CN112771104A - 聚烯烃系树脂发泡体片 - Google Patents
聚烯烃系树脂发泡体片 Download PDFInfo
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- CN112771104A CN112771104A CN201980062596.9A CN201980062596A CN112771104A CN 112771104 A CN112771104 A CN 112771104A CN 201980062596 A CN201980062596 A CN 201980062596A CN 112771104 A CN112771104 A CN 112771104A
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- CN
- China
- Prior art keywords
- foam sheet
- combustion gas
- polyolefin resin
- mass
- ratio
- Prior art date
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- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 71
- 239000000567 combustion gas Substances 0.000 claims abstract description 86
- 238000005259 measurement Methods 0.000 claims abstract description 49
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 9
- 239000003063 flame retardant Substances 0.000 claims description 78
- 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 description 70
- -1 polypropylene Polymers 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 229920000388 Polyphosphate Polymers 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 21
- 239000001205 polyphosphate Substances 0.000 claims description 21
- 235000011176 polyphosphates Nutrition 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000002367 halogens Chemical class 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 239000004743 Polypropylene Substances 0.000 claims description 16
- 229920001155 polypropylene Polymers 0.000 claims description 16
- 229920013716 polyethylene resin Polymers 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 33
- 238000004132 cross linking Methods 0.000 description 31
- 238000000034 method Methods 0.000 description 24
- 239000004088 foaming agent Substances 0.000 description 20
- 238000005187 foaming Methods 0.000 description 17
- 235000021317 phosphate Nutrition 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 11
- 229920000877 Melamine resin Polymers 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
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- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 7
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
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- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
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- 150000001451 organic peroxides Chemical class 0.000 description 6
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
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- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 150000003413 spiro compounds Chemical class 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
