EP3594424A1 - Multicolor molded article molding material with excellent rigidity and fire resistance - Google Patents
Multicolor molded article molding material with excellent rigidity and fire resistance Download PDFInfo
- Publication number
- EP3594424A1 EP3594424A1 EP18763284.9A EP18763284A EP3594424A1 EP 3594424 A1 EP3594424 A1 EP 3594424A1 EP 18763284 A EP18763284 A EP 18763284A EP 3594424 A1 EP3594424 A1 EP 3594424A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fire
- molding material
- resistant molding
- rubber
- resin
- 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.)
- Granted
Links
- 239000012778 molding material Substances 0.000 title claims abstract description 52
- 230000009970 fire resistant effect Effects 0.000 claims abstract description 55
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000010439 graphite Substances 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 description 23
- 239000011342 resin composition Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- -1 polyethylene Polymers 0.000 description 14
- 239000011247 coating layer Substances 0.000 description 13
- 239000000806 elastomer Substances 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- 239000011256 inorganic filler Substances 0.000 description 9
- 229910003475 inorganic filler Inorganic materials 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
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- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 229920002379 silicone rubber Polymers 0.000 description 5
- 239000004945 silicone rubber Substances 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229920001084 poly(chloroprene) Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 241000167562 Pittosporum tobira Species 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 229920006311 Urethane elastomer Polymers 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003677 Sheet moulding compound Substances 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 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
- 239000006229 carbon black Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000565357 Fraxinus nigra Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000008932 jinhong Substances 0.000 description 1
- 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
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
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- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 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
- 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.
- 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.
- 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 may be, for example, metal, a non-expandable resin, or a composite material thereof, and is preferably a non-expandable 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 as 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 may comprise 3 to 30 parts by mass of the thermally expandable graphite, based on 100 parts by mass of the resin component.
- the member B may further comprise 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 may comprise 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 preferably 1000 to 2500 Pa ⁇ s, and more preferably 1200 to 2100 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 production method of the fire-resistant molding material 1 is not particularly limited.
- the member A and the member B may be co-extruded, or integrally bound to each other using an adhesion means, such as an adhesion sheet or adhesive.
- the member A and the member B may be integrally bound by physical securing.
- the member A and the member B are preferably 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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Abstract
Description
- 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. In order to enhance fireproof performance, fire-resistant molding materials are mounted in fittings. In the frames of fittings placed in openings of structures, 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 1: Patent No.
3813955 - As fire-resistant molding materials having fire-resistant functions, flexible materials that easily conform to the deformation have been used in many cases so as to increase the airtightness and/or water tightness of openings. However, such materials are not applicable to parts requiring rigidity.
- 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. However, 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.
- According to the present invention, it was found that the above problems can be solved by increasing the viscosity of an expansion part to suppress the expansion of expandable graphite. Specifically, increase in the viscosity of the expansion part allows co-extrusion, which makes it possible to produce fire-resistant molding materials having excellent rigidity. Co-extrusion also enables the production of a fire-resistant molding material without an adhesive layer or an adhesion step.
- The present invention provides fire-resistant molding materials described below.
-
Item 1. A 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. -
Item 2. The fire-resistant molding material according toItem 1, wherein the member A has a Rockwell hardness of 70 or more. -
Item 3. The fire-resistant molding material according toItem - Item 4. The fire-resistant molding material according to any one of
Items 1 to 3, wherein the member A comprises a thermoplastic resin. - Item 5. The fire-resistant molding material according to any one of
Items 1 to 4, wherein the member B has a residue hardness of 0.3 kgf/cm2 or more. - Item 6. The fire-resistant molding material according to any one of
Items 1 to 5, wherein the member B comprises 3 to 300 parts by mass of a thermally expandable graphite based on 100 parts by mass of a resin component. - Item 7. The fire-resistant molding material according to any one of
Items 1 to 6, which is produced by co-extrusion. - The present invention provides a fire-resistant molding material integrally including a part having high rigidity and a thermal expansion part.
