JP2021195388A - Polyvinylchloride composition, and fireproof sheet - Google Patents
Polyvinylchloride composition, and fireproof sheet Download PDFInfo
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- JP2021195388A JP2021195388A JP2020100382A JP2020100382A JP2021195388A JP 2021195388 A JP2021195388 A JP 2021195388A JP 2020100382 A JP2020100382 A JP 2020100382A JP 2020100382 A JP2020100382 A JP 2020100382A JP 2021195388 A JP2021195388 A JP 2021195388A
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- polyvinyl chloride
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 118
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 118
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 38
- 239000010439 graphite Substances 0.000 claims abstract description 37
- 239000004014 plasticizer Substances 0.000 claims abstract description 30
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- -1 phosphorous acid aluminum Chemical compound 0.000 abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 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 description 13
- 239000003063 flame retardant Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000009970 fire resistant effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 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
- 239000002994 raw material Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- URJITOLRUFWZLN-DCVDYEDCSA-H (Z)-but-2-enedioate octyltin(3+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O.CCCCCCCC[Sn+3].CCCCCCCC[Sn+3] URJITOLRUFWZLN-DCVDYEDCSA-H 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- IRIAEMUUDSWZOX-UHFFFAOYSA-L 2,2-dibutyl-1,3,2-oxathiastanninan-6-one Chemical compound CCCC[Sn]1(CCCC)OC(=O)CCS1 IRIAEMUUDSWZOX-UHFFFAOYSA-L 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- RZBBHEJLECUBJT-UHFFFAOYSA-N 6-methylheptyl 2-sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS RZBBHEJLECUBJT-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AJDTZVRPEPFODZ-PAMPIZDHSA-J [Sn+4].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O Chemical compound [Sn+4].[O-]C(=O)\C=C/C([O-])=O.[O-]C(=O)\C=C/C([O-])=O AJDTZVRPEPFODZ-PAMPIZDHSA-J 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- XEUARARHXKIMHT-UHFFFAOYSA-K antimony(3+);sulfanylformate Chemical class [Sb+3].[O-]C(S)=O.[O-]C(S)=O.[O-]C(S)=O XEUARARHXKIMHT-UHFFFAOYSA-K 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 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
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- IESWIBSMHJCJAG-UHFFFAOYSA-L dibutyltin(2+);8-methyl-2-(6-methylheptyl)-2-sulfanylnonanoate Chemical compound CCCC[Sn+2]CCCC.CC(C)CCCCCC(S)(C([O-])=O)CCCCCC(C)C.CC(C)CCCCCC(S)(C([O-])=O)CCCCCC(C)C IESWIBSMHJCJAG-UHFFFAOYSA-L 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YDRIDNHBHBBQRF-UHFFFAOYSA-N ethyl 2,2-diaminooctadecanoate Chemical compound CCCCCCCCCCCCCCCCC(N)(N)C(=O)OCC YDRIDNHBHBBQRF-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XTQIDVCLCLXOKX-UHFFFAOYSA-N hydrogen phosphite;lead(2+);oxolead;hydrate Chemical compound O.[Pb+2].[Pb+2].[Pb]=O.[Pb]=O.[Pb]=O.[Pb]=O.OP([O-])[O-].OP([O-])[O-] XTQIDVCLCLXOKX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-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
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000001931 thermography Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ポリ塩化ビニル組成物及び耐火シートに関する。 The present invention relates to polyvinyl chloride compositions and refractory sheets.
リチウムイオン二次電池などの二次電池は複数のセルを筐体内に並置して使用されることが多い。複数のセルのうち一つが異常発火すると、隣接するセルが類焼して筐体内のセルが全損する問題がある。このような類焼を防止するために、特許文献１にはセル同士の間に難燃剤を含むシートの積層体を配置することが提案されている。 A secondary battery such as a lithium ion secondary battery is often used by arranging a plurality of cells side by side in a housing. If one of the plurality of cells ignites abnormally, there is a problem that the adjacent cells are burnt and the cells in the housing are completely damaged. In order to prevent such burning, Patent Document 1 proposes arranging a laminated body of sheets containing a flame retardant between cells.
特許文献１の耐火積層体では、絶縁性熱発泡層と熱膨張層とが積層されており、絶縁性熱発泡層は４００℃付近で発泡して粉体状から多孔体に変化する亜リン酸アルミニウムと樹脂とを含み、熱膨張層は２００℃付近で膨張作用を起こす熱膨張性黒鉛と樹脂とを含む。この耐火積層体が火炎等により加熱されると、熱膨張層が先んじて急激に膨張するため、耐火積層体の積層構造が維持されず、絶縁性熱発泡層が発泡する前に本来あるべき配置から脱落したり、外形が大きく変形したりする問題（耐火性が低い問題）があった。 In the fire-resistant laminated body of Patent Document 1, an insulating heat-foaming layer and a heat-expanding layer are laminated, and the insulating heat-foaming layer foams at around 400 ° C. to change from a powdery state to a porous body. It contains aluminum and a resin, and the heat-expanding layer contains a heat-expandable graphite and a resin that expands at around 200 ° C. When this refractory laminate is heated by a flame or the like, the thermal expansion layer expands rapidly in advance, so that the laminated structure of the refractory laminate is not maintained and the arrangement should be before the insulating thermal foam layer foams. There was a problem that it fell off from the surface or the outer shape was greatly deformed (problem with low fire resistance).
本発明は、高熱に暴露された際の耐火性及び遮熱性に優れた耐火シートを形成することが可能な、ポリ塩化ビニル組成物及び耐火シートの提供を課題とする。 An object of the present invention is to provide a polyvinyl chloride composition and a refractory sheet capable of forming a refractory sheet having excellent fire resistance and heat shielding property when exposed to high heat.
本発明者らは上記課題を解決するために、次のように検討した。
熱膨張層の外形の変形を和らげる（耐火性を高める）ことのみが目的であれば、熱膨張層に含まれる熱膨張性黒鉛の含有量を減らし、相対的に樹脂の量を増やすことが考えられる。しかし、そうすると熱膨張層の膨張後の遮熱性が低減してしまう。
In order to solve the above problems, the present inventors have examined as follows.