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- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical class NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- 235000019399 azodicarbonamide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- GRKDVZMVHOLESV-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(COC(=O)C=C)C(Br)=C1Br GRKDVZMVHOLESV-UHFFFAOYSA-N 0.000 description 2
- MWEXRLZUDANQDZ-RPENNLSWSA-N (2s)-3-hydroxy-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-(3-methylsulfanylpropyl)triazol-1-y Chemical compound N1=NC(CCCSC)=CN1[C@@H](CO)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 MWEXRLZUDANQDZ-RPENNLSWSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
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- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
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- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 2
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- NSMWYRLQHIXVAP-OLQVQODUSA-N (2r,5s)-2,5-dimethylpiperazine Chemical compound C[C@H]1CN[C@H](C)CN1 NSMWYRLQHIXVAP-OLQVQODUSA-N 0.000 description 1
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- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- XQKQZOLAVMIQHZ-UHFFFAOYSA-N 1,1-dibromo-3-(3,3-dibromopropoxy)propane Chemical compound BrC(Br)CCOCCC(Br)Br XQKQZOLAVMIQHZ-UHFFFAOYSA-N 0.000 description 1
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- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- YATIGPZCMOYEGE-UHFFFAOYSA-N 1,3,5-tribromo-2-[2-(2,4,6-tribromophenoxy)ethoxy]benzene Chemical compound BrC1=CC(Br)=CC(Br)=C1OCCOC1=C(Br)C=C(Br)C=C1Br YATIGPZCMOYEGE-UHFFFAOYSA-N 0.000 description 1
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- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
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- LRZPQLZONWIQOJ-UHFFFAOYSA-N 10-(2-methylprop-2-enoyloxy)decyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOC(=O)C(C)=C LRZPQLZONWIQOJ-UHFFFAOYSA-N 0.000 description 1
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- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 description 1
- HRIJSYATNFJXHM-UHFFFAOYSA-N 2,6-diamino-1h-1,3,5-triazine-4-thione Chemical compound NC1=NC(=S)N=C(N)N1 HRIJSYATNFJXHM-UHFFFAOYSA-N 0.000 description 1
- PAOXFRSJRCGJLV-UHFFFAOYSA-N 2-[4-(2-aminoethyl)piperazin-1-yl]ethanamine Chemical compound NCCN1CCN(CCN)CC1 PAOXFRSJRCGJLV-UHFFFAOYSA-N 0.000 description 1
- BELHUEMEOCZAGV-UHFFFAOYSA-N 2-[[3,4-bis(2-carboxyprop-2-enyl)phenyl]methyl]prop-2-enoic acid Chemical compound OC(=O)C(=C)CC1=CC=C(CC(=C)C(O)=O)C(CC(=C)C(O)=O)=C1 BELHUEMEOCZAGV-UHFFFAOYSA-N 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical class NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C08L23/10—Homopolymers or copolymers of propene
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- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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Abstract