-
-
Fig. 1 is a sectional view of a fire-resistant molding material according to one embodiment of the present invention. -
Fig. 2 is a perspective view showing another example of a molded article according to the present invention. -
Fig. 3 is a partial sectional view showing a state in which the molded article ofFig. 2 is used. - 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.
- In formula (I), Δσ represents a difference in stress according to an original average cross-sectional area of two points on a straight line, and Δε 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/cm2 or more, preferably 0.4 kgf/cm2 or more, and more preferably 0.5 kgf/cm2 or more. Although the upper limit of the residue hardness of the member B is not particularly limited, it is 3.0 kgf/cm2 or less.
- The material constituting the member A may be, for example, metal, a non-expandable resin, or a composite material thereof, and is preferably a non-expandable 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. Examples of 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. Examples of thermosetting resins include epoxy resins, phenol resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethane, thermosetting polyimide, and the like. Examples of 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.
- In a preferable embodiment of the present invention, the member B is a resin composition containing a thermally expandable graphite as a resin component.
- A wide range of known resin components may be used as the resin component. Examples include thermoplastic resins, thermosetting resins, rubber substances, and combinations thereof.
- Examples of 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.
- Examples of thermosetting resins include synthetic resins, such as polyurethane, polyisocyanate, polyisocyanurate, phenol resins, epoxy resins, urea resins, melamine resins, unsaturated polyester resins, and polyimide.
- Examples of 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.
- One or more kinds of these synthetic resins and/or rubber substances may be used.
- Among these synthetic resins and/or rubber substances, 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. To obtain a more flexible and easily manageable resin composition, a non-vulcanized rubber such as butyl and a polyethylene-based resin are preferably used.
- In terms of improving the fireproof performance by increasing the flame retardancy of the resin itself, 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.
- The 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. Examples of commercially available products of thermally expandable graphite include "GREP-EG" produced by Tosoh Corporation, "GRAFGUARD" produced by GRAFTECH, and the like.
- For example, the member B may comprise 3 to 30 parts by mass of the thermally expandable graphite, based on 100 parts by mass of the resin component. The member B may further comprise an inorganic filler.
- When an expandable heat insulating layer is formed, 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. Examples of 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.
- In addition to the above, 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. These inorganic fillers may be used singly, or in a combination of two or more.
- The resin composition constituting the member B may comprise 1 to 300 parts by mass of the inorganic filler, based on 100 parts by mass of the resin component.
- When the member B contains the inorganic filler, 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 preferably 1000 to 2500 Pa·s, and more preferably 1200 to 2100 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. According to this formulation, 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.
- In order to increase the strength of the expandable heat-insulating layer and to enhance the 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.
- In formula (1), R1 and R3 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. R2 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.
- Furthermore, 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.
- 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.
- When the fire-resistant molding material comprises a coating layer, the coating layer may be disposed so that it is in contact with the member B and/or member A.
- Although the combustible material is not particularly limited, it is preferable to use a thermoplastic resin, an elastomer, rubber, or a combination thereof. Examples of 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. Examples of 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 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.
- Moreover, 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. In one embodiment, 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. For example, when the fire-
resistant molding material 1 is attached to an aluminum window frame, the color of the coating layer can be aluminum color. The term "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. Moreover, designability can be imparted to the coating layer by forming any pattern, such as a wood grain pattern to give visual warmth. Thus, the designability of the member B having black ash color can be increased by coating the member B with the coating layer. Furthermore, 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). Moreover, in the case of a two-component thermosetting resin, particularly 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.
- As the method for molding resin compositions individually constituting the member A and the member B, the above kneaded product can be molded by a known method, such as press molding, calender molding, extrusion molding, or injection molding. Moreover, as the method for molding a two-component thermosetting resin, particularly an epoxy resin, 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.
