JP4270470B1 - Fireproof coating material, method for producing the fireproof coating material, and fireproof coating method using the fireproof coating material - Google Patents
Fireproof coating material, method for producing the fireproof coating material, and fireproof coating method using the fireproof coating material Download PDFInfo
- Publication number
- JP4270470B1 JP4270470B1 JP2007317718A JP2007317718A JP4270470B1 JP 4270470 B1 JP4270470 B1 JP 4270470B1 JP 2007317718 A JP2007317718 A JP 2007317718A JP 2007317718 A JP2007317718 A JP 2007317718A JP 4270470 B1 JP4270470 B1 JP 4270470B1
- Authority
- JP
- Japan
- Prior art keywords
- parts
- mass
- coating material
- fireproof coating
- rubber composition
- 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.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 124
- 239000000463 material Substances 0.000 title claims abstract description 123
- 239000011248 coating agent Substances 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 146
- 239000005060 rubber Substances 0.000 claims abstract description 146
- 239000000203 mixture Substances 0.000 claims abstract description 104
- 238000004073 vulcanization Methods 0.000 claims abstract description 61
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003063 flame retardant Substances 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000011256 inorganic filler Substances 0.000 claims abstract description 21
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000000465 moulding Methods 0.000 claims abstract description 20
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 14
- 238000003672 processing method Methods 0.000 claims abstract description 3
- 238000004898 kneading Methods 0.000 claims description 32
- 238000011282 treatment Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 15
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 13
- -1 phosphorus compound Chemical class 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 1
- 230000009970 fire resistant effect Effects 0.000 abstract description 81
- 239000006260 foam Substances 0.000 abstract description 11
- 229910000831 Steel Inorganic materials 0.000 description 32
- 239000010959 steel Substances 0.000 description 32
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000002485 combustion reaction Methods 0.000 description 14
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 230000001629 suppression Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000009413 insulation Methods 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
- 239000011490 mineral wool Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 150000003097 polyterpenes Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 2
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SRGBNANKQPZXFZ-UHFFFAOYSA-N aniline;butanal Chemical compound CCCC=O.NC1=CC=CC=C1 SRGBNANKQPZXFZ-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 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
- 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
- JWIGFTFUODAZBG-UHFFFAOYSA-N carbamodithioic acid dimethylcarbamodithioic acid Chemical class NC(S)=S.CN(C)C(S)=S JWIGFTFUODAZBG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 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
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-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
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 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
- 229960002261 magnesium phosphate Drugs 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 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
- 230000000149 penetrating effect Effects 0.000 description 1
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin 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
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 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
- 229910001479 sodium magnesium phosphate Inorganic materials 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
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-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
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】炎熱に曝された場合にも、発泡体が十分な難燃性と形状安定性を保持する耐火ゴム組成物であって、これを成形して得た耐火被覆材に対して優れた作業効率を付与し得る耐火ゴム組成物の提供すること。
【解決手段】液状ゴム３０〜６０質量部とブチルゴム４０〜７０からなるベースゴム成分１００質量部に対して、粘着付与剤を３〜５０質量部、熱膨張性黒鉛を１０〜１００質量部、難燃剤を３０〜１８０質量部、無機充填剤を３０〜２１０質量部、加硫剤を０．１〜１０質量部、加硫促進剤を０．１〜１０質量部を少なくとも含有し、未加硫の耐火ゴム組成物を提供する。また、該耐火ゴム組成物から成形した耐火被覆材、及び該耐火被覆材を用いた耐火被覆処理方法などを提供する。
【選択図】なしA fire resistant rubber composition in which a foam retains sufficient flame retardancy and shape stability even when exposed to flame heat, and is superior to a fire resistant coating material obtained by molding the same. To provide a fire resistant rubber composition capable of imparting work efficiency.
SOLUTION: 3 to 50 parts by mass of a tackifier and 10 to 100 parts by mass of thermally expandable graphite with respect to 100 parts by mass of a base rubber component composed of 30 to 60 parts by mass of liquid rubber and 40 to 70 of butyl rubber. 30 to 180 parts by mass of a flame retardant, 30 to 210 parts by mass of an inorganic filler, 0.1 to 10 parts by mass of a vulcanizing agent, 0.1 to 10 parts by mass of a vulcanization accelerator, and at least unvulcanized A refractory rubber composition is provided. Moreover, the fireproof coating material shape | molded from this fireproof rubber composition, the fireproof coating processing method using this fireproof coating material, etc. are provided.
[Selection figure] None
Description
本発明は、鉄骨の耐火被覆材や区画体貫通部の目地材等に使用される耐火ゴム組成物、該耐火ゴム組成物からなる耐火被覆材、耐火被覆材の製造方法、及び前記耐火被覆材を用いた耐火被覆処理方法などに関する。より詳しくは、炎熱に曝された場合にも、発泡体が優れた難燃性と十分な形状安定性を保持し、かつ、施工作業性に優れる耐火ゴム組成物、該耐火ゴム組成物からなる耐火被覆材、耐火被覆材の製造方法、及び前記耐火被覆材を用いた耐火被覆処理方法などに関する。 The present invention relates to a fire-resistant rubber composition used for a fire-resistant coating material for steel frames, joint materials for through-parts, etc., a fire-resistant coating material comprising the fire-resistant rubber composition, a method for producing the fire-resistant coating material, and the fire-resistant coating material The present invention relates to a method for treating a fireproof coating using the above. More specifically, even when exposed to flame heat, the foam retains excellent flame retardancy and sufficient shape stability, and is excellent in construction workability, and comprises the fire resistant rubber composition. The present invention relates to a fireproof coating material, a method for manufacturing the fireproof coating material, and a fireproof coating treatment method using the fireproof coating material.
鉄骨は通常その温度が約５５０℃以上になると強度が急激に低下するため、集合住宅や立体駐車場等の鉄骨構造の建築物で火災が発生すると倒壊の危険が生じる。そのため、火災時には鉄骨の表面を保護して、温度を上記５５０℃より低く保つ必要があり、これを目的として種々の耐火被覆処理方法が考案されている。 Since the strength of steel frames usually decreases sharply when the temperature reaches about 550 ° C. or higher, there is a risk of collapse when a fire occurs in a steel structure building such as an apartment house or a multi-story parking lot. Therefore, it is necessary to protect the surface of the steel frame in the event of a fire and keep the temperature lower than the above-mentioned 550 ° C., and various fireproof coating methods have been devised for this purpose.
従来用いられてきた耐火被覆処理法としては、鉄骨表面をケイ酸カルシウム板や石膏ボード等の無機系耐火材料で被覆する方法や、ロックウールなどの無機系繊維を鉄骨に吹き付ける方法がある。しかし、ケイ酸カルシウム板や石膏ボード等による被覆では、被覆部分の厚みが大きくなるため、被覆された鉄骨全体の体積が大きくなってしまい、施工上効率的でない。また、ロックウール等を吹き付ける方法では厚みにムラが生じやすく、鉄骨各所の耐火性にバラつきが生じ易い。さらに、施工時にミストが飛散したり、養生に長時間必要であったりと、効率の良い方法ではなかった。 Conventionally used fireproof coating methods include a method of coating the surface of a steel frame with an inorganic fireproof material such as a calcium silicate plate or a gypsum board, and a method of spraying inorganic fibers such as rock wool onto the steel frame. However, coating with a calcium silicate plate or a gypsum board increases the thickness of the coated portion, which increases the volume of the entire coated steel frame and is not efficient in construction. In addition, the method of spraying rock wool or the like tends to cause unevenness in thickness, and tends to cause variations in the fire resistance of various parts of the steel frame. Furthermore, it was not an efficient method, such as mist scattering at the time of construction or long time required for curing.
また、近年の耐火被覆処理においては、単に材料自体が燃えにくいという耐火性能ばかりでなく、火炎の延焼を防ぐ機能、すなわち防火性能も要求されるようになっている。そこで、防火用膨張材料を用いた耐火被覆処理方法が採用されるようになっている。防火用膨張材料とは、火災が発生した時に炎熱に曝されると瞬時に膨張（熱膨張）し、発泡断熱層（発泡体）を形成する材料である。この発泡体により、防火壁と電源ケーブル等の隙間を閉塞させて延焼しようとする火炎を遮断したり、鉄骨等の表面を高温から保護する断熱効果を発揮したりする。 Further, in recent fire-resistant coating treatments, not only fire resistance that the material itself is difficult to burn but also a function to prevent the spread of flame, that is, fire prevention performance is required. Therefore, a fireproof coating processing method using a fireproof expansion material has been adopted. The expansion material for fire prevention is a material that expands instantaneously (thermal expansion) and forms a foam heat insulating layer (foam) when exposed to flame heat when a fire occurs. With this foam, a flame that attempts to spread by blocking the gap between the fire wall and the power cable is shut off, or a heat insulating effect that protects the surface of the steel frame or the like from high temperatures is exhibited.
このような防火用膨張材料として、従来、ゴム成分に熱膨張性黒鉛や無機物等を配合した耐火性組成物が用いられている。しかし、ゴム成分や熱膨張性黒鉛は、本質的にそれ自体が燃焼したり熱溶融したりする性質を有するので、いかに長時間、熱膨張した発泡体の熱溶解を防止できるか、あるいは、無機成分を脱落させずに保持させることができるか、が耐火性組成物の性能を決定する上で重要な要素となる。 As such an expansion material for fire prevention, a fire-resistant composition in which a heat-expandable graphite or an inorganic substance is blended with a rubber component has been conventionally used. However, the rubber component and the thermally expandable graphite have the property that they inherently burn and melt, so that it is possible to prevent the foam from thermally expanding for a long time, Whether or not the components can be retained without dropping off is an important factor in determining the performance of the refractory composition.
そこで、出願人は特許文献１に、熱膨張した後も熱溶融を起こさずに所定の形状を長時間保持することができる防火用膨張材料として、ゴム成分に熱可塑性エラストマーを配合し、膨張性黒鉛、ホウ酸及び無機充填材を添加した防火用目地材を開示している。 Therefore, the applicant, in Patent Document 1, blends a thermoplastic elastomer into a rubber component as a fireproof expansion material capable of maintaining a predetermined shape for a long time without causing thermal melting even after thermal expansion. Disclosed is a fireproof joint material to which graphite, boric acid and an inorganic filler are added.
一方、耐火被覆材として鉄骨や壁に貼り付ける際に、仮止め固定を容易に行うために、粘着性を有する様々な耐火性樹脂組成物等が開発されている。例えば、特許文献２には、粘着性を有するゴム組成物、リン化合物、中和処理された熱膨張性黒鉛、含水無機物及び金属炭酸塩を混成した耐火性樹脂組成物が、特許文献３には、加熱によって膨張して耐火断熱層を形成し、常温で粘着性を有する熱膨張性シートの片面に基材層が積層され、該基材層の被積層面に離型処理が施されている粘着性耐火シートが、特許文献４には、非架橋ゴム及び／又は部分架橋ゴムからなるゴム成分に、熱膨張性無機物、無機充填材、及び平均分子量２０００〜４０００の液状樹脂を配合してなることを特徴とする粘着耐火性ゴム組成物が、開示されている。 On the other hand, various refractory resin compositions having adhesive properties have been developed to facilitate temporary fixing when affixed to a steel frame or wall as a fireproof covering material. For example, Patent Document 2 discloses a refractory resin composition in which an adhesive rubber composition, a phosphorus compound, neutralized thermally expandable graphite, a hydrated inorganic substance, and a metal carbonate are mixed. The base material layer is laminated on one side of a thermally expandable sheet having adhesiveness at room temperature, and a release treatment is applied to the laminated surface of the base material layer. The adhesive fireproof sheet is obtained by blending a rubber component composed of non-crosslinked rubber and / or partially crosslinked rubber with a thermally expandable inorganic substance, an inorganic filler, and a liquid resin having an average molecular weight of 2000 to 4000 in Patent Document 4. An adhesive refractory rubber composition characterized in that is disclosed.