本发明为一种聚烯烃系树脂发泡体片,其面密度为5g/m2以上且400g/m2以下,在升温速度10℃/分钟、以测定温度200~550℃作为整个测定温度范围的热重‑质谱中,上述聚烯烃系树脂发泡体片满足以下的条件(1)和条件(2)中的至少1者。条件(1):燃烧气体产生比率X为25%以下,上述燃烧气体产生比率X的定义为:在测定温度200~364℃的范围内燃烧气体P的产生量的峰面积值相对于在整个测定温度范围中燃烧气体P的产生量的峰面积值的比例,上述燃烧气体P的质荷比m/z为55。条件(2):燃烧气体产生比率Y为25%以下,上述燃烧气体产生比率Y的定义为:在测定温度200~364℃的范围内燃烧气体Q的产生量的峰面积值相对于在整个测定温度范围中燃烧气体Q的产生量的峰面积值的比例,上述燃烧气体Q的质荷比m/z为69。根据本发明,可以提供维持轻量性,同时具有高阻燃性的聚烯烃系树脂发泡体片。
Description
技术领域
本发明涉及将聚烯烃系树脂发泡而成的聚烯烃系树脂发泡体片,特别是涉及航空机的内装用冲击吸收材料等所使用的聚烯烃系树脂发泡体片。
背景技术
一直以来,聚烯烃系树脂发泡体由于轻量性、绝热性、冲击吸收性、耐水性、耐化学性、和机械强度等各特性优异,因此在建材、电器制品、汽车、航空机等广泛的领域中被使用。聚烯烃系树脂发泡体为易燃性,因此在使用于要求阻燃性的用途的情况下比较大量地混配各种阻燃剂。例如在专利文献1中公开了使含有由特定的乙烯系共聚物90~30重量%形成的树脂成分100重量份、规定的金属氢氧化物50~150重量份、红磷2~25重量份、氧化钛2~25重量份、和热稳定剂0.1~5重量份的树脂组合物进行了交联和发泡的无卤系阻燃性树脂发泡体。
现有技术文献
专利文献
专利文献1:日本专利第3580556号公报
发明内容
发明所要解决的课题
如专利文献1所记载的树脂发泡体那样如果对树脂组合物大量混配阻燃剂则超出适当的粘度范围,因此发泡性降低,发泡体的密度变高。其结果,发泡体片的重量增加,因此难以使用于例如航空机等要求轻量性的用途。
本发明是鉴于上述以往的情况而提出的,其课题是提供维持轻量性,同时具有高阻燃性的聚烯烃系树脂发泡体片。
用于解决课题的方法
本发明人等为了解决上述课题而进行了深入研究。其结果发现,通过使面密度为规定的范围,并且在热重-质谱中,使特定测定区域的产生量的峰面积值相对于特定的质荷比m/Z的燃烧气体的整个测定区域的产生量的峰面积值为一定值以下,可获得兼具轻量性和阻燃性的聚烯烃系树脂发泡体片,从而完成了本发明。
即,本发明以以下的[1]~[8]作为主旨。
[1]一种聚烯烃系树脂发泡体片,其面密度为5g/m2以上且400g/m2以下,在升温速度10℃/分钟、以测定温度200~550℃作为整个测定温度范围的热重-质谱中,上述聚烯烃系树脂发泡体片满足以下的条件(1)和条件(2)中的至少1者。
条件(1):燃烧气体产生比率X为25%以下,上述燃烧气体产生比率X的定义为:在测定温度200~364℃的范围内燃烧气体P的产生量的峰面积值相对于在整个测定温度范围中燃烧气体P的产生量的峰面积值的比例,上述燃烧气体P的质荷比m/z为55,
条件(2):燃烧气体产生比率Y为25%以下,上述燃烧气体产生比率Y的定义为:在测定温度200~364℃的范围内燃烧气体Q的产生量的峰面积值相对于在整个测定温度范围中燃烧气体Q的产生量的峰面积值的比例,上述燃烧气体Q的质荷比m/z为69,
[2]根据上述[1]所述的聚烯烃系树脂发泡体片,其厚度为15mm以下。
[3]根据上述[1]或[2]所述的聚烯烃系树脂发泡体片,构成上述聚烯烃系树脂发泡体片的聚烯烃系树脂为选自聚乙烯树脂和聚丙烯树脂中的1种以上。
[4]根据上述[3]所述的聚烯烃系树脂发泡体片,上述聚烯烃系树脂并用了聚乙烯树脂和聚丙烯树脂。
[5]根据上述[1]~[4]中任一项所述的聚烯烃系树脂发泡体片,其含有阻燃剂。
[6]根据上述[5]所述的聚烯烃系树脂发泡体片,上述阻燃剂为选自磷系阻燃剂和卤素系阻燃剂中的至少1种。
[7]根据上述[6]所述的聚烯烃系树脂发泡体片,上述磷系阻燃剂为选自磷酸盐、聚磷酸盐、和磷系螺环化合物中的1种以上。
[8]根据上述[6]或[7]所述的聚烯烃系树脂发泡体片,上述卤素系阻燃剂为溴系阻燃剂。
发明的效果
根据本发明,可以提供维持轻量性,同时具有高阻燃性的聚烯烃系树脂发泡体片。
具体实施方式
[聚烯烃系树脂发泡体片]
本发明的聚烯烃系树脂发泡体片(以下,也称为“发泡体片”)的面密度为5g/m2以上且400g/m2以下,在升温速度10℃/分钟、以测定温度200~550℃作为整个测定温度范围的热重-质谱中,上述聚烯烃系树脂发泡体片满足以下的条件(1)和条件(2)中的至少1者。
条件(1):燃烧气体产生比率X为25%以下,上述燃烧气体产生比率X的定义为:在测定温度200~364℃的范围内燃烧气体P的产生量的峰面积值相对于在整个测定温度范围中燃烧气体P的产生量的峰面积值的比例,上述燃烧气体P的质荷比m/z为55。
条件(2):燃烧气体产生比率Y为25%以下,上述燃烧气体产生比率Y的定义为:在测定温度200~364℃的范围内燃烧气体Q的产生量的峰面积值相对于在整个测定温度范围中燃烧气体Q的产生量的峰面积值的比例,上述燃烧气体Q的质荷比m/z为69。
在本发明中,由于发泡体片的面密度为5g/m2以上且400g/m2以下,因此是轻量的,可以用于航空机等需要轻量化的用途。此外,在热重-质谱中,满足上述条件(1)和条件(2)中的至少1者,因此阻燃性优异。
以下,对本发明的聚烯烃系树脂发泡体片进一步详细地说明。
<面密度>
本发明的发泡体片的面密度为5g/m2以上且400g/m2以下。如果上述面密度小于5g/m2,则发泡体片的密度过度变小而机械强度降低并且冲击吸收性也降低。另一方面,如果上述面密度超过400g/m2,则发泡体片的重量变大,不能用于航空机等要求轻量性的用途,此外阻燃性也变差。从这些观点考虑,发泡体片的面密度优选为10g/m2以上,更优选为20g/m2以上,进一步优选为30g/m2以上,而且,优选为350g/m2以下,更优选为300g/m2以下,进一步优选为250g/m2以下。一般而言含有阻燃剂的发泡体片的面密度有变高的倾向,但在本发明中可以通过调整交联度、发泡倍率和阻燃剂的量而使面密度为上述范围,可以制成轻量的发泡体片。
另外,本发明中的面密度可以通过实施例所记载的方法测定。
<热重-质谱中的条件(1)、(2)>
本发明的发泡体片在升温速度10℃/分钟、以测定温度200~550℃作为整个测定温度范围的热重-质谱中,上述发泡体片满足以下的条件(1)和条件(2)的至少1者。