If the only purpose is to mitigate the deformation of the outer shape of the thermal expansion layer (improve fire resistance), it is conceivable to reduce the content of thermal expansion graphite contained in the thermal expansion layer and increase the amount of resin relatively. Be done. However, doing so reduces the heat-shielding property of the thermal expansion layer after expansion.
そこで、熱膨張層に含有させる難燃剤として、熱膨張性黒鉛だけでなく、膨張による変形が比較的少ない亜リン酸アルミニウムを充分に含有させ、かつ樹脂としてポリ塩化ビニルを採用した。ところが、難燃剤を樹脂中に分散して得た樹脂組成物の粘度や流動性が安定せず、シート状に成形することの難しさに直面した。この原因を鋭意検討したところ、ポリ塩化ビニルの平均重合度を所定の範囲とし、可塑剤を所定量で充分に添加することにより、熱膨張性黒鉛と亜リン酸アルミニウムを含む樹脂組成物をシート状に成形することが可能となった。 Therefore, as a flame retardant to be contained in the heat-expanding layer, not only heat-expandable graphite but also aluminum phosphate, which is relatively less deformed by expansion, is sufficiently contained, and polyvinyl chloride is adopted as a resin. However, the viscosity and fluidity of the resin composition obtained by dispersing the flame retardant in the resin are not stable, and it is difficult to mold the resin composition into a sheet. After diligently investigating the cause of this, a resin composition containing heat-expandable graphite and aluminum phosphite was obtained by setting the average degree of polymerization of polyvinyl chloride within a predetermined range and adding a sufficient amount of a plasticizer in a predetermined amount. It has become possible to mold it into a shape.
上記の樹脂組成物を成形して得た耐火シートの耐火性及び遮熱性を評価したところ、耐火性（外形の変形の抑制）は向上していたが、期待した程度の遮熱性（熱膨張性黒鉛を含まず、亜リン酸アルミニウムだけを含む場合よりも優れる遮熱性）が得られなかった。この原因をさらに鋭意検討したところ、ポリ塩化ビニル及び可塑剤の合計量に対する難燃剤の合計の含有量を所定の範囲にするとともに、可塑剤としてリン酸エステル系可塑剤を採用することにより、充分な遮熱性も得られることを見出し、本発明を完成した。本発明は次の態様を有する。 When the fire resistance and heat-shielding property of the fire-resistant sheet obtained by molding the above resin composition were evaluated, the fire resistance (suppression of deformation of the outer shape) was improved, but the heat-shielding property (thermal expansion property) was as expected. It did not contain graphite and had better heat shielding properties than the case where it contained only aluminum phosphite). As a result of further diligent investigation of the cause, it is sufficient to keep the total content of the flame retardant with respect to the total amount of polyvinyl chloride and the plasticizer within a predetermined range and to adopt a phosphoric acid ester-based plasticizer as the plasticizer. The present invention has been completed by finding that a good heat-shielding property can be obtained. The present invention has the following aspects.
［１］ ポリ塩化ビニルと、リン酸エステル系可塑剤と、亜リン酸アルミニウムと、熱膨張性黒鉛と、を含むポリ塩化ビニル組成物であって、
前記ポリ塩化ビニルの平均重合度が１３００以上４０００以下であり、
前記ポリ塩化ビニルの１００質量部に対して前記リン酸エステル系可塑剤が５質量部以上１５０質量部以下で含まれ、
前記ポリ塩化ビニルと前記リン酸エステル系可塑剤の合計の１００質量部に対して、前記亜リン酸アルミニウムと前記熱膨張性黒鉛の合計が５０質量部以上２００質量部以下で含まれる、ポリ塩化ビニル組成物。
［２］ 前記リン酸エステル系可塑剤の１００質量部に対して前記熱膨張性黒鉛が６０質量部以上２５０質量部以下で含まれる、［１］に記載のポリ塩化ビニル組成物。
［３］ ［１］又は［２］に記載のポリ塩化ビニル組成物によって形成された、耐火シート。
[1] A polyvinyl chloride composition containing polyvinyl chloride, a phosphoric acid ester-based plasticizer, aluminum phosphite, and heat-expandable graphite.
The average degree of polymerization of the polyvinyl chloride is 1300 or more and 4000 or less.
The phosphoric acid ester-based plasticizer is contained in an amount of 5 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polyvinyl chloride.
Polyvinyl chloride containing 50 parts by mass or more and 200 parts by mass or less of the total of the aluminum phosphite and the heat-expandable graphite with respect to 100 parts by mass of the total of the polyvinyl chloride and the phosphoric acid ester-based plasticizer. Vinyl composition.
[2] The polyvinyl chloride composition according to [1], wherein the heat-expandable graphite is contained in an amount of 60 parts by mass or more and 250 parts by mass or less with respect to 100 parts by mass of the phosphoric acid ester-based plasticizer.
[3] A refractory sheet formed by the polyvinyl chloride composition according to [1] or [2].
本発明のポリ塩化ビニル組成物によれば、高熱に暴露された際の耐火性及び遮熱性に優れた耐火シートを形成することができる。 According to the polyvinyl chloride composition of the present invention, it is possible to form a refractory sheet having excellent fire resistance and heat shielding properties when exposed to high heat.