なお、上記のような、従来の粘着性を有する耐火性樹脂組成物等は、予め架橋されたゴム組成物と他の成分を配合しても、他の成分を配合する際同時にゴム組成物を架橋しても、他の成分を配合した後にゴム組成物を架橋してもよいが、耐火性樹脂組成物として製造する段階で架橋処理を完結させるものである。 In addition, the above-mentioned conventional fire-resistant resin composition having adhesiveness may be blended with a rubber composition that has been previously cross-linked and other components, but at the same time when the other components are blended, Even if it is crosslinked, the rubber composition may be crosslinked after blending other components, but the crosslinking treatment is completed at the stage of production as a refractory resin composition.
粘着性を有する従来の耐火性樹脂組成物等は、耐火被覆材として鉄骨や壁に貼り付ける際に仮止め固定が容易にできる。しかし、耐火性樹脂組成物の有する粘着力だけでは、耐火被覆処理後に炎熱に曝された場合の耐火被覆材の剥離、脱落を防止するには接着性が不十分である。そのため、耐火被覆材を鉄骨や壁に貼り付けた後に、外側から不織布、金網、セラミック材料等の面材を釘やピン、ネジ等によって固定し、補強される場合が多かった。（例えば、特許文献２段落００５１参照）。 A conventional fire-resistant resin composition or the like having adhesiveness can be easily temporarily fixed when affixed to a steel frame or wall as a fire-resistant coating material. However, the adhesive strength of the refractory resin composition is insufficient to prevent the refractory coating material from peeling off and falling off when exposed to flame heat after the refractory coating treatment. For this reason, after attaching the fireproof covering material to the steel frame or the wall, face materials such as a nonwoven fabric, a wire mesh, and a ceramic material are often fixed from the outside by a nail, a pin, a screw, or the like to be reinforced. (For example, see Patent Document 2, paragraph 0051).
従って、耐火被覆処理における初期の作業性は向上するものの、耐火被覆材として鉄骨や壁に仮止め固定後に、前記のような本止め固定作業を行う必要があり、耐火被覆処理作業の全体としては、作業効率を低下させる要因ともなっていた。 Therefore, although the initial workability in the fireproof coating process is improved, it is necessary to perform the permanent fixing work as described above after temporarily fixing the steel frame or wall as the fireproof coating material. It was also a factor of lowering work efficiency.
そこで、本発明は、耐火被覆処理における初期の作業性を維持しつつ、耐火被覆処理工程全体の作業効率も向上させ、更に、炎熱に曝された際、ゴム成分の燃焼による被覆された鉄骨等の内容物の温度上昇を防止し得る耐火被覆材を提供することを主目的とする Therefore, the present invention improves the work efficiency of the entire fireproof coating process while maintaining the initial workability in the fireproof coating process, and further, when exposed to flame heat, the coated steel frame by the combustion of the rubber component, etc. The main purpose is to provide a fire-resistant coating that can prevent the temperature rise of the contents of
上記の課題を解決するため、本発明者らは鋭意検討を重ねた結果、十分な形状安定性と難燃性を保持する耐火被覆材であって、該耐火被覆材の被覆処理工程全体の作業効率が大幅に向上し得る耐火被覆材として、以下の耐火被覆材を完成させるに至った。 To solve the above problems, the present inventors have result of intensive studies, a refractory coating material to retain sufficient shape stability and flame retardancy, the coating process overall working of the refractory dressing The following fire-resistant coating materials have been completed as fire-resistant coating materials that can greatly improve the efficiency.
すなわち、本発明は、まず、液状ゴム３０〜６０質量部、ブチルゴム４０〜７０質量部からなるベースゴム成分と、該ベースゴム成分１００質量部に対して、粘着付与剤を３〜５０質量部、熱膨張性黒鉛を１０〜１００質量部、難燃剤を３０〜１８０質量部、無機充填剤を３０〜２１０質量部、加硫剤を０．１〜１０質量部、加硫促進剤を０．１〜１０質量部、亜リン酸アルミニウムを１〜５０質量部、を少なくとも含有する耐火ゴム組成物を用いて、
６０〜１００℃にて混練されることにより未加硫のまま成形され自然加硫性を備えた耐火被覆材を提供するものである。
前記耐火ゴム組成物に含有される前記難燃剤は、難燃効果を有するものであれば特に限定されないが、一例としては、リン化合物を挙げることができる。
該リン酸化合物の種類も特に限定されないが、例えば、ポリリン酸アンモニウム類を含有させることができる。
更に、該ポリリン酸アンモニウム類の種類も特に限定されないが、一例としては、ポリリン酸アンモニウム又はポリリン酸アンモニウムアミドを挙げることができる。
本発明に係る耐火被覆材の形状は特に限定されないが、テープ状又はシート状に成形することも可能である。
本発明では、次に、前記耐火ゴム組成物を、６０〜１００℃にて混練したのち成形する耐火被覆材の製造方法を提供する。
本発明に係る耐火被覆材の製造方法において、成形温度は特に限定されないが、混練温度よりも低い温度で成形するとより好適である。
本発明では、更に、前記耐火被覆材を用いた耐火被覆処理方法を提供する。
本発明に係る耐火被覆処理方法は、前記耐火被覆材を用いていれば、具体的な処理方法は特に限定されないが、例えば、前記耐火被覆材を、該耐火被覆材の粘着力によって基材表面に粘着させた後、さらに、該耐火被覆材の自然加硫によって基材表面へ固着化させる方法が特に好適である。
That is, in the present invention, first, a base rubber component comprising 30 to 60 parts by mass of liquid rubber and 40 to 70 parts by mass of butyl rubber, and 3 to 50 parts by mass of a tackifier with respect to 100 parts by mass of the base rubber component, 10 to 100 parts by mass of thermally expandable graphite, 30 to 180 parts by mass of flame retardant, 30 to 210 parts by mass of inorganic filler, 0.1 to 10 parts by mass of vulcanizing agent, and 0.1 to 0.1 part of vulcanization accelerator. -10 parts by weight, using a fire resistant rubber composition containing at least 1 to 50 parts by weight of aluminum phosphite ,
The present invention provides a fireproof coating material which is kneaded at 60 to 100 ° C. and molded without being vulcanized and has natural vulcanization properties .
Although the said flame retardant contained in the said fire resistant rubber composition will not be specifically limited if it has a flame-retardant effect, As an example, a phosphorus compound can be mentioned.
The type of the phosphoric acid compound is not particularly limited, and for example, ammonium polyphosphates can be contained.
Furthermore, the type of the ammonium polyphosphates is not particularly limited, and examples thereof include ammonium polyphosphate and ammonium polyphosphate amide.
The shape of the fireproof coating material according to the present invention is not particularly limited, but can be formed into a tape shape or a sheet shape.
In this invention, next, the manufacturing method of the fireproof coating | covering material which shape | molds, after knead | mixing the said fireproof rubber composition at 60-100 degreeC is provided.
In the method for producing a fireproof coating material according to the present invention, the molding temperature is not particularly limited, but it is more preferable to mold at a temperature lower than the kneading temperature.
The present invention further provides a fireproof coating treatment method using the fireproof coating material.
The fireproof coating treatment method according to the present invention is not particularly limited as long as the fireproof coating material is used. For example, the fireproof coating material is formed on the surface of the base material by the adhesive force of the fireproof coating material. A method of adhering to the surface of the base material by natural vulcanization of the refractory coating material is particularly preferable.
ここで、本発明における技術用語の定義付けを行う。
本発明において「未加硫」とは、加硫性を有するものが未だ加硫されていない状態を示し、加硫性を有さない「非加硫」とは異なる概念である。
Here, technical terms in the present invention are defined.
In the present invention, “unvulcanized” refers to a state in which a vulcanizable material has not yet been vulcanized, and is a concept different from “non-vulcanized” which does not have vulcanizable properties.
本発明において「粘着」とは、粘り気を有することにより、基材表面等へ張り付くことをいい、再び、剥離することが可能な状態をいう。 In the present invention, “adhesion” means sticking to the surface of a base material by having stickiness, and means a state where it can be peeled again.
本発明において「固着」とは、硬度を増した状態で、基材表面等へ強固に固定することをいい、再び、剥離することが不可能な状態をいう。 In the present invention, “adhesion” refers to a state in which the hardness is increased and the substrate is firmly fixed to the surface of the substrate or the like and cannot be peeled again.
なお、本発明において「接着」とは、上記の「粘着」及び「固着」を包括する概念として用いるものとする。 In the present invention, “adhesion” is used as a concept encompassing the above “adhesion” and “adhesion”.
本発明に係る耐火ゴム組成物は粘着性を有するため、これを成形して得た耐火被覆材等は、耐火被覆処理における初期の作業性の向上が図れる。また、本発明に係る耐火ゴム組成物は未加硫であるため、これを成形して得た耐火被覆材等を用いた耐火被覆処理では、自然加硫による鉄骨や壁等への固着が実現でき、被覆処理工程全体の作業効率を飛躍的に高めることが可能である。更に、難燃剤を含有させることにより、炎熱に曝された際、ゴム成分の燃焼による被覆された鉄骨等の内容物の温度上昇を防止することが可能となる。 Since the fire resistant rubber composition according to the present invention has adhesiveness, the fire resistant coating material obtained by molding the fire resistant rubber composition can improve the initial workability in the fire resistant coating treatment. In addition, since the refractory rubber composition according to the present invention is unvulcanized, the refractory coating treatment using the refractory coating material obtained by molding the refractory rubber composition achieves fixation to a steel frame or wall by natural vulcanization. It is possible to dramatically increase the work efficiency of the entire coating process. Further, by containing a flame retardant, it is possible to prevent the temperature rise of the coated steel frame and other contents due to the combustion of the rubber component when exposed to flame heat.
以下、本発明を実施するための好適な形態について説明する。なお、以下に説明する実施形態は、本発明の代表的な実施形態の一例を示したものであり、これにより本発明の範囲が狭く解釈されることはない。 Hereinafter, preferred embodiments for carrying out the present invention will be described. In addition, embodiment described below shows an example of typical embodiment of this invention, and, thereby, the range of this invention is not interpreted narrowly.
＜耐火ゴム組成物＞
本発明に係る耐火ゴム組成物は、液状ゴム３０〜６０質量部、ブチルゴム４０〜７０質量部からなるベースゴム成分と、該ベースゴム成分１００質量部に対して、粘着付与剤を３〜５０質量部、熱膨張性黒鉛を１０〜１００質量部、難燃剤を３０〜１８０質量部、無機充填剤を３０〜２１０質量部、加硫剤を０．１〜１０質量部、加硫促進剤を０．１〜１０質量部を少なくとも含有し、未加硫の状態の組成物である。
<Fireproof rubber composition>
The fire resistant rubber composition according to the present invention comprises 3 to 50 parts by mass of a tackifier with respect to a base rubber component comprising 30 to 60 parts by mass of liquid rubber and 40 to 70 parts by mass of butyl rubber and 100 parts by mass of the base rubber component. Part, 10 to 100 parts by mass of thermally expandable graphite, 30 to 180 parts by mass of flame retardant, 30 to 210 parts by mass of inorganic filler, 0.1 to 10 parts by mass of vulcanizing agent, and 0 to vulcanization accelerator 0.1 to 10 parts by mass, and is an unvulcanized composition.