条件(1):燃烧气体产生比率X为25%以下,上述燃烧气体产生比率X的定义为:在测定温度200~364℃的范围内燃烧气体P的产生量的峰面积值相对于在整个测定温度范围中燃烧气体P的产生量的峰面积值,上述燃烧气体P的质荷比m/z为55,
条件(2):燃烧气体产生比率Y为25%以下,上述燃烧气体产生比率Y的定义为:在测定温度200~364℃的范围内燃烧气体Q的产生量的峰面积值相对于在整个测定温度范围中燃烧气体Q的产生量的峰面积值,上述燃烧气体Q的质荷比m/z为69,
热重-质谱(TG-MS分析)是在热重(TG)测定中,将通过加热试样而产生的气体在线导入到质谱仪(MS)而获得质量的方法,其可以测定伴随由加热引起的试样的重量变化、和由加热引起的测定试样的分解而产生的燃烧气体的种类(质荷比)及其量。一般而言,聚乙烯树脂、聚丙烯树脂等聚烯烃树脂如果加热则质荷比m/z为55的燃烧气体P、和质荷比m/z为69的燃烧气体Q中的至少任一燃烧气体产生。
上述条件(1)规定燃烧气体产生比率X为25%以下,上述燃烧气体产生比率X的定义为:在测定温度200~364℃的范围内燃烧气体P的产生量的峰面积值相对于在整个测定温度范围中燃烧气体P的产生量的峰面积值的比例,上述燃烧气体P的质荷比m/z为55。上述燃烧气体产生比率X可以基于以下式子求出。
燃烧气体产生比率X=100×在测定温度200~364℃的范围内燃烧气体P的产生量的峰面积值/在整个测定温度范围(200~550℃)中燃烧气体P的产生量的峰面积值
本发明的发泡体片通过满足上述条件(1),可以使放热量低,阻燃性优异。从更加使阻燃性提高的观点考虑,上述条件(1)中的燃烧气体产生比率X优选为23%以下,更优选为20%以下,进一步优选为16%以下。另外放热量为通过实施例所记载的方法测定的放热量。
上述条件(2)规定燃烧气体产生比率Y为25%以下,上述燃烧气体产生比率Y的定义为:在测定温度200~364℃的范围内燃烧气体Q的产生量的峰面积值相对于在整个测定温度范围中燃烧气体Q的产生量的峰面积值的比例,上述燃烧气体Q的质荷比m/z为69。上述燃烧气体产生比率Y可以基于以下式子求出。
燃烧气体产生比率Y=100×在测定温度200~364℃的范围内燃烧气体Q的产生量的峰面积值/在整个测定温度范围(200~550℃)中燃烧气体Q的产生量的峰面积值
本发明的发泡体片通过满足上述条件(2),可以使放热量低,阻燃性优异。从更加使阻燃性提高的观点考虑,上述条件(2)中的燃烧气体产生比率Y优选为23%以下,更优选为20%以下,进一步优选为16%以下。
本发明的发泡体片只要满足上述条件(1)和条件(2)中的至少任一条件即可,但从使放热量更低而使阻燃性优异的观点考虑,优选满足上述条件(1)和条件(2)两者。另外条件(1)和条件(2)中的、燃烧气体产生比率X和Y的值可以通过调整阻燃剂的种类和含量而使其为一定值以下的值。
<表观密度>
在本发明中,发泡体片的表观密度优选为45kg/m3以下。如果发泡体片的表观密度为45kg/m3以下,则可以将发泡体片充分轻量化。从发泡体片的轻量化的观点考虑,发泡体片的表观密度更优选为40kg/m3以下,进一步优选为35kg/m3以下。另一方面,发泡体片的表观密度优选为10kg/m3以上,更优选为20kg/m3以上。通过使发泡体片的表观密度为10kg/m3以上,可以维持轻量性同时确保机械强度。
如本发明那样在发泡体片含有阻燃剂的情况下,发泡性组合物的粘度变高,因此难以使发泡倍率高,使密度小,但在本发明中由于使用后述实施例中使用那样的阻燃剂,调整交联度等同时使其发泡,因此能够将表观密度调整为上述范围。
<交联度(凝胶分率)>
从即使轻量也使机械强度提高的观点考虑,本发明的发泡体片优选为进行了交联的发泡体片,该情况下的交联度(凝胶分率)优选为20~60质量%。如果凝胶分率为上述下限值以上,则在发泡体片中形成充分的交联,因此机械强度易于变高。此外,如果交联度为这些上限值以下,则易于确保发泡体片的柔软性等。进一步,通过使交联度为上述范围内从而易于将面密度调整为上述范围。从这样的观点考虑,交联度更优选为25~55质量%,进一步优选为30~55质量%,更进一步优选为32~45质量%。
另外,交联度可以通过后述测定方法测定。
<厚度>
从使机械强度和冲击吸收性良好的观点考虑,本发明的发泡体片的厚度优选为15mm以下,优选为2~15mm,更优选为3~14mm。
<25%压缩强度>
发泡体片的25%压缩强度优选为10~100kPa。如果25%压缩强度为上述上限值以下,则发泡体片的柔软性提高,在制成例如粘着带时对被粘物的追随性变得良好。另一方面,如果25%压缩强度为上述下限值以上,则冲击吸收性与耐冲击性两者提高。从这些观点考虑,发泡体片的25%压缩强度更优选为15~80kPa,进一步优选为20~75kPa。
另外,25%压缩强度可以按照后述实施例所记载的方法测定。
<聚烯烃系树脂>
本发明的聚烯烃系树脂发泡体片含有聚烯烃系树脂。作为聚烯烃系树脂,可举出聚乙烯树脂、聚丙烯树脂、乙烯-乙酸乙烯酯共聚物等,它们之中,优选使用选自聚乙烯树脂、聚丙烯树脂中的1种以上,更优选将聚乙烯树脂与聚丙烯树脂并用。通过将聚乙烯树脂与聚丙烯树脂并用从而易于调整交联度、发泡倍率,因此易于获得轻量性优异的发泡体片。
《聚乙烯树脂》
作为聚乙烯树脂,可举出低密度聚乙烯树脂(0.93g/cm3以下,LDPE)、中密度聚乙烯树脂(大于0.930g/cm3且小于0.942g/cm3,MDPE)、高密度聚乙烯树脂(0.942g/cm3以上,HDPE)。此外,作为低密度聚乙烯树脂的适合的具体例,可举出直链状低密度聚乙烯树脂(LLDPE)。
它们之中,优选为直链状低密度聚乙烯树脂、高密度聚乙烯树脂,更优选为直链状低密度聚乙烯树脂。通过使用这些树脂,易于获得轻量性优异的发泡体片。
另外,直链状低密度聚乙烯树脂的密度优选为0.90g/cm3以上,更优选为0.91g/cm3以上且0.93g/cm3以下。此外,高密度聚乙烯树脂的密度优选为0.98g/cm3以下,更优选为0.95g/cm3以上且0.97g/cm3以下。通过使高密度聚乙烯树脂、直链状低密度聚乙烯树脂的密度为这些范围内,从而易于获得轻量性优异的发泡体片。
聚乙烯树脂可以为乙烯的均聚物,但也可以为以乙烯作为主成分(全部单体的优选为75质量%以上,更优选为90质量%以上)的、乙烯与少量α-烯烃的共聚物等。作为α-烯烃,可举出优选为碳原子数3~12、更优选为碳原子数4~10的α-烯烃,具体而言,可举出1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-庚烯、1-辛烯等。另外,在共聚物中,这些α-烯烃可以单独使用或组合使用2种以上。
