for fittings, such as windows, shoji (paper sliding doors), tobira (i.e., doors), to (Japanese doors), fusuma (Japanese sliding screens), and ramma (transoms), used for the openings of structures, such as houses.
- fire-resistant molding materials are mounted in fittings.
- thermally expandable materials were conventionally mounted in the frames so as to prevent the penetration of flames.
- Patent Literature (PTL) 1 discloses a heat-resistant panel using a thermoplastic elastomer. However, since the material is flexible, such a panel cannot be used for parts requiring high rigidity.
- PTL 2 discloses a co-extruded thermally expandable multilayer packing for building material according to the preamble of claim 1.
- An object of the present invention is to provide a fire-resistant molding material having high rigidity and a high coefficient of thermal expansion.
- Co-extrusion which is a low-cost technique, is the most preferable option to produce a fire-resistant molding material integrally including a member requiring rigidity and a fire-resistant expansion part.
- highly rigid members generally require a high extrusion temperature, and at such a temperature, expansion parts start expanding, thus causing problems such as shape instability, poor appearance, and reduction in fire-resistant performance due to inactivation of expandable graphite.
- the present invention provides fire-resistant molding materials described below.
- a co-extruded fire-resistant molding material comprising a member A having a tensile elastic modulus rate of 600 MPa or more and a member B having a coefficient of expansion of 10 times or more, wherein the member A comprises a thermoplastic resin, the member B comprises a resin component, a thermally expandable graphite and an inorganic filler, the resin component including a thermoplastic resin and/or a rubber substance, the member B comprises 3 to 300 parts by mass of the thermally expandable graphite and 1 to 300 parts by mass of the inorganic filler based on 100 parts by mass of a resin component, the melt viscosity of the resin composition constituting the member B at a temperature of 160°C and a shear rate of 120 (1/s) is 1200 to 2500 Pa-s.
- the present invention provides a fire-resistant molding material integrally including a part having high rigidity and a thermal expansion part.
- a fire-resistant molding material of the present invention can be used for windows (including double sliding windows, casement windows, double hung windows, or the like), tobira (i.e., doors), to (Japanese doors), and like those requiring high rigidity.
- a member A provides the fire-resistant molding material with high rigidity and a member B provides the fire-resistant molding material with fire-resistance.
- the fire-resistant molding material of the present invention comprises a member A having a tensile elastic modulus rate of 600 MPa or more and a member B having a coefficient of expansion of 10 times or more.
- the member A and the member B are integrally formed.
- the tensile elastic modulus rate of the member A is 600 MPa or more, preferably 800 MPa or more, and more preferably 1000 MPa or more. Although the upper limit of the tensile elastic modulus rate of the member A is not particularly limited, it is 250000 MPa or less.
- the Rockwell hardness of the member A is preferably 70 or more, more preferably 75 or more, and even more preferably 80 or more. Although the upper limit of the Rockwell hardness of the member A is not particularly limited, it is 130 or less.
- the tensile yield strength of the member A is preferably 20 MPa or more, more preferably 25 MPa or more, and even more preferably 30 MPa or more. Although the tensile yield strength of the member A is not particularly limited, it is 3000 MPa or less.
- the "tensile elastic modulus rate” can be calculated as follows. A dumbbell-shaped specimen according to JIS K7161-2 is cut from the member A, and the dumbbell-shaped specimen is subjected to a tensile test according to JIS K7161-2. A stress-strain curve is drawn, and the tensile elastic modulus rate can be calculated according to formula (I) below based on the first linear part of the stress-strain curve.
- Em Tensile elastic modulus rate ⁇ ⁇ / ⁇ ⁇ N / mm 2
- ⁇ represents a difference in stress according to an original average cross-sectional area of two points on a straight line
- ⁇ represents a difference in strain between the same two points.
- the “tensile yield strength” can be measured according to JISK7161-2.
- the “Rockwell hardness” can be measured according to JISK7202-2.
- the coefficient of expansion of the member B of the present invention is 10 times or more, preferably 15 times or more, and more preferably 20 times or more. Although the upper limit of the coefficient of expansion of the member B is not particularly limited, it is 50 times or less.
