JP2019119859A - Thermally expandable sheet - Google Patents
Thermally expandable sheet Download PDFInfo
- Publication number
- JP2019119859A JP2019119859A JP2018240876A JP2018240876A JP2019119859A JP 2019119859 A JP2019119859 A JP 2019119859A JP 2018240876 A JP2018240876 A JP 2018240876A JP 2018240876 A JP2018240876 A JP 2018240876A JP 2019119859 A JP2019119859 A JP 2019119859A
- Authority
- JP
- Japan
- Prior art keywords
- thermally expandable
- expandable sheet
- mass
- resin
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011256 inorganic filler Substances 0.000 claims abstract description 39
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 39
- 239000010439 graphite Substances 0.000 claims abstract description 34
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 34
- 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 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 239000012766 organic filler Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- 239000004014 plasticizer Substances 0.000 claims description 34
- 229920001971 elastomer Polymers 0.000 claims description 28
- -1 melamine compound Chemical class 0.000 claims description 23
- 239000000806 elastomer Substances 0.000 claims description 16
- 229920000877 Melamine resin Polymers 0.000 claims description 15
- 229920005992 thermoplastic resin Polymers 0.000 claims description 15
- 239000004800 polyvinyl chloride Substances 0.000 claims description 14
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 14
- 239000005060 rubber Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000011819 refractory material Substances 0.000 claims description 10
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 9
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical group NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 6
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 6
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000011342 resin composition Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 150000007974 melamines Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000012790 adhesive layer Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- LWFBRHSTNWMMGN-UHFFFAOYSA-N 4-phenylpyrrolidin-1-ium-2-carboxylic acid;chloride Chemical compound Cl.C1NC(C(=O)O)CC1C1=CC=CC=C1 LWFBRHSTNWMMGN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 2
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 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
- 239000005819 Potassium phosphonate Substances 0.000 description 2
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 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
- 230000001588 bifunctional effect Effects 0.000 description 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 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
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 229940100539 dibutyl adipate Drugs 0.000 description 2
- 229940031769 diisobutyl adipate Drugs 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
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 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
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 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
- 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
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- QDNSOJDSRJOUHB-UHFFFAOYSA-N 2-methyloxirane;phenol Chemical compound CC1CO1.OC1=CC=CC=C1.OC1=CC=CC=C1 QDNSOJDSRJOUHB-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- KJHYQRFDFZXACH-UHFFFAOYSA-N C(CCCCCC)OC(=O)C1=C(C=CC=C1C(=O)OCCCCCCC)C1=CC(=C(C=C1)C(=O)OCCCCCCC)C(=O)OCCCCCCC Chemical compound C(CCCCCC)OC(=O)C1=C(C=CC=C1C(=O)OCCCCCCC)C1=CC(=C(C=C1)C(=O)OCCCCCCC)C(=O)OCCCCCCC KJHYQRFDFZXACH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- NEHDRDVHPTWWFG-UHFFFAOYSA-N Dioctyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC NEHDRDVHPTWWFG-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002841 Lewis acid Chemical class 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
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- ULNDMKJIMSSCBZ-UHFFFAOYSA-N P(=O)(OCCC(Cl)Br)(OCCC(Cl)Br)OCCC(Cl)Br.P(=O)(OCC(CBr)Br)(OCC(CBr)Br)OCC(CBr)Br Chemical compound P(=O)(OCCC(Cl)Br)(OCCC(Cl)Br)OCCC(Cl)Br.P(=O)(OCC(CBr)Br)(OCC(CBr)Br)OCC(CBr)Br ULNDMKJIMSSCBZ-UHFFFAOYSA-N 0.000 description 1
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- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- SMYKBXMWXCZOLU-UHFFFAOYSA-N tris-decyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCCCC)C(C(=O)OCCCCCCCCCC)=C1 SMYKBXMWXCZOLU-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
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 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
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
Description
本発明は熱膨張性シートに関し、例えば耐火材として使用される熱膨張性シートに関する。 The present invention relates to a thermally expandable sheet, for example, a thermally expandable sheet used as a refractory material.
建築分野においては防火のために、建具、柱、壁材等の建築材料に耐火材が用いられる。耐火材としては、樹脂を含むマトリックス成分中に、難燃剤、無機充填剤などに加えて、熱膨張性黒鉛が配合された熱膨張性シート等が用いられている（例えば、特許文献１参照）。このような耐火材は、加熱により膨張して燃焼残渣が耐火断熱層を形成し、耐火断熱性能を発現する。 In the construction field, refractory materials are used for construction materials such as fittings, columns, wall materials, etc. for fire protection. As a refractory material, a thermally expandable sheet or the like in which thermally expandable graphite is blended in addition to a flame retardant, an inorganic filler, etc. in a matrix component containing a resin is used (see, for example, Patent Document 1) . Such a refractory material is expanded by heating, and the combustion residue forms a fireproof heat insulation layer, and exhibits fireproof heat insulation performance.
また、特許文献２では、塩化ビニル系樹脂に、該樹脂用の可塑剤と、膨張開始温度が１８０〜２４０℃である熱膨張性黒鉛と、前記塩化ビニル系樹脂の脱塩酸触媒と、脱塩酸抑制化合物とを含む熱膨張性塩化ビニル系樹脂材料が開示されている。特許文献２によれば、低温域における火炎及び煙の遮断機能を効果的に発揮し得、加熱されて膨張した膨張体が形状保持性及び機械的強度に優れ、さらに、熱膨張性シート等の製品を耐水性に優れたものにできるとされている。 Further, in Patent Document 2, a vinyl chloride resin, a plasticizer for the resin, thermally expandable graphite having an expansion start temperature of 180 to 240 ° C., a dehydrochlorination catalyst of the vinyl chloride resin, and dehydrochlorination Disclosed is a thermally expandable vinyl chloride resin material containing an inhibitory compound. According to Patent Document 2, the function of blocking flames and smoke in the low temperature range can be exhibited effectively, and the expanded body which has been heated and expanded is excellent in shape retention and mechanical strength, and further, a thermally expandable sheet or the like. It is said that the product can be made excellent in water resistance.
特許文献１、２などに記載される従来の耐火材は、樹脂成分などのマトリックス成分が含有されるため、火災時にこの成分が燃焼することで発生した炎が他の部位に燃え移り、さらにその炎が防火設備の他の部分に燃え移ってしまうことで、耐火部材の耐火機能が充分に発揮されない場合があった。耐火材自身の燃焼を抑えるには可燃成分であるマトリックス成分の割合を少なくしつつ、例えば無機充填材の割合を多くすることが考えられる。 Since the conventional refractory materials described in Patent Documents 1 and 2 contain matrix components such as resin components, the flame generated by the combustion of this component at the time of a fire burns up to another part, and the flames further However, there is a case where the fireproof function of the fireproof member can not be sufficiently exhibited by the burning out to other parts of the fire protection equipment. In order to suppress the burning of the refractory material itself, it is conceivable to increase, for example, the ratio of the inorganic filler while reducing the ratio of the matrix component which is the combustible component.
しかし、無機充填剤を多量に配合させる一方でマトリックス成分を少なくすると、耐火材はシート状にうまく成形できず、成形できたとしてもシート切れ等の不具合が発生することが多い。すなわち、マトリックス成分と無機充填材とを含有する熱膨張性シートにおいては、耐火性と加工性とは相反する特性といえ、これらの両方を優れたものとすることは困難であった。
そこで、本発明は、耐火性及び加工性が共に優れた熱膨張性シートを提供することを課題とする。
However, if the inorganic filler is compounded in a large amount while the matrix component is reduced, the refractory material can not be formed into a sheet well, and even if it can be formed, problems such as sheet breakage often occur. That is, in a thermally expandable sheet containing a matrix component and an inorganic filler, it can be said that both fire resistance and processability are opposite properties, and it is difficult to make both of them excellent.
Then, this invention makes it a subject to provide the thermally expandable sheet | seat excellent in both fire resistance and processability.