此外,聚乙烯树脂可以单独使用1种,也可以并用2种以上。
《聚丙烯树脂》
作为聚丙烯树脂,可以为作为丙烯的均聚物的均聚丙烯,也可以为以丙烯作为主成分(全部单体的优选为75质量%以上,更优选为90质量%以上)的、丙烯与少量的乙烯和丙烯以外的α-烯烃的共聚物等。
作为丙烯、与乙烯和丙烯以外的α-烯烃的共聚物,可举出嵌段共聚物、无规共聚物、无规嵌段共聚物等,但它们之中,优选为无规共聚物(即,无规聚丙烯)。
作为丙烯以外的α-烯烃,可举出1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-庚烯、1-辛烯等碳原子数4~10左右的α-烯烃等,但它们之中,从成型性和耐热性的观点考虑,优选为乙烯。另外,在共聚物中,这些α-烯烃可以单独使用或组合使用2种以上。
此外,聚丙烯树脂可以单独使用,也可以并用2种以上。
作为聚烯烃系树脂使用的乙烯-乙酸乙烯酯共聚物可举出例如,含有来源于乙烯的结构单元50质量%以上的乙烯-乙酸乙烯酯共聚物。
在本发明中,可以使用通过齐格勒/纳塔化合物、金属茂化合物、氧化铬化合物等聚合催化剂进行了聚合的聚乙烯树脂、聚丙烯树脂、或它们的混合物中的任一者。通过使用通过金属茂化合物的聚合催化剂而获得的、聚乙烯树脂,特别是直链状低密度聚乙烯,从而易于获得柔软性高,具有高冲击吸收性的发泡体片。
<阻燃剂>
本发明的发泡体片优选包含阻燃剂,作为该阻燃剂,优选为磷系阻燃剂、和卤素系阻燃剂中的至少1种。通过使用这样的阻燃剂,可以使上述燃烧气体产生比率有效地减少。推测这是因为由阻燃剂产生的非活性气体使由发泡片的树脂等产生的燃烧气体的量减少。此外,由于这样的阻燃剂与后述发泡剂的关系而发泡性组合物的粘度不会过度变高,因此易于将发泡体片的表观密度调整为上述范围。因此,通过使用上述阻燃剂,易于获得兼具阻燃性和轻量性的发泡体片。从这样的观点考虑,作为上述磷系阻燃剂,优选为选自后述磷酸盐、聚磷酸盐、和磷系螺环化合物中的1种以上。此外,作为上述卤素系阻燃剂,优选为后述溴系阻燃剂。
《磷系阻燃剂》
作为磷系阻燃剂,可举出例如,正磷酸三聚氰胺盐、和正磷酸哌嗪盐等磷酸盐、聚磷酸铵盐、聚磷酸三聚氰胺盐、和聚磷酸三聚氰胺/蜜白胺/蜜勒胺盐等聚磷酸盐、磷腈系化合物、磷系螺环化合物等。它们之中,从对发泡性组合物的粘度的影响小,易于调整发泡倍率的观点考虑,更优选为磷酸盐、聚磷酸盐、磷系螺环化合物。
〔磷酸盐和聚磷酸盐〕
作为磷酸盐,可举出正磷酸三聚氰胺盐、正磷酸哌嗪盐、焦磷酸三聚氰胺盐、焦磷酸哌嗪盐、磷酸钙、和磷酸镁等。
作为聚磷酸盐,可举出聚磷酸铵盐、聚磷酸三聚氰胺盐、聚磷酸三聚氰胺/蜜白胺/蜜勒胺盐、和聚磷酸哌嗪盐等。
它们之中,优选为选自焦磷酸三聚氰胺盐、焦磷酸哌嗪盐、和聚磷酸铵盐中的1种以上,更优选将焦磷酸哌嗪盐与焦磷酸三聚氰胺盐并用。在将焦磷酸哌嗪盐与焦磷酸三聚氰胺盐并用的情况下,焦磷酸三聚氰胺盐相对于焦磷酸哌嗪盐的质量比(焦磷酸三聚氰胺盐/焦磷酸哌嗪盐)优选为0.25以上且1.0以下。
上述磷酸盐和聚磷酸盐的例示中的“三聚氰胺”或“哌嗪”也可以使用替换成N,N,N’,N’-四甲基二氨基甲烷、乙二胺、N,N’-二甲基乙二胺、N,N’-二乙基乙二胺、N,N-二甲基乙二胺、N,N-二乙基乙二胺、N,N,N’,N’-四甲基乙二胺、N,N,N’,N’-二乙基乙二胺、1,2-丙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺、1,7-二氨基庚烷、1,8-二氨基辛烷、1,9-二氨基壬烷、1,10-二氨基癸烷、反式-2,5-二甲基哌嗪、1,4-双(2-氨基乙基)哌嗪、1,4-双(3-氨基丙基)哌嗪、乙酰胍胺、苯胍胺、丙烯酰胍胺、2,4-二氨基-6-壬基-1,3,5-三嗪、2,4-二氨基-6-羟基-1,3,5-三嗪、2-氨基-4,6-二羟基-1,3,5-三嗪、2,4-二氨基-6-甲氧基-1,3,5-三嗪、2,4-二氨基-6-乙氧基-1,3,5-三嗪、2,4-二氨基-6-丙氧基-1,3,5-三嗪、2,4-二氨基-6-异丙氧基-1,3,5-三嗪、2,4-二氨基-6-巯基-1,3,5-三嗪、2-氨基-4,6-二巯基-1,3,5-三嗪、三聚氰酸二酰胺、邻苯二胍胺(phthalodiguanamine)、三聚氰胺氰脲酸盐、焦磷酸三聚氰胺、亚丁基二胍胺、降冰片烯二胍胺、亚甲基二胍胺、亚乙基二(三聚氰胺)、三亚甲基二(三聚氰胺)、四亚甲基二(三聚氰胺)、六亚甲基二(三聚氰胺)、1,3-亚己基二(三聚氰胺)的名称的化合物。
在本发明中,在使用上述磷酸盐和聚磷酸盐的情况下,可以分别单独使用,此外,作为膨胀系阻燃剂,也可以将选自上述磷酸盐和聚磷酸盐中的2种以上混合使用,进一步,作为膨胀系阻燃剂,也可以将选自上述磷酸盐和聚磷酸盐中的1种以上与金属氧化物混合使用。
作为与选自磷酸盐和聚磷酸盐中的1种以上并用的金属氧化物,可举出例如,氧化锌、氧化镁、氧化钙、二氧化硅、氧化钛、氧化锰(MnO、MnO2)、氧化铁(FeO、Fe2O3、Fe3O4)、氧化铜、氧化镍、氧化锡、氧化铝、和铝酸钙等。它们之中,优选为氧化锌、氧化镁、和氧化钙。
在将选自磷酸盐和聚磷酸盐中的1种以上、与金属氧化物混合使用的情况下,它们的质量比优选如下所述调整。从使阻燃性提高的观点考虑,,选自磷酸盐和聚磷酸盐中的1种以上相对于金属氧化物的质量比〔磷酸盐和聚磷酸盐的合计质量/金属氧化物的质量〕优选为4以上且100以下,更优选为6以上且50以下,进一步优选为10以上且35以下。
作为包含选自上述磷酸盐和聚磷酸盐中的1种以上的阻燃剂的市售品,可举出例如,株式会社ADEKA制“アデカスタブFP-2100J”、“アデカスタブFP-2200S”、“アデカスタブFP-2500S”、クラリアントジャパン株式会社制“EXOLIT AP422”、“EXOLIT AP462”等。
〔磷腈系化合物〕
磷腈系化合物为分子中具有-P=N-键的有机化合物。作为磷腈系化合物,从具有比较高的分解温度考虑,优选地,优选为下述通式(1)所示的化合物。
在上述式(1)中,R1~R6各自独立地表示碳原子数1~12的烷基、碳原子数1~12的烷氧基、碳原子数6~12的芳基氧基、氨基、卤原子中的任一者。
作为这样的磷腈系化合物的例子,可举出由大塚化学社市售的“SPB-100”等。
〔磷系螺环化合物〕
作为磷系螺环化合物,只要是具有磷原子的螺环化合物,就没有特别限定。另外,所谓螺环化合物,是具有二个环状化合物共用了一个碳的结构的化合物,所谓具有磷原子的螺环化合物,是构成上述二个环状化合物的元素的至少一个为磷原子的化合物。