- the residue hardness of the member B of the present invention is 0.3 kgf/cm 2 or more, preferably 0.4 kgf/cm 2 or more, and more preferably 0.5 kgf/cm 2 or more.
- the upper limit of the residue hardness of the member B is not particularly limited, it is 3.0 kgf/cm 2 or less.
- the material constituting the member A is a non-expandable resin comprising thermoplastic resin.
- the non-expandable resin is made of a thermoplastic resin, a thermosetting resin, an elastomer, rubber, or a combination thereof.
- a non-expandable resin containing a thermoplastic resin is preferred.
- thermoplastic resins include fluororesin, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polycarbonate, polyetherimide, polyetheretherketone, polyarylate, polyamide, polyamideimide, polybutadiene, polyimide, acrylic resin, polyacetal, polyamide, polyethylene, polyethylene terephthalate, polycarbonate, polyester, polystyrene, polyphenylene sulfide, polybutylene terephthalate, polypropylene, polyvinyl chloride, ABS resin, AS resin, and the like.
- thermosetting resins include epoxy resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethane, thermosetting polyimide, and the like.
- elastomers include olefin-based elastomers, styrene-based elastomers, ester-based elastomers, amide-based elastomers, vinyl chloride-based elastomers, 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, urethane rubber, silicone rubber, fluororubber, and the like.
- the member B is a resin composition containing a thermally expandable graphite, an inorganic filler and a resin component.
- thermoplastic resins thermosetting resins
- rubber substances thermosetting resins
- combinations thereof thermoplastic resins, thermosetting resins, rubber substances, and combinations thereof.
- thermoplastic resins include polyolefin resins, such as polypropylene resins, polyethylene resins, poly(1-)butene resins, and polypentene resins; and synthetic resins, such as polystyrene resins, acrylonitrile-butadienestyrene (ABS) resins, polycarbonate resins, polyphenylene ether resins, (meth)acryl-based resins, polyamide resins, polyvinyl chloride resins, novolac resins, polyurethane resins, polyisobutylene, and ethylene vinyl acetate resins.
- polyolefin resins such as polypropylene resins, polyethylene resins, poly(1-)butene resins, and polypentene resins
- synthetic resins such as polystyrene resins, acrylonitrile-butadienestyrene (ABS) resins, polycarbonate resins, polyphenylene ether resins, (meth)acryl-based resins
- thermosetting resins include synthetic resins, such as polyurethane, polyisocyanate, polyisocyanurate, phenol resins, epoxy resins, urea resins, melamine resins, unsaturated polyester resins, and polyimide.
- rubber substances include natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, highly vulcanized rubber, non-vulcanized rubber, silicone rubber, fluorine rubber, urethane rubber, thermoplastic olefinic elastomers (TPOs), and the like.
- natural rubber isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, highly vulcanized rubber, non-vulcanized rubber
- One or more kinds of these synthetic resins and/or rubber substances may be used.
- a flexible and rubbery substance is preferred.
- Resin components with such properties enable high filling of an inorganic filler, thereby obtaining a flexible and easily manageable resin composition.
- a non-vulcanized rubber such as butyl and a polyethylene-based resin are preferably used.
- an epoxy resin is preferred.
- the thermally expandable graphite is a conventionally known substance.
- the thermally expandable graphite is a graphite intercalation compound formed by treating a powder, such as natural flake graphite, pyrolytic graphite, or kish graphite, with an inorganic acid, such as concentrated sulfuric acid, nitric acid, or selenic acid, and with a strong oxidizing agent, such as concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, or hydrogen peroxide.
- the thermally expandable graphite is a kind of crystalline compound that retains the layered structure of the carbon.
- thermally expandable graphite obtained by acid treatment as described above may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like.
- thermally expandable graphite examples include "GREP-EG” produced by Tosoh Corporation, “GRAFGUARD” produced by GRAFTECH, and the like.
- the member B comprises 3 to 300 parts by mass of the thermally expandable graphite, based on 100 parts by mass of the resin component.