上記課題を解決すべく鋭意検討した結果、本発明者は、マトリックス成分、無機充填剤、熱膨張性黒鉛に加え、難燃性有機充填材を所定量含有させることで上記課題を解決できることを見出し、本発明を完成した。すなわち、本発明は下記のとおりである。
［１］マトリックス成分と、難燃性有機充填材と、熱膨張性黒鉛と、無機充填材とを含有し、
前記難燃性有機充填材の含有量が３〜４０質量％であり、前記熱膨張性黒鉛の含有量が２０〜３０質量％であり、かつ前記無機充填材の含有量が１０〜３０質量％である熱膨張性シート。
［２］前記難燃性有機充填材に対する前記無機充填材の質量比が、０．５〜７．５である上記［１］に記載の熱膨張性シート。
［３］前記難燃性有機充填材が、含窒素難燃剤である上記［１］又は［２］に記載の熱膨張性シート。
［４］前記難燃性有機充填材が、メラミン系化合物及びグアニジン系化合物からなる群から選択される少なくとも１種である上記［１］〜［３］のいずれか１項に記載の熱膨張性シート。
［５］前記難燃性有機充填材が、メラミンシアヌレートである上記［１］〜［４］のいずれか１項に記載の熱膨張性シート。
［６］前記マトリックス成分が、樹脂、エラストマー、及びゴムからなる群から選択される１種からなるか、又は、樹脂、エラストマー、及びゴムからなる群から選択される少なくとも１種と、可塑剤とからなる上記［１］〜［５］のいずれか１項に記載の熱膨張性シート。
［７］前記マトリックス成分が熱可塑性樹脂を含む上記［１］〜［６］のいずれか１項に記載の熱膨張性シート。
［８］前記熱可塑性樹脂がポリ塩化ビニル樹脂である上記［７］に記載の熱膨張性シート。
［９］さらに可塑剤を含有する上記［７］又は［８］に記載の熱膨張性シート。
［１０］前記マトリックス成分が２０〜５７質量％である上記［１］〜［９］のいずれか１項に記載の熱膨張性シート。
［１１］前記無機充填剤が、金属酸化物、金属炭酸塩、及びポリリン酸アンモニウムからなる群から選択される少なくとも１種である上記［１］〜［１０］のいずれか１項に記載の熱膨張性シート。
［１２］耐火材として使用される上記［１］〜［１１］のいずれか１項に記載の熱膨張性シート。
As a result of intensive studies to solve the above problems, the inventor found that the above problems can be solved by incorporating a predetermined amount of a flame retardant organic filler in addition to the matrix component, the inorganic filler, and the thermally expandable graphite. , Completed the present invention. That is, the present invention is as follows.
[1] A matrix component, a flame retardant organic filler, thermally expandable graphite, and an inorganic filler,
The content of the flame retardant organic filler is 3 to 40% by mass, the content of the thermally expandable graphite is 20 to 30% by mass, and the content of the inorganic filler is 10 to 30% by mass A thermally expandable sheet.
[2] The thermally expandable sheet according to the above [1], wherein the mass ratio of the inorganic filler to the flame retardant organic filler is 0.5 to 7.5.
[3] The thermally expandable sheet according to the above [1] or [2], wherein the flame retardant organic filler is a nitrogen-containing flame retardant.
[4] The thermally expandable material according to any one of the above [1] to [3], wherein the flame retardant organic filler is at least one selected from the group consisting of melamine compounds and guanidine compounds Sheet.
[5] The thermally expandable sheet according to any one of the above [1] to [4], wherein the flame retardant organic filler is melamine cyanurate.
[6] The matrix component is one selected from the group consisting of a resin, an elastomer and a rubber, or at least one selected from a group consisting of a resin, an elastomer and a rubber, and a plasticizer The thermally expandable sheet | seat of any one of said [1]-[5] which consists of these.
[7] The thermally expandable sheet according to any one of the above [1] to [6], wherein the matrix component comprises a thermoplastic resin.
[8] The thermally expandable sheet as described in the above [7], wherein the thermoplastic resin is a polyvinyl chloride resin.
[9] The thermally expandable sheet as described in the above [7] or [8], further containing a plasticizer.
[10] The thermally expandable sheet according to any one of the above [1] to [9], wherein the matrix component is 20 to 57% by mass.
[11] The heat according to any one of the above [1] to [10], wherein the inorganic filler is at least one selected from the group consisting of metal oxides, metal carbonates, and ammonium polyphosphates. Intumescent sheet.
[12] The thermally expandable sheet according to any one of the above [1] to [11], which is used as a refractory material.
本発明によれば、耐火性及び加工性が共に優れた熱膨張性シートを提供することができる。 According to the present invention, it is possible to provide a thermally expandable sheet excellent in both fire resistance and processability.
［熱膨張性シート］
本発明の熱膨張性シートは、マトリックス成分と、難燃性有機充填材と、熱膨張性黒鉛と、無機充填材とを含有し、難燃性有機充填材の含有量が３〜４０質量％であり、熱膨張性黒鉛の含有量が２０〜３０質量％であり、かつ無機充填材の含有量が１０〜３０質量％である。本発明では、熱膨張性黒鉛を２０〜３０質量％、難燃性有機充填材を３〜４０質量％含有させることで、無機充填材の割合を上記のようにそれほど高くしなくても、耐火性が良好となる。また、無機充填材の割合がそれほど高くないので、熱膨張性シートに加工するときの加工性も優れたものとなる。以下、本発明についてさらに詳細に説明する。
[Thermal expansion sheet]
The thermally expandable sheet of the present invention contains a matrix component, a flame retardant organic filler, a thermally expandable graphite, and an inorganic filler, and the content of the flame retardant organic filler is 3 to 40% by mass. The content of the thermally expandable graphite is 20 to 30% by mass, and the content of the inorganic filler is 10 to 30% by mass. In the present invention, by containing 20 to 30% by mass of thermally expandable graphite and 3 to 40% by mass of a flame-retardant organic filler, fire resistance can be achieved even if the proportion of the inorganic filler is not so high as described above. The quality is good. In addition, since the proportion of the inorganic filler is not so high, the processability when processed into a thermally expandable sheet is also excellent. Hereinafter, the present invention will be described in more detail.
（マトリックス成分）
マトリックス成分としては、樹脂、エラストマー、ゴム、及びこれらの組み合わせが挙げられる。また、マトリックス成分は、これらに可塑剤がさらに含有されていてもよい。
熱膨張性シートにおけるマトリックス成分の含有量は、熱膨張性シート全量基準で、２０〜５７質量％が好ましい。この範囲内とすることで、熱膨張性シートの加工性及び耐火性の両方を優れたものとしやすくなる。加工性を向上する観点から、マトリックス成分の含有量は、３０質量％以上が好ましく、４０質量％以上がより好ましい。また、耐火性の観点からは、５５質量％以下が好ましく、４５質量％以下がより好ましい。
(Matrix component)
Matrix components include resins, elastomers, rubbers, and combinations thereof. Moreover, the matrix component may further contain a plasticizer in these.
The content of the matrix component in the thermally expandable sheet is preferably 20 to 57% by mass based on the total mass of the thermally expandable sheet. Within this range, both the processability and the fire resistance of the thermally expandable sheet can be easily made excellent. From a viewpoint of improving processability, 30 mass% or more is preferable, and, as for content of a matrix component, 40 mass% or more is more preferable. Moreover, from a viewpoint of fire resistance, 55 mass% or less is preferable, and 45 mass% or less is more preferable.
樹脂としては、熱可塑性樹脂、熱硬化性樹脂、及びこれらの組み合わせが挙げられる。熱可塑性樹脂としては、例えば、ポリプロピレン樹脂、ポリエチレン樹脂、ポリ（１−）ブテン樹脂、ポリペンテン樹脂等のポリオレフィン樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、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、エチレン酢酸ビニル共重合体（ＥＶＡ）、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、ポリ塩化ビニル樹脂（ＰＶＣ）、ノボラック樹脂、ポリウレタン樹脂、ポリイソブチレン等の合成樹脂が挙げられる。
熱硬化性樹脂としては、例えば、ポリウレタン、ポリイソシアネート、ポリイソシアヌレート、フェノール樹脂、エポキシ樹脂、尿素樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ポリイミド等の合成樹脂が挙げられる。
Resins include thermoplastic resins, thermosetting resins, and combinations thereof. Examples of the thermoplastic resin include polyolefin resins such as polypropylene resin, polyethylene resin, poly (1-) butene resin, polypentene resin, polyester resin such as polyethylene terephthalate, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, ethylene Examples include synthetic resins such as vinyl acetate copolymer (EVA), polycarbonate resin, polyphenylene ether resin, (meth) acrylic resin, polyamide resin, polyvinyl chloride resin (PVC), novolac resin, polyurethane resin, polyisobutylene and the like.
Examples of the thermosetting resin include synthetic resins such as polyurethane, polyisocyanate, polyisocyanurate, phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide.
エラストマーとしてはオレフィン系エラストマー、スチレン系エラストマー、エステル系エラストマー、アミド系エラストマー、塩化ビニル系エラストマー等が挙げられる。
ゴムとしては、天然ゴム、イソプレンゴム、ブタジエンゴム、１，２−ポリブタジエンゴム、スチレン−ブタジエンゴム、クロロプレンゴム、ニトリルゴム、ブチルゴム、塩素化ブチルゴム、エチレン−プロピレンゴム、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）、クロロスルホン化ポリエチレン、アクリルゴム、エピクロルヒドリンゴム、多加硫ゴム、非加硫ゴム、シリコンゴム、フッ素ゴム、ウレタンゴム等のゴム等が挙げられる。
これらの樹脂、エラストマー、及びゴムの各々は、１種単独で使用してもよいし、２種以上を併用してよい。
Examples of the elastomer include olefin elastomers, styrene elastomers, ester elastomers, amide elastomers, vinyl chloride elastomers and the like.
Examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber (EPDM) Chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polyvulcanized rubber, non-vulcanized rubber, silicone rubber, fluororubber, rubber such as urethane rubber, etc. may be mentioned.
Each of these resins, elastomers, and rubbers may be used alone or in combination of two or more.
上記の樹脂、エラストマー、及びゴムの中でも、加工性を良好にする観点からは、樹脂、特に熱可塑性樹脂が好ましい。熱可塑性樹脂は、熱硬化性樹脂、エラストマー、及びゴムの少なくともいずれかと併用してもよいが、単独で使用してもよい。
また、熱可塑性樹脂の中でも、ポリエチレン樹脂、エチレン酢酸ビニル共重合体、（ＥＶＡ）、及びポリ塩化ビニル樹脂から選択される少なくとも１種が好ましい。これらの中でも、耐火性の点で含有炭素の割合を低くする観点から、ポリ塩化ビニル樹脂がより好ましい。
Among the above-mentioned resins, elastomers and rubbers, resins, particularly thermoplastic resins, are preferable from the viewpoint of improving processability. The thermoplastic resin may be used in combination with at least one of a thermosetting resin, an elastomer, and a rubber, but may be used alone.
Further, among thermoplastic resins, at least one selected from polyethylene resins, ethylene vinyl acetate copolymers, (EVA), and polyvinyl chloride resins is preferable. Among these, polyvinyl chloride resins are more preferable from the viewpoint of reducing the proportion of carbon contained in terms of fire resistance.
ポリ塩化ビニル樹脂は、塩化ビニル単独重合体であってもよいし、塩化ビニル系共重合体でよい。塩化ビニル系共重合体は、塩化ビニル及び塩化ビニルと共重合可能な不飽和結合を有する単量体の共重合体であって、塩化ビニル由来の構成単位を５０質量％以上含有する。
塩化ビニルと共重合可能な不飽和結合を有する単量体としては、例えば、酢酸ビニル、プロピオン酸ビニル等のビニルエステル、アクリル酸、メタクリル酸、アクリル酸メチル、アクリル酸エチル等のアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル等のメタクリル酸エステル、エチレン、プロピレン等のオレフィン、アクリロニトリル、スチレン等の芳香族ビニル、塩化ビニリデン等が挙げられる。
また、ポリ塩化ビニル樹脂は、ポリ塩素化塩化ビニル樹脂でもよい。ポリ塩素化塩化ビニル樹脂は、塩化ビニル単独重合体、塩化ビニル系共重合体などを塩素化したポリ塩素化塩化ビニル樹脂である。
ポリ塩化ビニル樹脂は、上記したものの中から１種単独で使用してもよいし、２種以上を併用してもよい。
The polyvinyl chloride resin may be a vinyl chloride homopolymer or a vinyl chloride copolymer. The vinyl chloride-based copolymer is a copolymer of vinyl chloride and a monomer having an unsaturated bond copolymerizable with vinyl chloride, and contains 50% by mass or more of structural units derived from vinyl chloride.
As a monomer having an unsaturated bond copolymerizable with vinyl chloride, for example, vinyl esters such as vinyl acetate and vinyl propionate, and acrylic esters such as acrylic acid, methacrylic acid, methyl acrylate and ethyl acrylate, Methacrylates such as methyl methacrylate and ethyl methacrylate; olefins such as ethylene and propylene; aromatic vinyls such as acrylonitrile and styrene; and vinylidene chloride.
The polyvinyl chloride resin may also be a polyvinyl chloride resin. The polychlorinated vinyl chloride resin is a polychlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride homopolymer, a vinyl chloride copolymer and the like.
The polyvinyl chloride resin may be used alone or in combination of two or more of the above-mentioned ones.
ポリ塩化ビニル樹脂の平均重合度は特に限定されないが、好ましくは、４００〜３０００である。平均重合度を４００以上にすることで、熱膨張性シートの機械的特性が良好となる。また、平均重合度を３０００以下とすることで、加工性が良好になりやすい。これら観点から、平均重合度は、より好ましくは７００〜１５００である。なお、平均重合度は、ＪＩＳ Ｋ６７２０−２に準拠して測定したものである。 The average degree of polymerization of the polyvinyl chloride resin is not particularly limited, but is preferably 400 to 3,000. By setting the average degree of polymerization to 400 or more, the mechanical properties of the thermally expandable sheet become good. In addition, by setting the average degree of polymerization to 3000 or less, the processability tends to be good. From these viewpoints, the average degree of polymerization is more preferably 700 to 1,500. The average degree of polymerization is measured in accordance with JIS K6720-2.
また、熱硬化性樹脂は、例えば、主剤と硬化剤とを硬化させることで得ることができるが、主剤のみを硬化して得たものであってもよい。熱硬化性樹脂を使用する場合、主剤、または主剤及び硬化剤をマトリックス成分として熱膨張性樹脂組成物に配合して、硬化させればよい。
例えば、熱硬化性樹脂がエポキシ樹脂である場合には、主剤は、エポキシ化合物である。エポキシ化合物は、エポキシ基を有する化合物であり、具体的には、グリシジルエーテル型、グリシジルエステル型が例示される。グリジシルエーテル型は、２官能でもよいし、３官能以上の多官能でもよい。また、グリシジルエステル型も同様である。エポキシ化合物は、架橋度を調整するためなどに１官能のものを含んでもよい。これらの中では、２官能のグリシジルエーテル型が好ましい。
The thermosetting resin can be obtained, for example, by curing the main agent and the curing agent, but may be obtained by curing only the main agent. When a thermosetting resin is used, a main ingredient, or a main ingredient and a curing agent may be blended as a matrix component into the thermally expandable resin composition and cured.
For example, when the thermosetting resin is an epoxy resin, the main agent is an epoxy compound. The epoxy compound is a compound having an epoxy group, and specific examples thereof include glycidyl ether type and glycidyl ester type. The glycidyl ether type may be bifunctional or trifunctional or higher polyfunctional. The same applies to the glycidyl ester type. The epoxy compound may contain a monofunctional one to adjust the degree of crosslinking. Among these, the difunctional glycidyl ether type is preferred.
上記２官能のグリシジルエーテル型のエポキシ化合物としては、例えば、ポリエチレングリコール型、ポリプロピレングリコール型などのアルキレングリコール型、ネオペンチルグリコール型、１、６−ヘキサンジオール型、水添ビスフェノールＡ型等の脂肪族エポキシ化合物が例示される。さらには、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡＤ型、エチレンオキサイド−ビスフェノールＡ型、プロピレンオキサイド−ビスフェノールＡ型などの芳香族環を含む芳香族エポキシ化合物が挙げられる。これらの中では、ビスフェノールＡ型、ビスフェノールＦ型などの芳香族エポキシ化合物が好ましい。
上記グリシジルエステル型のエポキシ化合物としては、例えば、ヘキサヒドロ無水フタル酸型、テトラヒドロ無水フタル酸型、ダイマー酸型、ｐ−オキシ安息香酸型等のエポキシ化合物が例示される。
３官能以上のグリシジルエーテル型エポキシ化合物としては、例えば、フェノールノボラック型、オルソクレゾールノボラック型、ＤＰＰノボラック型、ジシクロペンタジエン・フェノール型等が例示される。
これらのエポキシ化合物は、１種単独で用いられてもよく、２種以上が併用されてもよい。
Examples of the bifunctional glycidyl ether type epoxy compound include alkylene glycol types such as polyethylene glycol type and polypropylene glycol type, neopentyl glycol type, 1, 6-hexanediol type, and aliphatic such as hydrogenated bisphenol A type Epoxy compounds are exemplified. Furthermore, aromatic epoxy compounds containing aromatic rings such as bisphenol A type, bisphenol F type, bisphenol AD type, ethylene oxide-bisphenol A type, and propylene oxide-bisphenol A type can be mentioned. Among these, aromatic epoxy compounds such as bisphenol A type and bisphenol F type are preferable.
Examples of the above glycidyl ester type epoxy compound include epoxy compounds such as hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, p-hydroxybenzoic acid type and the like.
Examples of trifunctional or higher glycidyl ether type epoxy compounds include phenol novolac type, ortho cresol novolac type, DPP novolac type and dicyclopentadiene / phenol type.
These epoxy compounds may be used alone or in combination of two or more.