作为磷系螺环化合物,优选使用例如,分子内具有以下式(2)所示的结构的化合物。另外,在式(2)中*表示与其它取代基的连接部分。
《卤素系阻燃剂》
在本发明中,可以使用卤素系阻燃剂。卤素系阻燃剂通过气相中的自由基捕获效果而使活性OH自由基稳定化。此外,在燃烧时,通过由卤素系阻燃剂生成的卤化氢而成为燃烧促进剂的活性的OH自由基、H自由基被捕获而稳定化。进一步,在燃烧时,由卤素系阻燃剂生成的卤化氢为不燃性,因此使稀释效果产生,进一步也使氧气阻隔效果产生。
作为卤素系阻燃剂,只要是在分子结构中含有卤素的阻燃剂,就没有特别限定。作为卤素系阻燃剂,可举出例如,溴系阻燃剂和氯系阻燃剂,其中,优选为溴系阻燃剂。
作为溴系阻燃剂,只要是分子结构中含有溴的阻燃剂,就没有特别限定。在溴系阻燃剂中,可举出例如,十溴二苯基醚、八溴二苯基醚、四溴双酚A(TBBA)、TBBA环氧低聚物、TBBA碳酸酯低聚物、TBBA双(二溴丙基醚)、TBBA双(芳基醚)、双(五溴苯基)乙烷、1,2-双(2,4,6-三溴苯氧基)乙烷、2,4,6-三(2,4,6-三溴苯氧基)-1,3,5-三嗪、2,6-或(2,4-)二溴苯酚均聚物、溴化聚苯乙烯、聚溴化苯乙烯、亚乙基双四溴邻苯二甲酰亚胺、六溴环十二烷、六溴苯、五溴苄基丙烯酸酯单体、五溴苄基丙烯酸酯聚合物等。它们之中,从阻燃性和发泡性的观点考虑,优选为双(五溴苯基)乙烷。这些溴系阻燃剂可以单独使用1种,也可以混合使用2种以上。
在使用上述卤素系阻燃剂的情况下,可以并用锑系阻燃助剂。锑系阻燃助剂通过与卤素系阻燃剂的协同效果,可以使上述燃烧气体产生比率X和Y小,并可以改善发泡体片的阻燃性,并且可以减少卤素系阻燃剂的含量。如果使用锑系阻燃助剂,则在燃烧时,与卤素系阻燃剂反应,成为不燃性的卤化锑。由此,产生氧遮蔽效果。
作为锑系阻燃助剂,可举出例如,三氧化锑、五氧化二锑等,作为市售品,可举出例如,日本精矿株式会社制的“PATOX-M”、“PATOX-MK”、“PATOX-K”等。
从与卤素系阻燃剂的协同效果的观点考虑,锑系阻燃助剂的混配量相对于卤素系阻燃剂100质量份,优选为20~80质量份,更优选为30~70质量份,进一步优选为40~60质量份。
《阻燃剂的熔点》
在本发明中使用的阻燃剂的熔点优选为与发泡体片的发泡温度同等程度、或其以上的熔点。如果阻燃剂的熔点为与发泡温度同等程度或其以上则通过燃烧时的热而易于熔化,可以抑制发泡体片的燃烧。从该观点考虑,阻燃剂的熔点优选为240~600℃,更优选为250~550℃,进一步优选为255~500℃。
发泡体片中的阻燃剂的含量相对于聚烯烃系树脂100质量份,优选为1~100质量份,更优选为3~80质量份,进一步优选为5~50质量份。通过使阻燃剂的含量为1质量份以上,从而发泡体片的阻燃性提高,通过为100质量份以下,从而维持发泡体片的轻量化并且加工性等变得良好。
<发泡剂>
本发明的发泡体片通过将包含聚烯烃系树脂、和发泡剂的发泡性组合物进行发泡而获得。作为发泡剂,优选为热分解型发泡剂。
作为热分解型发泡剂,能够使用有机发泡剂、无机发泡剂。作为有机发泡剂,可举出偶氮二碳酰胺、偶氮二羧酸金属盐(偶氮二羧酸钡等)、偶氮二异丁腈等偶氮化合物、N,N’-二亚硝基五亚甲基四胺等亚硝基化合物、联二脲、4,4’-氧基双(苯磺酰肼)、甲苯磺酰肼等肼衍生物、甲苯磺酰氨基脲等氨基脲化合物等。
作为无机发泡剂,可举出碳酸铵、碳酸钠、碳酸氢铵、碳酸氢钠、亚硝酸铵、氢化硼钠、柠檬酸酐单钠等。
它们之中,从获得微细的气泡的观点、和经济性、安全方面的观点考虑,优选为偶氮化合物,更优选为偶氮二碳酰胺。
热分解型发泡剂可以单独使用1种,也可以并用2种以上。
发泡性组合物中的发泡剂的含量相对于聚烯烃系树脂100质量份,优选为1质量份以上且40质量份以下,更优选为5质量份以上且35质量份以下,进一步优选为10质量份以上且30质量份以下。通过使发泡剂的混配量为1质量份以上,从而发泡性片被适度地发泡,能够对发泡体片赋予适度的柔软性和冲击吸收性。此外,通过使发泡剂的混配量为30质量份以下,从而防止发泡体片过度发泡,可以使发泡体片的机械强度等良好。
<添加剂>
在发泡性组合物中,可以混配交联助剂。作为交联助剂,可以使用多官能单体。通过将交联助剂添加于聚烯烃系树脂,从而减少在后述工序(2)中照射的电离性放射剂量,防止伴随电离性放射线的照射的树脂分子的切断、劣化。
作为交联助剂,具体而言,可举出三羟甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、偏苯三甲酸三烯丙酯、1,2,4-苯三甲酸三烯丙酯、异氰脲酸三烯丙酯等1分子中具有3个官能团的化合物、1,6-己二醇二甲基丙烯酸酯、1,9-壬二醇二甲基丙烯酸酯、1,10-癸二醇二甲基丙烯酸酯、二乙烯基苯等1分子中具有2个官能团的化合物、邻苯二甲酸二烯丙酯、对苯二甲酸二烯丙酯、间苯二甲酸二烯丙酯、乙基乙烯基苯、新戊二醇二甲基丙烯酸酯、甲基丙烯酸月桂基酯、甲基丙烯酸硬脂基酯等。
这些交联助剂可以单独使用或组合使用2以上。
交联助剂的添加量相对于聚烯烃系树脂100质量份优选为0.5~10质量份,更优选为1.0~8质量份,进一步优选为1.5~5质量份。通过使该添加量为0.5质量份以上,从而发泡体片能够稳定地获得所希望的交联度,通过为10质量份以下,从而发泡体片的交联度的控制变得容易。
在发泡性组合物中,可以混配分解温度调节剂。分解温度调节剂是作为使热分解型发泡剂的分解温度低、或加快分解速度进行调节的物质而混配的,作为具体的化合物,可举出氧化锌、硬脂酸锌、脲等。为了调整发泡体片的表面状态等,分解温度调节剂例如相对于聚烯烃系树脂100质量份混配0.01~5质量份。
在发泡性组合物中,可以混配抗氧化剂。作为抗氧化剂,可举出2,6-二叔丁基对甲酚等酚系抗氧化剂、硫代二丙酸二月桂酯等硫系抗氧化剂、磷系抗氧化剂、胺系抗氧化剂等。抗氧化剂例如相对于聚烯烃系树脂100质量份混配0.01~5质量份。
在发泡性组合物中,除了它们以外,也可以混配热稳定剂、着色剂、抗静电剂、填充材料等一般使用于发泡体的添加剂。
在发泡体片中,聚烯烃系树脂成为主成分,聚烯烃系树脂的含量以发泡体片总量基准计,例如为45质量%以上,优选为50质量%以上,更优选为55质量%以上。
<发泡体片的制造方法>
本发明的发泡体片可以通过将聚烯烃系树脂通过一般的方法进行发泡来制造,对其制造方法没有限制,也可以通过将至少包含聚烯烃系树脂和发泡剂的发泡性组合物根据需要进行了交联后,进行发泡来制造。