- the member B further comprises an inorganic filler.
- the inorganic filler contained therein increases heat capacity and suppresses heat transfer, and also functions as an aggregate, thereby improving the strength of the expandable heat insulating layer.
- inorganic fillers include, but are not particularly limited to, metal oxides, such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; hydrated inorganic substances, such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite; metal carbonates, such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate; and the like.
- examples of inorganic fillers also include calcium salts, such as calcium sulfate, gypsum fiber, and calcium silicate; silica, diatomaceous earth, dawsonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass bead, silica balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various types of metal powder, potassium titanate, magnesium sulfate, lead zirconate titanate, zinc stearate, calcium stearate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various types of magnetic powder, slag fiber, fly ash, dehydrated sludge, and the like.
- calcium salts such as calcium sulfate, g
- the resin composition constituting the member B comprises 1 to 300 parts by mass of the inorganic filler, based on 100 parts by mass of the resin component.
- the total amount of the thermally expandable graphite and the inorganic filler is preferably in the range of 3 to 300 parts by mass, based on 100 parts by mass of the resin component.
- the melt viscosity of the resin composition constituting the member B at a temperature of 160°C and a shear rate of 120 (1/s) is 1200 to 2500 Pa ⁇ s. Increasing the viscosity of the resin composition of the member B can suppress the expansion of the member B when the member A and the member B are co-extruded.
- This resin composition is expanded by heating and forms a fire-resistant heat-insulating layer.
- the fire-resistant molding material can be expanded by the heating of fire to obtain a necessary coefficient of cubical expansion.
- the expanded fire-resistant molding material can form a residue having predetermined heat-insulating capacity and predetermined strength, and can achieve stable fireproof performance.
- the resin composition that constitutes the fire-resistant molding material may optionally contain, in addition to the above components, the following components within a range that does not impair the object of the present invention: red phosphorus; various phosphates, such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl phosphate; metal salts of phosphoric acids, such as sodium phosphate, potassium phosphate, and magnesium phosphate; ammonium polyphosphates; phosphorus compounds, such as compounds represented by formula (1) below; and the like.
- red phosphorus such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl phosphate
- metal salts of phosphoric acids such as sodium phosphate, potassium phosphate, and magnesium
- R 1 and R 3 are the same or different, and each represents 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 represents 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 an aryloxy group having 6 to 16 carbon atoms.
- the resin composition constituting the fire-resistant molding material may optionally contain, within a range that does not impair the object of the present invention, an antioxidant, based on phenol, amine, sulfur, or the like, a metal deterioration inhibitor, an antistatic agent, a stabilizer, a crosslinking agent, a lubricant, a softening agent, a pigment, a tackifier resin, a molding auxiliary material, and like additives; a polybutene, a petroleum resin, and a like tackifier.
- an antioxidant based on phenol, amine, sulfur, or the like
- a metal deterioration inhibitor an antistatic agent, a stabilizer, a crosslinking agent, a lubricant, a softening agent, a pigment, a tackifier resin, a molding auxiliary material, and like additives
- an antioxidant based on phenol, amine, sulfur, or the like
- a metal deterioration inhibitor an antistatic agent, a stabilizer
- the member B is also commercially available.
- Examples include Fire Barrier produced by Sumitomo 3M (a fire-resistant molding material comprising a resin composition containing chloroprene rubber and vermiculite; coefficient of expansion: 3 times, heat conductivity: 0.20 kcal/m ⁇ h ⁇ °C), Mejihikatto produced by Mitsui Kinzoku Paints & Chemicals Co., Ltd. (a fire-resistant molding material comprising a resin composition containing a polyurethane resin and thermally expandable graphite; coefficient of expansion: 4 times, heat conductivity: 0.21 kcal/m ⁇ h ⁇ °C), Fi-Block produced by Sekisui Chemical Co., Ltd.; and the like.
- the fire-resistant molding material of the present invention may further comprise a coating layer.
- the coating layer may be made of any material that allows expansion of the member B upon heating. Combustible materials and noncombustible materials can be used. When the coating layer is made of a combustible material, the member B can be more easily expanded, and predetermined fireproof performance can be well exhibited.