このように、ベースゴム成分に、粘着付与剤、熱膨張性黒鉛、難燃剤、無機充填剤を上記の特定質量比で配合することにより、好適な熱膨張倍率と加工性を備え、長時間高温に曝され熱膨張してもその発泡体が脆弱化し難く十分な形状安定性を有する耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等を得ることができる。以下、液状ゴム、ブチルゴム、粘着付与剤、熱膨張性黒鉛、難燃剤、無機充填剤、加硫剤、加硫促進剤の各成分の含有比率を前記範囲に特定した意義及び、各含有物質の具体例等について、詳細に述べる。なお、本発明に係る耐火ゴム組成物は、少なくとも未加硫の状態であれば、前記の各成分を混練した状態のものも、混練前の状態のものも、どちらも包含する。 Thus, by adding a tackifier, a thermally expandable graphite, a flame retardant, and an inorganic filler to the base rubber component at the specific mass ratio described above, it has a suitable thermal expansion ratio and workability, and is heated for a long time. It is possible to obtain a fire resistant rubber composition having sufficient shape stability that is difficult to be weakened even if it is exposed to thermal expansion, and a fire resistant coating material using the fire resistant rubber composition. Hereinafter, the meaning of specifying the content ratio of each component of liquid rubber, butyl rubber, tackifier, thermally expandable graphite, flame retardant, inorganic filler, vulcanizing agent, and vulcanization accelerator within the above ranges, and Specific examples will be described in detail. The refractory rubber composition according to the present invention includes both the above-mentioned components kneaded and those before kneading as long as they are at least in an unvulcanized state.
ベースゴム成分は、液状ゴム３０〜６０質量部に、ブチルゴム４０〜７０質量部を混合してなる。液状ゴムが３０質量部未満の場合、ベースゴム成分は硬く（針入度は小さく）なりすぎ、耐火ゴム組成物の加工性は低下し、また該耐火ゴム組成物を用いた耐火被覆材等の粘着性が不十分となる。また、液状ゴムが６０質量部を超えると、ベースゴム成分は柔らかく（針入度が大きく）なりすぎ、該耐火ゴム組成物を用いた耐火被覆材等が取り扱いづらくなり、操作性が低下する。従って、液状ゴム及びブチルゴムを上記特定質量比で配合してベースゴム成分とすることにより、好適な加工性を備えた耐火ゴム組成物が得られ、該耐火ゴム組成物を用いた耐火被覆材等は、操作性と、特に粘着性に優れた特性を得ることができる。 The base rubber component is obtained by mixing 40 to 70 parts by mass of butyl rubber with 30 to 60 parts by mass of liquid rubber. When the liquid rubber is less than 30 parts by mass, the base rubber component is too hard (the penetration is too small), the processability of the fire resistant rubber composition is reduced, and the fire resistant coating material using the fire resistant rubber composition is not suitable. Adhesiveness becomes insufficient. On the other hand, when the liquid rubber exceeds 60 parts by mass, the base rubber component becomes too soft (the penetration is too high), and it becomes difficult to handle a fireproof coating material using the fireproof rubber composition, resulting in a decrease in operability. Accordingly, by blending liquid rubber and butyl rubber at the above specific mass ratio to form a base rubber component, a fire resistant rubber composition having suitable processability is obtained, and a fire resistant coating material using the fire resistant rubber composition, etc. Can obtain characteristics excellent in operability and particularly adhesiveness.
本発明で用いることができる液状ゴムの種類は特に限定されず、公知の液状ゴムを採用することができる。特に、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等に粘着性を付与できるものが望ましい。一例としては、ポリブタジエン、ポリイソプレン、ポリブテン等を挙げることができる。ベースゴム成分に含有させる液状ゴムは１種類に限定されず、２種類以上を組み合わせて用いることも可能である。 The kind of liquid rubber that can be used in the present invention is not particularly limited, and a known liquid rubber can be employed. In particular, a fire-resistant rubber composition and a fire-resistant coating material using the fire-resistant rubber composition and the like that can impart tackiness are desirable. Examples include polybutadiene, polyisoprene, polybutene and the like. The liquid rubber contained in the base rubber component is not limited to one type, and two or more types can be used in combination.
前記ベースゴム成分により、本発明に係る耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等には、粘着性が付与されるが、さらに本発明では、粘着付与剤を配合することにより、粘着性を一層向上させる。 The base rubber component imparts tackiness to the fireproof rubber composition according to the present invention and the fireproof coating material using the fireproof rubber composition, but in the present invention, a tackifier is further blended. Thus, the adhesiveness is further improved.
本発明で用いることができる粘着付与剤の種類は特に限定されず、公知の粘着付与剤を採用することができる。例えば、クマロン−インデン樹脂、フェノール−ホルムアルデヒド樹脂、テルペン−フェノール樹脂、ポリテルペン樹脂、石油系炭化水素樹脂等が挙げられる。この中でも特に好ましい粘着付与剤は、ポリテルペン樹脂である。また、本発明に係る耐火ゴム組成物に含有させる粘着付与剤は１種類に限定されず、２種類以上を組み合わせて用いることも可能である。 The kind of tackifier which can be used by this invention is not specifically limited, A well-known tackifier can be employ | adopted. Examples thereof include coumarone-indene resin, phenol-formaldehyde resin, terpene-phenol resin, polyterpene resin, petroleum hydrocarbon resin, and the like. Among these, a particularly preferable tackifier is a polyterpene resin. Moreover, the tackifier contained in the fire resistant rubber composition according to the present invention is not limited to one type, and two or more types can be used in combination.
耐火ゴム組成物における粘着付与剤の含有量は、ベースゴム成分１００質量部に対して３〜５０質量部であり、好ましくは５〜３０質量部である。３質量部未満であると、本発明に係る耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等の粘着性が不十分となり、５０質量部を超えて使用すると前記耐火被覆材の強度が低くなるためである。 Content of the tackifier in a fireproof rubber composition is 3-50 mass parts with respect to 100 mass parts of base rubber components, Preferably it is 5-30 mass parts. When the amount is less than 3 parts by mass, the adhesiveness of the fire resistant rubber composition according to the present invention and the fire resistant coating material using the fire resistant rubber composition becomes insufficient. This is because the strength is lowered.
熱膨張性黒鉛は、２２０℃程度以上の温度に曝されると１００倍以上に熱膨張し、火災発生時には鉄骨等の被覆表面に強固な発泡断熱層を形成して鉄骨等の温度上昇を防止し、また、防火壁と電源ケーブル等の隙間を閉塞させて火炎の流入を防止する機能を発揮する。 Thermally expandable graphite expands more than 100 times when exposed to temperatures of about 220 ° C or higher, and in the event of a fire, forms a strong foam insulation layer on the surface of the steel frame to prevent temperature rise of the steel frame, etc. In addition, the gap between the fire wall and the power cable is closed to exert the function of preventing the inflow of flame.
熱膨張性黒鉛は、天然グラファイト、熱分解グラファイト等の粉末を、硫酸や硝酸等の無機酸と、濃硝酸や過マンガン酸塩等の強酸化剤とで処理されたもので、グラファイト層状構造を維持した結晶化合物が用いられる。なお、天然グラファイト、熱分解グラファイト等の粉末には、脱酸処理や中和処理を行った各種品種があるが、いずれを使用してもよい。熱膨張性黒鉛の粒度は、２０〜４００メッシュ程度が好ましい。４００メッシュより粒度が小さくなると熱膨張性黒鉛の膨張度が小さく、得られた耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等が火災時に充分熱膨張しない場合があり、また２０メッシュより粒度が大きくなると分散性が悪くなり、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等の弾性が低下する場合がある。 Thermally expandable graphite is a powder of natural graphite, pyrolytic graphite, etc., treated with an inorganic acid such as sulfuric acid or nitric acid and a strong oxidizing agent such as concentrated nitric acid or permanganate. A maintained crystalline compound is used. There are various types of powders such as natural graphite and pyrolytic graphite, which have been subjected to deoxidation treatment or neutralization treatment, and any of them may be used. The particle size of the thermally expandable graphite is preferably about 20 to 400 mesh. When the particle size is smaller than 400 mesh, the expansion coefficient of the thermally expandable graphite is small, and the obtained fire resistant rubber composition and the fire resistant coating material using the fire resistant rubber composition may not be sufficiently thermally expanded in a fire. When the particle size is larger than the mesh, the dispersibility is deteriorated, and the elasticity of the fire resistant rubber composition and the fire resistant coating material using the fire resistant rubber composition may be lowered.
耐火ゴム組成物における熱膨張性黒鉛の含有量は、ベースゴム成分１００質量部に対して１０〜１００質量部であり、好ましくは２０〜７０質量部である。熱膨張性黒鉛の含有量が１０質量部未満であると、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等が充分熱膨張しない（膨張倍率が小さい）場合があり、１００質量部を超えると、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等の熱膨張倍率は大きくなるものの、熱膨張後の発泡体の形状安定性が低下する場合がある。 The content of the heat-expandable graphite in the fire resistant rubber composition is 10 to 100 parts by mass, preferably 20 to 70 parts by mass with respect to 100 parts by mass of the base rubber component. When the content of the heat-expandable graphite is less than 10 parts by mass, the fire-resistant rubber composition and the fire-resistant coating material using the fire-resistant rubber composition may not be sufficiently thermally expanded (expansion magnification is small), and may be 100 mass. If it exceeds the part, the thermal expansion ratio of the fireproof rubber composition and the fireproof coating material using the fireproof rubber composition is increased, but the shape stability of the foam after thermal expansion may be lowered.
難燃剤は、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等が、火炎に曝され熱膨張性黒鉛が熱膨張を開始する際に、成形体内部から熱分解ガスが発生しそれに火炎が引火し燃焼するのを防止するため用いる。熱膨張性黒鉛が耐火ゴム組成物を発泡させて断熱層を形成し、被覆された鉄骨等の基材表面の温度上昇を抑制する効果があるが、この熱分解ガスの燃焼による被覆材の発火により、内部の鉄骨温度が上昇してしまう問題がある。そこで、前記のように特定質量比で配合した各構成成分と、特定質量比の難燃剤を配合することにより、燃焼を抑制し鉄骨温度の上昇を防止することに成功した。 The flame retardant is a fire-resistant rubber composition and a fire-resistant coating material using the fire-resistant rubber composition is exposed to a flame, and when the thermally expandable graphite starts thermal expansion, pyrolysis gas is generated from the inside of the molded body. It is used to prevent the flame from igniting and burning. Thermally expansive graphite foams the refractory rubber composition to form a heat insulation layer and has the effect of suppressing the temperature rise on the surface of the coated steel and other base materials. As a result, there is a problem that the internal steel temperature rises. Then, it succeeded in suppressing a combustion and preventing the raise of steel frame temperature by mix | blending each structural component mix | blended by specific mass ratio as mentioned above and the flame retardant of specific mass ratio.
本発明で用いることができる難燃剤の種類は特に限定されず、公知の難燃剤を採用することができる。特に環境面を考慮すると、非ハロゲン系の難燃剤が好ましい。非ハロゲン系の難燃剤の種類も特に限定されないが、例えば、リン化合物が好適である。リン化合物としては、例えば、赤リン、トリオクチルホスフェート、トリブトキシエチルホスフェート等の非ハロゲン系リン酸エステル、リン酸ナトリウム、リン酸マグネシウム等のリン酸金属塩、ポリリン酸アンモニウム、ポリリン酸アンモニウムアミド等のポリリン酸アンモニウム類、リン酸アルミニウム、リン酸メラミン等が挙げられる。 The kind of flame retardant that can be used in the present invention is not particularly limited, and a known flame retardant can be employed. In particular, in consideration of the environment, a non-halogen flame retardant is preferable. The kind of the non-halogen flame retardant is not particularly limited, but, for example, a phosphorus compound is preferable. Examples of phosphorus compounds include non-halogen phosphates such as red phosphorus, trioctyl phosphate, and tributoxyethyl phosphate, metal phosphates such as sodium phosphate and magnesium phosphate, ammonium polyphosphate, and ammonium polyphosphate amide. And ammonium polyphosphates, aluminum phosphate, melamine phosphate and the like.