具体而言,本发明的发泡体片可以通过例如具有以下工序(1)~(3)的方法来制造。
工序(1):将聚烯烃系树脂、热分解型发泡剂、和其它添加剂供给到挤出机进行熔融混炼,从挤出机挤出成片状,从而获得形成为片状的发泡性组合物的工序
工序(2):将形成为片状的发泡性组合物交联的工序
工序(3):将进行了交联的片状的发泡性组合物加热,使热分解型发泡剂发泡,优选沿MD方向或TD方向的任一者或两者拉伸的工序
另外,作为交联聚烯烃系树脂发泡体片的制造方法,除了该方法以外,也能够通过国际公开第2005/007731号所记载的方法来制造。
作为使发泡性组合物发泡的方法,没有特别限制,可举出例如,将发泡性组合物通过热风进行加热的方法、通过红外线进行加热的方法、通过盐浴进行加热的方法、通过油浴进行加热的方法等,它们可以并用。
另外,发泡性组合物的发泡不限定于使用热分解型发泡剂的例子,可以使用采用丁烷气体等的物理发泡。
作为将发泡性组合物交联的方法,可举出例如,向发泡性组合物照射电子射线、α射线、β射线、γ射线等电离性放射线的方法、在发泡性组合物中预先混配有机过氧化物将发泡性组合物加热而使有机过氧化物分解的方法等,这些方法可以并用。它们之中,优选为照射电离性放射线的方法。
为了使凝胶分率为上述范围,电离性放射线的照射量优选为0.5~20Mrad,更优选为1.0~12Mrad。
作为交联所使用的有机过氧化物,可举出例如,1,1-双(叔丁基过氧化)3,3,5-三甲基环己烷、1,1-双(叔丁基过氧化)环己烷等。它们可以单独使用1种,也可以并用2种以上。有机过氧化物的添加量相对于聚烯烃系树脂100质量份,优选为0.01~5质量份,更优选为0.1~3质量份。如果有机过氧化物的添加量为上述范围内,则发泡性组合物的交联易于进行,此外,在所得的交联聚烯烃系树脂发泡体片中抑制有机过氧化物的分解残渣的量。
本发明的聚烯烃系树脂发泡体片如上所述优选被拉伸。拉伸可以在使发泡性组合物发泡而获得了发泡体片后进行,也可以在使发泡性组合物发泡的同时进行。另外,在使发泡性组合物发泡而获得了发泡体片后,将发泡体片拉伸的情况下,不将发泡体片冷却而在维持发泡时的熔融状态下直接继续将发泡体片拉伸为好,但也可以在将发泡体片冷却后,再次,将发泡体片加热而形成熔融或软化状态后将发泡体片进行拉伸。
此外,聚烯烃系树脂发泡体片的MD方向的拉伸倍率优选为1.1~3.0倍,更优选为1.3~2.8倍。如果使聚烯烃系树脂发泡体片的MD方向的拉伸倍率为上述下限值以上,则聚烯烃系树脂发泡体片的柔软性和抗拉强度易于变得良好。另一方面,如果为上限值以下,则易于制成防止发泡体片在拉伸中断裂、或发泡气体从发泡中的发泡体片脱出而发泡倍率降低,聚烯烃系树脂发泡体片的柔软性、抗拉强度变得良好,品质也均匀的物质。此外,聚烯烃系树脂发泡体片可以沿TD方向也以上述范围的拉伸倍率被拉伸。
[粘着带]
在本发明中,可以使用本发明涉及的发泡体片作为基材,在发泡体片的一个面或两面设置粘着剂层,制成粘着带。粘着带的厚度通常为2~16mm左右。
构成粘着带的粘着剂层的厚度优选为5~200μm,更优选为7~150μm,进一步优选为10~100μm。如果构成粘着带的粘着剂层的厚度为5~200μm,则可以使粘着带的厚度薄。
作为构成设置在发泡体片的一个面或两面的粘着剂层的粘着剂,没有特别限制,使用例如,丙烯酸系粘着剂、氨基甲酸酯系粘着剂、橡胶系粘着剂等。
作为在发泡体片涂布粘着剂,将粘着剂层叠层在发泡体片上的方法,可举出例如,使用涂布机等涂覆机在发泡体片的至少一个面涂布粘着剂的方法、使用喷雾器在发泡体片的至少一个面喷雾、涂布粘着剂的方法、使用毛刷在发泡体片的一个面涂布粘着剂的方法等。
使用了本发明的发泡体片的粘着带可以作为航空机内的冲击吸收材料而适合使用。此外,也可以作为内装在电子设备主体内的冲击吸收材料等而使用。
实施例
通过实施例对本发明进一步详细地说明,但本发明不受这些例子任何限定。
[测定方法]
本说明书中的各物性的测定方法如下所述。
<表观密度和面密度>
发泡体片的表观密度按照JIS K7222:2005测定。
发泡体片的面密度由表观密度和厚度通过计算而求出。
<25%压缩强度>
发泡体片的25%压缩强度按照JIS K6767,在23℃下测定。
<热重-质谱>
以各实施例和比较例的发泡体片作为试样,如下所述进行热重-质谱(TG-MS分析),求出燃烧气体产生比率X和燃烧气体产生比率Y。除上述以外的测定条件如下所述。
(条件)
装置:NETZSCH社制的STA449F1和QMS403
试样:25mg
TG测定条件:在40℃下使试样室真空脱气后,再次用空气(He/O2=4/1体积比)恢复直到常压后一边以50ml/min导入到试样室一边以10℃/min的升温速度升温直到550℃,在550℃下保持10分钟。
MS测定:SCAN模式
输送管线温度:280℃
进样系统温度:250℃
使用NETZSCH社制“Proteus Thermal Analysis”实施了在上述条件下测定而获得的数据的解析。为了求出燃烧气体产生比率,将横轴设为温度,将第一纵轴(或右纵轴)设为TG/%,将第二纵轴(或左纵轴)设为离子强度而记载了图。由将质荷比m/z为55或69记载于图时的温度200℃~364℃的峰面积相对于200℃~550℃的峰总面积的比算出燃烧气体产生比率。关于基线类型,在求解200℃~364℃的峰面积时使用了左起点正切,200℃~550℃的峰总面积值时使用了直线。
(燃烧气体产生比率X)
燃烧气体产生比率X(%)=100×在测定温度200~364℃的范围内燃烧气体P的产生量的峰面积值/在整个测定温度范围(200~550℃)中燃烧气体P的产生量的峰面积值
(燃烧气体产生比率Y)
燃烧气体产生比率Y(%)=100×在测定温度200~364℃的范围内燃烧气体Q的产生量的峰面积值/在整个测定温度范围(200~550℃)中燃烧气体Q的产生量的峰面积值
<最大放热量、和合计放热量>
发泡体片的最大放热量、和合计放热量按照FAR PART 25Appendix F Part IV测定。
<交联度(凝胶分率)>
从发泡体片采取约100mg的试验片,精密称量试验片的重量A(mg)。接下来,将该试验片在120℃的二甲苯30cm3中浸渍而放置24小时后,用200目的金属网过滤而采取金属网上的不溶解成分,真空干燥,精密称量不溶解成分的重量B(mg)。由所得的值,通过下述式算出交联度(质量%)。
交联度(质量%)=(B/A)×100
<阻燃性的评价>
关于发泡体片的阻燃性评价,基于已经描述的最大放热量、合计放热量来评价。
具体而言,将5分钟的试验中的最大放热量为65kw/m2以下、试验开始后2分钟的合计放热量为65kw·min/m2以下的情况设为合格,将除此以外的情况设为不合格。