- the coating layer may be disposed so that it is in contact with the member B and/or member A.
- thermoplastic resin examples include fluororesin, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polycarbonate, polyetherimide, polyetheretherketone, polyarylate, polyamide, polyamideimide, polybutadiene, polyimide, acrylic resin, polyacetal, polyamide, polyethylene, polyethylene terephthalate, polycarbonate, polyester, polystyrene, polyphenylene sulfide, polybutylene terephthalate, polypropylene, polyvinyl chloride, ABS resin, AS resin, and the like.
- elastomers include olefin-based elastomers, styrene-based elastomers, ester-based elastomers, amide-based elastomers, vinyl chloride-based elastomers, and the like.
- 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, urethane rubber, silicone rubber, fluororubber, and the like.
- the thickness of the coating layer made of a thermoplastic resin, an elastomer, rubber, or a combination thereof is not particularly limited, but is generally 0.5 to 6 mm.
- the coating layer may be made of metal, a metal alloy, or a combination of metal and a combustible material mentioned above.
- the coating layer may have any appearance, and the color and pattern can be determined depending on the purpose.
- the color of the coating layer is similar to the color of a frame of the fitting to which the fire-resistant molding material is attached.
- the color of the coating layer can be aluminum color.
- similar color means that, among the three elements represented by the characteristics of color, i.e., hue, brightness, and saturation, the hue is the same or similar. Specifically, warm colors, cold colors, white and opaque white, transparent and semi-transparent colors, or the like can be specified as similar colors.
- designability can be imparted to the coating layer by forming any pattern, such as a wood grain pattern to give visual warmth.
- the designability of the member B having black ash color can be increased by coating the member B with the coating layer.
- coating with the coating layer enhances the weather resistance of the member B, and also increases the long-term durability of the fire-resistant molding material.
- the kneaded product of resin compositions individually constituting the member A and the member B can be obtained by mixing and kneading the above components by using a known kneading apparatus, such as an extruder, a Banbury mixer, a kneader mixer, or a kneading roll (and further a Raikai mixer, a planetary stirrer, or the like in the case of a thermosetting resin, such as an epoxy resin).
- a known kneading apparatus such as an extruder, a Banbury mixer, a kneader mixer, or a kneading roll (and further a Raikai mixer, a planetary stirrer, or the like in the case of a thermosetting resin, such as an epoxy resin).
- the kneaded product may be produced by separately producing kneaded products of each of the two components and a filler by a kneading method mentioned above, supplying each kneaded product by a plunger pump, a snake pump, a gear pump, or the like, and mixing them by a static mixer, a dynamic mixer, or the like.
- the above kneaded product can be molded by a known method, such as press molding, calender molding, extrusion molding, or injection molding.
- a known method can be suitably used depending on the shape, such as roll molding of a sheet molding compound (SMC), coater molding by a roll coater or a blade coater.
- SMC sheet molding compound
- the member A and the member B are co-extruded.
- the thickness of the member B is not limited, but is preferably 0.1 to 6 mm. When the thickness of the member B is 0.1 mm or more, sufficient fireproof performance can be exhibited due to the thickness of the expandable heat-insulating layer formed by heating. Moreover, when the thickness of the member B is 6 mm or less, insertion into the hollow can be easy.
- the fire-resistant molding material of the present invention can be mounted in fittings, such as windows, shoji (paper sliding doors), tobira (i.e., doors), to (Japanese doors), fusuma (Japanese sliding screens), and ramma (transoms), used for the openings of structures, such as houses and buildings.
- the fire-resistant molding material of the present invention can be also used in shoji frames or frames of resin sashes.
- the fire-resistant molding material according to one embodiment of the present invention is explained with reference to Fig. 1 .
- the fire-resistant molding material 1 includes the member A having a tensile elastic modulus rate of 600 MPa or more and the member B having a coefficient of expansion of 10 times or more.
- the member A and the member B are integrally molded in a sheet form.