≪ポリ塩化ビニル組成物≫
本発明の第一態様は、ポリ塩化ビニルと、リン酸エステル系可塑剤と、亜リン酸アルミニウムと、熱膨張性黒鉛と、を含むポリ塩化ビニル組成物であって、前記ポリ塩化ビニルの平均重合度が１３００以上４０００以下であり、前記ポリ塩化ビニルの１００質量部に対して前記リン酸エステル系可塑剤が５質量部以上１５０質量部以下で含まれ、前記ポリ塩化ビニルと前記リン酸エステル系可塑剤の合計の１００質量部に対して、前記亜リン酸アルミニウムと前記熱膨張性黒鉛の合計が５０質量部以上２００質量部以下で含まれる、ポリ塩化ビニル組成物である。
≪Polyvinyl chloride composition≫
A first aspect of the present invention is a polyvinyl chloride composition containing polyvinyl chloride, a phosphoric acid ester-based plasticizer, aluminum phosphite, and heat-expandable graphite, which is an average of the polyvinyl chloride. The degree of polymerization is 1300 or more and 4000 or less, and the polyvinyl chloride-based plasticizer is contained in an amount of 5 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polyvinyl chloride, and the polyvinyl chloride and the phosphoric acid ester are contained. It is a polyvinyl chloride composition containing 50 parts by mass or more and 200 parts by mass or less of the total of the aluminum phosphite and the heat-expandable graphite with respect to 100 parts by mass of the total of the plasticizer.
以下、亜リン酸アルミニウムと熱膨張性黒鉛をまとめて難燃剤ということがある。また、ポリ塩化ビニルをＰＶＣの略称で記載し、ポリ塩化ビニル組成物をＰＶＣ組成物と記載することがある。また、「〜」で示す数値範囲の下限値及び上限値はその数値範囲に含まれるものとする。 Hereinafter, aluminum phosphate and heat-expandable graphite may be collectively referred to as a flame retardant. Further, polyvinyl chloride may be described as an abbreviation for PVC, and a polyvinyl chloride composition may be described as a PVC composition. Further, the lower limit value and the upper limit value of the numerical value range indicated by "~" shall be included in the numerical value range.
本態様のＰＶＣの平均重合度は、１３００〜４０００であり、１７００〜３０００が好ましく、２０００〜２５００がより好ましい。
上記範囲の下限値以上であると、ＰＶＣ組成物の粘度が高まるとともに、難燃剤の分散性も向上し、シート状に成形することが容易になる。
上記範囲の上限値以下であると、ＰＶＣ組成物の流動性が高まるとともに、難燃剤の分散性も向上し、シート状に成形することが容易になる。
ここで、ＰＶＣの平均重合度は、ＪＩＳ Ｋ６７２０−２に準拠して測定される平均重合度である。平均重合度はＫ値から換算して求められる。Ｋ値は、ＪＩＳ Ｋ７３６７−２（ＩＳＯ１６２８−２）に準拠して測定された値である。
The average degree of polymerization of PVC in this embodiment is 1300 to 4000, preferably 1700 to 3000, and more preferably 2000 to 2500.
When it is at least the lower limit of the above range, the viscosity of the PVC composition is increased, the dispersibility of the flame retardant is also improved, and it becomes easy to mold into a sheet.
When it is not more than the upper limit of the above range, the fluidity of the PVC composition is increased, the dispersibility of the flame retardant is also improved, and it becomes easy to form the PVC composition into a sheet.
Here, the average degree of polymerization of PVC is the average degree of polymerization measured according to JIS K6720-2. The average degree of polymerization is obtained by converting from the K value. The K value is a value measured in accordance with JIS K7367-2 (ISO1628-2).
本態様のＰＶＣは、塩化ビニルの単独重合体であってもよいし、共重合体であってもよい。ＰＶＣに共重合可能なモノマーとしては、例えば、エチレン、プロピレン、アクリロニトリル、酢酸ビニル、マレイン酸又はそのエステル、アクリル酸又はそのエステル、メタクリル酸又はそのエステル、塩化ビニリデン等が挙げられる。
本態様のＰＶＣは、塩化ビニル単独重合体であることが好ましい。
本態様のＰＶＣは、塩素化された塩素化塩化ビニル樹脂であってもよい。
The PVC of this embodiment may be a homopolymer of vinyl chloride or a copolymer. Examples of the monomer copolymerizable with PVC include ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or an ester thereof, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, vinylidene chloride and the like.
The PVC of this embodiment is preferably a vinyl chloride homopolymer.
The PVC of this embodiment may be a chlorinated vinyl chloride resin.
本態様のＰＶＣ組成物の総質量に対するＰＶＣの含有量は、１０〜４０質量％が好ましく、１５〜３５質量％がより好ましく、２０〜３０質量％がさらに好ましい。
上記範囲であると、ＰＶＣ組成物中の難燃剤の分散性が高まり、ＰＶＣ組成物をシート状に成形することがより容易になる。
The content of PVC with respect to the total mass of the PVC composition of this embodiment is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, still more preferably 20 to 30% by mass.
Within the above range, the dispersibility of the flame retardant in the PVC composition is enhanced, and it becomes easier to mold the PVC composition into a sheet.
本態様のＰＶＣ組成物には、ＰＶＣ以外の樹脂が含まれていてもよいが、本発明の効果を充分に得る観点から、ＰＶＣ１００質量部に対するＰＶＣ以外の樹脂の含有量は、５０質量部以下であれば添加してもよい。 The PVC composition of this embodiment may contain a resin other than PVC, but from the viewpoint of sufficiently obtaining the effects of the present invention, the content of the resin other than PVC with respect to 100 parts by mass of PVC is 50 parts by mass or less. If so, it may be added.
ＰＶＣ以外の樹脂としては、例えば、ポリプロピレン樹、ポリエチレン樹脂等のポリオレフィン樹脂、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、（メタ）アクリル系樹脂、ポリアミド樹脂、ノボラック樹脂、ポリウレタン樹脂、ポリイソブチレン、ポリ酢酸ビニル、エチレン−酢酸ビニル（ＥＶＡ）等の熱可塑性樹脂が挙げられる。 Examples of resins other than PVC include polyolefin resins such as polypropylene trees and polyethylene resins, polystyrene resins, acrylonitrile-butadiene-styrene (ABS) resins, polycarbonate resins, polyphenylene ether resins, (meth) acrylic resins, polyamide resins, and novolak. Examples thereof include thermoplastic resins such as resins, polyurethane resins, polyisobutylene, polyvinyl acetate, and ethylene-vinyl acetate (EVA).