<使用原料>
实施例和比较例中使用的材料如下所述。
〔聚烯烃系树脂〕
·聚丙烯:乙烯-丙烯无规共聚物,日本ポリプロ株式会社制“EG7F”
·聚乙烯:直链状低密度聚乙烯,ダウ·ケミカル社制“5220G”
〔交联助剂〕
·交联助剂:三羟甲基丙烷三甲基丙烯酸酯
〔发泡剂〕
·热分解型发泡剂:偶氮二碳酰胺
〔抗氧化剂〕
·抗氧化剂A:2,6-二叔丁基对甲酚
·抗氧化剂B:硫代二丙酸二月桂酯
〔阻燃剂〕
·阻燃剂A:磷系阻燃剂,帝人株式会社“ファイヤガードFCX-210”,熔点257℃
·阻燃剂B:双(五溴苯基)乙烷,アルベマール日本株式会社“SAYTEX8010”,熔点350℃
·阻燃剂C:磷酸酯,大八化学工业株式会社“TMCPP”
〔阻燃助剂〕
·阻燃助剂:三氧化锑,日本精矿株式会社“PATOX-M”,熔点656℃
实施例1
将聚丙烯80质量份、聚乙烯20质量份、交联助剂3.2质量份、热分解型发泡剂20质量份、阻燃剂A15质量份、和抗氧化剂A 0.5质量份、抗氧化剂B 0.3质量份用ラボプラストミル(Plastmill)进行了混炼,制作出发泡性组合物。然后,通过在180℃、15MPa下热压,从而制作出2mm的片状的发泡性组合物(以下,称为“发泡性片”)。
接着,从制作出的发泡性片的两面照射加速电压1000kV、1.4Mrad的电子射线。然后,将发泡性片投入到设定为250℃的热风炉中4分钟后迅速取出,获得了聚烯烃系树脂发泡体片。
将所得的发泡体片的评价结果示于表1中。
实施例2~4、比较例1~2
将发泡性组合物的混配如表1所示那样变更,并且以成为表1的交联度(凝胶分率)的方式调整交联时的剂量,除此以外,与实施例1同样地实施。
将所得的发泡体片的评价结果示于表1中。
[表1]
表1
由上述结果明确了,本发明的聚烯烃系树脂发泡体片由于维持轻量性,同时具有高阻燃性,因此关于航空机等要求轻量化的用途可以适合使用。
Claims (8)
1.一种聚烯烃系树脂发泡体片,其面密度为5g/m2以上且400g/m2以下,在升温速度10℃/分钟、以测定温度200~550℃作为整个测定温度范围的热重-质谱中,所述聚烯烃系树脂发泡体片满足以下的条件(1)和条件(2)中的至少1者,
条件(1):燃烧气体产生比率X为25%以下,所述燃烧气体产生比率X的定义为:在测定温度200~364℃的范围内燃烧气体P的产生量的峰面积值相对于在整个测定温度范围中燃烧气体P的产生量的峰面积值的比例,所述燃烧气体P的质荷比m/z为55,
条件(2):燃烧气体产生比率Y为25%以下,所述燃烧气体产生比率Y的定义为:在测定温度200~364℃的范围内燃烧气体Q的产生量的峰面积值相对于在整个测定温度范围中燃烧气体Q的产生量的峰面积值的比例,所述燃烧气体Q的质荷比m/z为69。
2.根据权利要求1所述的聚烯烃系树脂发泡体片,其厚度为15mm以下。
3.根据权利要求1或2所述的聚烯烃系树脂发泡体片,构成所述聚烯烃系树脂发泡体片的聚烯烃系树脂为选自聚乙烯树脂和聚丙烯树脂中的1种以上。
4.根据权利要求3所述的聚烯烃系树脂发泡体片,所述聚烯烃系树脂并用了聚乙烯树脂和聚丙烯树脂。
5.根据权利要求1~4中任一项所述的聚烯烃系树脂发泡体片,其含有阻燃剂。
6.根据权利要求5所述的聚烯烃系树脂发泡体片,所述阻燃剂为选自磷系阻燃剂和卤素系阻燃剂中的至少1种。
7.根据权利要求6所述的聚烯烃系树脂发泡体片,所述磷系阻燃剂为选自磷酸盐、聚磷酸盐和磷系螺环化合物中的1种以上。
8.根据权利要求6或7所述的聚烯烃系树脂发泡体片,所述卤素系阻燃剂为溴系阻燃剂。
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- 2019-09-27 US US17/279,321 patent/US20210395476A1/en active Pending
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- 2019-09-27 EP EP19864329.8A patent/EP3858903A4/en active Pending
- 2019-09-27 CN CN201980062596.9A patent/CN112771104B/zh active Active
- 2019-09-27 JP JP2019557508A patent/JP6845349B2/ja active Active
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2021
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JPWO2020067525A1 (ja) | 2021-02-15 |
JP6845348B2 (ja) | 2021-03-17 |
CN112771104B (zh) | 2022-12-02 |
EP3858903A1 (en) | 2021-08-04 |
EP3858902C0 (en) | 2023-08-30 |
JP2021080480A (ja) | 2021-05-27 |
JP2021080479A (ja) | 2021-05-27 |
CN112771105B (zh) | 2022-09-20 |
EP3858903A4 (en) | 2022-06-15 |
US20210395477A1 (en) | 2021-12-23 |
JP7377235B2 (ja) | 2023-11-09 |
EP3858902A1 (en) | 2021-08-04 |
JPWO2020067521A1 (ja) | 2021-02-15 |
JP6845349B2 (ja) | 2021-03-17 |
CN112771105A (zh) | 2021-05-07 |
EP3858902A4 (en) | 2022-07-27 |
JP7377236B2 (ja) | 2023-11-09 |
US12060470B2 (en) | 2024-08-13 |
WO2020067521A1 (ja) | 2020-04-02 |
US20210395476A1 (en) | 2021-12-23 |
EP3858902B1 (en) | 2023-08-30 |
WO2020067525A1 (ja) | 2020-04-02 |
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