このなかでも特に、ポリリン酸アンモニウム、ポリリン酸アンモニウムアミド等のポリリン酸アンモニウム類が、発泡性・形状安定性の面から好ましい。これらのリン化合物は、有機物の脱水炭化作用を有するとともに、不燃性の無機系リン酸被膜を形成するため、難燃効果を優れるものである。 Among these, ammonium polyphosphates such as ammonium polyphosphate and ammonium polyphosphate amide are particularly preferable in terms of foamability and shape stability. Since these phosphorus compounds have a dehydration carbonization action of organic matter and form a nonflammable inorganic phosphate film, they have excellent flame retardancy.
耐火ゴム組成物における難燃剤の含有量は、ベースゴム成分１００質量部に対して３０〜１８０質量部であり、好ましくは５０〜１５０質量部である。３０質量部未満であると、燃焼を抑制する効果が小さく、耐火ゴム組成物を用いた耐火被覆材等の燃焼が継続することによって鉄骨等の基材温度の上昇を促進してしまい、逆に、１８０質量部を超えると耐火ゴム組成物の加工性、粘着性が低下するためである。 The content of the flame retardant in the fire resistant rubber composition is 30 to 180 parts by mass, preferably 50 to 150 parts by mass with respect to 100 parts by mass of the base rubber component. If the amount is less than 30 parts by mass, the effect of suppressing combustion is small, and the increase in the base material temperature of the steel frame or the like is promoted by continuing the combustion of the fireproof coating material using the fireproof rubber composition. If the amount exceeds 180 parts by mass, the workability and tackiness of the refractory rubber composition are lowered.
無機充填剤は、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等の中で骨材的な働きをし、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等が火災で熱膨張した後は、その発泡体の強度を向上させたり、熱容量の増大に寄与し耐熱性を増強させたりするために用いる。 The inorganic filler acts as an aggregate in the fire resistant rubber composition and the fire resistant coating material using the fire resistant rubber composition, and the like, and the fire resistant rubber composition and the fire resistant coating material using the fire resistant rubber composition, etc. After thermal expansion due to fire, it is used to improve the strength of the foam or to increase the heat capacity by increasing the heat capacity.
本発明で用いることができる無機充填剤の種類は特に限定されず、公知の無機充填剤を採用することができる。一例としては、アルミナ、酸化亜鉛、酸化チタン、酸化カルシウム、酸化マグネシウム、酸化アンチモン等の金属酸化物、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、ハイドロタルサイト等の含水無機物、塩基性炭酸マグネシウム、炭酸マグネシウム、炭酸カルシウム、炭酸亜鉛、炭酸バリウム等の金属炭酸塩、硫酸カルシウム、ケイ酸カルシウム等のカルシウム塩、シリカ、珪藻土、硫酸バリウム、タルク、クレー、マイカ、ベントナイト、活性白土、セピオライト、ガラス繊維、ガラスビーズ、シリカ系バルーン、窒化アルミニウム、窒化ケイ素、グラファイト、カーボンブラック、炭素繊維、各種金属粉、チタン酸カリウム、硫酸マグネシウム、ホウ酸亜鉛、フライアッシュ、フライアッシュバルーン等が挙げられる。この中でも特に好ましい無機充填剤は、水酸化アルミニウム、炭酸カルシウム、クレーである。これらは、単独で用いてもよいが、２種以上を組み合わせて用いることも可能である。 The kind of inorganic filler that can be used in the present invention is not particularly limited, and a known inorganic filler can be employed. Examples include metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, and antimony oxide, hydrous minerals such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite, and basic magnesium carbonate. , Magnesium carbonate, Calcium carbonate, Zinc carbonate, Barium carbonate metal carbonates, Calcium sulfate, Calcium silicate calcium salts, Silica, Diatomite, Barium sulfate, Talc, Clay, Mica, Bentonite, Activated clay, Sepiolite, Glass Fiber, glass beads, silica-based balloon, aluminum nitride, silicon nitride, graphite, carbon black, carbon fiber, various metal powders, potassium titanate, magnesium sulfate, zinc borate, fly ash, fly ash balloon, etc. . Among these, particularly preferred inorganic fillers are aluminum hydroxide, calcium carbonate, and clay. These may be used singly or in combination of two or more.
耐火ゴム組成物における無機充填剤の含有量は、ベースゴム成分１００質量部に対して３０〜２１０質量部であり、好ましくは５０〜１８０質量部である。３０質量部未満であると、耐火ゴム組成物の発泡体の強度が不足し、耐熱性、難燃性が発揮されず、２１０質量部を超えると耐火ゴム組成物の加工性が低下するためである。 Content of the inorganic filler in a fireproof rubber composition is 30-210 mass parts with respect to 100 mass parts of base rubber components, Preferably it is 50-180 mass parts. If the amount is less than 30 parts by mass, the strength of the foam of the refractory rubber composition is insufficient, heat resistance and flame retardancy are not exhibited, and if it exceeds 210 parts by mass, the workability of the refractory rubber composition is reduced. is there.
加硫剤及び加硫促進剤は、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等に自然加硫性を付与するため配合される。ここで、本発明における「自然加硫」とは、混練処理等で発生する熱や人工的な加熱による加硫ではなく、太陽光の輻射熱等による環境下での加硫をいう。 A vulcanizing agent and a vulcanization accelerator are blended in order to impart natural vulcanizability to a fire resistant rubber composition and a fire resistant coating material using the fire resistant rubber composition. Here, “natural vulcanization” in the present invention refers to vulcanization under the environment by sunlight radiant heat or the like, not by heat generated by a kneading process or the like or by artificial heating.
本発明に係る耐火ゴム組成物は、加硫剤及び加硫促進剤を配合するにも関わらず、耐火ゴム組成物又はこれを成形して得た耐火被覆材の製造段階では加硫を行わず、未加硫のまま製造する。このように、本願発明者らは、未加硫のままの耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等を、その優れた柔軟性と粘着性を活かして基材表面に粘着させ、そして、特定質量比の加硫剤及び加硫促進剤を配合させることにより、太陽光の輻射熱等による環境下での自然加硫によって基材表面へ固着化させることを見出した。 Refractory rubber composition according to the present invention, despite the compounding a vulcanizing agent and the vulcanization accelerator, without vulcanization at the manufacturing stage of the refractory rubber compositions or fireproofing material obtained by molding this The unvulcanized product is produced. As described above, the inventors of the present invention applied an unvulcanized refractory rubber composition and a refractory coating material using the refractory rubber composition to the surface of the base material by taking advantage of its excellent flexibility and adhesiveness. It has been found that by adhering and blending a vulcanizing agent and a vulcanization accelerator having a specific mass ratio, it is fixed to the surface of the substrate by natural vulcanization under the environment of sunlight radiant heat or the like.
すなわち、本発明に係る耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等は、当初は優れた柔軟性と粘着性を有し、耐火被覆処理の初期工程には優れた粘着性を発揮して基材等に粘着し、そして、太陽光の輻射熱等により自然加硫して次第に強度を増し、基材等に強固に固着化するという特性を備えている。 That is, the fireproof rubber composition according to the present invention and the fireproof coating material using the fireproof rubber composition have excellent flexibility and tackiness at the beginning, and excellent tackiness in the initial stage of the fireproof coating treatment. It adheres to the base material and the like, and is naturally vulcanized by radiant heat of sunlight and the like to gradually increase the strength and firmly adhere to the base material.
このような自然加硫性に基づく特性を最適化するため、加硫剤及び加硫促進剤の含有比率を、それぞれベースゴム成分１００質量部に対して０．１〜１０質量部の範囲に特定した。これらの含有量は、さらに好ましくは１〜５質量部範囲である。加硫剤及び加硫促進剤がそれぞれベースゴム成分１００質量部に対して０．１質量部未満であると、自然加硫性が発揮されなかったり、自然加硫の進行（自然加硫速度）が遅すぎたりして、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等の固着化強度が不十分となり、１０質量部を超えて使用すると、自然加硫速度が速くなりすぎて粘着性が低下し、また保管時の安定性も劣るためである。 In order to optimize the characteristics based on such natural vulcanizability, the content ratio of the vulcanizing agent and the vulcanization accelerator is specified in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the base rubber component, respectively. did. These contents are more preferably in the range of 1 to 5 parts by mass. When the vulcanizing agent and the vulcanization accelerator are each less than 0.1 parts by mass with respect to 100 parts by mass of the base rubber component, the natural vulcanizing property is not exhibited or the natural vulcanization progresses (natural vulcanization rate). Is too slow, the fixing strength of the fireproof rubber composition and the fireproof coating material using the fireproof rubber composition is insufficient, and if it is used in excess of 10 parts by mass, the natural vulcanization rate becomes too fast. This is because the adhesiveness is lowered and the stability during storage is poor.
本発明で用いることができる加硫剤の種類は特に限定されず、公知の加硫剤を採用することができる。一例としては、硫黄、ポリスルフィド等の硫黄系化合物、ｐ−キノンジオキシム、ｐ−ｐ−ジベンゾイルキノンオキシム等のオキシム系化合物、ｔ−ブチルハイドロパーオキサイド、アセチルアセトンパーオキサイド、クメンハイドロパーオキサイド等の有機過酸化物系化合物等を挙げることができる。この中でも特に好ましい加硫剤は、硫黄、ポリスルフィド等の硫黄系化合物である。これらは、単独で用いてもよいが、例えば、硫黄系化合物と、それ以外の加硫剤とを組み合わせる等、２種以上を組み合わせて用いることも可能である。 The kind of vulcanizing agent that can be used in the present invention is not particularly limited, and a known vulcanizing agent can be employed. Examples include sulfur-based compounds such as sulfur and polysulfide, oxime-based compounds such as p-quinone dioxime and p-p-dibenzoylquinone oxime, t-butyl hydroperoxide, acetylacetone peroxide, cumene hydroperoxide, and the like. Examples thereof include organic peroxide compounds. Among these, particularly preferred vulcanizing agents are sulfur compounds such as sulfur and polysulfide. These may be used alone, but may be used in combination of two or more, for example, a combination of a sulfur compound and other vulcanizing agent.
本発明で用いることができる加硫促進剤の種類も特に限定されず、公知の加硫促進剤を採用することができる。一例としては、テトラメチルチウラムジスルフィドやテトラブチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド、ジペンタメチレンチウラムテトラスルフィド等のチウラム系化合物、２−メルカプトベンゾチアゾールやジベンゾチアゾールジスルフィド等のチアゾール系化合物、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジ−ｎ−ブチルジチオカルバミン酸亜鉛等のジチオカルバミン酸塩系化合物、ｎ−ブチルアルデヒドアニリン等のアルデヒドアミン系化合物、Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド等のスルフェンアミド系化合物、ジオルソトリルグアニジンやジオルソニトリルグアニジン等のグアニジン系化合物、チオカルバニリドやジエチルチオユリア、トリメチルチオユリア等のチオユリア系化合物、亜鉛華などの化合物が挙げられる。この中でも特に好ましい加硫促進剤は、ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジ−ｎ−ブチルジチオカルバミン酸亜鉛等のジチオカルバミン酸塩系化合物である。これらは、単独で用いてもよいが、２種以上を組み合わせて用いることも可能である。 The kind of vulcanization accelerator that can be used in the present invention is not particularly limited, and a known vulcanization accelerator can be employed. Examples include thiuram compounds such as tetramethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide, thiazole compounds such as 2-mercaptobenzothiazole and dibenzothiazole disulfide, dimethyldithiocarbamic acid Dithiocarbamate compounds such as zinc, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, aldehyde amine compounds such as n-butyraldehyde aniline, sulfur such as N-cyclohexyl-2-benzothiazylsulfenamide Fenamide compounds, guanidine compounds such as diorthotolyl guanidine and diorthonitrile guanidine, thiocarbanilide, diethylthiourea, trimethyl Chioyuria compounds such Oyuria, compounds such as zinc oxide and the like. Of these, particularly preferred vulcanization accelerators are dithiocarbamate compounds such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, and zinc di-n-butyldithiocarbamate. These may be used singly or in combination of two or more.