- The production method of the fire-
resistant molding material 1 is not particularly limited. The member A and the member B may be co-extruded, or integrally bound to each other using an adhesion means, such as an adhesion sheet or adhesive. Alternatively, the member A and the member B may be integrally bound by physical securing. The member A and the member B are preferably 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 . - As shown in
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 raisedportions frame 2. The raisedportions projections 3, have an approximately L-shaped cross-section in the longitudinal direction of the fire-resistant molding material 1. Each of the raisedportions projections 3. -
Figs. 2 and3 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 toFig. 3). Fig. 3 is a sectional view describing a state in which thegasket 30 ofFig. 2 is used in the glass panel. - The
gasket 30 comprises abottom wall 32 oppositely facing anend surface 39 of theglass panel 38, andside walls 33 that are continuously formed with thebottom wall 32 at both sides of thebottom wall 32 and that cover theglass panel periphery 40 along the longitudinal direction of the glasspanel end surface 39. Thebottom wall 32 andside walls 33 form themain body 31 of thegasket 30. Themain body 31 is made of the member A. - A
protrusion 34 is formed on the upper end of eachside wall 33. Eachprotrusion 34 has anoutside fillet 35 and aninside fillet 36 that are projected toward the inside, i.e., the side of theglass panel 38. - Each
protrusion 34 includes agroove 37 outside, i.e., a side opposite to the glass panel side. By inserting the ends of a sash in thegrooves 37, thegasket 30 can be secured to the sash. Theprotrusions 34 are constituted of the member B. Thegasket 30 can be molded by co-extrusion of themain body 31 and theprotrusions 34. - The present invention is explained in detail below with reference to the Examples. The present invention is not limited to these Examples.
- 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. For the obtained 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.
- A sample immersed in a wire sieve with 200 mesh was placed in a box frame made of SUS. The box frame was placed in an electric furnace that had been heated beforehand at 600°C, and was heated for 30 minutes. The residue thickness of the extracted sample was measured with a caliper, and the coefficient of expansion was calculated according to the following formula:
- After the measurement of the coefficient of expansion, the residue was compressed with an indenter having an area of 0.25 cm2 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.
Table 1 Material name Manufacturer and product name Example 1 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 3 Calcium stearate Sakai Chemical Industry Co., Ltd., SC-100 5 5 5 Polymethyl methacrylate Mitsubishi Rayon Co., Ltd., P-530A 0.5 0.5 0.5 Table 2 Example 1 Example 2 Example 3 Chlorinated vinyl chloride Tokuyama Sekisui Co., Ltd., HA53K 100 100 100 DIDP J-PLUS Co., Ltd. 55 55 70 Expanded graphite Tosoh Corporation, GREP-EG 145 110 150 Calcium carbonate Shiraishi Calcium Kaisha, Ltd., Whiton BF300 15 50 15 Chlorinated polyethylene Weihai Jinhong Chemical Industry Co., Ltd., 135A 20 20 20 Ca-Zn heat stabilizer Mizusawa Industrial Chemicals, Ltd., NT-231 3 3 3 Calcium stearate Sakai Chemical Industry Co., Ltd., SC-100 5 5 5 Polymethyl methacrylate Mitsubishi Rayon Co., Ltd., P-530A 20 20 20 DIDP: Diisodecyl phthalate Table 3 Example 1 Measurement conditions Member A, rigid part Member B, expansion part Determination Melt viscosity Pa·s Capillary type rheometer 160°C, 120(1/s) (2310) 1980 A Tensile elastic modulus rate MPa JISK7161-2 1590 - A Rockwell hardness - JISK7202-2 94 - A Tensile yield strength MPa JISK7161-2 41.5 - A Coefficient of expansion Times 600°C, 30 min. - 57 A Residue hardness kgf/cm2 600°C, 30 min. - 0.60 A Appearance of member B: Excellent Table 4 Example 2 Measurement conditions Member A, rigid part Member B, expansion part Determination Melt viscosity Pa·s Capillary-type rheometer 160°C, 120(1/s) (1810) 2010 A Tensile elastic modulus rate MPa JISK7161-2 1100 - A Rockwell hardness - JISK7202-2 80 - A Tensile yield strength MPa JISK7161-2 26.5 - A Coefficient of expansion Times 600°C, 30 min. - 44 A Residue hardness kgf/cm2 600°C, 30 min. - 0.78 A Appearance of member B: Excellent Table 5 Example 3 Measurement conditions Member A, rigid part Member B, expansion part Determination Melt viscosity Pa·s Capillary-type rheometer 160°C, 120(1/s) (2310) 1439 A Tensile elastic modulus rate MPa JISK7161-2 1100 - A Rockwell hardness - JISK7202-2 80 - A Tensile yield strength MPa JISK7161-2 26.5 - A Coefficient of expansion Times 600°C, 30 min. - 56 A Residue hardness kgf/cm2 600°C, 30 min. - 0.62 A Appearance of member B: Excellent - Because the member B had high melt viscosity, expansion was suppressed, and appearance was excellent. The "determination" criteria of Tables 3, 4, 5, 10, and 11 are shown below.