硬化剤としては、重付加型又は触媒型のものが用いられる。重付加型の硬化剤としては、例えば、ポリアミン系硬化剤、酸無水物系硬化剤、ポリフェノール系硬化剤、ポリメルカプタン等が挙げられる。また、上記触媒型の硬化剤としては、例えば、３級アミン、イミダゾール類、ルイス酸錯体等が例示される。硬化剤は、１種単独で用いられてもよく、２種以上が併用されてもよい。 As the curing agent, those of polyaddition type or catalyst type are used. Examples of the polyaddition type curing agent include polyamine based curing agents, acid anhydride based curing agents, polyphenol based curing agents, polymercaptans and the like. Moreover, as a catalyst type curing agent, for example, tertiary amines, imidazoles, Lewis acid complexes and the like are exemplified. A hardening agent may be used individually by 1 type, and 2 or more types may be used together.
（可塑剤）
マトリックス成分は、樹脂、エラストマー、ゴム、又はこれらの組み合わせからなるものでもよいが、これらの少なくとも１種と、可塑剤とからなるものでもよい。熱膨張性シートは、可塑剤を含有することで、熱膨張性シートの柔軟性を高めて、加工性を良好にしやすくなる。可塑剤は、マトリックス成分が熱可塑性樹脂を使用する場合に好適であり、ポリ塩化ビニル樹脂を使用する場合に特に好ましく使用される。
なお、可塑剤は、一般的に常温（２３℃）、常圧（１気圧）で液状となる液状成分が使用される。
(Plasticizer)
The matrix component may be composed of a resin, an elastomer, a rubber, or a combination thereof, but may be composed of at least one of them and a plasticizer. By containing a plasticizer, the thermally expandable sheet is likely to enhance the flexibility of the thermally expandable sheet and to improve the processability. A plasticizer is suitable when the matrix component uses a thermoplastic resin, and is particularly preferably used when using a polyvinyl chloride resin.
As the plasticizer, a liquid component which is liquid at normal temperature (23 ° C.) and normal pressure (1 atm) is generally used.
可塑剤の具体例としては、ジ−２−エチルヘキシルフタレート（ＤＯＰ）、ジ−ｎ−オクチルフタレート、ジイソノニルフタレート（ＤＩＮＰ）、ジイソデシルフタレート（ＤＩＤＰ）、ジウンデシルフタレート（ＤＵＰ）、又は炭素原子数１０〜１３程度の高級アルコール又は混合アルコールのフタル酸エステル等のフタル酸エステル系可塑剤、ジ−２−エチルヘキシルアジペート（ＤＯＡ）、ジイソブチルアジペート（ＤＩＢＡ）、ジブチルアジペート（ＤＢＡ）、ジ−ｎ−オクチルアジペート、ジ−ｎ−デシルアジペート、ジイソデシルアジペート、ジ−２−エチルヘキシルアゼレート、ジブチルセバケート、ジ−２−エチルヘキシルセバケート等の脂肪族エステル系可塑剤、トリ−２−エチルヘキシルトリメリテート（ＴＯＴＭ）、トリ−ｎ−オクチルトリメリテート、トリデシルトリメリテート、トリイソデシルトリメリテート、ジ−ｎ−オクチル−ｎ−デシルトリメリレート等のトリメリット酸エステル系可塑剤、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、オクチルジフェニルホスフェート、トリブトキシエチルホスフェート、トリクロロエチルホスフェート、トリス（２−クロロプロピル）ホスフェート、トリス（２，３−ジクロロプロピル）ホスフェート、トリス（２，３−ジブロモプロピル）ホスフェート、トリス（ブロモクロロプロピル）ホスフェート、ビス（２，３−ジブロモプロピル）−２，３−ジクロロプロピルホスフェート、ビス（クロロプロピル）モノオクチルホスフェート、トリス（２エチルヘキシル）ホスフェート、トリフェニルホスフェート、トリクレジルホスフェート（ＴＣＰ）、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート等のリン酸エステル系可塑剤、２，３，３'，４'−ビフェニルテトラカルボン酸テトラヘプチルエステル等のビフェニルテトラカルボン酸テトラアルキルエステル系可塑剤、ポリエステル系高分子可塑剤、エポキシ化大豆油、エポキシ化亜麻仁油、エポキシ化綿実油、液状エポキシ樹脂等のエポキシ系可塑剤、塩素化パラフィン、及び五塩化ステアリン酸アルキルエステル等の塩素化脂肪酸エステル等が挙げられる。
これら可塑剤は、１種単独で使用してもよいし、２種以上の可塑剤を組み合わせて使用してもよい。
上記の可塑剤のうち、フタル酸系可塑剤及びリン酸エステル系可塑剤から選択される少なくとも１種が難燃性と経済的な点で好ましく、フタル酸系可塑剤が特に好ましい。フタル酸系可塑剤は、フタル酸系可塑剤単独で使用してもよいが、リン酸エステル系可塑剤と併用してもよい。
Specific examples of the plasticizer include di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), or 10 to 10 carbon atoms. Phthalate plasticizers such as phthalic acid esters of 13 or more higher alcohols or mixed alcohols, di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), di-n-octyl adipate, Aliphatic ester plasticizers such as di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethyl hexyl sebacate, tri-2-ethylhexyl trimellitate (TOTM), Trimellitic acid ester plasticizers such as ly-n-octyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, di-n-octyl-n-decyl trimellilate, trimethyl phosphate, triethyl phosphate, Tributyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tributoxyethyl phosphate, trichloroethyl phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate Tris (bromochloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, bis (chloropropyl) monooctyl phosphate, tri (2 ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate (TCP), trixylenyl phosphate, cresyl diphenyl phosphate, phosphoric acid ester plasticizers such as xylenyl diphenyl phosphate, 2,3,3 ′, 4 '-Biphenyltetracarboxylic acid tetraheptyl ester and other biphenyltetracarboxylic acid tetraalkyl ester based plasticizers, polyester based polymer plasticizers, epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxy based resins such as liquid epoxy resin Examples thereof include plasticizers, chlorinated paraffins, and chlorinated fatty acid esters such as pentachlorostearic acid alkyl ester.
These plasticizers may be used singly or in combination of two or more plasticizers.
Among the above-mentioned plasticizers, at least one selected from phthalic acid-based plasticizers and phosphoric acid ester-based plasticizers is preferable in terms of flame retardancy and economy, and phthalic acid-based plasticizers are particularly preferable. The phthalic acid based plasticizer may be used alone as the phthalic acid based plasticizer, but may be used in combination with the phosphate ester based plasticizer.
可塑剤の含有量は、マトリックス成分全量基準で、６０質量％以下が好ましく、５５質量％以下がより好ましい。これら上限値以下とすることで、熱膨張性シートが柔らかくなり過ぎるのを防止する。また、柔軟性を高めて、加工性を良好にする観点から、可塑剤の含有量は、マトリックス成分全量基準で、３０質量％以上が好ましく、４０質量％以上がより好ましい。
また、上記したように、マトリックス成分は、熱可塑性樹脂を使用することが好ましく、熱可塑性樹脂と可塑剤を併用することが好ましい。熱可塑性樹脂と可塑剤を併用する場合、熱可塑性樹脂の含有量は、マトリックス成分全量基準で、４０質量％以上が好ましく、４５質量％以上がより好ましく、また、７０質量％以下が好ましく、６０質量％以下がより好ましい。
60 mass% or less is preferable on a matrix component whole quantity basis, and, as for content of a plasticizer, 55 mass% or less is more preferable. By setting the upper limit value or less, it is possible to prevent the thermally expandable sheet from becoming too soft. Further, from the viewpoint of enhancing the flexibility and improving the processability, the content of the plasticizer is preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total amount of the matrix component.
As described above, it is preferable to use a thermoplastic resin as the matrix component, and it is preferable to use a thermoplastic resin and a plasticizer in combination. When using a thermoplastic resin and a plasticizer in combination, the content of the thermoplastic resin is preferably 40% by mass or more, more preferably 45% by mass or more, and preferably 70% by mass or less, based on the total amount of the matrix component. % Or less is more preferable.
（難燃性有機充填材）
難燃性有機充填材は、炭素及び水素に加えて、窒素、リンなどのヘテロ原子を有する有機化合物であり、熱膨張性シートに難燃性を付与できる化合物である。
本発明において、熱膨張性シートにおける難燃性有機充填材の含有量は、熱膨張性シート全量基準で、３〜４０質量％である。難燃性有機充填材の含有量が３質量％未満では、例えば可燃成分となるマトリックス成分の割合が相対的に高くなりやすくなり、無機充填材の割合を所定の範囲としても、耐火性を十分に向上させることができない。また、難燃性有機充填材が４０質量％を超えると、マトリックス成分の割合が相対的に低くなりすぎて加工性が低下したり、無機充填剤の量が少なくなり耐火性が低くなったりする。
難燃性有機充填材の含有量は、加工性及び難燃性の観点から、５質量％以上が好ましく、１０質量％以上がより好ましく、また、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下が更に好ましい。
(Flame retardant organic filler)
The flame retardant organic filler is an organic compound having a heteroatom such as nitrogen and phosphorus in addition to carbon and hydrogen, and is a compound capable of imparting flame retardancy to the thermally expandable sheet.