本態様のリン酸エステル系可塑剤はリン酸エステル構造を有する公知の可塑剤である。ここで、リン酸エステル構造とは、リン酸(O=P(OH)3)が持つ３個の水素の全てまたは一部が有機基で置換された構造である。
好適なリン酸エステル系可塑剤としては、例えば、トリクレジルホスフェート（TCP）、Tetra-C12-15-alkyl (propane-2,2-diylbis(4,1-phenylene)) bis(phosphite)が挙げられる。
本態様のＰＶＣ組成物に含まれるリン酸エステル系可塑剤は１種でもよいし、２種以上でもよい。
The phosphoric acid ester-based plasticizer of this embodiment is a known plasticizer having a phosphoric acid ester structure. Here, the phosphoric acid ester structure is a structure in which all or part of the three hydrogens of phosphoric acid (O = P (OH) 3) is substituted with an organic group.
Suitable phosphate ester plasticizers include, for example, tricresyl phosphate (TCP), Tetra-C12-15-alkyl (propane-2,2-diylbis (4,1-phenylene)) bis (phosphite). Be done.
The phosphoric acid ester-based plasticizer contained in the PVC composition of this embodiment may be one kind or two or more kinds.
本態様のＰＶＣ組成物において、ＰＶＣの１００質量部に対するリン酸エステル系可塑剤の含有量は、５〜１５０質量部であり、３０〜１２０質量部が好ましく、５０〜１００質量部がより好ましく、６０〜９０質量部がさらに好ましい。
上記範囲の下限値以上であると、ＰＶＣ組成物の流動性が高まるとともに、難燃剤の分散性も向上し、シート状に成形することが容易になる。
上記範囲の上限値以下であると、ＰＶＣ組成物の粘度が高まるとともに、難燃剤の分散性も向上し、シート状に成形することが容易になる。
In the PVC composition of this embodiment, the content of the phosphoric acid ester-based plasticizer with respect to 100 parts by mass of PVC is 5 to 150 parts by mass, preferably 30 to 120 parts by mass, and more preferably 50 to 100 parts by mass. 60 to 90 parts by mass is more preferable.
When it is at least the lower limit of the above range, the fluidity of the PVC composition is increased, the dispersibility of the flame retardant is also improved, and it becomes easy to form the PVC composition into a sheet.
When it is not more than the upper limit of the above range, the viscosity of the PVC composition is increased, the dispersibility of the flame retardant is also improved, and it becomes easy to mold into a sheet.
本態様の熱膨張性黒鉛は公知の炭素材料である。熱膨張性黒鉛は２００℃以上で膨張作用が起こり、火炎等の高熱に曝されると急激に膨張する性質を有することが好ましい。
公知の熱膨張性黒鉛としては、例えば、グラファイトの粉末を無機酸と強酸化剤とで処理することにより、グラファイト層間化合物を生成させたものが挙げられる。ここで、グラファイトとしては、例えば、天然鱗状グラファイト、熱分解グラファイト、キッシュグラファイト等が挙げられる。無機酸としては、例えば、濃硫酸、硝酸、セレン酸等が挙げられる。強酸化剤としては、例えば、濃硝酸、過塩素酸、過塩素酸塩、過マンガン酸塩、重クロム酸塩、重クロム酸塩、過酸化水素等が挙げられる。上記処理で得られた熱膨張性黒鉛は、アンモニア、脂肪族低級アミン、アルカリ金属化合物、アルカリ土類金属化合物等でさらに中和されていてもよい。市販品の熱膨張性黒鉛を使用することができる。
The heat-expandable graphite of this embodiment is a known carbon material. It is preferable that the heat-expandable graphite has a property of expanding at 200 ° C. or higher and rapidly expanding when exposed to high heat such as a flame.
Examples of known heat-expandable graphite include those obtained by treating graphite powder with an inorganic acid and a strong oxidizing agent to form a graphite interlayer compound. Here, examples of graphite include natural scaly graphite, pyrolytic graphite, quiche graphite and the like. Examples of the inorganic acid include concentrated sulfuric acid, nitric acid, selenic acid and the like. Examples of the strong oxidizing agent include concentrated nitric acid, perchloric acid, perchlorate, permanganate, permanganate, dichromate, hydrogen peroxide and the like. The heat-expandable graphite obtained by the above treatment may be further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound or the like. Commercially available heat-expandable graphite can be used.
本態様のＰＶＣ組成物の総質量に対する熱膨張性黒鉛の含有量は、１０〜４０質量％が好ましく、１５〜３５質量％がより好ましく、２０〜３０質量％がさらに好ましい。
上記範囲であると、ＰＶＣ組成物をシート状に成形することがより容易になり、得られた耐火シートの耐火性及び遮熱性が高まる。
The content of the heat-expandable graphite with respect to the total mass of the PVC composition of this embodiment is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, still more preferably 20 to 30% by mass.
Within the above range, it becomes easier to mold the PVC composition into a sheet, and the fire resistance and heat shielding property of the obtained refractory sheet are enhanced.
本態様のＰＶＣ組成物において、ＰＶＣの１００質量部に対する熱膨張性黒鉛の含有量は、５〜２００質量部が好ましく、５０〜１５０質量部がより好ましく、７５〜１２５質量部がさらに好ましい。
上記範囲であると、ＰＶＣ組成物をシート状に成形することがより容易になり、得られた耐火シートの耐火性及び遮熱性のバランスが優れる。
In the PVC composition of this embodiment, the content of the heat-expandable graphite with respect to 100 parts by mass of PVC is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass, still more preferably 75 to 125 parts by mass.
Within the above range, it becomes easier to mold the PVC composition into a sheet, and the balance between the fire resistance and the heat shielding property of the obtained refractory sheet is excellent.
本態様のＰＶＣ組成物において、リン酸エステル系可塑剤の１００質量部に対する熱膨張性黒鉛の含有量は、６０〜２５０質量部が好ましく、８０〜２００質量部がより好ましく、１００〜１５０質量部がさらに好ましい。
上記範囲であると、ＰＶＣ組成物をシート状に成形することがより容易になり、得られた耐火シートの耐火性及び遮熱性のバランスが優れる。
In the PVC composition of this embodiment, the content of the heat-expandable graphite with respect to 100 parts by mass of the phosphoric acid ester-based plasticizer is preferably 60 to 250 parts by mass, more preferably 80 to 200 parts by mass, and 100 to 150 parts by mass. Is even more preferable.