本発明に係る耐火ゴム組成物には、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等の熱膨張後の型崩れ防止のために、形状安定化剤として亜リン酸アルミニウムを用いることができる。本発明においては、亜リン酸アルミニウムは必須ではなく、含有されない場合でも他の成分の組み合わせ及びその配合量を前記のように特定質量比で配合することにより、良好な形状安定性および加工性が得られるが、さらに形状安定性の向上を図るために含有させることが望ましい。 In the fire resistant rubber composition according to the present invention, aluminum phosphite is used as a shape stabilizer in order to prevent deformation after thermal expansion of the fire resistant rubber composition and a fire resistant coating material using the fire resistant rubber composition. Can be used. In the present invention, aluminum phosphite is not essential, and even when it is not contained, by combining the combination of other components and the blending amount thereof at a specific mass ratio as described above, good shape stability and workability can be obtained. Although it can be obtained, it is desirable to contain it in order to further improve the shape stability.
亜リン酸アルミニウムを含有させる場合、その平均粒径は、分散性の観点から、１〜１００μｍが好ましい。なお、この平均粒径は、レーザー回析法による粒子分布測定に基づく値である。粒子分布測定に用いる粒子分布測定機の種類は特に限定されないが、例えば、ベックマンコールター社製商品名「モデルＬＳ−２３０」を用いて粒子分布測定を行うことができる。 When aluminum phosphite is contained, the average particle size is preferably 1 to 100 μm from the viewpoint of dispersibility. The average particle diameter is a value based on particle distribution measurement by a laser diffraction method. The type of the particle distribution measuring instrument used for the particle distribution measurement is not particularly limited. For example, the particle distribution measurement can be performed using a product name “Model LS-230” manufactured by Beckman Coulter, Inc.
また、亜リン酸アルミニウムを含有させる場合、耐火ゴム組成物における亜リン酸アルミニウムの含有量は、ベースゴム成分１００質量部に対して１〜５０質量部であり、好ましくは１〜３０質量部である。５０質量部を超えると、本発明に係る耐火ゴム組成物においては、加工性が低下するとともに、熱膨張性が抑制され、膨張倍率が低下する場合がある。 Moreover, when aluminum phosphite is contained, the content of aluminum phosphite in the refractory rubber composition is 1 to 50 parts by mass, preferably 1 to 30 parts by mass with respect to 100 parts by mass of the base rubber component. is there. When the amount exceeds 50 parts by mass, the fireproof rubber composition according to the present invention may be deteriorated in workability, suppressed in thermal expansion, and reduced in expansion ratio.
以上説明した液状ゴム、ブチルゴム、粘着付与剤、熱膨張性黒鉛、亜リン酸アルミニウム、難燃剤、無機充填剤の各成分と、加硫剤、加硫促進剤を上記の特定比率で含有させ、未加硫のままの耐火ゴム組成物とすることで、これを用いた耐火被覆材等は好適な柔軟性と粘着性を有し、更に、好適な自然加硫性を備え、適切な加硫速度と十分な加硫後の強度を発揮するとともに良好な難燃性を有するものとなる。 Each component of the liquid rubber, butyl rubber, tackifier, thermally expandable graphite, aluminum phosphite, flame retardant, inorganic filler explained above, vulcanizing agent, vulcanization accelerator is contained in the above specific ratio, By using an unvulcanized refractory rubber composition, the refractory coating material using the refractory rubber composition has suitable flexibility and adhesiveness, and further has suitable natural vulcanizability, suitable vulcanization. It exhibits speed and sufficient strength after vulcanization and has good flame retardancy.
なお、本発明に係る耐火ゴム組成物には、その効果を阻害しない範囲で、可塑剤、軟化剤、老化防止剤、加工助剤、滑剤等を併用して用いてもよい。加工性の調整に有効な軟化剤や可塑剤の例としては、パラフィン系やナフテン系等のプロセスオイル、流動パラフィンやその他のパラフィン類、ワックス類、フタル酸やアジピン酸系、セバシン酸系やリン酸系等のエステル系可塑剤類、ステアリン酸やそのエステル類などがあげられる。 The fireproof rubber composition according to the present invention may be used in combination with plasticizers, softeners, anti-aging agents, processing aids, lubricants and the like as long as the effects thereof are not impaired. Examples of softeners and plasticizers that are effective in adjusting processability include paraffinic and naphthenic process oils, liquid paraffin and other paraffins, waxes, phthalic acid, adipic acid, sebacic acid and phosphorus. Examples include acid-based ester plasticizers, stearic acid and esters thereof.
本発明に係る耐火ゴム組成物は、少なくとも未加硫の状態であれば、前記の各成分を混練した状態のものも、混練前の状態のものも、どちらも包含する。前記各成分を混練する場合、その混練方法は、耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等が、混練後に自然加硫可能な状態であれば、特に限定されないが、例えば、６０〜１００℃にて前記各成分を混練すれば、混練中の加硫反応を確実に抑制することができる。仮に、１００℃を超えた温度で混練処理を行った場合には、混練中に加硫反応が進行してしまう場合が生じ、得られる耐火ゴム組成物の柔軟性に支障をきたしたり、適切な自然加硫性が発揮されない可能性も生じる場合がある。 The fire-resistant rubber composition according to the present invention includes both a kneaded state of the above components and a state before kneading as long as it is at least in an unvulcanized state. When kneading each component, the kneading method is not particularly limited as long as the refractory rubber composition and the refractory coating material using the refractory rubber composition can be naturally vulcanized after kneading, for example, If the components are kneaded at 60 to 100 ° C., the vulcanization reaction during kneading can be reliably suppressed. If the kneading treatment is performed at a temperature exceeding 100 ° C., the vulcanization reaction may proceed during the kneading, which may hinder the flexibility of the resulting refractory rubber composition or may be appropriate. There is a possibility that the natural vulcanizability may not be exhibited.
より具体的には、例えば、ツーローター式混練装置を用いて８０℃にて４０回転／分の回転速度で５分間混練し、加硫剤及び加硫促進剤を添加し、更に１００℃にて前記回転数で５分間混練する混練処理工程を行った場合、耐火ゴム組成物の加硫度が５％以下となるものが望ましい。また、同様の条件で混練処理を行った後の耐火ゴム組成物の針入度が３０〜６５度となれば、好適な柔軟性を具備するものとなる。なお、この針入度は、ＪＩＳ Ｋ２２０７に準拠し、荷重１００ｇ、温度２５℃において、規定の針を試験片に垂直に貫入させ、その深さを０．１ｍｍ単位で測定した値である。 More specifically, for example, using a two-rotor kneader, kneading for 5 minutes at a rotation speed of 40 rpm at 80 ° C., adding a vulcanizing agent and a vulcanization accelerator, and further at 100 ° C. When the kneading treatment step of kneading for 5 minutes at the rotation speed is performed, it is desirable that the refractory rubber composition has a vulcanization degree of 5% or less. Moreover, if the penetration of the refractory rubber composition after the kneading treatment under the same conditions is 30 to 65 degrees, suitable flexibility is provided. This penetration is a value obtained by measuring the depth in units of 0.1 mm by penetrating a specified needle vertically into a test piece at a load of 100 g and a temperature of 25 ° C. in accordance with JIS K2207.
本発明に係る耐火ゴム組成物及び該耐火ゴム組成物を用いた耐火被覆材等が有する自然加硫性は、太陽光の輻射熱等により自然加硫して次第に強度を増し、固着化できることを示すが、例えば、上記混練処理ののち、５０℃雰囲気下１２０日後において７０％以上まで加硫するように形成できれば、特に好適である。なお、この自然加硫速度は、異なる温度及び期間において評価することも当然に可能である。 The natural vulcanizability of the refractory rubber composition according to the present invention and the refractory coating material using the refractory rubber composition indicates that it can be naturally vulcanized by radiant heat of sunlight, etc., to gradually increase the strength and fix it. However, for example, it is particularly suitable if it can be formed to vulcanize to 70% or more after 120 days in a 50 ° C. atmosphere after the kneading treatment. Of course, the natural vulcanization rate can be evaluated at different temperatures and periods.
なお、上記混練処理工程に用いることができるツーローター式混練装置は、例えば、８０℃ないしは１００℃において回転速度４０回転／分での混練を可能とする装置であれば特に限定されず、公知の装置を用いることができる。例えば、バンバリーミキサー、ニーダーミキサー等を用いることができる。本発明においては、現在広く普及している加圧ニーダー（株式会社モリヤマ製の混合容量３リットル：ＤＳ３−１０ＭＷＢ−Ｓ型）を用いた。 The two-rotor kneading apparatus that can be used in the kneading treatment step is not particularly limited as long as it is an apparatus that can knead at 80 ° C. or 100 ° C. at a rotation speed of 40 rotations / min. An apparatus can be used. For example, a Banbury mixer, a kneader mixer, or the like can be used. In the present invention, a pressure kneader (mixed volume 3 liters manufactured by Moriyama Co., Ltd .: DS3-10MWB-S type) that is currently widely used was used.
＜耐火被覆材・耐火被覆材の製造方法＞
本発明に係る耐火ゴム組成物は、好適な柔軟性と粘着性を有し、更に、好適な自然加硫性を備え、適切な加硫速度と十分な加硫後の強度を発揮するとともに良好な難燃性を有するため、耐火被覆材に好適に用いることができる。
<Manufacturing method of fireproof coating / fireproof coating>
The refractory rubber composition according to the present invention has suitable flexibility and adhesiveness, further has suitable natural vulcanizability, exhibits an appropriate vulcanization speed and sufficient strength after vulcanization, and is good Therefore, it can be suitably used as a fireproof coating material.
本発明に係る耐火被覆材の形状は、特に限定されず、被覆する基材に合わせ、適宜設計することができる。例えば、テープ状あるいはシート状に成形すれば、鉄骨や壁等により簡便に貼り付けることができ、さらに作業効率を高めることが可能となる。 The shape of the fireproof coating material according to the present invention is not particularly limited, and can be appropriately designed according to the substrate to be coated. For example, if it is formed into a tape shape or a sheet shape, it can be easily attached by a steel frame or a wall, and the working efficiency can be further increased.
本発明に係る耐火被覆材は、前記耐火ゴム組成物を混練処理したのち、成形処理を行うことにより製造する。この際、混練処理温度を６０〜１００℃に保つと、上記混練処理後の耐火ゴム組成物の加硫度を５％以下に維持できるため、好適である。混練処理温度が１００℃を超えると、耐火ゴム組成物の加硫反応が進行してしまい、得られる耐火被覆材の粘着性及び柔軟性が低下したり、適切な自然加硫性が発揮されない可能性が生じるためである。 The fireproof coating material according to the present invention is produced by kneading the fireproof rubber composition and then performing a molding process. At this time, it is preferable to keep the kneading treatment temperature at 60 to 100 ° C. because the vulcanization degree of the refractory rubber composition after the kneading treatment can be kept at 5% or less. When the kneading temperature exceeds 100 ° C., the vulcanization reaction of the refractory rubber composition proceeds, and the adhesiveness and flexibility of the resulting refractory coating material may be reduced, or appropriate natural vulcanizability may not be exhibited. This is because sex occurs.