In the present invention, the content of the flame retardant organic filler in the thermally expandable sheet is 3 to 40% by mass based on the total amount of the thermally expandable sheet. If the content of the flame retardant organic filler is less than 3% by mass, for example, the proportion of the matrix component to be the combustible component tends to be relatively high, and the fire resistance is sufficient even if the proportion of the inorganic filler is within the predetermined range. Can not improve. In addition, when the content of the flame retardant organic filler exceeds 40% by mass, the proportion of the matrix component becomes too low to lower the processability, or the amount of the inorganic filler decreases and the fire resistance becomes low. .
The content of the flame retardant organic filler is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, and 25% by mass or less from the viewpoint of processability and flame retardancy. More preferably, 20% by mass or less is more preferable.
難燃性有機充填材を構成する化合物は、化合物中における炭素原子の割合が好ましくは３５質量％以下、より好ましくは３０質量％以下の有機材料である。炭素の割合をこれら上限値以下とすることで、熱膨張性シートに耐火性を付与しやすくなる。また、炭素の割合は、３質量％以上がより好ましく、７質量％以上がさらに好ましく、１２質量％以上がさらに好ましい。炭素数をこれら下限値以上とすることで、加工性を向上させやすい。
なお、炭素原子の割合は、化学構造から算出でき、また、高分子化合物においては、公知の元素分析などにより測定できる。
The compound constituting the flame retardant organic filler is an organic material in which the ratio of carbon atoms in the compound is preferably 35% by mass or less, more preferably 30% by mass or less. By setting the ratio of carbon to the upper limit value or less, it becomes easy to provide the thermally expandable sheet with fire resistance. The proportion of carbon is preferably 3% by mass or more, more preferably 7% by mass or more, and still more preferably 12% by mass or more. By setting the carbon number to the lower limit or more, the processability can be easily improved.
The proportion of carbon atoms can be calculated from the chemical structure, and in the case of a polymer compound, it can be measured by known elemental analysis or the like.
難燃性有機充填材は、好ましくは含窒素難燃剤が挙げられる。より具体的には、メラミン系化合物及びグアニジン系化合物から選択される少なくとも１種が挙げられる。
メラミン系化合物としては、メラミン、メレム、メロンなどのメラミン又はメラミン誘導体、又はこれら塩が挙げられる。メラミン又はメラミン誘導体の塩としては、メラミンシアヌレート、硫酸メラミン、ポリリン酸メラミン、ピロリン酸メラミン、オルトリン酸メラミン、ポリリン酸メラミン・メラム・メレム、ポリメタリン酸メラミン、ピロ硫酸メラム、有機スルホン酸メラム、有機ホスホン酸メラミン、有機ホスフィン酸メラミン、ホウ酸メラミン等が挙げられる。
グアニジン系化合物としては、スルファミン酸グアニジン、リン酸グアニジン、リン酸グアニル尿素等が挙げられる。
これらの化合物は、１種単独で使用してもよいし、２種以上を併用してもよい。
The flame retardant organic filler is preferably a nitrogen-containing flame retardant. More specifically, at least one selected from melamine based compounds and guanidine based compounds can be mentioned.
As a melamine type compound, melamine or melamine derivatives, such as melamine, melem and melon, or these salts are mentioned. As a salt of melamine or a melamine derivative, melamine cyanurate, melamine sulfate, melamine polyphosphate, melamine pyrophosphate, melamine orthophosphate, melamine polyphosphate / melam melem, polymeta melamine, polysulfate melam, organic sulfonate melam, organic sulfonate Examples thereof include melamine phosphonate, melamine organic phosphinate, and melamine borate.
Examples of guanidine compounds include guanidine sulfamate, guanidine phosphate, and guanyl urea phosphate.
These compounds may be used alone or in combination of two or more.
また、上記した中では、メラミン又はメラミン誘導体の塩、又はグアニジン系化合物が好ましく、具体的には、メラミンシアヌレート、ポリリン酸メラミン・メラム・メレム、ポリリン酸メラミン、硫酸メラミン、スルファミン酸グアニジン、リン酸グアニジン、及びリン酸グアニル尿素から選択される少なくとも１種がより好ましく、さらに好ましくはメラミンシアヌレートである。
本発明では、上記したメラミン系化合物又はグアニジン系化合物、中でもメラミンシアヌレートを使用することで、加工性を良好に維持しつつ、耐火性をより優れたものにしやすくなる。
Further, among the above, a salt of melamine or a melamine derivative, or a guanidine compound is preferable, and specifically, melamine cyanurate, melamine polymelic acid melam melemem, melamine polyphosphoric acid, melamine sulfuric acid, guanidine sulfamate, phosphorus More preferred is at least one selected from acid guanidine and guanylurea phosphate, and more preferred is melamine cyanurate.
In the present invention, by using the above-mentioned melamine compound or guanidine compound, particularly melamine cyanurate, while maintaining good processability, it becomes easy to make fire resistance more excellent.
（熱膨張性黒鉛）
本発明の熱膨張性シートは、熱膨張性黒鉛を含有する。熱膨張性シートにおいて、熱膨張性黒鉛の含有量は、熱膨張性シート全量基準で、２０〜３０質量％である。含有量が２０質量％未満では、火の通過を阻止するのに適した膨張を得ることができず、３０質量％を超えると、熱膨張性シートの加工性、形状安定性などが低下する。耐火性及び加工性をより優れたものとする観点から、熱膨張性黒鉛の含有量は、２２〜２８質量％が好ましい。
(Thermally expandable graphite)
The thermally expandable sheet of the present invention contains thermally expandable graphite. In the thermally expandable sheet, the content of the thermally expandable graphite is 20 to 30% by mass based on the total amount of the thermally expandable sheet. If the content is less than 20% by mass, expansion suitable for preventing the passage of fire can not be obtained, and if it exceeds 30% by mass, the processability, the shape stability and the like of the thermally expandable sheet are deteriorated. The content of the thermally expandable graphite is preferably 22 to 28% by mass from the viewpoint of improving the fire resistance and the processability.
熱膨張性黒鉛は、加熱時に膨張する従来公知の物質である。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の粉末を濃硫酸、硝酸、セレン酸等の無機酸と濃硝酸、過塩素酸、過塩素酸塩、過マンガン酸塩、重クロム酸塩、過酸化水素等の強酸化剤とで処理してグラファイト層間化合物を生成させたもので、炭素の層状構造を維持したままの結晶化合物である。 Thermally expandable graphite is a conventionally known substance that expands when heated. For example, powders of natural scaly graphite, pyrolytic graphite, quiche graphite etc., inorganic acids such as concentrated sulfuric acid, nitric acid, selenic acid and concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, It is a crystalline compound which is treated with a strong oxidizing agent such as hydrogen peroxide to form a graphite intercalation compound, and maintains the layered structure of carbon.
熱膨張性黒鉛は中和処理されてもよい。つまり、上記のように強酸化剤などで処理して得られた熱膨張性黒鉛を、更にアンモニア、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中和してもよい。
熱膨張性黒鉛の粒度は、２０〜２００メッシュが好ましい。粒度が２００メッシュかそれより小さいと、黒鉛の膨張度が膨張断熱層を得るのに十分であり、また粒度が２０メッシュかそれより大きいと、樹脂に配合する際の分散性が良く、物性が良好である。なお、粒度は、ＪＩＳＺ８８０１−１に準拠した篩によって測定されたものである。
The thermally expandable graphite may be neutralized. That is, the thermally expandable graphite obtained by treating with a strong oxidizing agent or the like as described above may be further neutralized with ammonia, aliphatic lower amines, alkali metal compounds, alkaline earth metal compounds or the like.
The particle size of the thermally expandable graphite is preferably 20 to 200 mesh. When the particle size is 200 mesh or less, the degree of expansion of the graphite is sufficient to obtain the expanded heat insulating layer, and when the particle size is 20 mesh or more, the dispersibility in blending with the resin is good and the physical properties are It is good. In addition, a particle size is measured by the sieve based on JISZ8801-1.
（無機充填剤）
本発明の熱膨張性シートは、無機充填剤を含有する。無機充填剤の含有量は、熱膨張性シート全量基準で、１０〜３０質量％である。本発明では、含有量が１０質量％未満では、十分な耐火性が得られない。また、３０質量％を超えると、機械的物性を良好に維持することが困難になり、加工性も低下する。加工性、及び耐火性をより優れたものとする観点から、無機充填剤の含有量は、２０〜３０質量％が好ましく、２２〜２８質量％がより好ましく、２３〜２７質量％が更に好ましい。
(Inorganic filler)
The thermally expandable sheet of the present invention contains an inorganic filler. The content of the inorganic filler is 10 to 30% by mass based on the total amount of the thermally expandable sheet. In the present invention, when the content is less than 10% by mass, sufficient fire resistance can not be obtained. Moreover, when it exceeds 30 mass%, it will become difficult to maintain mechanical physical property favorable and workability will also fall. From a viewpoint of making processability and fire resistance more excellent, 20-30 mass% is preferable, as for content of an inorganic filler, 22-28 mass% is more preferable, and 23-27 mass% is still more preferable.