- the upper end of the frame 2 is provided with a pair of opposite rail-like raised portions 2a and 2b extending along the longitudinal direction of the frame 2.
- the raised portions 2a and 2b, and the two projections 3 have an approximately L-shaped cross-section in the longitudinal direction of the fire-resistant molding material 1.
- Each of the raised portions 2a and 2b is individually engaged with corresponding one of the two projections 3.
- Figs. 2 and 3 each show another embodiment of the heat-resistant material of the present invention.
- Fig. 2 shows a glazing-channel-type construction gasket 30 that is mounted in the periphery of a glass panel 38 (refer to Fig. 3).
- Fig. 3 is a sectional view describing a state in which the gasket 30 of Fig. 2 is used in the glass panel.
- the gasket 30 comprises a bottom wall 32 oppositely facing an end surface 39 of the glass panel 38, and side walls 33 that are continuously formed with the bottom wall 32 at both sides of the bottom wall 32 and that cover the glass panel periphery 40 along the longitudinal direction of the glass panel end surface 39.
- the bottom wall 32 and side walls 33 form the main body 31 of the gasket 30.
- the main body 31 is made of the member A.
- a protrusion 34 is formed on the upper end of each side wall 33.
- Each protrusion 34 has an outside fillet 35 and an inside fillet 36 that are projected toward the inside, i.e., the side of the glass panel 38.
- Each protrusion 34 includes a groove 37 outside, i.e., a side opposite to the glass panel side. By inserting the ends of a sash in the grooves 37, the gasket 30 can be secured to the sash.
- the protrusions 34 are constituted of the member B.
- the gasket 30 can be molded by co-extrusion of the main body 31 and the protrusions 34.
- a resin composition containing components of member A in amounts (parts by mass) shown in Table 1 and a resin composition containing components of member B in amounts (parts by mass) shown in Table 2 were mixed and kneaded, followed by co-extrusion to obtain a sheet-like fire-resistant molding material.
- the melt viscosity, tensile elastic modulus rate, Rockwell hardness, tensile yield strength, coefficient of expansion, and residue hardness were measured under the measurement conditions described in Tables 3, 4, or 5. Measurement conditions for the coefficient of expansion and residue hardness are described in Items (i) and (ii) below. Tables 3, 4, and 5 show the results.
- the residue was compressed with an indenter having an area of 0.25 cm 2 at a compression speed of 0.1 cm/min by using a tensile tester (Tensilon RTC, Orientec Corporation).
- the maximum load point that appeared first was defined as the residue hardness.
- Example 1 Material name Manufacturer and product name
- Example 2 Example 3 Polyvinyl chloride Shin-Etsu Chemical Co., Ltd., TK-800 100 100 100 Epoxy soybean oil ADEKA Corporation, O-130P 0 20 0 Calcium carbonate Shiraishi Calcium Kaisha, Ltd., Whiton B 15 15 15 Ca-Zn heat stabilizer Mizusawa Industrial Chemical Ltd., NT-231 3 3 Calcium stearate Sakai Chemical Industry Co., Ltd., SC-100 5 5 5 5 5 Polymethyl methacrylate Mitsubishi Rayon Co., Ltd., P-530A 0.5 0.5 0.5 Table 2
- Example 2 Example 3 Chlorinated vinyl chloride Tokuyama Sekisui Co., Ltd., HA53K 100 100 100 DIDP J-PLUS Co., Ltd.
- a resin composition containing components of member A in amounts (parts by mass) shown in Table 6 or 8 and a resin composition containing components of member B in amounts (parts by mass) shown in Table 7 or 9 were mixed and kneaded, followed by co-extrusion to obtain a sheet-like fire-resistant molding material.
- the melt viscosity, tensile elastic modulus rate, Rockwell hardness, tensile yield strength, coefficient of expansion, and residue hardness were measured under the measurement conditions described in Table 10 or 11. Measurement conditions for the coefficient of expansion and residue hardness are the same as those described in Items (i) and (ii) above. Tables 10 and 11 show the results.