Within the above range, it becomes easier to mold the PVC composition into a sheet, and the balance between the fire resistance and the heat shielding property of the obtained refractory sheet is excellent.
本態様の亜リン酸アルミニウムは公知の化合物である。亜リン酸アルミニウムは４００℃付近で組成変化が起こり、発泡して粉体状から多孔体に変化する性質を有することが好ましい。市販品の亜リン酸アルミニウムを使用することができる。 The aluminum phosphate of this embodiment is a known compound. It is preferable that aluminum phosphite has a property that the composition changes at around 400 ° C. and foams to change from a powdery state to a porous body. Commercially available aluminum phosphite can be used.
本態様のＰＶＣ組成物の総質量に対する亜リン酸アルミニウムの含有量は、１０〜４０質量％が好ましく、１５〜３５質量％がより好ましく、２０〜３０質量％がさらに好ましい。
上記範囲であると、ＰＶＣ組成物をシート状に成形することがより容易になり、得られた耐火シートの耐火性及び遮熱性が高まる。
The content of aluminum phosphate with respect to the total mass of the PVC composition of this embodiment is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, still more preferably 20 to 30% by mass.
Within the above range, it becomes easier to mold the PVC composition into a sheet, and the fire resistance and heat shielding property of the obtained refractory sheet are enhanced.
本態様のＰＶＣ組成物において、ＰＶＣの１００質量部に対する亜リン酸アルミニウムの含有量は、５〜２００質量部が好ましく、５０〜１５０質量部がより好ましく、７５〜１２５質量部がさらに好ましい。
上記範囲であると、ＰＶＣ組成物をシート状に成形することがより容易になり、得られた耐火シートの耐火性及び遮熱性のバランスが優れる。
In the PVC composition of this embodiment, the content of aluminum phosphate with respect to 100 parts by mass of PVC is preferably 5 to 200 parts by mass, more preferably 50 to 150 parts by mass, still more preferably 75 to 125 parts by mass.
Within the above range, it becomes easier to mold the PVC composition into a sheet, and the balance between the fire resistance and the heat shielding property of the obtained refractory sheet is excellent.
本態様のＰＶＣ組成物において、ポリ塩化ビニルとリン酸エステル系可塑剤の合計の含有量を１００質量部としたとき、この１００質量部に対する、亜リン酸アルミニウムと熱膨張性黒鉛の合計の含有量は、５０〜２００質量部であり、６０〜１８０質量部が好ましく、７０〜１６０質量部がより好ましく、８０〜１４０質量部がさらに好ましく、９０〜１２０質量部が特に好ましい。
上記範囲であると、ＰＶＣ組成物をシート状に成形することが容易になるとともに、得られた耐火シートの耐火性及び遮熱性のバランスが優れる。
In the PVC composition of this embodiment, when the total content of polyvinyl chloride and the phosphate ester plasticizer is 100 parts by mass, the total content of aluminum phosphite and thermally expandable graphite is 100 parts by mass. The amount is 50 to 200 parts by mass, preferably 60 to 180 parts by mass, more preferably 70 to 160 parts by mass, further preferably 80 to 140 parts by mass, and particularly preferably 90 to 120 parts by mass.
Within the above range, it becomes easy to mold the PVC composition into a sheet, and the balance between the fire resistance and the heat shielding property of the obtained refractory sheet is excellent.
本態様のＰＶＣ組成物において、亜リン酸アルミニウムの含有量１００質量部に対して、熱膨張性黒鉛の含有量は、５０〜２００質量部が好ましく、７０〜１５０質量部がより好ましく、８０〜１００質量部がさらに好ましい。
上記範囲であると、本態様のＰＶＣ組成物から得られた耐火シートの耐火性及び遮熱性のバランスが優れる。
In the PVC composition of this embodiment, the content of the heat-expandable graphite is preferably 50 to 200 parts by mass, more preferably 70 to 150 parts by mass, and 80 to 80 to 100 parts by mass with respect to 100 parts by mass of aluminum phosphate. 100 parts by mass is more preferable.
Within the above range, the balance between the fire resistance and the heat shielding property of the refractory sheet obtained from the PVC composition of this embodiment is excellent.
＜その他の任意成分＞
本態様のＰＶＣ組成物には、必要に応じて、ＰＶＣ、リン酸エステル系可塑剤、亜リン酸アルミニウム及び熱膨張性黒鉛以外の任意成分を含有していてもよい。
<Other optional ingredients>
The PVC composition of this embodiment may contain any component other than PVC, a phosphoric acid ester-based plasticizer, aluminum phosphite, and heat-expandable graphite, if necessary.