無機充填剤は、加熱されて膨張断熱層が形成される際、熱容量を増大させ伝熱を抑制しつつ、骨材的に働いて膨張断熱層の強度を向上させる。無機充填剤としては特に限定されず、例えば、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、酸化鉄、酸化錫、酸化アンチモン、フェライト等の金属酸化物、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金属水酸化物、塩基性炭酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、炭酸ストロンチウム、炭酸バリウム等の金属炭酸塩、硫酸カルシウム、石膏繊維、ケイ酸カルシウム等のカルシウム塩、シリカ、珪藻土、ドーソナイト、硫酸バリウム、タルク、クレー、マイカ、モンモリロナイト、ベントナイト、活性白土、セピオライト、イモゴライト、セリサイト、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、窒化ホウ素、窒化ケイ素、カーボンブラック、グラファイト、炭素繊維、炭素バルーン、各種金属粉、チタン酸カリウム、硫酸マグネシウム、チタン酸ジルコン酸鉛、アルミニウムボレート、硫化モリブデン、炭化ケイ素、ステンレス繊維、ホウ酸亜鉛、各種磁性粉、スラグ繊維、フライアッシュ、リン酸ナトリウム、リン酸カリウム、リン酸マグネシウム、リン酸アルミニウム等のリン酸金属塩、亜リン酸ナトリウム、亜リン酸カリウム、亜リン酸マグネシウム、亜リン酸アルミニウム等の亜リン酸金属塩、ポリリン酸アンモニウム、オルトリン酸金属塩、メタリン酸金属塩、トリポリリン酸金属塩などが挙げられる。無機充填剤は一種単独で使用してもよいし、二種以上を併用してもよい。
これらの中では、金属酸化物、金属炭酸塩、及びポリリン酸アンモニウムから選択される少なくとも１種好ましく、中でも、金属酸化物及び金属炭酸塩から選択される少なくとも１種がより好ましい。また、無機充填剤として、金属酸化物及び金属炭酸塩から選択される少なくとも１種は、亜リン酸金属塩、ポリリン酸アンモニウムなどの無機リン化合物と併用してもよいが、金属酸化物及び金属炭酸塩から選択される少なくとも１種の含有量は、無機充填剤全量に対して、２５〜１００質量％が好ましく、４０〜１００質量％がより好ましい。
When the inorganic filler is heated to form the expanded heat insulating layer, the inorganic filler acts as an aggregate and improves the strength of the expanded heat insulating layer while increasing the heat capacity and suppressing the heat transfer. The inorganic filler is not particularly limited, and examples thereof include: alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, metal oxides such as ferrite, calcium hydroxide, magnesium hydroxide, Metal hydroxides such as aluminum hydroxide and hydrotalcite, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, zinc carbonate, strontium carbonate, metal carbonates such as barium carbonate, calcium sulfate, gypsum fiber, calcium silicate, etc. Calcium salt, silica, diatomaceous earth, dawsonite, barium sulfate, talc, clay, mica, montmorillonite, bentonite, activated white earth, sepiolite, imogolite, sericite, glass fiber, glass beads, silica based balloon, aluminum nitride, boron nitride, carbonated silica Carbon black, graphite, carbon fiber, carbon balloon, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, silicon carbide, stainless steel, zinc borate, various magnetic powders, Metal phosphate such as slag fiber, fly ash, sodium phosphate, potassium phosphate, magnesium phosphate, aluminum phosphate, sodium phosphite, potassium phosphite, potassium phosphite, magnesium phosphite, aluminum phosphite etc Examples thereof include metal phosphates, ammonium polyphosphates, metal salts of orthophosphates, metal salts of metaphosphates and metal salts of tripolyphosphates. The inorganic filler may be used alone or in combination of two or more.
Among these, at least one selected from metal oxides, metal carbonates, and ammonium polyphosphates is preferable, and at least one selected from metal oxides and metal carbonates is more preferable among them. In addition, as the inorganic filler, at least one selected from metal oxides and metal carbonates may be used in combination with an inorganic phosphorus compound such as metal phosphite and ammonium polyphosphate, but metal oxides and metals 25-100 mass% is preferable with respect to the inorganic filler whole quantity, and, as for content of at least 1 sort (s) selected from carbonate, 40-100 mass% is more preferable.
無機充填剤の粒径は、０．５〜１００μｍが好ましく、より好ましくは１〜５０μｍである。これら下限値以上とすることで、二次凝集が起こったりすることを防止して分散性が良好になる。また、下限値以上とすると、後述する熱膨張性樹脂組成物の粘度を低下させることができ、加工性が良好になりやすい。また、上限値以下とすることで、熱膨張性シートの表面性や樹脂組成物の力学的性能が良好になる。
なお、無機充填剤の粒径は、例えば熱膨張性シートの断面ＳＥＭ（走査型電子顕微鏡像）を観察して熱膨張性黒鉛の粒径分布を求め、そこから得られる体積基準粒度分布において、小粒径側からの通過分積算５０％の粒子径を平均粒子径として求める。
The particle size of the inorganic filler is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. By setting the content to the lower limit value or more, the occurrence of secondary aggregation is prevented, and the dispersibility becomes good. Moreover, when it is more than the lower limit value, the viscosity of the thermally expandable resin composition described later can be reduced, and the processability tends to be favorable. Further, by setting the content to the upper limit value or less, the surface properties of the thermally expandable sheet and the mechanical performance of the resin composition become good.
The particle size of the inorganic filler can be determined, for example, by observing the cross-sectional SEM (scanning electron microscope image) of the thermally expandable sheet to obtain the particle size distribution of the thermally expandable graphite, and in the volume-based particle size distribution obtained therefrom, The particle diameter of 50% of the passing portion integration from the small particle diameter side is determined as the average particle diameter.
また、難燃性有機充填材に対する無機充填材の質量比（無機充填材／難燃性有機充填材）は０．５〜７．５であることが好ましい。質量比をこれら範囲内とすることで、耐火性と、加工性をいずれも向上させやすくなる。上記質量比は、より好ましくは１．５〜６．０、さらに好ましくは３．０〜５．５である。 The mass ratio of the inorganic filler to the flame retardant organic filler (inorganic filler / flame retardant organic filler) is preferably 0.5 to 7.5. By setting the mass ratio within these ranges, it is easy to improve both the fire resistance and the processability. The mass ratio is more preferably 1.5 to 6.0, and still more preferably 3.0 to 5.5.
本発明の熱膨張性シートは、上記以外のその他の成分を含有してもよい。その他の成分としては、その物性を損なわない範囲で、フェノール系、アミン系、イオウ系等の酸化防止剤、金属害防止剤、帯電防止剤、安定剤、架橋剤、滑剤、軟化剤、顔料等の各種添加剤が挙げられる。 The thermally expandable sheet of the present invention may contain other components other than the above. As other components, antioxidants such as phenol type, amine type and sulfur type, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, etc., as long as the physical properties are not impaired. And various additives.
熱膨張性シートの厚さは特に限定されないが、耐火性及び取扱い性の観点から、０．２〜１０ｍｍが好ましく、０．５〜３．０ｍｍがより好ましい。 The thickness of the thermally expandable sheet is not particularly limited, but is preferably 0.2 to 10 mm, and more preferably 0.5 to 3.0 mm from the viewpoint of fire resistance and handleability.
熱膨張性シートは、加熱により熱膨張性黒鉛が膨張して、膨張断熱層を形成する。熱膨張性シートは、このような膨張断熱層により、火災時などの高温にさらされた際に断熱し、耐火材として機能する。熱膨張性シートは、例えば、５０ｋＷ／ｍ2の加熱条件下で３０分間加熱した後の膨張倍率が３〜５０倍となる。なお、膨張倍率は、熱膨張性シートの試験片の（加熱後の試験片の厚さ）／（加熱前の試験片の厚さ）として算出される。 In the thermally expandable sheet, the thermally expandable graphite is expanded by heating to form an expanded heat insulating layer. The thermally expandable sheet insulates when it is exposed to a high temperature such as a fire, and functions as a fireproof material by such an expandable heat insulating layer. The thermally expandable sheet has, for example, an expansion ratio of 3 to 50 times after heating for 30 minutes under a heating condition of 50 kW / m 2 . The expansion ratio is calculated as (the thickness of the test piece after heating) / (the thickness of the test piece before heating) of the test piece of the thermally expandable sheet.