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- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Building Environments (AREA)
- Special Wing (AREA)
Claims (4)
- Matériau de moulage résistant au feu, coextrudé, comportant un élément A ayant un module d'élasticité en traction de 600 MPa ou plus et un élément B ayant un coefficient de dilatation de 10 fois ou plus, dans lequell'élément A comporte une résine thermoplastique,l'élément B comporte un composant de résine, un graphite thermiquement extensible et une charge inorganique, le composant de résine incluant une résine thermoplastique et/ou une substance à base de caoutchouc,l'élément B comporte 3 à 300 parties en masse du graphique thermiquement extensible et 1 à 300 parties en masse de la charge inorganique sur la base de 100 parties en masse d'un composant de résine, caractérisé en ce que la viscosité à l'état fondu de la composition de résine constituant l'élément B à une température de 160 °C et une vitesse de cisaillement de 120 (1/s) est de 1200 à 2500 Pa·s.
- Matériau de moulage résistant au feu selon la revendication 1, dans lequel l'élément A a une limite d'élasticité en traction de 20 MPa ou plus.
- Matériau de moulage résistant au feu selon la revendication 1 ou 2, dans lequel la résine thermoplastique de l'élément A comporte un polychlorure de vinyle.
- Matériau de moulage résistant au feu selon l'une quelconque des revendications 1 à 3, dans lequel l'élément B a une dureté de résidu de 0,3 kgf/cm2 ou plus.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017042157 | 2017-03-06 | ||
PCT/JP2018/008488 WO2018164095A1 (fr) | 2017-03-06 | 2018-03-06 | Matériau de moulage d'article moulé multicolore ayant une excellente rigidité et une excellente résistance au feu |
Publications (3)
Publication Number | Publication Date |
---|---|
EP3594424A1 EP3594424A1 (fr) | 2020-01-15 |
EP3594424A4 EP3594424A4 (fr) | 2020-12-02 |
EP3594424B1 true EP3594424B1 (fr) | 2022-12-28 |
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ID=63448627
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP18763284.9A Active EP3594424B1 (fr) | 2017-03-06 | 2018-03-06 | Matériau de moulage d'article moulé multicolore ayant une excellente rigidité et une excellente résistance au feu |
Country Status (3)
Country | Link |
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EP (1) | EP3594424B1 (fr) |
JP (1) | JP6748194B2 (fr) |
WO (1) | WO2018164095A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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PT3698852T (pt) * | 2019-02-19 | 2024-01-04 | Dallmer Gmbh & Co Kg | Dispositivo de protecção contra incêndios |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3813955B2 (ja) | 2003-09-02 | 2006-08-23 | 電気化学工業株式会社 | 防火用パネル |
WO2013080562A1 (fr) * | 2011-11-29 | 2013-06-06 | 積水化学工業株式会社 | Emballage thermo-expansible à couches multiples pour des matériaux de construction |
JP6147101B2 (ja) * | 2013-01-22 | 2017-06-14 | 積水化学工業株式会社 | 熱膨張性耐火樹脂組成物 |
JP6023652B2 (ja) * | 2013-05-13 | 2016-11-09 | 三協立山株式会社 | 上げ下げ窓 |
US20170253716A1 (en) * | 2014-08-27 | 2017-09-07 | Sekisui Chemical Co., Ltd. | Resin composition |
JP6145198B2 (ja) * | 2015-06-19 | 2017-06-07 | 積水化学工業株式会社 | 耐火樹脂成形体およびそれを備えた建具 |
-
2018
- 2018-03-06 EP EP18763284.9A patent/EP3594424B1/fr active Active
- 2018-03-06 WO PCT/JP2018/008488 patent/WO2018164095A1/fr unknown
- 2018-03-06 JP JP2018513027A patent/JP6748194B2/ja active Active
Also Published As
Publication number | Publication date |
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JP6748194B2 (ja) | 2020-08-26 |
JPWO2018164095A1 (ja) | 2019-03-14 |
EP3594424A1 (fr) | 2020-01-15 |
EP3594424A4 (fr) | 2020-12-02 |
WO2018164095A1 (fr) | 2018-09-13 |
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