また、ＰＶＣ樹脂に一般に使用される、安定剤、滑剤、改質剤、充填剤、着色剤等を、本発明の目的を損なわない範囲で添加混合することができる。
安定剤としては、例えば、三塩基性硫酸鉛、二塩基性亜リン酸鉛、塩基性亜硫酸鉛、二塩基性フタル酸鉛、鉛白、鉛のラウレートまたはステアレート等の鉛系安定剤；ブチル錫マレエート、オクチル錫マレエート、ジ−ｎ−アルキル錫メルカプチド、ジ−ｎ−アルキル錫ジラウレート、ジブチル錫ジマレエート、ジブチル錫ラウリルメルカプチド、ジ−オクチル錫−Ｓ, Ｓ’−ビス−（イソオクチル−メルカプトアセテート) 、ジブチル錫ビス−イソオクチルチオグリコレート、ジ−（ｎ−オクチル）錫マレエートポリマー、ジブチル錫メルカプトプロピオナート等の錫系安定剤；カルシウム、カドミウム、バリウムまたは亜鉛のラウレートまたはステアレート等の有機金属塩系安定剤および金属石けん系安定剤；アンチモンメルカプトカルボン酸塩またはエステル塩のようなアンチモン系安定剤；ホスフェート系安定剤；エポキシ化大豆油、エポキシ化アマニ油等のエポキシ化油系安定剤；が挙げられ、これらは単独または２種以上の組み合わせで使用される。
滑剤としては、例えば、低分子ワックス、ポリエチレンワックス、パラフィンワックス、流動パラフィン等の脂肪族炭化水素系滑剤；ステアリルアルコール等の高級脂肪族アルコール系滑剤；ステアリン酸、パルミチン酸、ミリスチン酸等の脂肪酸系滑剤；ステアリン酸アミド、パルミチン酸アミド、メチレンビスステアロアミド等の脂肪族アミド系滑剤；モノステアリン酸グリセリン、ジアミノステアリン酸エチル、ブチルステアレート等の脂肪酸エステル系滑剤；または金属石けん、シリコーンオイル等が挙げられ、これらは単独または２種以上の組み合わせで使用される。
改質剤としては、例えば、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸エチル共重合体、塩素化ポリエチレン、メチルメタクリレート・ブタジエン・スチレン共重合体、アクリロニトリル・ブタジエン・スチレン共重合体、アクリルゴム等の耐衝撃改良剤；ポリメチルメタクリレート等のゲル化促進剤；アクリロニトリル・ブタジエン・α−メチルスチレン共重合体、メチルメタクリレート・アクリル酸エステル共重合体等が挙げられ、これらは単独または２種以上の組み合わせで使用される。
Further, stabilizers, lubricants, modifiers, fillers, colorants and the like generally used for PVC resins can be added and mixed within a range that does not impair the object of the present invention.
Stabilizers include, for example, lead tribasic lead sulfate, lead dibasic phosphite, basic lead sulfite, lead dibasic phthalate, lead white, lead-based stabilizers such as laurate or stearate of lead; butyl. Tin maleate, octyl tin maleate, di-n-alkyl tin mercaptide, di-n-alkyl tin dilaurate, dibutyl tin dimalate, dibutyl tin lauryl mercaptide, di-octyl tin-S, S'-bis- (isooctyl-mercaptoacetate) ), Dibutyltin bis-isooctylthioglycolate, di- (n-octyl) tin maleate polymer, tin-based stabilizers such as dibutyltin mercaptopropionate; laurate or stearate of calcium, cadmium, barium or zinc, etc. Organic metal salt stabilizers and metal soap stabilizers; antimony stabilizers such as antimony mercaptocarboxylates or ester salts; phosphate stabilizers; epoxidized oils such as epoxidized soybean oil and epoxidized flaxseed oil. Stabilizers; these are used alone or in combination of two or more.
Examples of the lubricant include aliphatic hydrocarbon-based lubricants such as low-molecular-weight wax, polyethylene wax, paraffin wax, and liquid paraffin; higher aliphatic alcohol-based lubricants such as stearyl alcohol; fatty acid-based lubricants such as stearic acid, palmitic acid, and myristic acid. Lubricants; aliphatic amide lubricants such as stearic acid amide, palmitate amide, methylene bisstearoamide; fatty acid ester lubricants such as glycerin monostearate, ethyl diaminostearate, butyl stearate; or metal soap, silicone oil, etc. These are used alone or in combination of two or more.
Examples of the modifier include ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, chlorinated polyethylene, methyl methacrylate / butadiene / styrene copolymer, acrylonitrile / butadiene / styrene copolymer, and acrylic rubber. Impact resistance improvers such as; Gelation accelerators such as polymethylmethacrylate; Acrylonitrile / butadiene / α-methylstyrene copolymers, methylmethacrylate / acrylic acid ester copolymers, etc., which may be used alone or in combination of two or more. Used in combination of.
＜ＰＶＣ組成物の製造方法＞
本態様のＰＶＣ組成物は、常法に従い、各成分を混合することにより得られる。
まず、ＰＶＣ、リン酸エステル系可塑剤及び任意成分を配合したＰＶＣ配合物を得て、次に、ＰＶＣ配合物に亜リン酸アルミニウム及び熱膨張性黒鉛を添加して混練すると、難燃剤の分散性が優れるので好ましい。
<Manufacturing method of PVC composition>
The PVC composition of this embodiment is obtained by mixing each component according to a conventional method.
First, a PVC compound containing PVC, a phosphoric acid ester-based plasticizer, and an optional component is obtained, and then aluminum phosphite and heat-expandable graphite are added to the PVC compound and kneaded to disperse the flame retardant. It is preferable because it has excellent properties.
≪耐火シート≫
本発明の第二態様は、第一態様のＰＶＣ組成物によって形成された耐火シートである。
本態様の耐火シートの縦×横×厚さのサイズは特に制限されず、例えば、縦が１〜１００ｃｍ、横が１〜１００ｃｍ、厚さが１〜１０ｍｍのサイズが挙げられる。
本態様の耐火シートは、１層であってもよいし、複数の耐火シートが積層された積層シートであってもよい。積層シートを構成する各耐火シートの組成は同じであってもよいし、異なっていてもよい。
本態様の耐火シートには、任意の樹脂含有層が積層されていてもよい。
≪Fireproof sheet≫
The second aspect of the present invention is a refractory sheet formed by the PVC composition of the first aspect.
The size of the vertical × horizontal × thickness of the refractory sheet of this embodiment is not particularly limited, and examples thereof include a size of 1 to 100 cm in length, 1 to 100 cm in width, and 1 to 10 mm in thickness.
The refractory sheet of this embodiment may be a single layer or a laminated sheet in which a plurality of refractory sheets are laminated. The composition of each refractory sheet constituting the laminated sheet may be the same or different.
Any resin-containing layer may be laminated on the refractory sheet of this embodiment.