（熱膨張性シートの製造方法）
本発明の熱膨張性シートは例えば下記のようにして製造することができる。
まず、所定量のマトリックス成分、無機充填材、有機充填材、熱膨張性黒鉛、及びその他の必要に応じて配合される添加剤を、混練ロールなどの混練機で混練して、熱膨張性樹脂組成物を得る。
次に、樹脂が熱可塑性樹脂、ゴム、エラストマー、又はこれらの組み合わせである場合、得られた熱膨張性樹脂組成物を、例えば、プレス成形、カレンダー成形、押出成形等、公知の成形方法によりシート状に成形することで熱膨張性シートを得る。
マトリックス成分が熱硬化性樹脂を含む場合、得られた熱膨張性樹脂組成物を、例えばプレス成形などで加熱かつ加圧することで、シート状にしつつ熱硬化して熱膨張性シートを得るとよい。
(Method of manufacturing thermally expandable sheet)
The thermally expandable sheet of the present invention can be produced, for example, as follows.
First, a predetermined amount of a matrix component, an inorganic filler, an organic filler, a thermally expandable graphite, and other additives added as needed are kneaded using a kneader such as a kneader roll to obtain a thermally expandable resin. The composition is obtained.
Next, when the resin is a thermoplastic resin, rubber, elastomer, or a combination thereof, the obtained thermally expandable resin composition is sheeted by a known molding method such as press molding, calendar molding, extrusion molding, etc. By forming into a shape, a thermally expandable sheet is obtained.
When the matrix component contains a thermosetting resin, the obtained thermally expandable resin composition may be thermally cured while being formed into a sheet by heating and pressing, for example, by press molding, to obtain a thermally expandable sheet. .
［積層シート］
本発明の熱膨張性シートは、他のシート部材や粘着剤層が積層され積層シートを構成してもよい。積層シートは、例えば、基材と、基材の片面又は両面に積層される熱膨張性シートとを備える。基材は通常、織布又は不織布である。織布又は不織布に使用される繊維としては、特に限定はされないが、不燃性料又は準不燃材料が好ましく、例えば、ガラス繊維、セラミック繊維、セルロース繊維、ポリエステル繊維、炭素繊維、グラファイト繊維、熱硬化性樹脂繊維等が好ましい。
上記積層シートは、例えば、熱膨張性樹脂組成物を基材の上にシート状に成形し、また、必要に応じて熱膨張性樹脂組成物を熱硬化するなどして得ることができる。
[Laminated sheet]
In the thermally expandable sheet of the present invention, other sheet members and an adhesive layer may be laminated to constitute a laminated sheet. The laminated sheet includes, for example, a base and a thermally expandable sheet laminated on one side or both sides of the base. The substrate is usually a woven or non-woven fabric. The fibers used for the woven or non-woven fabric are not particularly limited, but non-combustible or semi-incombustible materials are preferable. For example, glass fibers, ceramic fibers, cellulose fibers, polyester fibers, carbon fibers, graphite fibers, thermosetting Resin fibers are preferable.
The laminated sheet can be obtained, for example, by molding a thermally expandable resin composition on a base material into a sheet, and if necessary, thermally curing the thermally expandable resin composition.
また、積層シートは、熱膨張性シートと粘着剤層を備えるものであってもよい。粘着剤層は、例えば、熱膨張性シートの片面又は両面に積層されてもよい。
さらに、積層シートは、熱膨張性シートと、基材と、粘着剤層とを備えてもよい。そのような積層シートは、基材の一方の面に熱膨張性シート、他方の面に粘着剤層が設けられてもよいし、基材の一方の面の上に、熱膨張性シート及び粘着剤層がこの順に設けられてもよい。粘着剤層は、例えば、離型紙に塗工した粘着剤を積層シートに転写することで形成できる。
The laminated sheet may also be provided with a thermally expandable sheet and an adhesive layer. The pressure-sensitive adhesive layer may be laminated, for example, on one side or both sides of the thermally expandable sheet.
Furthermore, the laminated sheet may include a thermally expandable sheet, a substrate, and an adhesive layer. Such a laminated sheet may be provided with a thermally expandable sheet on one side of the substrate and an adhesive layer on the other side, or on one side of the substrate, a thermally expandable sheet and an adhesive. An agent layer may be provided in this order. The pressure-sensitive adhesive layer can be formed, for example, by transferring the pressure-sensitive adhesive coated on a release paper to a laminated sheet.
本発明の熱膨張性シート及び積層シートはそれぞれ、上記のように耐火材として使用できるものである。熱膨張性シート及び積層シートはそれぞれ、具体的には、一戸建住宅、集合住宅、高層住宅、高層ビル、商業施設、公共施設等の各種の建築物、自動車、電車などの各種車両、船舶、航空機などに使用できるが、これらの中では建築物に使用されることが好ましい。
熱膨張性シート及び積層シートはそれぞれ、上記建築物、車両、船舶、航空機などを構成する部材に取り付けられて使用される。熱膨張性シート及び積層シートはそれぞれ、より具体的には、壁、床、レンガ、屋根、板材、窓、障子、扉、ドア、戸、ふすま、欄間、配線、配管などに取り付けられるが、これらに限定されないが、窓、障子、扉、ドア等の建具が好ましい。
The thermally expandable sheet and the laminated sheet of the present invention can each be used as a refractory material as described above. Specifically, each of the thermally expandable sheet and the laminated sheet is a single-family house, an apartment house, a high-rise house, a high-rise building, a commercial facility, various buildings such as public facilities, various vehicles such as automobiles and trains, ships, Although it can be used for an aircraft etc., it is preferable to use for a building in these.
The thermally expandable sheet and the laminated sheet are used by being attached to members constituting the above-mentioned building, vehicle, ship, aircraft and the like. More specifically, the thermally expandable sheet and the laminated sheet are attached to walls, floors, bricks, roofs, plate materials, windows, shoji, doors, doors, doors, bran, cross sections, wiring, piping, etc. Although not limited thereto, fittings such as windows, shoji, doors and doors are preferable.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明はこれらに限定されない。 EXAMPLES Although an Example is given to the following and this invention is more concretely demonstrated to it, this invention is not limited to these.
［評価方法］
実施例、比較例で得られた熱膨張性シートについて、下記耐火性試験及び加工性試験を行った。
（耐火性試験）
耐火炉にてエーアンドエーマテリアル社製の５ｍｍのケイ酸カルシウム板を１１８０ｍｍ×１１８０ｍｍに切り出し、その中央部に厚さ１．６ｍｍで３００ｍｍ×３００ｍｍに耐火シートをステーブルガンを用い、鉄針にて貼り付けた。鉄針の固定位置は中央部ならびに四隅及び各辺の中点の９ヶ所固定し、試験体を作成した。この試験体をＩＳＯ８３４の標準加熱曲線に従い、温度を調整し、かつ、炉圧を２０Ｐａの設定で、２０分間の耐火試験を実施した。耐火試験中の試験体を観察し、試験体に貼り付けした膨張材が着火したものの３秒以内に消化したものをＡ、１０秒以に消火したものをＢ、１０秒を超えて膨張材が燃焼継続したものをＣとした。
（加工性試験）
＜シート成形性＞
得られたシートの外観を目視にて観察し、以下のように評価した。
Ａ：ヒビ等がなく、表面が平滑であるもの
Ｂ：ヒビ等はないが、若干、表面が荒れているもの
Ｃ：ワレやシワ、ヒビが存在するもの
＜作業性＞
実施例及び比較例の各々の熱膨張性シートをローラーに巻付け、作業性としての巻き付け易さを作業者の感覚で評価すると共に、巻きつけたテープの割れなどを観察し、以下のように評価した。
Ａ：ローラーの直径が１００ｍｍでヒビ等なし
Ｂ：ローラーの直径が２００ｍｍでヒビ等なし
Ｃ：ローラーの直径が２００ｍｍでヒビ等あり
[Evaluation method]
The following fire resistance test and processability test were done about the thermally expandable sheet obtained by the example and the comparative example.
(Fire resistance test)
Using a fireproof furnace, cut out a 5 mm calcium silicate plate made by A & A Material Co., Ltd. into 1180 mm x 1180 mm, and attach a fireproof sheet to the center part of it with a thickness of 1.6 mm and 300 mm x 300 mm using a stable gun and iron needle I put it. The fixed position of the iron needle was fixed in nine places of the center part and the middle point of the four corners and each side, and the test body was made. The test piece was subjected to a fire resistance test for 20 minutes at a furnace temperature set at 20 Pa according to the standard heating curve of ISO 834 and at a furnace pressure setting of 20 Pa. The specimen under fire resistance test was observed, and the expansive material attached to the specimen ignited but the digested material within 3 seconds was A, the one extinguished for 10 seconds or less B, and the expansive material over 10 seconds. The thing which continued combustion was set to C.
(Processability test)
<Sheet formability>
The appearance of the obtained sheet was visually observed and evaluated as follows.
A: There is no crack and the surface is smooth. B: There is no crack and the like, but some is rough. C: Cracks, wrinkles and cracks are present <Workability>.