また、成形処理温度も１００℃以下に保つことが望ましい。同様に、成形処理温度が１００℃を超えると、耐火ゴム組成物の加硫反応が進行してしまい、得られる耐火被覆材の粘着性及び柔軟性が低下したり、適切な自然加硫性が発揮されない可能性が生じるためである。さらに、成形処理温度は、混練処理の温度よりも低く保つことがより望ましい。 Further, it is desirable to keep the molding processing temperature at 100 ° C. or lower. Similarly, when the molding treatment temperature exceeds 100 ° C., the vulcanization reaction of the refractory rubber composition proceeds, the adhesiveness and flexibility of the obtained refractory coating material are reduced, and appropriate natural vulcanizability is obtained. This is because there is a possibility that it will not be exhibited. Furthermore, it is more desirable to keep the molding process temperature lower than the temperature of the kneading process.
なお、上記混練処理工程に用いることができるツーローター式混練装置は、特に限定されず、公知の装置を用いることができる。例えば、バンバリーミキサー、ニーダーミキサー等を用いることができる。また、耐火ゴム組成物から耐火被覆材を成形する際の方法も特に限定されず、従来のプレス成形、押出成形、カレンダー成形等の方法を自由に採用することができる。 In addition, the two-rotor kneading apparatus that can be used in the kneading treatment step is not particularly limited, and a known apparatus can be used. For example, a Banbury mixer, a kneader mixer, or the like can be used. Moreover, the method at the time of shape | molding a fireproof coating material from a fireproof rubber composition is not specifically limited, The methods, such as conventional press molding, extrusion molding, and calendar molding, can be employ | adopted freely.
このようにして成形された耐火被覆材は、優れた粘着性を有するので、基材表面に耐火被覆材を施工する際に、耐火被覆材は自身の有する粘着力に基づいて基材表面へ接着し、保持される。従って、従来の防火用膨張材料と異なり、鉄骨や壁等へ貼り付ける際に、不織布、金網、セラミック材料等の面材を釘やピン、ネジ等によって補強固定する必要がない。また、粘着状態の耐火被覆材は、柔軟性を維持しているので、一旦基材表面へ貼り付けて位置決めを行った後にも、再度、剥離して貼りかえることが可能である。 The fire-resistant coating material formed in this way has excellent adhesiveness, so when applying the fire-resistant coating material to the substrate surface, the fire-resistant coating material adheres to the substrate surface based on its own adhesive strength. And retained. Therefore, unlike conventional fire-resistant expansion materials, it is not necessary to reinforce and fix face materials such as non-woven fabrics, wire meshes, and ceramic materials with nails, pins, screws, and the like when affixing to steel frames or walls. In addition, since the fire-resistant coating material in an adhesive state maintains flexibility, it can be peeled and replaced again after it is once attached to the surface of the substrate and positioned.
さらに、鉄骨や壁等へ貼り付けられた耐火被覆材は、自然加硫により次第に硬度を増して、貼り付け当初の粘着状態から、次第に固着状態へと変化し、鉄骨や壁等の表面に強固な被覆を形成する。このように強固な被覆を形成するに至った耐火被覆材は、もはや容易に剥離、脱落することがないので、従来の防火用膨張材料のように、鉄骨や壁等へ貼り付けた後、外側から不織布、金網、セラミック材料等の面材を釘やピン、ネジ等によって補強固定する必要がなく、炎熱に曝された場合にも剥離、脱落しにくい。 In addition, fireproof coatings applied to steel frames and walls, etc., gradually increase in hardness by natural vulcanization, and gradually change from an adhesive state at the time of application to a fixed state, and firmly adhere to the surfaces of steel frames and walls. A smooth coating. Since the fireproof coating material that has led to the formation of such a strong coating can no longer be easily peeled off and dropped off, after being attached to a steel frame or wall, etc. Therefore, it is not necessary to reinforce and fix face materials such as non-woven fabrics, wire meshes, and ceramic materials with nails, pins, screws, and the like, and even when exposed to flame heat, they do not easily peel off or fall off.
加えて、本発明に係る耐火被覆材には、前記の粘着性や自然加硫性を損なわない程度の特定質量比の難燃剤を含有するため、火炎に曝され、含有する熱膨張性黒鉛が熱膨張を開始する際に、成形体内部から熱分解ガスが発生しそれに火炎が引火し燃焼するのを防止することができる。そのため、耐火被覆材自身の発火による、内部の鉄骨温度の上昇を防止する効果も発揮する。 In addition, since the fireproof coating material according to the present invention contains a flame retardant having a specific mass ratio that does not impair the above-mentioned adhesiveness and natural vulcanizability, it is exposed to a flame and contains thermally expandable graphite. When thermal expansion is started, it is possible to prevent pyrolysis gas from being generated from the inside of the molded body and the flame to ignite and burn. Therefore, the effect which prevents the raise of an internal steel frame temperature by the ignition of a fireproof coating material itself is also exhibited.
＜耐火被覆処理方法＞
本発明に係る耐火被覆処理方法は、前記耐火被覆材の特性を利用したものである。まず、前記耐火被覆材の有する粘着力に基づいて基材表面へ粘着させる。前記耐火被覆材は粘着性を有するため、従来の防火用膨張材料と異なり、鉄骨や壁等へ貼り付ける際に、接着剤、釘、ピン、ネジ等を用いる必要がない。また、粘着状態の耐火被覆材は、柔軟性を維持しているので、一旦基材表面へ貼り付けて位置決めを行った後にも、再度、剥離して貼りかえることが可能である。
<Fireproof coating treatment method>
The fireproof coating treatment method according to the present invention utilizes the characteristics of the fireproof coating material. First, it adheres to the base-material surface based on the adhesive force which the said fireproof coating material has. Since the fireproof covering material has adhesiveness, it is not necessary to use an adhesive, a nail, a pin, a screw, or the like when affixing to a steel frame, a wall or the like unlike a conventional fireproof expansion material. In addition, since the fire-resistant coating material in an adhesive state maintains flexibility, it can be peeled and replaced again after it is once attached to the surface of the substrate and positioned.
次に、基材表面へ粘着された耐火被覆材を、自然加硫により基材表面へ固着化させる。前記耐火被覆材は、自然加硫性を有するため、太陽光の輻射熱等により自然加硫して次第に強度を増し、基材表面へ固着化させることができる。このように本発明に係る耐火被覆処理では、貼り付け当初の粘着状態から、次第に固着状態へと変化し、鉄骨や壁等の表面に強固な被覆を形成する。 Next, the fireproof coating material adhered to the substrate surface is fixed to the substrate surface by natural vulcanization. Since the refractory coating material has natural vulcanization properties, it can be naturally vulcanized by radiant heat of sunlight, etc. to gradually increase the strength, and can be fixed to the substrate surface. As described above, in the fireproof coating treatment according to the present invention, the adhesive state at the time of application is gradually changed to the fixed state, and a strong coating is formed on the surface of a steel frame, a wall or the like.
自然加硫が進行した後の耐火被覆材は、強固な被覆を形成するため、もはや容易に剥離、脱落することがないので、従来の防火用膨張材料のように、鉄骨や壁等へ貼り付けた後、外側から不織布、金網、セラミック材料等の面材を釘やピン、ネジ等によって補強固定する必要がなく、炎熱に曝された場合にも剥離、脱落しにくい。 Since the fireproof coating after natural vulcanization has progressed, it forms a strong coating and can no longer be easily peeled off or dropped off, so it can be applied to steel frames, walls, etc. like conventional fireproof expansion materials. After that, it is not necessary to reinforce and fix a face material such as a nonwoven fabric, a wire mesh, or a ceramic material from the outside with a nail, a pin, a screw, or the like, and it is difficult to peel off or fall off even when exposed to flame heat.
また、本発明に係る耐火被覆処理では、耐火被覆材の基材表面への固定を、自然加硫で行うため、前記のような、固定作業を省略でき、耐火被覆処理に要するコストや時間の軽減も実現できる。 Further, in the fireproof coating treatment according to the present invention, since the fireproof coating material is fixed to the base material surface by natural vulcanization, the fixing work as described above can be omitted, and the cost and time required for the fireproof coating treatment are reduced. Mitigation is also possible.
以下、本発明を実施例及び比較例により具体的に説明するが、これらの実施例は本発明を限定するものでない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, these Examples do not limit this invention.
なお、以下の説明における部及び％は質量基準に基づく。実施例において使用した材料は、それぞれ以下に示したものである。
（１）液状ゴム：ポリブテン；ＢＰ Ｊａｐａｎ（株）製、「Ｈ−３００」
（２）ブチルゴム：ＪＳＲ（株）製、「ブチル２６８」
（３）粘着付与剤：テルペン系樹脂；ヤスハラケミカル（株）製、「ＹＳレジンＰＸ−１００」
（４）熱膨張性黒鉛：エア・ウオーター・ケミカル（株）製、「ＳＳ−３」（熱膨張開始温度２２０℃）
（５）亜リン酸アルミニウム：太平化学産業（株）、「ＡＰＡ―１００」
（６）難燃剤：ポリリン酸アンモニウムアミド；太平化学産業（株）、「タイエンＳ」、ポリリン酸アンモニウム；クラリアント社製、「ＡＰ−４２２」
（７）無機充填剤：クレー；（株）群馬長石御座入鉱山製、「ＦＡ−８０」、炭酸カルシウム；備北粉化工業（株）、「ホワイトンＳＢ」、カーボンブラック；旭カーボン（株）製、「＃８０」、水酸化アルミニウム；昭和電工（株）製、「ハイジライトＨ３１」、フライアッシュバルーン；巴工業（株）製「セノライトＳＡ」
（８）加硫剤：粉末硫黄（細井化学工業（株）製）
（９）加硫促進剤：ジメチルジチオカルバミン酸亜鉛；大内新興（株）製、「ノクセラーＰＺ」、ジ−ｎ−ブチルジチオカルバミン酸亜鉛；大内新興（株）製、「ノクセラーＢＺ」
In addition, the part and% in the following description are based on a mass reference | standard. The materials used in the examples are as shown below.
(1) Liquid rubber: polybutene; “H-300” manufactured by BP Japan
(2) Butyl rubber: “Butyl 268” manufactured by JSR Corporation
(3) Tackifier: Terpene resin; “YS Resin PX-100” manufactured by Yasuhara Chemical Co., Ltd.
(4) Thermally expandable graphite: “SS-3” (thermal expansion start temperature 220 ° C.), manufactured by Air Water Chemical Co., Ltd.
(5) Aluminum phosphite: Taihei Chemical Industry Co., Ltd., “APA-100”
(6) Flame retardant: Polyphosphate ammonium amide; Taihei Chemical Sangyo Co., Ltd., “Tyen S”, ammonium polyphosphate; manufactured by Clariant, “AP-422”
(7) Inorganic filler: Clay; “FA-80”, Gunma Nagaishi Gozairi Mine Co., Ltd .; Calcium carbonate; Bihoku Flour Chemical Co., Ltd., “Whiteon SB”, Carbon Black; Asahi Carbon Co., Ltd. “# 80”, aluminum hydroxide; Showa Denko Co., Ltd., “Heidilite H31”, fly ash balloon; Sakai Kogyo Co., Ltd. “Cenolite SA”
(8) Vulcanizing agent: Powdered sulfur (made by Hosoi Chemical Co., Ltd.)