＜耐火シートの製造方法＞
第一態様のＰＶＣ組成物を、常法に従い、一軸押出機、二軸押出機等の押出機で溶融押出成形や、カレンダー成形・プレス成形することにより、シート状に成形された耐火シートを得ることができる。
ＰＶＣ組成物の溶融温度は、ＰＶＣが焼けず、熱膨張性黒鉛が膨張しない程度に低くする必要があり、１３０〜１７０℃が好ましい。
<Manufacturing method of refractory sheet>
The PVC composition of the first aspect is melt-extruded by an extruder such as a single-screw extruder or a twin-screw extruder, or is calendar-molded or press-molded according to a conventional method to obtain a fire-resistant sheet formed into a sheet. be able to.
The melting temperature of the PVC composition needs to be low so that the PVC does not burn and the heat-expandable graphite does not expand, and is preferably 130 to 170 ° C.
＜耐火シートの用途＞
本態様の耐火シートの用途は特に制限されず、例えば、電池や種々の電源装置等の発火性の物品を遮蔽したり、保存したり、梱包したりする用途に好適である。
<Use of refractory sheet>
The use of the refractory sheet of this embodiment is not particularly limited, and is suitable for, for example, shielding, storing, or packing flammable articles such as batteries and various power supply devices.
以下、本発明について実施例を示して具体的に説明するが、本発明はこれら実施例だけに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
表１に記載の原材料の詳細は次の通りである。
「ＴＫ−１０００」：信越化学工業社製、平均重合度１０００のポリ塩化ビニル
「ＴＫ−２５００ＨＳ」：信越化学工業社製、平均重合度２５００のポリ塩化ビニル
「Ｓ−５０００」：信越化学工業社製、平均重合度５０００のポリ塩化ビニル
「レオフォス６５」：味の素ファインテクノ社製、リン酸トリアリールイソプロピル化物
「ＤＩＮＰ」：新日本理化社製、フタル酸ジイソノニル
「Ｗ−１００ＥＬ」：ＤＩＣ社製
「アデカスタブＮＰＳ−３０９」：ＡＤＥＫＡ社製
「アデカスタブ１５００」：ＡＤＥＫＡ社製、Tetra-C12-15-alkyl (propane-2,2-diylbis(4,1-phenylene)) bis(phosphite)
「ＣＳ−６」：日東化成工業社製、ステアリン酸カルシウム
「ＮＳＦ」：太平化学産業社製
「膨張黒鉛 Ｎ９９５０３００」：西村黒鉛社製
The details of the raw materials shown in Table 1 are as follows.
"TK-1000": Polyvinyl chloride with an average degree of polymerization of 1000 manufactured by Shin-Etsu Chemical Co., Ltd. "TK-2500HS": Polyvinyl chloride with an average degree of polymerization of 2500 manufactured by Shin-Etsu Chemical Co., Ltd .: Shin-Etsu Chemical Co., Ltd. Polyvinyl chloride "Leofos 65" with an average degree of polymerization of 5000: Ajinomoto Fine Techno Co., Ltd., Triaryl isopropyl phosphate "DINP": Shin-Etsu Chemical Co., Ltd., Diisononyl phthalate "W-100EL": DIC Co., Ltd. "Adecastab NPS-309": Made by ADEKA "Adecastab 1500": Made by ADEKA, Tetra-C12-15-alkyl (propane-2,2-diylbis (4,1-phenylene)) bis (phosphite)
"CS-6": Nitto Kasei Kogyo Co., Ltd., calcium stearate "NSF": Taihei Kagaku Sangyo Co., Ltd. "Expanded Graphite N9950300": Nishimura Graphite Co., Ltd.
［ＰＶＣ組成物の作成］
表１に記載の量（質量部）で各原材料を二軸式混練機で混合したＰＶＣ組成物を得た。例えば実施例１において、ＰＶＣの１００質量部に対してリン酸エステル系可塑剤の７５質量部とその他の添加剤約５質量部を配合し、さらに亜リン酸アルミニウム９０．０５質量部と、熱膨張性黒鉛９０．０５質量部を配合して目的のＰＶＣ組成物を得た。
[Preparation of PVC composition]
A PVC composition was obtained by mixing each raw material with a biaxial kneader in the amount (part by mass) shown in Table 1. For example, in Example 1, 75 parts by mass of a phosphoric acid ester plasticizer and about 5 parts by mass of other additives are blended with 100 parts by mass of PVC, and 90.05 parts by mass of aluminum phosphite and heat are added. 90.05 parts by mass of expandable graphite was added to obtain the desired PVC composition.
［耐火シートの作成］
（実施例１）
実施例１のＰＶＣ組成物80ｇをラボプラストミル（東洋精機社製：型番：4C150、ローター：R30）に投入し、150℃設定で30回転／分にて7分混錬した。得られた混練物を１分以内に150℃設定の6インチロールにて3分素通して、約１ｍｍ厚の耐火シートを作成した。この耐火シートを１０ｃｍ×５ｃｍのサイズに裁断して試験片とした。
[Creating a refractory sheet]
(Example 1)
80 g of the PVC composition of Example 1 was put into a lab plast mill (manufactured by Toyo Seiki Co., Ltd .: model number: 4C150, rotor: R30) and kneaded at 30 rpm at 150 ° C. for 7 minutes. The obtained kneaded material was passed through a 6-inch roll set at 150 ° C. for 3 minutes within 1 minute to prepare a refractory sheet having a thickness of about 1 mm. This refractory sheet was cut into a size of 10 cm × 5 cm to obtain a test piece.
（比較例１）
比較例１のＰＶＣ組成物を用い、実施例１と同様に耐火シートの作成を試みたが、ＰＶＣ組成物の流動性が過度に高く、シート状に成形することができなかった。
(Comparative Example 1)
Using the PVC composition of Comparative Example 1, an attempt was made to prepare a refractory sheet in the same manner as in Example 1, but the fluidity of the PVC composition was excessively high and it could not be formed into a sheet.
（比較例２）
比較例２のＰＶＣ組成物を用い、実施例１と同様に耐火シートの作成を試みたが、ＰＶＣ組成物のまとまりが悪く、粘度が過度に高く、シート状に成形することができなかった。
(Comparative Example 2)
Using the PVC composition of Comparative Example 2, an attempt was made to prepare a refractory sheet in the same manner as in Example 1, but the PVC composition was poorly organized, had an excessively high viscosity, and could not be formed into a sheet.
（比較例３〜５）
比較例３〜５のＰＶＣ組成物を用い、実施例１と同様に耐火シートを作成し、試験片を得た。
(Comparative Examples 3 to 5)
Using the PVC compositions of Comparative Examples 3 to 5, a refractory sheet was prepared in the same manner as in Example 1 to obtain test pieces.
（比較例６）
比較例６のＰＶＣ組成物を用い、実施例１と同様に耐火シートの作成を試みたが、ＰＶＣ組成物のまとまりが悪く、辛うじて厚いシート（板）に成形できても、実施例１と同じ厚さに薄くすることができなかった。
(Comparative Example 6)
Using the PVC composition of Comparative Example 6, an attempt was made to prepare a refractory sheet in the same manner as in Example 1. However, even if the PVC composition was poorly organized and could be molded into a barely thick sheet (plate), it was the same as in Example 1. Could not be thinned to thickness.
［耐火性と遮熱性の評価］
各例で作成した軟質ＰＶＣシートの試験片を、水平に固定して９００℃に加熱した金網に載せ、１２０秒間加熱した。この際の試験片の上面の温度変化をサーモグラフィーで測定した。
[Evaluation of fire resistance and heat insulation]
The test piece of the soft PVC sheet prepared in each example was fixed horizontally and placed on a wire mesh heated to 900 ° C. and heated for 120 seconds. The temperature change on the upper surface of the test piece at this time was measured by thermography.
（実施例１）
試験片の上面の最高温度は３５０℃であった。また、反りや細り（収縮）などの外形の変化は小さかった。
(Example 1)
The maximum temperature of the upper surface of the test piece was 350 ° C. In addition, changes in the outer shape such as warpage and thinning (shrinkage) were small.
（比較例３）
試験片の上面の最高温度は４０５℃に達し、その後で発火した。
(Comparative Example 3)
The maximum temperature of the upper surface of the test piece reached 405 ° C., and then ignited.
（比較例４）
試験片は、加熱後直ぐに外形が大きく変形したので加熱を中止した。
(Comparative Example 4)
Immediately after heating, the outer shape of the test piece was significantly deformed, so heating was stopped.
（比較例５）
試験片の上面の最高温度は４００℃に達した。
(Comparative Example 5)
The maximum temperature of the upper surface of the test piece reached 400 ° C.
＜考察＞
実施例１の耐火シートは、優れた遮熱性を示し、外形の変形も少なく耐火性も優れていた。
比較例１のＰＶＣ組成物は、ＰＶＣの平均重合度が小さいため、ＰＶＣ組成物がシート成形に適した状態にならなかった。
比較例２のＰＶＣ組成物は、ＰＶＣの平均重合度が大きいため、ＰＶＣ組成物がシート成形に適した状態にならなかった。
比較例３の耐火シートは、リン酸エステル系可塑剤を含まず、フタル酸系可塑剤を含んでいたので、遮熱性に劣り、発火した。
比較例４の耐火シートは、難燃剤の総量が少ないため、加熱後直ぐに外形が激しく変形し、遮熱性を発揮することはできなかった。
比較例５の耐火シートは、シート成形可能な範囲で多量の亜リン酸アルミニウムを含むが、熱膨張性黒鉛を含まないため、遮熱性が劣っていた。
比較例６のＰＶＣ組成物は、難燃剤の総量が多いため、所望の厚さのシートを得るためにプレスすることができなかった。
以上の結果から、本発明のＰＶＣ組成物は、所望の厚さでシートを成形することができ、得られた耐火シートは、耐火性及び遮熱性が共に優れていることが明らかである。
<Discussion>
The refractory sheet of Example 1 showed excellent heat-shielding properties, had little deformation in the outer shape, and had excellent fire resistance.
In the PVC composition of Comparative Example 1, the average degree of polymerization of PVC was small, so that the PVC composition was not in a state suitable for sheet molding.
In the PVC composition of Comparative Example 2, the average degree of polymerization of PVC was large, so that the PVC composition was not in a state suitable for sheet molding.
Since the fireproof sheet of Comparative Example 3 did not contain a phosphoric acid ester-based plasticizer and contained a phthalic acid-based plasticizer, it was inferior in heat-shielding property and ignited.
Since the total amount of the flame retardant was small in the refractory sheet of Comparative Example 4, the outer shape was severely deformed immediately after heating, and the heat-shielding property could not be exhibited.
The refractory sheet of Comparative Example 5 contained a large amount of aluminum phosphite within a range in which the sheet could be molded, but did not contain heat-expandable graphite, so that the heat-shielding property was inferior.
The PVC composition of Comparative Example 6 could not be pressed to obtain a sheet of a desired thickness due to the large amount of flame retardant.
From the above results, it is clear that the PVC composition of the present invention can form a sheet with a desired thickness, and the obtained refractory sheet is excellent in both fire resistance and heat shielding property.
Claims (3)
前記ポリ塩化ビニルの平均重合度が１３００以上４０００以下であり、
前記ポリ塩化ビニルの１００質量部に対して前記リン酸エステル系可塑剤が５質量部以上１５０質量部以下で含まれ、
前記ポリ塩化ビニルと前記リン酸エステル系可塑剤の合計の１００質量部に対して、前記亜リン酸アルミニウムと前記熱膨張性黒鉛の合計が５０質量部以上２００質量部以下で含まれる、ポリ塩化ビニル組成物。 A polyvinyl chloride composition containing polyvinyl chloride, a phosphoric acid ester-based plasticizer, aluminum phosphite, and heat-expandable graphite.
The average degree of polymerization of the polyvinyl chloride is 1300 or more and 4000 or less.
The phosphoric acid ester-based plasticizer is contained in an amount of 5 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polyvinyl chloride.
Polyvinyl chloride containing 50 parts by mass or more and 200 parts by mass or less of the total of the aluminum phosphite and the heat-expandable graphite with respect to 100 parts by mass of the total of the polyvinyl chloride and the phosphoric acid ester-based plasticizer. Vinyl composition.
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