The thermally expandable sheet of each of the examples and comparative examples is wound on a roller, and the ease of winding as the workability is evaluated by the operator's sense, and the crack of the wound tape is observed, as follows. evaluated.
A: Roller diameter is 100 mm and no cracks B: Roller diameter is 200 mm and no cracks C: Roller diameter is 200 mm and there are cracks
（実施例１〜３３、比較例１〜４）
下記表１〜５、７に示す配合にて、樹脂、無機充填材、有機充填材、可塑剤、熱膨張性黒鉛をロールに投入して混練して、熱膨張性樹脂組成物を得た。得られた熱膨張性樹脂組成物をプレス成型により、１５０℃で５分間プレス成形して、厚さ１．６ｍｍの熱膨張性シートを得た。各実施例、比較例で使用した各成分は下記のとおりである。
なお、表１〜５の配合における数値の単位は質量％である。
(Examples 1 to 33, Comparative Examples 1 to 4)
Resin, an inorganic filler, an organic filler, a plasticizer, and a thermally expansible graphite were thrown into a roll by the mixing | blending shown to following Tables 1-5, 7, it knead | mixed, and the thermally expansible resin composition was obtained. The obtained thermally expandable resin composition was press-molded for 5 minutes at 150 ° C. by press molding to obtain a thermally expandable sheet having a thickness of 1.6 mm. Each component used by each Example and a comparative example is as follows.
In addition, the unit of the numerical value in mixing | blending of Tables 1-5 is the mass%.
（実施例３４〜３７）
下記表６に示す各成分を遊星式攪拌機（シンキー社製ＡＲＥ５００）に供給し、常温下で７００ｒｐｍで３分間混練し、熱膨張性樹脂組成物を得た。その後、ＰＥＴフィルム上に熱膨張性樹脂組成物を塗布し、２０℃にて１０ＭＰａでプレス成型を実施し、厚み１．５ｍｍのシート状の成形体を得た。その後、その成形体を９０℃の恒温槽に１０時間配置して硬化させ、熱膨張性耐火シートを製造した。
(Examples 34 to 37)
Each component shown in the following Table 6 was supplied to a planetary stirrer (ARE 500 manufactured by Shinky Co., Ltd.), and was kneaded for 3 minutes at 700 rpm under normal temperature to obtain a thermally expandable resin composition. Thereafter, the thermally expandable resin composition was applied onto a PET film, and press molding was performed at 20 ° C. and 10 MPa, to obtain a sheet-like formed body having a thickness of 1.5 mm. Thereafter, the molded product was placed in a thermostat at 90 ° C. for 10 hours and cured to produce a thermally expandable refractory sheet.
（１）樹脂
・ＰＶＣ：ポリ塩化ビニル樹脂、信越化学工業株式会社製、商品名「ＴＫ−１０００」、平均重合度１０３０
・ポリエチレン：日本ポリエチレン株式会社製、商品名「ノバテックＴＭＬＬ ＵＥ３２０」
・ＥＶＡ：エチレン酢酸ビニル共重合体、三井・デュポンポリケミカル株式会社製、商品名「エバフレックス ＥＶ４６０」
・エポキシ樹脂（主剤）：三菱ケミカル株式会社製、製品名「Ｅ−８０７」
・エポキシ樹脂（硬化剤）：三菱ケミカル株式会社製、商品名「ＦＬ−０７９」
（２）可塑剤
・ＤＯＰ：ジ−２−エチルヘキシルフタレート、株式会社ジェイプラス製ＤＯＰ
・ＴＣＰ：トリクレジルホスフェート、新日本理化株式会社製、商品名「サンソサイザーＴＣＰ」
(1) Resin / PVC: Polyvinyl chloride resin, manufactured by Shin-Etsu Chemical Co., Ltd., trade name "TK-1000", average degree of polymerization 1030
-Polyethylene: Nippon Polyethylene Co., Ltd., trade name "Novatec TMLL UE320"
-EVA: ethylene vinyl acetate copolymer, manufactured by Mitsui-Dupont Polychemicals Co., Ltd., trade name "Evaflex EV460"
-Epoxy resin (main agent): manufactured by Mitsubishi Chemical Corporation, product name "E-807"
Epoxy resin (hardening agent): manufactured by Mitsubishi Chemical Corporation, trade name "FL-079"
(2) Plasticizer · DOP: Di-2-ethylhexyl phthalate, made by J Plus Co., Ltd. DOP
・ TCP: Tricresyl phosphate, manufactured by Shin Nippon Rika Co., Ltd., trade name “San-Sizer TCP”
（３）有機充填材
・メラミンシアヌレート：日産化学工業株式会社製、商品名「ＭＣ−４０００」、炭素割合：２８．２質量％
・ポリリン酸メラミン・メラム・メレム：日産化学工業株式会社製、商品名「Ｐｈｏｓｍｅｌ２００」、炭素割合：１９．７質量％
・ポリリン酸メラミン：株式会社三和ケミカル製、商品名「ＭＰＰ−Ａ」、炭素割合：１６．８質量％
・スルファミン酸グアニジン：株式会社三和ケミカル製、商品名「アピノン−１０１」、炭素割合７．７質量％
・リン酸グアニジン：株式会社三和ケミカル製、商品名「アピノン−３０３」、炭素割合７．７質量％
・リン酸グアニル尿素：株式会社三和ケミカル製、商品名「アピノン−４０５」、炭素割合１２質量％
・硫酸メラミン：株式会社三和ケミカル製、商品名「アピノン−９０１」、炭素割合２０．６質量％
(3) Organic filler, melamine cyanurate: manufactured by Nissan Chemical Industries, Ltd., trade name "MC-4000", carbon ratio: 28.2% by mass
-Polyphosphate melamine-Melam-Melem: Nissan Chemical Industries, Ltd., trade name "Phosmel 200", carbon ratio: 19.7 mass%
-Polyphosphate melamine: Sanwa Chemical Co., Ltd., trade name "MPP-A", carbon ratio: 16.8 mass%
-Guanidine sulfamate: Sanwa Chemical Co., Ltd., trade name "Apinon-101", carbon ratio 7.7 mass%
-Phosphoric acid guanidine: Sanwa Chemical Co., Ltd. make, brand name "Apinon-303", carbon ratio 7.7 mass%
-Guanyl urea phosphate: Sanwa Chemical Co., Ltd. make, brand name "Apinon-405", carbon ratio 12 mass%
-Melamine sulfate: Sanwa Chemical Co., Ltd. make, brand name "Apinon-901", carbon ratio 20.6 mass%
（４）熱膨張性黒鉛
・熱膨張性黒鉛：ＡＤＴ社製、商品名「ＡＤＴ３５１」
（５）無機充填材
・炭酸カルシウム：白石カルシウム株式会社製、商品名「ＢＦ３００」
・酸化亜鉛：堺化学工業株式会社製、商品名「酸化亜鉛１種」
・ポリリン酸アンモニウム：クラリアントジャパン株式会社製、商品名「ＡＰ４２２」
(4) Thermal expandable graphite · Thermal expandable graphite: manufactured by ADT, trade name "ADT 351"
(5) Inorganic filler, calcium carbonate: manufactured by Shiraishi Calcium Co., Ltd., trade name "BF300"
-Zinc oxide: Made by Sakai Chemical Industry Co., Ltd., trade name "Zinc oxide type 1"
-Ammonium polyphosphate: manufactured by Clariant Japan Co., Ltd., trade name "AP422"
以上の実施例に示すように、熱膨張性シートは、難燃性有機充填材、熱膨張性黒鉛、及び無機充填材をそれぞれ所定量含有することで、耐火性、加工性のいずれも優れたものにすることができた。 As shown in the above examples, the thermally expandable sheet is excellent in both fire resistance and processability by containing predetermined amounts of the flame retardant organic filler, thermally expandable graphite and inorganic filler, respectively. I was able to make things.
Claims (12)
前記難燃性有機充填材の含有量が３〜４０質量％であり、前記熱膨張性黒鉛の含有量が２０〜３０質量％であり、かつ前記無機充填材の含有量が１０〜３０質量％である熱膨張性シート。 Containing a matrix component, a flame retardant organic filler, thermally expandable graphite, and an inorganic filler,
The content of the flame retardant organic filler is 3 to 40% by mass, the content of the thermally expandable graphite is 20 to 30% by mass, and the content of the inorganic filler is 10 to 30% by mass A thermally expandable sheet.
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| WO2021039013A1 (en) * | 2019-08-26 | 2021-03-04 | 積水化学工業株式会社 | Heat-expanding fire retardant |
| JP2022053474A (en) * | 2020-09-24 | 2022-04-05 | 積水化学工業株式会社 | Refractory resin composition, refractory material, and fixtures |
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| JP2022053384A (en) * | 2020-09-24 | 2022-04-05 | 積水化学工業株式会社 | Refractory resin composition, refractory material, and fixtures |
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