(9) Vulcanization accelerator: zinc dimethyldithiocarbamate; manufactured by Ouchi Eshin Co., Ltd., “Noxeller PZ”, zinc di-n-butyldithiocarbamate; manufactured by Ouchi Eshin Co., Ltd., “Noxeller BZ”
実施例１〜６及び比較例１〜９において、下記の各特性を評価した。各特性の測定方法を以下に示す。なお、試験片には耐火ゴム組成物を縦２５ｍｍ×横100ｍｍ×厚み２ｍｍのテープ状に加工した耐火被覆材を用いた。
（１）熱膨張倍率：試験片を３００℃で保持された雰囲気内に０．５時間放置した後の膨張倍率を測定した。
（２）加工性：カレンダー成形機で試験片を成形する際に、問題なく成形できたものを「良」、外観不良発生あるいは安定した成形が出来なかったものを「不可」と評価した。
（３）形状安定性：熱膨張倍率測定後の試験片の形状を目視と指触で評価した。型崩れせず指で触っても崩れないものを「良」、指触ですぐ崩れるか、あるいは既に崩れてしまったものを「不可」と評価した。
（４）燃焼抑制効果：電気炉（（株）デンケン製、ＫＤＦ−Ｓ９０）を６００℃に昇温し、上記試験片を炉内に入れた後扉を閉め５分間放置。その後開閉し内部の試験片の燃焼状態を目視で観察した。試験片の燃焼が３０秒間以内に収まった場合を「良」、３０秒間以上継続した場合を「不可」と評価した。
（５）針入度：ＪＩＳ Ｋ２２０７に準拠し荷重１００ｇ、温度２５℃において測定を行った。規定の針を試験片に垂直に貫入させ、その深さを０．１ｍｍ単位で測定した。
（６）加硫度：ＪＩＳ Ｋ６３００記載の方法で、キュラストメーターIII型（ＪＳＲトレーディング社製）でトルクを測定した。加硫度（％）＝（MX−ML）／（MM−ML）×１００（MXはある期間を経た材料のトルク値、MLは測定曲線におけるトルクの最小値、MMは測定曲線におけるトルクの最大値）
（７）Ｔ型剥離接着強さ：ＪＩＳ Ｋ６８５４の剥離接着強さ試験方法に準拠して接着強度を測定した。大きさが縦２５ｍｍ×横１５０ｍｍ×厚み２ｍｍのＳＵＳ板に試験片を挟んでハンドローラーで圧着した。貼り付け直後及び５０℃オーブン中に４ヶ月放置後において剥離速度を５０ｍｍ／ｍｉｎとし、Ｔ型剥離接着強さ試験を行った。
In Examples 1 to 6 and Comparative Examples 1 to 9, the following characteristics were evaluated. The measuring method of each characteristic is shown below. In addition, the fireproof coating material which processed the fireproof rubber composition into the tape shape of 25 mm long x 100 mm wide x 2 mm thickness was used for the test piece.
(1) Thermal expansion ratio: The expansion ratio after the test piece was left in an atmosphere maintained at 300 ° C. for 0.5 hours was measured.
(2) Workability: When a test piece was molded with a calender molding machine, those that could be molded without any problem were evaluated as “good”, and those that had poor appearance or could not be stably molded were evaluated as “impossible”.
(3) Shape stability: The shape of the test piece after the measurement of the thermal expansion ratio was evaluated by visual observation and finger touch. Those that did not lose shape and did not collapse even when touched with a finger were evaluated as “good”, and those that immediately collapsed with a finger touch or that had already collapsed were evaluated as “impossible”.
(4) Combustion suppression effect: The temperature of the electric furnace (KDF-S90, manufactured by Denken Co., Ltd.) is raised to 600 ° C., and the test piece is placed in the furnace, and then the door is closed and left for 5 minutes. Thereafter, it was opened and closed, and the combustion state of the internal test piece was visually observed. The case where the test piece burned within 30 seconds was evaluated as “good”, and the case where the test piece continued for 30 seconds or more was evaluated as “impossible”.
(5) Penetration: Measurement was performed at a load of 100 g and a temperature of 25 ° C. according to JIS K2207. A specified needle was vertically penetrated into the test piece, and the depth was measured in units of 0.1 mm.
(6) Vulcanization degree: Torque was measured with a curast meter type III (manufactured by JSR Trading) by the method described in JIS K6300. Vulcanization degree (%) = (MX−ML) / (MM−ML) × 100 (MX is the torque value of the material after a certain period, ML is the minimum torque value in the measurement curve, MM is the maximum torque value in the measurement curve) value)
(7) T-type peel bond strength: The bond strength was measured in accordance with the peel bond strength test method of JIS K6854. A test piece was sandwiched between SUS plates having a size of 25 mm in length, 150 mm in width, and 2 mm in thickness, and pressed with a hand roller. Immediately after pasting and after leaving in a 50 ° C. oven for 4 months, the peel rate was set to 50 mm / min, and a T-type peel adhesion strength test was performed.
表１及び表２は、液状ゴム、ブチルゴム、粘着付与剤、熱膨張性黒鉛、亜リン酸アルミニウム、難燃剤、無機充填剤、加硫剤、加硫促進剤の配合比率を変化させて成形した試験片の各特性を示す。試験片は、液状ゴム、ブチルゴム、粘着付与剤、熱膨張性黒鉛、亜リン酸アルミニウム、難燃剤、無機充填剤を、株式会社モリヤマ製の混合容量３リットルの加圧ニーダー（機器名：ＤＳ３−１０ＭＷＢ−Ｓ型）を用いて８０℃にて４０回転／分の回転速度で５分間混練し、加硫剤および加硫促進剤を添加し更に１００℃にて同じ回転数で５分間混練した後、カレンダー成形機を用い８０℃にて試験片を成形した。 Tables 1 and 2 were molded by changing the blending ratio of liquid rubber, butyl rubber, tackifier, thermally expandable graphite, aluminum phosphite, flame retardant, inorganic filler, vulcanizing agent, and vulcanization accelerator. Each characteristic of a test piece is shown. The test piece was liquid rubber, butyl rubber, tackifier, thermally expandable graphite, aluminum phosphite, flame retardant, inorganic filler, and a pressure kneader (equipment name: DS3-) manufactured by Moriyama Corporation. 10MWB-S type) at 80 ° C. at a rotation speed of 40 rpm for 5 minutes, after adding a vulcanizing agent and a vulcanization accelerator and further kneading at 100 ° C. at the same rotational speed for 5 minutes. A test piece was molded at 80 ° C. using a calendar molding machine.
表１に示すとおり、本発明の実施例１〜５は、十分な熱膨張倍率と良好な加工性を保持しながら、優れた形状安定性をも具備するものとなっていた。また、針入度が３０〜６５度、貼り付け直後のＴ型剥離接着強さが４．５Ｎ／２５ｍｍ以上であって、好適な柔軟性と十分な粘着性を備えるものとなっていた。 As shown in Table 1, Examples 1 to 5 of the present invention had excellent shape stability while maintaining sufficient thermal expansion ratio and good workability. Further, the penetration was 30 to 65 degrees, and the T-type peel adhesion strength immediately after pasting was 4.5 N / 25 mm or more, and it had suitable flexibility and sufficient tackiness.
さらに、自然加硫性の評価においては、実施例１〜５とも、５０℃雰囲気下４ヶ月後における加硫度が７０％以上となり、Ｔ剥離接着強さは、貼り付け直後の５Ｎ／２５ｍｍ程度から３５〜４９Ｎ／２５ｍｍへ７倍以上増加していた。これらの数値より実施例１〜５にかかる耐火被覆材が、好適な加硫速度と加硫後の固着性を具備することを示すものである。 Furthermore, in the evaluation of natural vulcanizability, in all of Examples 1 to 5 , the vulcanization degree after 4 months in a 50 ° C. atmosphere is 70% or more, and the T peel adhesion strength is about 5 N / 25 mm immediately after pasting. From 35 to 49 N / 25 mm. From these numerical values, it is shown that the fireproof coating materials according to Examples 1 to 5 have a suitable vulcanization speed and adhesiveness after vulcanization.
加えて、燃焼抑制効果の評価においても、実施例１〜５とも、難燃剤を特定質量比配合することにより、前記の加工性、形状安定性、柔軟性、粘着性、自然加硫性などの機能に影響を与えることなく、燃焼抑制効果をも著しく改善されていた。 In addition, also in the evaluation of the combustion suppression effect, in Examples 1 to 5 , the above-described processability, shape stability, flexibility, adhesiveness, natural vulcanizability, etc. are obtained by blending a specific mass ratio of flame retardant. The combustion suppression effect was also significantly improved without affecting the function.
比較例１は、粘着付与剤、熱膨張性黒鉛、難燃剤、無機充填剤が配合されていないため、接着性が不十分で、熱膨張性を欠き、燃焼抑制効果も劣り、各構成成分のバランスも欠いているために形状安定性も劣っていた。また、針入度が１６０度と高すぎることから、柔軟性が高すぎて、貼り付け時の操作性が低下すると考えられる。 In Comparative Example 1, since no tackifier, thermally expandable graphite, flame retardant, and inorganic filler are blended, the adhesiveness is insufficient, the thermal expandability is lacking, and the combustion suppressing effect is inferior. Due to lack of balance, shape stability was also inferior. Further, since the penetration is too high at 160 degrees, it is considered that the flexibility is too high and the operability at the time of pasting is lowered.
比較例２は、難燃剤が配合されないため、燃焼抑制効果を欠き、また、粘着付与剤も配合されないため、接着性も不十分で、各構成成分のバランスも欠いているために形状安定性も劣っていた。さらに、針入度が１０５度と高すぎることから、柔軟性が高すぎて、貼り付け時の操作性が低下すると考えられる。 Comparative Example 2 lacks a flame suppression effect because it does not contain a flame retardant, and also lacks adhesion because it does not contain a tackifier. It was inferior. Further, since the penetration is too high at 105 degrees, it is considered that the flexibility is too high and the operability at the time of pasting is lowered.
比較例３は、熱膨張性黒鉛及び難燃剤が配合されないため、熱膨張性及び燃焼抑制効果を欠き、また、各構成成分のバランスも欠いているために形状安定性も劣っていた。 Comparative Example 3 lacked thermal expansibility and combustion suppression effect because no thermal expansive graphite and flame retardant were blended, and also lacked the balance of each constituent component, resulting in poor shape stability.
比較例４は、難燃剤が配合されないため、燃焼抑制効果を欠き、各構成成分のバランスも欠いているために形状安定性も劣っていた。 Since the flame retardant was not mix | blended with the comparative example 4, the combustion suppression effect was missing, and since the balance of each component was also missing, shape stability was also inferior.
比較例５は、難燃剤が配合されないため、燃焼抑制効果を欠き、また、加硫剤及び加硫促進剤が配合されないため、自然加硫性を欠いていた。 In Comparative Example 5, since no flame retardant was blended, the effect of suppressing combustion was lacking, and since no vulcanizing agent and vulcanization accelerator were blended, natural vulcanizability was lacking.
比較例６は、熱膨張性黒鉛を１１０質量部にまで配合したため、熱膨張倍率は向上するものの、形状安定性が不良となっていた。また、難燃剤が配合されないため、燃焼抑制効果も欠いていた。 In Comparative Example 6, since the thermal expansion graphite was blended up to 110 parts by mass, the thermal expansion ratio was improved, but the shape stability was poor. Moreover, since a flame retardant was not blended, the combustion suppression effect was also lacking.
比較例７は、液状ゴム４０質量部、ブチルゴムを６０質量部としたベースゴム成分１００質量部に対して、無機充填剤を２５０質量部まで配合したため、加工性不良となった。 Since the comparative example 7 mix | blended the inorganic filler with 250 mass parts with respect to 100 mass parts of base rubber components which used 40 mass parts of liquid rubbers and 60 mass parts of butyl rubbers, it became workability defect.