- A: Excellent
- B: Poor
- 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. For the obtained 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.
Table 6 Material name Manufacturer and product name Example 4 Polyvinyl chloride Shin-Etsu Chemical Co., Ltd., TK-800 100 Epoxy soybean oil ADEKA Corporation, O-130P 0 Calcium carbonate Shiraishi Calcium Kaisha, Ltd., Whiton B 15 Ca-Zn heat stabilizer Mizusawa Industrial Chemicals, Ltd., NT-231 3 Calcium stearate Sakai Chemical Industry Co., Ltd., SC-100 5 Polymethyl methacrylate Mitsubishi Rayon Co., Ltd., P-530A 0.5 Table 7 Manufacturer and product name Example 4 Ethylene vinyl acetate resin Mitsubishi Chemical Corporation., UF420 100 Aluminum phosphite Taihei Chemical Industrial Co., Ltd., APA100 50 Expandable graphite Air Water Inc., CA-60N 40 Calcium carbonate Shiraishi Calcium Kaisha, Ltd., Whiton BF300 15 PTFE-based auxiliary agent Mitsubishi Chemical Corporation., A-3000 2 Table 8 Material name Manufacturer and product name Example 5 Polypropylene Novatec EA9 100 Hindered phenol-based ADEKA Corporation, AO60 0.3 Calcium carbonate Shiraishi Calcium Kaisha, Ltd., Whiton B 15 Phosphoric acid amine salt ADEKA Corporation, T1063F 30 Table 9 Manufacturer and product name Example 5 TPO Sumitomo Chemical Co., Ltd., Esporex 822 100 Aluminum phosphite Taihei Chemical Industrial Co., Ltd, APA100 50 Expandable graphite Air Water Inc., CA-60N 40 Carbon black Asahi Carbon Co., Ltd., #55G 15 PTFE-based auxiliary agent Mitsubishi Chemical Corporation., A-3000 2 Table 10 Example 4 Measurement conditions Member A, rigid part Member B, expansion part Determination Melt viscosity Pa·s Capillary-type rheometer 195°C, 120(1/s) (2280) 1422 A Tensile elastic modulus rate MPa JISK7161-2 1590 - A Rockwell hardness - JISK7202-2 94 - A Tensile yield strength MPa JISK7161-2 41.5 - A Coefficient of expansion Times 600°C, 30 min. - 18 A Residue hardness kgf/cm2 600°C, 30 min. - 0.38 A Appearance of member B: Excellent Table 11 Example 5 Measurement conditions Member A, rigid part Member B, expansion part Determination Melt viscosity Pa·s Capillary-type rheometer 195°C, 120(1/s) (1632) 1474 A Tensile elastic modulus rate MPa JISK7161-2 1250 - A Rockwell hardness - JISK7202-2 95 - A Tensile yield strength MPa JISK7161-2 35 - A Coefficient of expansion Times 600°C, 30 min. - 17 A Residue hardness kgf/cm2 600°C, 30 min. - 0.42 A Appearance of member B: Excellent -
- 1.
- Fire-resistant molding material
- 2.
- Frame
- 2a.
- Raised portion
- 2b.
- Raised portion
- 3.
- Projection
- 30.
- Gasket
- 31.
- Main body
- 32.
- Bottom wall
- 33.
- Side wall
- 34.
- Protrusion
- 35.
- Outside fillet
- 36.
- Inside fillet
- 37.
- Groove
- 38.
- Glass panel
- 39.
- Glass panel end surface
- 40.
- Glass panel periphery
Claims (7)
- A 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.
- The fire-resistant molding material according to claim 1, wherein the member A has a Rockwell hardness of 70 or more.
- The fire-resistant molding material according to claim 1 or 2, wherein the member A has a tensile yield strength of 20 MPa or more.
- The fire-resistant molding material according to any one of claims 1 to 3, wherein the member A comprises a thermoplastic resin.
- The fire-resistant molding material according to any one of claims 1 to 4, wherein the member B has a residue hardness of 0.3 kgf/cm2 or more.
- The fire-resistant molding material according to any one of claims 1 to 5, wherein the member B comprises 3 to 300 parts by mass of a thermally expandable graphite based on 100 parts by mass of a resin component.
- The fire-resistant molding material according to any one of claims 1 to 6, which is produced by co-extrusion.
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JP2017042157 | 2017-03-06 | ||
PCT/JP2018/008488 WO2018164095A1 (en) | 2017-03-06 | 2018-03-06 | Multicolor molded article molding material with excellent rigidity and fire resistance |
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Publication Number | Publication Date |
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EP3594424A1 true EP3594424A1 (en) | 2020-01-15 |
EP3594424A4 EP3594424A4 (en) | 2020-12-02 |
EP3594424B1 EP3594424B1 (en) | 2022-12-28 |
Family
ID=63448627
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18763284.9A Active EP3594424B1 (en) | 2017-03-06 | 2018-03-06 | Multicolor molded article molding material with excellent rigidity and fire resistance |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3594424B1 (en) |
JP (1) | JP6748194B2 (en) |
WO (1) | WO2018164095A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3698852B1 (en) * | 2019-02-19 | 2023-11-01 | Dallmer GmbH & Co. KG | Fire protection device |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3813955B2 (en) | 2003-09-02 | 2006-08-23 | 電気化学工業株式会社 | Fire protection panel |
WO2013080562A1 (en) * | 2011-11-29 | 2013-06-06 | 積水化学工業株式会社 | Thermally expandable multilayer packing for building material |
JP6147101B2 (en) * | 2013-01-22 | 2017-06-14 | 積水化学工業株式会社 | Thermally expandable refractory resin composition |
JP6023652B2 (en) * | 2013-05-13 | 2016-11-09 | 三協立山株式会社 | Raising and lowering window |
WO2016031905A1 (en) * | 2014-08-27 | 2016-03-03 | 積水化学工業株式会社 | Resin composition |
JP6145198B2 (en) * | 2015-06-19 | 2017-06-07 | 積水化学工業株式会社 | Fireproof resin molded body and joinery provided with the same |
-
2018
- 2018-03-06 EP EP18763284.9A patent/EP3594424B1/en active Active
- 2018-03-06 WO PCT/JP2018/008488 patent/WO2018164095A1/en unknown
- 2018-03-06 JP JP2018513027A patent/JP6748194B2/en active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3698852B1 (en) * | 2019-02-19 | 2023-11-01 | Dallmer GmbH & Co. KG | Fire protection device |
Also Published As
Publication number | Publication date |
---|---|
JP6748194B2 (en) | 2020-08-26 |
WO2018164095A1 (en) | 2018-09-13 |
EP3594424A4 (en) | 2020-12-02 |
JPWO2018164095A1 (en) | 2019-03-14 |
EP3594424B1 (en) | 2022-12-28 |
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