比較例８は、ベースゴム成分１００質量部に対して、加硫剤を１１質量部配合し、更に加硫促進剤を１１質量部（ノクセラーＰＺ：５．５質量部、ＢＺ：５．５質量部の合計）配合した。この場合、加工性が不良となることが分かった。これは自然加硫速度が速くなりすぎて、混練・成形工程中に加硫反応が進み、柔軟性が失われたためと考えられる。 In Comparative Example 8, 11 parts by mass of the vulcanizing agent is blended with 100 parts by mass of the base rubber component, and further 11 parts by mass of the vulcanization accelerator (Noxeller PZ: 5.5 parts by mass, BZ: 5.5 parts by mass). Part total). In this case, it was found that workability was poor. This is presumably because the natural vulcanization speed became too high, and the vulcanization reaction progressed during the kneading and molding process, resulting in loss of flexibility.
比較例９は、ベースゴム成分１００質量部に対して、亜リン酸アルミニウムを１３０質量部配合したため、熱膨張倍率が低下し、加工性も不良であった。 Since the comparative example 9 mix | blended 130 mass parts of aluminum phosphites with respect to 100 mass parts of base rubber components, the thermal expansion magnification fell and workability was also inferior.
表３は加硫剤および加硫促進剤を添加した後の混練工程（５分間）及びカレンダー成形機にて成形する際の温度を変化させて得た試験片の各特性を示す。実施例６及び比較例１０は、液状ゴム、ブチルゴム、粘着付与剤、熱膨張性黒鉛、亜リン酸アルミニウム、難燃剤、無機充填剤、加硫剤、加硫促進剤の配合比率は同じであるが、実施例６においては混練工程及び成形工程の温度がそれぞれ１００℃、８０℃であるのに対して、比較例１０においてはともに１３０℃に設定した。 Table 3 shows each characteristic of the test piece obtained by changing the kneading step (5 minutes) after adding the vulcanizing agent and the vulcanization accelerator and the temperature at the time of molding with a calendar molding machine. In Example 6 and Comparative Example 10, the mixing ratios of liquid rubber, butyl rubber, tackifier, thermally expandable graphite, aluminum phosphite, flame retardant, inorganic filler, vulcanizing agent, and vulcanization accelerator are the same. However, in Example 6 , the temperatures of the kneading step and the forming step were 100 ° C. and 80 ° C., respectively, whereas in Comparative Example 10, both were set to 130 ° C.
実施例６では、混練・成形工程の温度を１００℃以下に維持することで、試験片の加硫度は３％に抑制されるのに対して、比較例１０では混練・成形工程の温度を１３０℃と高く設定したことにより、試験片の加硫が１５％にまで進んでいた。比較例１０では、このように加硫が進行してしまうことにより、接着性の低下が引き起こされていた。 In Example 6 , by maintaining the temperature of the kneading / molding step at 100 ° C. or lower, the vulcanization degree of the test piece is suppressed to 3%, whereas in Comparative Example 10, the temperature of the kneading / molding step is By setting the temperature as high as 130 ° C., the vulcanization of the test piece progressed to 15%. In Comparative Example 10, the vulcanization proceeded in this manner, which caused a decrease in adhesiveness.
本発明に係る耐火ゴム組成物、該耐火ゴム組成物からなる耐火被覆材、及び
該耐火被覆材を用いた耐火被覆処理方法は、鉄骨等の耐火被覆処理に用いることができる。さらに、防火壁と電源ケーブル間等の防火用目地材として電源ケーブルに巻きつけて開口部に挿入することで、火災時の延焼防止や建造物の倒壊防止にも有用である。
The fire-resistant rubber composition according to the present invention, the fire-resistant coating material comprising the fire-resistant rubber composition, and the fire-resistant coating treatment method using the fire-resistant coating material can be used for fire-resistant coating treatment of steel frames and the like. Furthermore, it is also useful for preventing the spread of fire in the event of fire and preventing the collapse of the building by wrapping around the power cable as a fireproof joint material between the fire wall and the power cable and inserting it into the opening.
Claims (9)
６０〜１００℃にて混練されることにより未加硫のまま成形され自然加硫性を備えた耐火被覆材。 3 to 50 parts by mass of a tackifier and 10 to 100 of thermally expandable graphite with respect to 100 parts by mass of a base rubber component composed of 30 to 60 parts by mass of liquid rubber and 40 to 70 parts by mass of butyl rubber. 30 parts by mass, flame retardant 30-180 parts by mass, inorganic filler 30-210 parts by mass, vulcanizing agent 0.1-10 parts by mass, vulcanization accelerator 0.1-10 parts by mass, phosphorous acid Using a refractory rubber composition containing at least 1 to 50 parts by mass of aluminum ,
A refractory coating material which is molded without being vulcanized by being kneaded at 60 to 100 ° C. and has a natural vulcanization property .
さらに、該耐火被覆材の自然加硫によって基材表面へ固着化させることを特徴とする請求項８記載の耐火被覆処理方法。 After the fireproof coating material is adhered to the substrate surface by the adhesive force of the fireproof coating material,
The fireproof coating treatment method according to claim 8, further comprising fixing the fireproof coating material to the surface of the substrate by natural vulcanization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007317718A JP4270470B1 (en) | 2007-12-07 | 2007-12-07 | Fireproof coating material, method for producing the fireproof coating material, and fireproof coating method using the fireproof coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007317718A JP4270470B1 (en) | 2007-12-07 | 2007-12-07 | Fireproof coating material, method for producing the fireproof coating material, and fireproof coating method using the fireproof coating material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008274271A Division JP4312254B2 (en) | 2008-10-24 | 2008-10-24 | Refractory rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP4270470B1 true JP4270470B1 (en) | 2009-06-03 |
| JP2009138147A JP2009138147A (en) | 2009-06-25 |
Family
ID=40821504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007317718A Active JP4270470B1 (en) | 2007-12-07 | 2007-12-07 | Fireproof coating material, method for producing the fireproof coating material, and fireproof coating method using the fireproof coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4270470B1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7668401B2 (en) | 2003-09-03 | 2010-02-23 | Nec Corporation | Form changing device, object action encoding device, and object action decoding device |
| JP2018090754A (en) * | 2016-01-27 | 2018-06-14 | 積水化学工業株式会社 | Fire-resistant resin composition |
| JP2021063233A (en) * | 2016-02-02 | 2021-04-22 | 積水化学工業株式会社 | Fire-resistant resin composition |
| CN115232577A (en) * | 2022-08-01 | 2022-10-25 | 科建高分子材料（上海）股份有限公司 | Fireproof butyl rubber and application thereof in multilayer composite fireproof coiled material |
| CN115772297A (en) * | 2021-09-06 | 2023-03-10 | 深圳科创新源新材料股份有限公司 | Expansion type fire-retardant wrapping tape with self-adhesion property and preparation method and application thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4669573B1 (en) * | 2010-07-07 | 2011-04-13 | 電気化学工業株式会社 | Thermally expandable joint material for fire protection |
| KR20180103841A (en) * | 2016-01-20 | 2018-09-19 | 세키스이가가쿠 고교가부시키가이샤 | Refractory resin composition |
| JP6875139B2 (en) * | 2016-02-02 | 2021-05-19 | 積水化学工業株式会社 | Refractory resin composition |
| WO2017150515A1 (en) * | 2016-02-29 | 2017-09-08 | 積水化学工業株式会社 | Refractory elastomer composition and molded article thereof |
| JP2018150391A (en) * | 2017-03-09 | 2018-09-27 | 旭化成建材株式会社 | Heat expansion refractory composition |
| JP6991839B2 (en) * | 2017-11-20 | 2022-01-13 | タイガースポリマー株式会社 | Refractory laminate, tubular laminate using it, and battery isolation structure |
| WO2020065243A1 (en) | 2018-09-28 | 2020-04-02 | Tremco Illbruck Limited | Fire-stopping product |
| JP7018108B1 (en) | 2020-10-15 | 2022-02-09 | デンカ株式会社 | Refractory material |
-
2007
- 2007-12-07 JP JP2007317718A patent/JP4270470B1/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7668401B2 (en) | 2003-09-03 | 2010-02-23 | Nec Corporation | Form changing device, object action encoding device, and object action decoding device |
| JP2018090754A (en) * | 2016-01-27 | 2018-06-14 | 積水化学工業株式会社 | Fire-resistant resin composition |
| JP2022048180A (en) * | 2016-01-27 | 2022-03-25 | 積水化学工業株式会社 | Fire-resistant resin composition |
| JP2021063233A (en) * | 2016-02-02 | 2021-04-22 | 積水化学工業株式会社 | Fire-resistant resin composition |
| JP7084511B2 (en) | 2016-02-02 | 2022-06-14 | 積水化学工業株式会社 | Refractory resin composition |
| CN115772297A (en) * | 2021-09-06 | 2023-03-10 | 深圳科创新源新材料股份有限公司 | Expansion type fire-retardant wrapping tape with self-adhesion property and preparation method and application thereof |
| CN115772297B (en) * | 2021-09-06 | 2024-04-23 | 深圳科创新源新材料股份有限公司 | Self-adhesive expansion type fire-retardant belting and preparation method and application thereof |
| CN115232577A (en) * | 2022-08-01 | 2022-10-25 | 科建高分子材料（上海）股份有限公司 | Fireproof butyl rubber and application thereof in multilayer composite fireproof coiled material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009138147A (en) | 2009-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4270470B1 (en) | Fireproof coating material, method for producing the fireproof coating material, and fireproof coating method using the fireproof coating material | |
| JP4312254B2 (en) | Refractory rubber composition | |
| JP4021934B1 (en) | Refractory rubber composition, refractory coating comprising the refractory rubber composition, and refractory coating treatment method using the refractory coating | |
| JP4669573B1 (en) | Thermally expandable joint material for fire protection | |
| JP3363156B2 (en) | Fire-resistant sheet-like molded product, fire-resistant laminate for steel frame coating, fire-resistant structure for wall, and method of construction of fire-resistant steel frame and fire-resistant wall | |
| JP4450760B2 (en) | Joint materials and gaskets | |
| JP2002540285A (en) | Inflatable fire sealing composition | |
| WO2016117702A1 (en) | Refractory resin composition | |
| CA2928916C (en) | Hot melt intumescent materials for fire protection | |
| WO2013008819A1 (en) | Covering material | |
| JP4490860B2 (en) | Joint materials and gaskets | |
| JP2000038785A (en) | Adhesive fire resistant sheet | |
| WO2000032707A1 (en) | Fire-resistant coating material | |
| US20230407109A1 (en) | Thermoexpandable refractory material composition, thermoexpandable refractory material, and method for producing thermoexpandable refractory material | |
| JP2003192840A (en) | Adhesive fireproof rubber composition and sheet | |
| JP4277029B2 (en) | Foam molding | |
| JP2018035299A (en) | Thermally expanded fire-resistant resin composition | |
| JP3832703B2 (en) | Fire resistant paint | |
| JPWO2012132475A1 (en) | High fire resistant rubber composition sheet | |
| JP7545377B2 (en) | Fire-resistant resin composition, fire-resistant sheet and fittings | |
| JP2001011979A (en) | Fire-resistant member | |
| JP6270199B2 (en) | Laminated structure and method for forming the same | |
| JP2011063783A (en) | Intumescent resin composition for fire prevention | |
| JPH11138678A (en) | Fire resistant and heat insulating multilayer sheet | |
| JP2006247626A (en) | Method for manufacturing fireproof coating material and fireproof coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20081125 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090217 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090219 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120306 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4270470 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120306 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130306 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140306 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |