JP4425346B2 - Flame retardant resin composition - Google Patents
Flame retardant resin composition Download PDFInfo
- Publication number
- JP4425346B2 JP4425346B2 JP2009509088A JP2009509088A JP4425346B2 JP 4425346 B2 JP4425346 B2 JP 4425346B2 JP 2009509088 A JP2009509088 A JP 2009509088A JP 2009509088 A JP2009509088 A JP 2009509088A JP 4425346 B2 JP4425346 B2 JP 4425346B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- vinyl acetate
- mass
- flame retardant
- acetate copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims description 91
- 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 title claims description 86
- 239000011342 resin composition Substances 0.000 title claims description 53
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 87
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 86
- 239000005977 Ethylene Substances 0.000 claims description 62
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 61
- 229920000800 acrylic rubber Polymers 0.000 claims description 35
- 238000004132 cross linking Methods 0.000 claims description 35
- 229920000058 polyacrylate Polymers 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 31
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 27
- 239000011118 polyvinyl acetate Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229920001971 elastomer Polymers 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229920006229 ethylene acrylic elastomer Polymers 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 239000001993 wax Substances 0.000 description 30
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 150000001336 alkenes Chemical class 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 17
- 150000001451 organic peroxides Chemical class 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 11
- 238000013329 compounding Methods 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- -1 Butylperoxy Chemical group 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 229920006132 styrene block copolymer Polymers 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- 229920005601 base polymer Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 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
- 239000002904 solvent Substances 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- SYXTYIFRUXOUQP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy butaneperoxoate Chemical compound CCCC(=O)OOOC(C)(C)C SYXTYIFRUXOUQP-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QEZDYNRKJXCIFE-WAYWQWQTSA-N (z)-3-carbonoperoxoylhept-2-enoic acid Chemical group CCCC\C(=C\C(O)=O)C(=O)OO QEZDYNRKJXCIFE-WAYWQWQTSA-N 0.000 description 1
- FWUIHQFQLSWYED-ARJAWSKDSA-N (z)-4-oxo-4-propan-2-yloxybut-2-enoic acid Chemical compound CC(C)OC(=O)\C=C/C(O)=O FWUIHQFQLSWYED-ARJAWSKDSA-N 0.000 description 1
- IMYCVFRTNVMHAD-UHFFFAOYSA-N 1,1-bis(2-methylbutan-2-ylperoxy)cyclohexane Chemical compound CCC(C)(C)OOC1(OOC(C)(C)CC)CCCCC1 IMYCVFRTNVMHAD-UHFFFAOYSA-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
- WVGXBYVKFQJQGN-UHFFFAOYSA-N 1-tert-butylperoxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OOC(C)(C)C WVGXBYVKFQJQGN-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical group CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- CAQZZDUSUDAUGQ-UHFFFAOYSA-N 5-benzoylperoxyheptan-2-yl benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(CC)CCC(C)OOC(=O)C1=CC=CC=C1 CAQZZDUSUDAUGQ-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- FSRYENDEMMDKMT-UHFFFAOYSA-N butoxy ethaneperoxoate Chemical group CCCCOOOC(C)=O FSRYENDEMMDKMT-UHFFFAOYSA-N 0.000 description 1
- RHZIVIGKRFVETQ-UHFFFAOYSA-N butyl 2-methylpropaneperoxoate Chemical group CCCCOOC(=O)C(C)C RHZIVIGKRFVETQ-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical group CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NHEUUFQZSIJBCY-UHFFFAOYSA-N butylperoxy 2-ethylhexyl carbonate Chemical group CCCCOOOC(=O)OCC(CC)CCCC NHEUUFQZSIJBCY-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 238000004073 vulcanization Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Description
本発明は、エチレン−酢酸ビニル共重合体を含む難燃性樹脂組成物に関する。より詳しくは、エチレン−酢酸ビニル共重合体の微架橋物を含む柔軟性と難燃性のバランスに優れた難燃性樹脂組成物に関する。 The present invention relates to a flame retardant resin composition containing an ethylene-vinyl acetate copolymer. More specifically, the present invention relates to a flame retardant resin composition having an excellent balance between flexibility and flame retardancy, including a micro-crosslinked product of an ethylene-vinyl acetate copolymer.
オレフィン系樹脂は、一般に電気的特性、機械的性質、加工性等が優れているところから、電気絶縁材料として広く使用されている。とくに電線、ケーブル等の用途には、強度、低温特性、耐擦傷性、硬度等のバランスが良好であるところから、エチレン・不飽和エステルランダム共重合体が広く使用されている。 Olefin resins are widely used as electrical insulating materials because they are generally excellent in electrical characteristics, mechanical properties, processability, and the like. Particularly for applications such as electric wires and cables, ethylene / unsaturated ester random copolymers are widely used because of a good balance of strength, low temperature characteristics, scratch resistance, hardness and the like.
このようなエチレン共重合体は易燃性であるため、用途によっては難燃化する必要があり、そのため古くはハロゲン系難燃剤を配合することにより対処してきた。しかしながらこのような配合物は燃焼時に有害ガスを発生するという問題があり、そのため近年では非ハロゲン系の水酸化マグネシウム、水酸化アルミニウム等の金属水酸化物難燃剤を配合する処方が採用されるようになってきた。ところが金属水酸化物難燃剤は、かなり大量に配合しないと充分な難燃効果を発揮することができないため、往々にしてエチレン共重合体の加工性、耐擦傷性、その他機械的特性を犠牲にすることがあった。とくに薄肉電線、薄肉建材シート、薄肉車両シート等の用途においては、薄肉における高度な難燃性と良好な成形性および機械物性が求められており、これら性能を満たす金属水酸化物配合難燃処方の開発は容易でなかった。 Since such an ethylene copolymer is flammable, it needs to be flame retardant depending on the application, and for that reason, it has been dealt with in the past by blending a halogen-based flame retardant. However, such a compound has a problem of generating a harmful gas during combustion, and therefore, in recent years, a formulation in which a metal hydroxide flame retardant such as non-halogenated magnesium hydroxide or aluminum hydroxide is blended is adopted. It has become. However, metal hydroxide flame retardants cannot exert a sufficient flame retardant effect unless they are incorporated in a considerably large amount, and often sacrifice the processability, scratch resistance, and other mechanical properties of ethylene copolymers. There was something to do. In particular, in applications such as thin wire, thin building material sheets, and thin vehicle seats, high flame retardancy and good moldability and mechanical properties are required for thin walls. The development of was not easy.
エチレン−酢酸ビニル共重合体を用いた難燃化樹脂組成物では、機械物性が不十分であることから、有機過酸化物で架橋してなる微架橋性エチレン−酢酸ビニル共重合体からなる難燃性が良好でかつ機械的特性に優れた難燃性樹脂組成物が提案されている（例えば、特開２００３−１７１４２１号公報、特開２００５−１８７４９７号公報）。 The flame retardant resin composition using an ethylene-vinyl acetate copolymer has insufficient mechanical properties, so that it is difficult to form a slightly crosslinkable ethylene-vinyl acetate copolymer crosslinked with an organic peroxide. Flame retardant resin compositions having good flammability and excellent mechanical properties have been proposed (for example, JP-A Nos. 2003-171421 and 2005-187497).
しかしながら、エチレン−酢酸ビニル共重合体は、特に、酢酸ビニル含有量の高いものは多量の難燃剤を配合することができるフィラーローディング性や柔軟性を有しており、またエチレン−不飽和カルボン酸エステル共重合体に比較して安価であり魅力的な材料であるが、特に薄肉電線では難燃性が充分でなく、しかも難燃剤を多量に配合すると伸び、柔軟性、電気特性も低下するなどして、同様に上記用途への適用は難しかった。 However, ethylene-vinyl acetate copolymers, especially those having a high vinyl acetate content, have filler loading properties and flexibility in which a large amount of flame retardant can be blended, and ethylene-unsaturated carboxylic acids. It is an inexpensive and attractive material compared to ester copolymers, but it is not particularly fire retardant especially for thin-walled electric wires. Moreover, if a large amount of flame retardant is blended, elongation, flexibility, and electrical properties are reduced. Similarly, it was difficult to apply to the above uses.
従って、従来、エチレン−酢酸ビニル共重合体からなる難燃性樹脂組成物においては、柔軟性と難燃性のバランスに優れ，しかも加工性にも優れたエチレン−酢酸ビニル共重合体含有難燃性樹脂組成物材料が望まれているが、未だ満足のできる材料は提案されていず、更なる改善が求められていた。 Therefore, conventionally, in a flame retardant resin composition comprising an ethylene-vinyl acetate copolymer, the flame retardant resin-containing flame retardant having an excellent balance between flexibility and flame retardancy and excellent workability is also obtained. However, satisfactory materials have not been proposed yet, and further improvements have been demanded.
本発明者らは、前記した従来の問題点を改良し、電線被覆や建材などの難燃性が求められる用途に好適に使用できる難燃性樹脂組成物の開発を鋭意注力した結果本発明に到達したものである。 As a result of improving the above-mentioned conventional problems, the present inventors have intensively developed a flame-retardant resin composition that can be suitably used for applications requiring flame retardancy such as wire coating and building materials. It has been reached.
本発明は、エチレン−酢酸ビニル共重合体の本来的特徴である好ましい物性を維持しながら、引っ張り強さ等の機械物性に優れ、しかも柔軟性と難燃性のバランスに優れ、加工性や低温特性にも優れた難燃性樹脂組成物を提供することを課題とする。
更に詳細には、酢酸ビニル含量の低い微架橋エチレン−酢酸ビニル共重合体を含む、柔軟性と難燃性のバランスに優れ、しかも加工性や低温特性にも優れた難燃性樹脂組成物を提供することを課題とする。
The present invention is excellent in mechanical properties such as tensile strength, excellent balance between flexibility and flame retardancy, while maintaining the preferable physical properties that are the inherent characteristics of ethylene-vinyl acetate copolymer, processability and low temperature. It is an object of the present invention to provide a flame retardant resin composition having excellent characteristics.
More specifically, a flame-retardant resin composition comprising a micro-crosslinked ethylene-vinyl acetate copolymer having a low vinyl acetate content, which has an excellent balance between flexibility and flame retardancy, and also has excellent processability and low-temperature characteristics. The issue is to provide.
本発明は、高圧重合法により製造された酢酸ビニル単位含有量（JIS K7192法：1999）が４３質量％〜４７質量％のエチレン-酢酸ビニル共重合体（ａ−１）を微架橋してなる、メルトフローレイト（JIS K7210：1999法、190℃、加重2.160ｋｇ）が０．０１〜０．６ｇ/１０分である微架橋エチレン-酢酸ビニル共重合体（Ａ）と、エチレン・アクリルゴム（ａ−２）の非架橋物または微架橋物と、ポリ酢酸ビニル（Ｂ）と難燃剤（Ｃ）とが含まれてなる難燃性樹脂組成物であって、
エチレン・アクリルゴム（ａ−２）が、ムーニー粘度（ＭＬ1+4、１００℃）が１０〜７０であり、エチレンと３０〜６５重量％の（メタ）アクリル酸エステルとからなる二元共重合体またはさらに０．３〜７重量％の架橋サイトとなり得るモノマーを含む多元共重合体であって、エチレン−酢酸ビニル共重合体（ａ−１）とエチレン・アクリルゴム（ａ−２）の合計量１００質量部に対し、５０〜５質量部の範囲で含有されており、
ポリ酢酸ビニル（Ｂ）の重合度が６００〜２，０００であり、（Ａ）と（Ｂ）の合計量１００質量部に対し、６０〜１０質量部の範囲にあり、
難燃剤（Ｃ）が水酸化マグネシウムまたは水酸化アルミニウムであって、微架橋エチレン-酢酸ビニル共重合体（Ａ）とポリ酢酸ビニル（Ｂ）の合計量１００質量部に対して７５〜１８０質量部の範囲である難燃性樹脂組成物を提供する。
The present invention is obtained by finely crosslinking an ethylene-vinyl acetate copolymer (a-1) having a vinyl acetate unit content (JIS K7192 method: 1999) of 43 mass% to 47 mass% produced by a high pressure polymerization method. , A slightly cross-linked ethylene-vinyl acetate copolymer (A) having a melt flow rate (JIS K7210: 1999 method, 190 ° C., weight 2.160 kg) of 0.01 to 0.6 g / 10 min, and ethylene / acrylic rubber A flame retardant resin composition comprising (a-2) a non-crosslinked product or a slightly crosslinked product, polyvinyl acetate (B) and a flame retardant (C),
A binary copolymer of ethylene / acrylic rubber (a-2) having a Mooney viscosity (ML1 + 4, 100 ° C.) of 10 to 70 and comprising ethylene and 30 to 65% by weight of (meth) acrylic acid ester Or a multi-component copolymer containing a monomer capable of becoming a crosslinking site in an amount of 0.3 to 7% by weight, the total amount of the ethylene-vinyl acetate copolymer (a-1) and the ethylene-acrylic rubber (a-2) It is contained in the range of 50 to 5 parts by mass with respect to 100 parts by mass,
The degree of polymerization of polyvinyl acetate (B) is 600 to 2,000, and in the range of 60 to 10 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B) ,
The flame retardant (C) is magnesium hydroxide or aluminum hydroxide, and is 75 to 180 parts by mass with respect to 100 parts by mass of the total amount of the finely crosslinked ethylene-vinyl acetate copolymer (A) and polyvinyl acetate (B). The flame-retardant resin composition which is the range is provided.
前記前記微架橋エチレン−酢酸ビニル共重合体（Ａ）と、エチレン・アクリルゴム(ａ−２)の非架橋物または微架橋物が、エチレン−酢酸ビニル共重合体(ａ−１)とエチレン・アクリルゴム(ａ−２)の混合物を微架橋して得られるものである前記難燃性樹脂組成物は、本発明の好ましい態様である。 The finely crosslinked ethylene-vinyl acetate copolymer (A) and the non-crosslinked product or finely crosslinked product of ethylene / acrylic rubber (a-2) are ethylene-vinyl acetate copolymer (a-1) and ethylene The flame retardant resin composition obtained by finely crosslinking a mixture of acrylic rubber (a-2) is a preferred embodiment of the present invention.
前記前記微架橋エチレン−酢酸ビニル共重合体（Ａ）と、エチレン・アクリルゴム(ａ−２)の非架橋物または微架橋物が、エチレン−酢酸ビニル共重合体(ａ−１)の微架橋物とエチレン・アクリルゴム(ａ−２)の非架橋物または微架橋物を混合してなる前記した難燃性樹脂組成物は、本発明の好ましい態様である。 The finely crosslinked ethylene-vinyl acetate copolymer (A) and the non-crosslinked or slightly crosslinked product of the ethylene / acrylic rubber (a-2) are the finely crosslinked ethylene-vinyl acetate copolymer (a-1). The above-mentioned flame retardant resin composition obtained by mixing a non-crosslinked product or a slightly crosslinked product of ethylene / acrylic rubber (a-2) is a preferred embodiment of the present invention.
前記した難燃性樹脂組成物を用いて得られる成形物は、本発明の好ましい態様である。 A molded product obtained by using the flame retardant resin composition described above is a preferred embodiment of the present invention.
本発明により、引っ張り強さ等の機械物性に優れ、しかも柔軟性と難燃性のバランスに優れ、加工性にも優れたエチレン−酢酸ビニル共重合体の微架橋物を含む難燃性樹脂組成物が提供される。
本発明により、エチレン−酢酸ビニル共重合体の本来有する諸物性を実質的に、損なうことなく優れた難燃性が付与された難燃性樹脂組成物が提供される。
According to the present invention, a flame-retardant resin composition comprising a micro-crosslinked product of an ethylene-vinyl acetate copolymer having excellent mechanical properties such as tensile strength, excellent balance between flexibility and flame retardancy, and excellent workability Things are provided.
According to the present invention, there is provided a flame retardant resin composition to which excellent flame retardancy is imparted without substantially impairing various physical properties of an ethylene-vinyl acetate copolymer.
また、本発明により提供される難燃性樹脂組成物は、とくにＵＬ耐炎性試験規格において、薄肉の０．５ｍｍという過酷な条件下でもＶ−１レベルを達成することが可能な難燃性樹脂組成物であり、柔軟性、耐溶剤性も備えているので、各種成形方法によって種々の成形品に加工して使用することができるものである。 In addition, the flame retardant resin composition provided by the present invention is a flame retardant resin capable of achieving the V-1 level even under severe conditions of 0.5 mm, especially in the UL flame resistance test standard. Since it is a composition and has flexibility and solvent resistance, it can be processed into various molded products by various molding methods.
微架橋エチレン−酢酸ビニル共重合体（Ａ）
本発明に用いられる微架橋エチレン−酢酸ビニル共重合体（Ａ）のメルトフローレイト(ＭＦＲ)は、ＪＩＳ Ｋ ７２１０−１９９９に従って、１９０℃、２，１６０ｇ荷重で測定した値が、０．０１〜３ｇ／１０分、好ましくは０．０１〜１ｇ／１０分、より好ましくは０．０１〜０．６ｇ／１０分であることが望ましい。
Micro-crosslinked ethylene-vinyl acetate copolymer (A)
The melt flow rate (MFR) of the microcrosslinked ethylene-vinyl acetate copolymer (A) used in the present invention has a value measured at 190 ° C. under a load of 2,160 g according to JIS K 7210-1999, It is desired to be 3 g / 10 minutes, preferably 0.01 to 1 g / 10 minutes, more preferably 0.01 to 0.6 g / 10 minutes.
本発明において微架橋エチレン−酢酸ビニル共重合体（Ａ）は、エチレン−酢酸ビニル共重合体を微架橋して得ることができるが、微架橋エチレン−酢酸ビニル共重合体（Ａ）を得るために用いられるエチレン−酢酸ビニル共重合体（Ａ−１）は高圧重合法により製造されたエチレン共重合体であり、酢酸ビニル含有量（JIS K7192法：1999）は、４０質量％〜４９質量％未満、好ましくは４１〜４７質量％、一層好ましくは４３〜４７質量％であり、架橋前のメルトフローレイト（JIS K7210：1999法、190℃、荷重2,160gで測定）は、好ましくは、４〜１５０ｇ／１０分、より好ましくは１０〜１２０ｇ／１０分、一層好ましくは３０〜１２０ｇ／１０分のものを挙げることができる。
また、本発明のエチレン−酢酸ビニル共重合体のゲルパーミエーションクロマトグラフ（ＧＰＣ）法で測定したＭｗ／Ｍｎ値は、６〜１２、好ましくは６〜１０であることが好ましい。
In the present invention, the finely crosslinked ethylene-vinyl acetate copolymer (A) can be obtained by finely crosslinking an ethylene-vinyl acetate copolymer, but in order to obtain a finely crosslinked ethylene-vinyl acetate copolymer (A). The ethylene-vinyl acetate copolymer (A-1) used in the invention is an ethylene copolymer produced by a high pressure polymerization method, and the vinyl acetate content (JIS K7192 method: 1999) is 40 mass% to 49 mass%. Less than, preferably 41 to 47% by mass, more preferably 43 to 47% by mass, and the melt flow rate before cross-linking (JIS K7210: 1999 method, measured at 190 ° C. under a load of 2,160 g) is preferably 4 to 4%. An example is 150 g / 10 minutes, more preferably 10 to 120 g / 10 minutes, and still more preferably 30 to 120 g / 10 minutes.
Further, the Mw / Mn value of the ethylene-vinyl acetate copolymer of the present invention measured by gel permeation chromatography (GPC) method is 6 to 12, preferably 6 to 10.
なお、本発明におけるエチレン−酢酸ビニル共重合体の微架橋は、本発明の目的に合うようにメルトフロ−レイト（JIS K7210：1999法、190℃、荷重2,160g）が０．０１〜３ｇ／１０分の範囲にあるように微架橋を行えばよい。微架橋の程度の目安として、以下の式で定義されるメルトフローレイトの降下率が７０〜９９．９％の範囲になるように微架橋された状態が推奨される。
メルトフローレイト降下率＝（Ｘ−Ｙ）／Ｘ×１００
Ｘ：エチレン−酢酸ビニル共重合体（Ａ−１）のメルトフローレイト
Ｙ：架橋後のエチレン−酢酸ビニル共重合体（Ａ）のメルトフローレイト
The fine crosslinking of the ethylene-vinyl acetate copolymer in the present invention has a melt flow rate (JIS K7210: 1999 method, 190 ° C., load 2,160 g) of 0.01 to 3 g / 10 so as to meet the object of the present invention. What is necessary is just to perform a microbridge so that it may exist in the range of minutes. As a measure of the degree of micro-crosslinking, a micro-cross-linked state is recommended so that the rate of decrease in melt flow rate defined by the following formula is in the range of 70 to 99.9%.
Melt flow rate drop rate = (X−Y) / X × 100
X: Melt flow rate of ethylene-vinyl acetate copolymer (A-1) Y: Melt flow rate of ethylene-vinyl acetate copolymer (A) after crosslinking
本発明の微架橋エチレン−酢酸ビニル共重合体（Ａ）を得る方法として、前記エチレン−酢酸ビニル共重合体（Ａ−１）を、有機過酸化物、電子線架橋（放射線架橋）、シラン架橋剤などによって架橋する架橋技術を用いることができる。有機過酸化物で架橋する場合はエチレン−酢酸ビニル共重合体に所定量の有機過酸化物を加えて１軸または２軸の押出機等の混練装置で溶融混練することによって製造することができる。 As a method for obtaining the micro-crosslinked ethylene-vinyl acetate copolymer (A) of the present invention, the ethylene-vinyl acetate copolymer (A-1) is converted into an organic peroxide, electron beam cross-linking (radiation cross-linking), silane cross-linking. A crosslinking technique for crosslinking with an agent or the like can be used. In the case of crosslinking with an organic peroxide, it can be produced by adding a predetermined amount of an organic peroxide to an ethylene-vinyl acetate copolymer and melt-kneading with a kneading apparatus such as a single-screw or twin-screw extruder. .
エチレン−酢酸ビニル共重合体を有機過酸化物で架橋する場合、有機過酸化物としては、第３ブチルクミルパーオキサイド、ジクミルパーオキサイド、２，５−ジメチル−２，５−ビス（第３ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ビス（第３ブチルパーオキシ）ヘキシン−３、１，３−ビス（２−第３ブチルパーオキシイソプロピル）ベンゼン、ジ第３ブチルパーオキサイドなどのジアルキルパーオキサイド；第３ブチルパーオキシイソブチレート、第３ブチルパーオキシマレイン酸、第３ブチルパーオキシイソナノエート、第３ブチルパーオキシイソプロピルカーボネート、第３ブチルパーオキシ−２−エチルヘキシルカーボネート、第３ブチルパーオキシアセテート、第３ブチルパーオキシベンゾエート、２，５−ジメチル−２，５−ビス（ベンゾイルパーオキシ）ヘキサン、２，５−ジメチルヘキシル−２，５−ビスパーオキシベンゾエートなどのアルキルパーオキシエステル；１，１−ビス（第３ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（第３ブチルパーオキシ）シクロヘキサン、１，１−ビス（第３アミルパーオキシ）シクロヘキサン、２，２−ビス（第３ブチルパーオキシ）ブタン、ｎ−ブチル−４，４−ビス（第３ブチルパーオキシ）バレレート、エチル−３，３−ビス（第３ブチルパーオキシ）ブチレートなどのパーオキシケタールなどを例示することができる。 When the ethylene-vinyl acetate copolymer is crosslinked with an organic peroxide, examples of the organic peroxide include tertiary butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (third Butylperoxy) hexane, 2,5-dimethyl-2,5-bis (tertiary butylperoxy) hexyne-3, 1,3-bis (2-tertiary butylperoxyisopropyl) benzene, di-tertiary butyl peroxy Dialkyl peroxides such as oxides; tertiary butyl peroxyisobutyrate, tertiary butyl peroxymaleic acid, tertiary butyl peroxyisonanoate, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peroxy-2-ethylhexyl Carbonate, tertiary butyl peroxyacetate, tertiary butyl peroxybenzoate, 2,5- Alkyl peroxyesters such as methyl-2,5-bis (benzoylperoxy) hexane, 2,5-dimethylhexyl-2,5-bisperoxybenzoate; 1,1-bis (tertiarybutylperoxy) -3 , 3,5-trimethylcyclohexane, 1,1-bis (tertiarybutylperoxy) cyclohexane, 1,1-bis (tertiary amylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, Examples thereof include peroxyketals such as n-butyl-4,4-bis (tert-butylperoxy) valerate and ethyl-3,3-bis (tert-butylperoxy) butyrate.
有機化酸化物の添加量は、使用するエチレン−酢酸ビニル共重合体（Ａ−１）のメルトフローレイト、有機過酸化物の種類、所望のメルトフローレイトによって異なるが、５０〜１０,０００ｐｐｍの範囲にある。また、架橋する際の温度条件は有機化酸化物の種類によって異なるが、５０〜２３０℃の範囲にあることが望ましい。 The addition amount of the organic oxide varies depending on the melt flow rate of the ethylene-vinyl acetate copolymer (A-1) to be used, the type of organic peroxide, and the desired melt flow rate, but it is 50 to 10,000 ppm. Is in range. Moreover, although the temperature condition at the time of bridge | crosslinking changes with kinds of organic oxide, it is desirable to exist in the range of 50-230 degreeC.
本発明の難燃性樹脂組成物は、前記微架橋エチレン−酢酸ビニル共重合体（Ａ）とともにエチレン・アクリルゴム(ａ−２)の非架橋物または微架橋物を含有するものである。
エチレン・アクリルゴム(ａ−２)の含有量としては、好ましくはエチレン−酢酸ビニル共重合体（ａ−１）とエチレン・アクリルゴム(ａ−２)の合計量１００重量部に対し、９５〜５重量部の範囲、好ましくは７５〜５重量部の範囲、より好ましくは５０〜５重量部の範囲であることが望ましい。
The flame-retardant resin composition of the present invention contains a non-crosslinked product or a finely crosslinked product of ethylene / acrylic rubber (a-2) together with the finely crosslinked ethylene-vinyl acetate copolymer (A).
The content of the ethylene / acrylic rubber (a-2) is preferably from 95 to 95 parts by weight based on 100 parts by weight of the total amount of the ethylene-vinyl acetate copolymer (a-1) and the ethylene / acrylic rubber (a-2). The range is 5 parts by weight, preferably 75 to 5 parts by weight, more preferably 50 to 5 parts by weight.
前記微架橋エチレン−酢酸ビニル共重合体（Ａ）を含む樹脂組成物がエチレン−酢酸ビニル共重合体（ａ−１）に加えてエチレン・アクリルゴム(ａ−２)の非架橋物または微架橋物を含有するものである場合のメルトフローレイト(ＭＦＲ)は、ＪＩＳ Ｋ ７２１０−１９９９に従って、１９０℃、２，１６０ｇ荷重で測定した値が、０．０１〜３ｇ／１０分の範囲、好ましくは０．０１〜１ｇ／１０分の範囲、より好ましくは０．０１〜０．６ｇ／１０分の範囲であることが望ましい。 In addition to the ethylene-vinyl acetate copolymer (a-1), the resin composition containing the finely crosslinked ethylene-vinyl acetate copolymer (A) is a non-crosslinked product or microcrosslinked of ethylene / acrylic rubber (a-2). The melt flow rate (MFR) in the case of containing a product has a value measured at 190 ° C. under a load of 2,160 g according to JIS K 7210-1999, preferably in the range of 0.01 to 3 g / 10 min. It is desirable that the range be 0.01 to 1 g / 10 min, more preferably 0.01 to 0.6 g / 10 min.
本発明においては、前記微架橋エチレン−酢酸ビニル共重合体（Ａ）を含む樹脂組成物が、エチレン・アクリルゴム(ａ−２)の非架橋物または微架橋物を含有する態様としては、エチレン−酢酸ビニル共重合体(ａ−１)とエチレン・アクリルゴム(ａ−２)を公知の適宜の樹脂混合方法で予め混合した混合物を前記した微架橋方法により微架橋したもの（態様１）でもよいし、或いはまた、エチレン−酢酸ビニル共重合体(ａ−１)の微架橋物とエチレン・アクリルゴム(ａ−２)の非架橋物または前記した微架橋方法により微架橋した微架橋物を別々に調製し、これを同様に公知の適宜の樹脂混合方法で混合をしたもの(態様２)でもよい In the present invention, the resin composition containing the finely crosslinked ethylene-vinyl acetate copolymer (A) contains an ethylene-acrylic rubber (a-2) non-crosslinked product or a finely crosslinked product. -A mixture obtained by previously mixing a vinyl acetate copolymer (a-1) and an ethylene / acrylic rubber (a-2) by a known appropriate resin mixing method and finely cross-linking by the above-mentioned micro-crosslinking method (Aspect 1) Or a finely cross-linked product of ethylene-vinyl acetate copolymer (a-1) and a non-crosslinked product of ethylene / acrylic rubber (a-2) or a micro-crosslinked product micro-crosslinked by the above-mentioned micro-crosslinking method. It may be prepared separately and similarly mixed by a known appropriate resin mixing method (aspect 2).
態様１においては微架橋前のエチレン・アクリルゴム(ａ−２)の含有量としては、好ましくはエチレン−酢酸ビニル共重合体（ａ−１）とエチレン・アクリルゴム(ａ−２)の合計量１００重量部に対し、９５〜５重量部の範囲、好ましくは７５〜５重量部の範囲、より好ましくは５０〜５重量部の範囲であることが望ましい。
また態様２においてはエチレン−酢酸ビニル共重合体(ａ−１)の微架橋物に混合するエチレン・アクリルゴム(ａ−２)の非架橋物または微架橋物の量としては、好ましくはエチレン−酢酸ビニル共重合体（ａ−１）の微架橋物とエチレン・アクリルゴム(ａ−２)の非架橋物または微架橋物の合計量１００重量部に対し、９５〜５重量部の範囲、好ましくは７５〜５重量部の範囲、より好ましくは５０〜５重量部の範囲であることが望ましい。
In aspect 1, the content of ethylene / acrylic rubber (a-2) before fine crosslinking is preferably the total amount of ethylene-vinyl acetate copolymer (a-1) and ethylene / acrylic rubber (a-2). It is desirable that the range is 95 to 5 parts by weight, preferably 75 to 5 parts by weight, and more preferably 50 to 5 parts by weight with respect to 100 parts by weight.
In Embodiment 2, the amount of the non-crosslinked product or the slightly crosslinked product of the ethylene / acrylic rubber (a-2) mixed with the finely crosslinked product of the ethylene-vinyl acetate copolymer (a-1) is preferably ethylene- The range of 95-5 parts by weight, preferably 100 parts by weight of the total amount of the finely crosslinked product of vinyl acetate copolymer (a-1) and the non-crosslinked product or slightly crosslinked product of ethylene / acrylic rubber (a-2), Is preferably in the range of 75 to 5 parts by weight, more preferably in the range of 50 to 5 parts by weight.
本発明の微架橋エチレン−酢酸ビニル共重合体（Ａ）の組成物を得るのに、エチレン−酢酸ビニル共重合体(ａ−１)の微架橋物とエチレン・アクリルゴム(Ａ−２)の非架橋物または微架橋物を混合する方法を採用する場合、エチレン・アクリルゴム(ａ−２)の微架橋はメルトフロ−レイト（JIS K7210：1999法、190℃、荷重2,160g）が０．０１〜３ｇ／１０分の範囲にあるように、例えば有機化酸化物等の架橋剤を用いて、微架橋を行えばよい。微架橋の程度の目安として、エチレン−酢酸ビニル共重合体(Ａ−１)と同様にメルトフローレイトの降下率が７０〜９９．９％の範囲になるように微架橋された状態が推奨される。 In order to obtain the composition of the finely crosslinked ethylene-vinyl acetate copolymer (A) of the present invention, the finely crosslinked product of the ethylene-vinyl acetate copolymer (a-1) and the ethylene-acrylic rubber (A-2) When adopting a method of mixing non-cross-linked or micro-cross-linked products, the melt flow rate (JIS K7210: 1999 method, 190 ° C., load 2,160 g) is 0.01 for micro-crosslinking of ethylene / acrylic rubber (a-2). What is necessary is just to perform micro-crosslinking, for example using crosslinking agents, such as an organic-ized oxide, so that it may exist in the range of -3g / 10min. As a measure of the degree of micro-crosslinking, it is recommended that the micro-cross-linked state is such that the rate of decrease in the melt flow rate is in the range of 70 to 99.9%, similar to the ethylene-vinyl acetate copolymer (A-1). The
本発明において用いられる前記エチレン・アクリルゴム(ａ−２)（以下、エチレン・アクリル酸エステル共重合体ということがある。）としては、エチレンと（メタ）アクリル酸エステルとからなる二元共重合体、またはエチレンと（メタ）アクリル酸エステル及び架橋サイトとなり得るモノマーとからなる多元共重合体を挙げることができる。なお、ここに（メタ）アクリル酸エステルという記載は、アクリル酸エステル又はメタクリル酸エステルを意味するものである。 The ethylene / acrylic rubber (a-2) (hereinafter sometimes referred to as ethylene / acrylic acid ester copolymer) used in the present invention is a binary copolymer consisting of ethylene and (meth) acrylic acid ester. Examples thereof include a polymer or a multi-component copolymer composed of ethylene and a monomer capable of forming a (meth) acrylic acid ester and a crosslinking site. Here, the description of (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester.
エチレン・アクリル酸エステル共重合体における（メタ）アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチルなどを例示することができる。これらの中では、アクリル酸メチル、アクリル酸エチル又はアクリル酸ｎ−ブチルを共重合成分とする共重合体の使用が好ましい。 Examples of the (meth) acrylic acid ester in the ethylene / acrylic acid ester copolymer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Examples thereof include n-butyl methacrylate and isobutyl methacrylate. Among these, it is preferable to use a copolymer having methyl acrylate, ethyl acrylate, or n-butyl acrylate as a copolymerization component.
前記多元共重合体における架橋サイトとなり得るモノマーとしては、アクリル酸、メタクリル酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノイソプロピルのようなマレイン酸モノエステル、アクリル酸グリシジル、メタクリル酸グリシジルのような不飽和モノカルボン酸グリシジルなどを例示することができる。とくにマレイン酸モノメチル及びマレイン酸モノエチルのようなマレイン酸モノエステルの使用が好ましい。 Examples of the monomer that can be a crosslinking site in the multi-component copolymer include maleic acid monoesters such as acrylic acid, methacrylic acid, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, glycidyl acrylate, and glycidyl methacrylate. Examples thereof include glycidyl unsaturated monocarboxylate. In particular, the use of maleic acid monoesters such as monomethyl maleate and monoethyl maleate is preferred.
本発明におけるエチレン・アクリルゴムは、ゴム的特性を考慮すると、一般には（メタ）アクリル酸エステルの重合単位を２５〜７０重量％程度、好ましくは３０〜６５重量％程度の範囲で含有しているものが好ましい。また多元共重合体の場合、加硫特性を考慮すると、架橋サイトとなり得るモノマーの重合単位を１０重量％まで、例えば０．１〜１０重量％、とくに０．３〜７重量％の範囲で含有することが望ましい。 In view of rubber characteristics, the ethylene / acrylic rubber in the present invention generally contains a polymerization unit of (meth) acrylic acid ester in the range of about 25 to 70% by weight, preferably about 30 to 65% by weight. Those are preferred. In the case of a multi-component copolymer, in consideration of the vulcanization characteristics, it contains up to 10% by weight, for example, 0.1 to 10% by weight, particularly 0.3 to 7% by weight, of a monomer unit that can become a crosslinking site. It is desirable to do.
またエチレン・アクリルゴムは、その加工性、加硫物性などを考慮すると、ムーニー粘度（ＭＬ（１＋４）、１００℃）が５〜１００、好ましくは１０〜７０程度のものを使用することが好ましい。 In view of the processability and vulcanized physical properties, ethylene / acrylic rubber having a Mooney viscosity (ML (1 + 4) , 100 ° C.) of 5 to 100, preferably about 10 to 70 is preferably used.
ポリ酢酸ビニル（Ｂ）
本発明の難燃性樹脂組成物における、ポリ酢酸ビニル（Ｂ）としては、製造法は特に限定されないが、一般には懸濁重合法や溶液重合法により製造される。
Polyvinyl acetate (B)
The production method of polyvinyl acetate (B) in the flame retardant resin composition of the present invention is not particularly limited, but is generally produced by a suspension polymerization method or a solution polymerization method.
ポリ酢酸ビニルとしては、好ましくは重合度が６００〜５,０００の範囲、より好ましくは６００〜３,０００の範囲、一層好ましくは６００〜２,０００の範囲である。また、これらは架橋されていても構わない。さらに、例えば無水マレイン酸などにより変性されていても構わない。 The polyvinyl acetate preferably has a degree of polymerization in the range of 600 to 5,000, more preferably in the range of 600 to 3,000, and still more preferably in the range of 600 to 2,000. These may be cross-linked. Furthermore, it may be modified with, for example, maleic anhydride.
ポリ酢酸ビニルの含有量としては、微架橋エチレン−酢酸ビニル共重合体（Ａ）とポリ酢酸ビニル（Ｂ）の合計量１００重量部に対し、９５〜５重量部、好ましくは８０〜５重量部、より好ましくは７５〜１０重量部、一層好ましくは６０〜１０重量部の範囲にある。 The content of polyvinyl acetate is 95 to 5 parts by weight, preferably 80 to 5 parts by weight, with respect to 100 parts by weight of the total amount of the finely crosslinked ethylene-vinyl acetate copolymer (A) and polyvinyl acetate (B). More preferably, it is in the range of 75 to 10 parts by weight, more preferably 60 to 10 parts by weight.
難燃剤（Ｃ）
本発明で使用される難燃剤（Ｃ）としては、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のような金属水和物、塩基性炭酸マグネシウム、炭酸カルシウム、シリカ、アルミナ、タルク、クレイ、ゼオライト、臭素系難燃剤、三酸化アンチモン、ポリリン酸系難燃剤などを例示することができる。これらの中でも金属水和物が好ましい。充分な難燃性を求める場合には、水酸化マグネシウムまたは水酸化アルミニウムを使用するかあるいは水酸化マグネシウムまたは水酸化アルミニウムを少なくとも５０重量％以上占めるような混合無機難燃剤を使用するのがよい。
Flame retardant (C)
Examples of the flame retardant (C) used in the present invention include magnesium hydroxide, aluminum hydroxide, metal hydrate such as hydrotalcite, basic magnesium carbonate, calcium carbonate, silica, alumina, talc, clay, zeolite. Examples thereof include brominated flame retardants, antimony trioxide, and polyphosphoric acid flame retardants. Of these, metal hydrates are preferred. When sufficient flame retardancy is required, it is preferable to use magnesium hydroxide or aluminum hydroxide or a mixed inorganic flame retardant containing at least 50% by weight of magnesium hydroxide or aluminum hydroxide.
難燃剤（Ｃ）の混和性、難燃性樹脂組成物から得られる成形物外観などを考慮すると、平均粒径が０．０５〜２０μｍ、とくに０．１〜５μｍ程度のものを使用するのが望ましい。また同様の理由で、無機難燃剤の表面が、脂肪酸、脂肪酸アミド、脂肪酸塩、脂肪酸エステル、脂肪族アルコール、シランカップリング剤、チタンカップリング剤、シリコンオイル、シリコンポリマー、リン酸エステル等で表面処理されたものを使用するのが望ましい。 Considering the miscibility of the flame retardant (C) and the appearance of the molded product obtained from the flame retardant resin composition, it is preferable to use those having an average particle size of 0.05 to 20 μm, particularly about 0.1 to 5 μm. desirable. For the same reason, the surface of the inorganic flame retardant is the surface of fatty acid, fatty acid amide, fatty acid salt, fatty acid ester, aliphatic alcohol, silane coupling agent, titanium coupling agent, silicone oil, silicone polymer, phosphate ester, etc. It is desirable to use the processed one.
本発明の難燃性樹脂組成物において、難燃剤（Ｃ）の割合は、微架橋エチレン−酢酸ビニル共重合体（Ａ）とポリ酢酸ビニル(Ｂ)の合計量１００質量部に対し、２０〜２５０質量部、好ましくは５０〜２００質量部、より好ましくは７５〜１８０質量部であることが望ましい。 In the flame retardant resin composition of the present invention, the ratio of the flame retardant (C) is 20 to 20 parts by mass with respect to 100 parts by mass of the total amount of the finely crosslinked ethylene-vinyl acetate copolymer (A) and the polyvinyl acetate (B). It is desirable that it is 250 mass parts, Preferably it is 50-200 mass parts, More preferably, it is 75-180 mass parts.
本発明の難燃剤（Ｃ）とともに、本発明の目的を損なわない範囲で赤リン、硼酸亜鉛、錫酸亜鉛、ステアリン酸アルミニウムなどの公知の難燃助剤を配合してもよい。 Along with the flame retardant (C) of the present invention, known flame retardant aids such as red phosphorus, zinc borate, zinc stannate and aluminum stearate may be blended within a range not impairing the object of the present invention.
本発明の難燃性樹脂組成物には、さらにオレフィン系重合体（Ｄ−１）やスチレン系重合体（Ｄ−２）、並びに、不飽和カルボン酸及び／又はその誘導体で変性されたオレフィン系重合体（Ｄ−３）及び不飽和カルボン酸及び／又はその誘導体で変性されたスチレン系重合体（Ｄ−４）からなる群より選ばれる少なくとも一種の重合体（Ｄ）が含まれていてもよい。 The flame retardant resin composition of the present invention further includes an olefin polymer (D-1), a styrene polymer (D-2), and an olefin modified with an unsaturated carboxylic acid and / or a derivative thereof. Even if at least one polymer (D) selected from the group consisting of a polymer (D-3) and a styrene polymer (D-4) modified with an unsaturated carboxylic acid and / or a derivative thereof is included. Good.
本発明の難燃性樹脂組成物における（Ｄ）の割合は、微架橋エチレン−酢酸ビニル共重合体（Ａ）及びポリ酢酸ビニル（Ｂ）の合計量１００質量部に対し、５０質量部以下の割合であることが好ましい。 The proportion of (D) in the flame retardant resin composition of the present invention is 50 parts by mass or less with respect to 100 parts by mass of the total amount of the finely crosslinked ethylene-vinyl acetate copolymer (A) and polyvinyl acetate (B). A ratio is preferred.
不飽和カルボン酸又はその誘導体で変性されたオレフィン系重合体(Ｄ−３)は、樹脂状あるいはエラストマー状のオレフィン系重合体（Ｄ−１）を不飽和カルボン酸又はその誘導体でグラフト変性又は共重合変性したものである。ベースポリマーとなるオレフィン系重合体は（Ｄ−１）、オレフィンの単独重合体、２種以上のオレフィンの共重合体、オレフィンと極性モノマーの共重合体などである。具体的には、樹脂状オレフィン重合体として、高、中、低密度ポリエチレン、エチレン・α−オレフィン共重合体、エチレン・不飽和エステル共重合体などのエチレン系共重合体、プロピレン単独重合体、プロピレン・α−オレフィンランダム共重合体、プロピレン・α−オレフィンブロック共重合体などのプロピレン系重合体、ポリ−１−ブテンなどを挙げることができる。またエラストマー状オレフィン重合体としては、エチレン・プロピレン共重合体ゴムのようなエチレン・α−オレフィン共重合体ゴム、プロピレン・α−オレフィン共重合体ゴム、エチレン・プロピレン・ジエン共重合体ゴムのようなエチレン・α−オレフィン・ジエン共重合体ゴム、規則性を制御したポリプロピレンにエチレン・プロピレン共重合体部を共重合したブロック共重合体、エチレン・アクリル酸メチル共重合体ゴム、エチレン・アクリル酸メチル・架橋サイトモノマー共重合体ゴムなどを挙げることができる。上記各共重合体におけるα−オレフィンとしては、炭素数２〜１２程度のものが好ましい。 The olefin polymer (D-3) modified with an unsaturated carboxylic acid or derivative thereof is obtained by graft-modifying or co-polymerizing a resinous or elastomeric olefin polymer (D-1) with an unsaturated carboxylic acid or derivative thereof. Polymerized and modified. The olefin polymer used as the base polymer is (D-1), an olefin homopolymer, a copolymer of two or more olefins, a copolymer of an olefin and a polar monomer, and the like. Specifically, as the resinous olefin polymer, high-, medium-, low-density polyethylene, ethylene / α-olefin copolymer, ethylene-based copolymer such as ethylene / unsaturated ester copolymer, propylene homopolymer, Examples thereof include propylene-based polymers such as propylene / α-olefin random copolymers and propylene / α-olefin block copolymers, and poly-1-butene. The elastomeric olefin polymer includes ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber, propylene / α-olefin copolymer rubber, ethylene / propylene / diene copolymer rubber, and the like. Ethylene / α-olefin / diene copolymer rubber, block copolymer obtained by copolymerizing ethylene / propylene copolymer with polypropylene with controlled regularity, ethylene / methyl acrylate copolymer rubber, ethylene / acrylic acid Mention may be made, for example, of a methyl / crosslinked site monomer copolymer rubber. As an alpha olefin in each said copolymer, a C2-C12 thing is preferable.
不飽和カルボン酸又はその誘導体で変性されたスチレン系重合体(Ｄ−４)は、樹脂状あるいはエラストマー状のスチレン系重合体（Ｄ−２）を不飽和カルボン酸又はその誘導体でグラフト変性又は共重合変性したものである。ベースポリマーとなるスチレン系重合体としては（Ｄ−２）、例えばポリスチレン、スチレン・ジエンブロック共重合体及びその水素添加物を挙げることができる。スチレン・ジエンブロック共重合体及びその水素添加物の具体例としては、スチレン・ブタジエン・スチレンブロック共重合体（ＳＢＳ）及びその水素添加物であるスチレン・エチレン／ブテン・スチレンブロック共重合体（ＳＥＢＳ）、スチレン・イソプレン・スチレンブロック共重合体（ＳＩＳ）及びその水素添加物であるスチレン・エチレン／プロピレン・スチレンブロック共重合体（ＳＥＰＳ）、スチレン・エチレン・エチレン／プロピレン・スチレンブロック共重合体（ＳＥＥＰＳ）などを挙げることができる。 The styrene polymer (D-4) modified with an unsaturated carboxylic acid or derivative thereof is obtained by graft-modifying or co-polymerizing a resinous or elastomeric styrene polymer (D-2) with an unsaturated carboxylic acid or derivative thereof. Polymerized and modified. Examples of the styrenic polymer serving as the base polymer include (D-2), for example, polystyrene, styrene-diene block copolymer, and hydrogenated products thereof. Specific examples of styrene / diene block copolymers and hydrogenated products thereof include styrene / butadiene / styrene block copolymers (SBS) and hydrogenated styrene / ethylene / butene / styrene block copolymers (SEBS). ), Styrene / isoprene / styrene block copolymer (SIS) and its hydrogenated styrene / ethylene / propylene / styrene block copolymer (SEPS), styrene / ethylene / ethylene / propylene / styrene block copolymer ( (SEEPS)).
本発明の難燃性樹脂組成物には、その加工性、物性および難燃性を損なわない範囲で、微架橋エチレン−酢酸ビニル共重合体（Ａ）とポリ酢酸ビニル（Ｂ）の合計量１００重量部に対し２００重量部までの割合で植物由来プラスチック（セルロース系、デンプン系、乳酸系、コハク酸系、酪酸系、グリコール系）などを配合することができる。 In the flame-retardant resin composition of the present invention, the total amount of the micro-crosslinked ethylene-vinyl acetate copolymer (A) and polyvinyl acetate (B) is 100 as long as the processability, physical properties and flame retardancy are not impaired. Plant-derived plastics (cellulose-based, starch-based, lactic acid-based, succinic acid-based, butyric acid-based, glycol-based) and the like can be blended at a ratio of up to 200 parts by weight with respect to parts by weight.
上記ベースポリマーのオレフィン系重合体（Ｄ−１）やスチレン系重合体（Ｄ−２）の変性に用いる不飽和カルボン酸又はその誘導体としては、アクリル酸、メタクリル酸、エタクリル酸、マレイン酸、フマル酸、イタコン酸等の不飽和カルボン酸、無水マレイン酸、無水イタコン酸などの不飽和カルボン酸無水物を例示することができる。変性されたオレフィン系重合体（Ｄ−３）やスチレン系重合体（Ｄ−４）におけるグラフトモノマー単位あるいは共重合モノマー単位の含有量は、変性重合体を基準として好ましくは０．０１〜２０重量％、とくに好ましくは０．１〜５重量％である。上記変性重合体としてはまた、ベースポリマーがエチレン系重合体の場合は、ＪＩＳ Ｋ７２１０−１９９９、１９０℃、２１６０ｇ荷重におけるメルトフローレイトが０．１〜５０ｇ／１０分、とくに０．２〜１０ｇ／１０分のものを使用するのが好ましい。また変性重合体のベースポリマーがプロピレン系重合体やスチレン系重合体の場合は、ＪＩＳ Ｋ７２１０−１９９９、２３０℃、２１６０ｇ荷重におけるメルトフローレイトが０．１〜５０ｇ／１０分、とくに０．２〜１０ｇ／１０分のものを使用するのが好ましい。 The unsaturated carboxylic acid or derivative thereof used for modification of the olefin polymer (D-1) or styrene polymer (D-2) of the base polymer includes acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid. Examples thereof include unsaturated carboxylic acids such as acid and itaconic acid, and unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. The content of the graft monomer unit or copolymer monomer unit in the modified olefin polymer (D-3) or styrene polymer (D-4) is preferably 0.01 to 20 weights based on the modified polymer. %, Particularly preferably 0.1 to 5% by weight. As the modified polymer, when the base polymer is an ethylene polymer, the melt flow rate at JIS K7210-1999, 190 ° C., 2160 g load is 0.1 to 50 g / 10 min, particularly 0.2 to 10 g / min. It is preferred to use a 10 minute one. When the base polymer of the modified polymer is a propylene-based polymer or a styrene-based polymer, the melt flow rate at JIS K7210-1999, 230 ° C., 2160 g load is 0.1 to 50 g / 10 min, particularly 0.2 to It is preferable to use those of 10 g / 10 min.
本発明の難燃性樹脂組成物には、またさらにオレフィン系ワックス（Ｅ）が含まれていてもよい。
オレフィン系ワックス としては、高分子量ポリオレフィンの熱分解によって得られるワックス、オレフィンの単独重合または他のオレフィンとの共重合によって得られるワックスなどがあり、適宜選択して使用することができるが、相溶性の点から本発明の目的にはエチレン系ワックスが好ましい。
The flame retardant resin composition of the present invention may further contain an olefin wax (E).
Examples of olefin waxes include waxes obtained by thermal decomposition of high molecular weight polyolefins, waxes obtained by homopolymerization of olefins or copolymerization with other olefins, etc., which can be appropriately selected and used. In view of the above, ethylene wax is preferred for the purpose of the present invention.
エチレン系ワックスとしては、高分子量ポリエチレンの熱分解で得られるポリエチレンワックス、高圧法におけるエチレンの遊離基重合により得られたポリエチレンワックス、またはエチレンを金属触媒の存在下に単独重合するか、エチレンとα−オレフィンとを金属触媒の存在下に共重合することによって得られるポリエチレンワックスなどがある。中でも上記相溶性の点からエチレン・α−オレフィン共重合体ワックスがより好ましく使用される。α−オレフィンとしては、前記で例示したようなものを、好ましい例として挙げることができる。エチレン・α−オレフィン共重合体ワックスにおけるα−オレフィンの含量は、１５モル％以下であることが好ましく、より好ましくは１０モル％以下であることが望ましい。 Examples of the ethylene wax include polyethylene wax obtained by thermal decomposition of high molecular weight polyethylene, polyethylene wax obtained by free radical polymerization of ethylene in a high pressure method, or ethylene is homopolymerized in the presence of a metal catalyst, or ethylene and α -Polyethylene waxes obtained by copolymerizing olefins in the presence of metal catalysts. Among these, ethylene / α-olefin copolymer wax is more preferably used from the viewpoint of compatibility. As the α-olefin, those exemplified above can be mentioned as preferred examples. The content of α-olefin in the ethylene / α-olefin copolymer wax is preferably 15 mol% or less, more preferably 10 mol% or less.
このようなエチレン系ワックスの製造に好適に用いられる金属触媒としては、チーグラー系触媒などのマルチサイト触媒、メタロセン系触媒などのシングルサイト触媒などがある。メタロセン系触媒を用いてエチレン系ワックスを使用すると、機械物性の向上の観点から好ましい結果が得られるので、シングルサイト触媒とくにはメタロセン系触媒によって製造されたエチレン系ワックスが好ましい。 Examples of the metal catalyst suitably used for the production of such an ethylene wax include a multi-site catalyst such as a Ziegler catalyst and a single site catalyst such as a metallocene catalyst. When an ethylene-based wax is used with a metallocene-based catalyst, favorable results can be obtained from the viewpoint of improving mechanical properties, and therefore, a single-site catalyst, particularly an ethylene-based wax produced with a metallocene-based catalyst is preferable.
本発明で使用されるオレフィン系ワックスの粘度平均分子量は３０，０００以下、好ましくは８０００以下、より好ましくは１，０００〜８，０００であり、密度は８８０〜９８０ｋｇ／ｍ３、好ましくは９００〜９８０ｋｇ／ｍ３であり、融点は６０〜１６０℃、好ましくは６０〜１３０℃であることが望ましい。 The viscosity average molecular weight of the olefin wax used in the present invention is 30,000 or less, preferably 8000 or less, more preferably 1,000 to 8,000, and the density is 880 to 980 kg / m 3 , preferably 900 to It is 980 kg / m 3 and the melting point is 60 to 160 ° C., preferably 60 to 130 ° C.
粘度平均分子量が８，０００以下であり、密度が８８０〜９８０ｋｇ／ｍ３であり、融点が６０〜１３０℃であるエチレン系ワックスは、本発明のオレフィンワックスのより好ましいオレフィン系ワックスである。 An ethylene wax having a viscosity average molecular weight of 8,000 or less, a density of 880 to 980 kg / m 3 , and a melting point of 60 to 130 ° C. is a more preferable olefin wax of the olefin wax of the present invention.
本発明のオレフィン系ワックスは、分子中に水酸基、カルボン酸基、エポキシ基などの反応性基を含有していてもよい。これらの反応性基は、反応性基を含む不飽和化合物をワックス製造時に共重合させたり、オレフィン系ワックスにグラフト反応させたりして導入することができる。オレフィン系ワックスの分子中に反応性基を含有させることを、オレフィン系ワックスの変性と呼ぶ。また、変性されたオレフィン系ワックスとして、オレフィン系ワックスの酸化反応によって得られる酸化オレフィン系ワックスを使用することもできる。変性されたオレフィン系ワックスとしては、オレフィン系ワックスに、不飽和化合物をグラフト反応させたものが好ましい。不飽和化合物としては、不飽和カルボン酸、その無水物または誘導体を挙げることができ、中でも無水マレイン酸を特に好ましいものとして挙げることができる。 The olefin wax of the present invention may contain a reactive group such as a hydroxyl group, a carboxylic acid group, or an epoxy group in the molecule. These reactive groups can be introduced by copolymerizing an unsaturated compound containing a reactive group at the time of wax production or by causing a graft reaction to an olefin wax. Inclusion of a reactive group in the molecule of the olefin wax is called modification of the olefin wax. Moreover, the olefin oxide wax obtained by the oxidation reaction of an olefin wax can also be used as the modified olefin wax. The modified olefin wax is preferably an olefin wax obtained by graft reaction of an unsaturated compound. As an unsaturated compound, unsaturated carboxylic acid, its anhydride, or a derivative can be mentioned, Among these, maleic anhydride can be mentioned as a particularly preferable thing.
本発明難燃性樹脂組成物におけるオレフィン系ワックスの量は、微架橋エチレン−酢酸ビニル共重合体（Ａ）およびポリ酢酸ビニル（Ｂ）の合計量１００質量部に対し、１０質量部以下、好ましくは０．５〜５質量部、より好ましくは０．５〜３であることが望ましい。 The amount of the olefinic wax in the flame retardant resin composition of the present invention is preferably 10 parts by mass or less, preferably 100 parts by mass of the total amount of the finely crosslinked ethylene-vinyl acetate copolymer (A) and polyvinyl acetate (B). Is 0.5-5 parts by mass, more preferably 0.5-3.
本発明の難燃性樹脂組成物にはまた、本発明の目的を損なわない範囲において必要に応じ各種添加剤を配合することができる。このような添加剤の例として、酸化防止剤；光安定剤；紫外線吸収剤；カーボンブラックのような顔料；染料；シリコーンオイル、脂肪族系化合物、樹脂ワックスのような滑剤；ブロッキング防止剤；発泡剤；発泡助剤；架橋剤；架橋助剤などを例示することができる。 In the flame-retardant resin composition of the present invention, various additives may be blended as necessary within a range not impairing the object of the present invention. Examples of such additives include antioxidants; light stabilizers; UV absorbers; pigments such as carbon black; dyes; lubricants such as silicone oils, aliphatic compounds and resin waxes; Examples include agents; foaming aids; cross-linking agents; cross-linking aids.
本発明の難燃性樹脂組成物を調製するには、微架橋エチレン−酢酸ビニル共重合体（Ａ）、ポリ酢酸ビニル（Ｂ）、難燃剤（Ｃ）および必要に応じて配合される他の成分を、１軸押出機、２軸押出機、バンバリーミキサー、加圧ニーダー、ロール等の通常の混練機を使用し混練すればよい。また有機過酸化物を配合する場合には、その融点以下の温度で溶融混練すればよい。このようなブレンドは一括して行ってもよく、また段階的に行ってもよい。さらに、成形物の耐熱性を向上させる目的で、例えば有機過酸化物、シラン、電子線照射等により架橋を施しても構わない。 To prepare the flame retardant resin composition of the present invention, a finely crosslinked ethylene-vinyl acetate copolymer (A), polyvinyl acetate (B), a flame retardant (C), and other compounds blended as necessary. The components may be kneaded using a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader, or a roll. Moreover, what is necessary is just to melt-knead at the temperature below the melting | fusing point, when mix | blending an organic peroxide. Such blending may be performed all at once or in stages. Furthermore, for the purpose of improving the heat resistance of the molded product, for example, crosslinking may be performed by organic peroxide, silane, electron beam irradiation or the like.
本発明の難燃性樹脂組成物の調整方法においては、各々の成分の微架橋順序、混合順序には制限はなく、いかなる手順においても調整することができるが、例えば、
（１）エチレン−酢酸ビニル共重合体（Ａ−１）、エチレン・アクリルゴム（Ａ−２）を例えば有機過酸化物の存在下で通常の混練機を使用し混練し、得られた微架橋エチレン−酢酸ビニル共重合体組成物（Ａ）に更にポリ酢酸ビニル（Ｂ）、難燃剤（Ｃ）および必要に応じて配合される他の成分を加えて通常の混練機を使用し混練する方法、
（２）エチレン−酢酸ビニル共重合体（Ａ−１）、エチレン・アクリルゴム（Ａ−２）更にポリ酢酸ビニル（Ｂ）を例えば有機過酸化物の存在下で通常の混練機を使用し混練し、得られた微架橋エチレン−酢酸ビニル共重合体組成物（Ａ）とポリ酢酸ビニル（Ｂ）混合物に難燃剤（Ｃ）および必要に応じて配合される他の成分を加えて通常の混練機を使用し混練する方法、
（３）通常の混練機を使用し有機過酸化物の存在下で予め微架橋されたエチレン−酢酸ビニル共重合体（Ａ−１）と、同様に微架橋されたエチレン・アクリルゴム（Ａ−２）、更にポリ酢酸ビニル（Ｂ）、難燃剤（Ｃ）および必要に応じて配合される他の成分を加えて通常の混練機を使用し混練する方法、
などが挙げられる。
In the method for preparing a flame retardant resin composition of the present invention, the order of micro-crosslinking of each component and the order of mixing are not limited and can be adjusted by any procedure.
(1) Microcrosslinking obtained by kneading ethylene-vinyl acetate copolymer (A-1) and ethylene / acrylic rubber (A-2) using an ordinary kneader in the presence of an organic peroxide, for example. A method of adding a polyvinyl acetate (B), a flame retardant (C) and other components to be blended as necessary to the ethylene-vinyl acetate copolymer composition (A) and kneading using a normal kneader. ,
(2) Kneading ethylene-vinyl acetate copolymer (A-1), ethylene / acrylic rubber (A-2), and polyvinyl acetate (B) in the presence of an organic peroxide using an ordinary kneader. Then, the obtained finely crosslinked ethylene-vinyl acetate copolymer composition (A) and the polyvinyl acetate (B) mixture are added with a flame retardant (C) and other components blended as necessary, and then kneaded normally. Kneading using a machine,
(3) An ethylene-vinyl acetate copolymer (A-1) finely crosslinked in advance in the presence of an organic peroxide using an ordinary kneader, and an ethylene / acrylic rubber (A-) similarly finely crosslinked 2) A method of further kneading using a normal kneader with addition of polyvinyl acetate (B), flame retardant (C) and other components blended as necessary,
Etc.
本発明の難燃性樹脂組成物の用途としての成形品の具体例としては、例えば、玩具、人工芝、マット、止水シート、トンネルシート、ルーフィング等の土木分野、ホース、チューブ等のパイプ用途、パッキング、制振シート等の家電製品、カーペット等の裏打ち材、ドアパネル防水シート、泥よけ、モール等の自動車用途、壁紙、家具、床材、発泡シート等の建材用途、配線ケーブル、通信ケーブル、機器用ケーブル、電源コード、プラグ、耐火ケーブル、制御・計装ケーブル、収縮チューブ等のケーブル用途、粘着テープ等の接着用途等の分野で用いられるものが挙げられる。 Specific examples of molded articles as uses of the flame-retardant resin composition of the present invention include, for example, civil engineering fields such as toys, artificial turf, mats, waterproof sheets, tunnel sheets, roofing, and pipe applications such as hoses and tubes. , Packing, home appliances such as vibration damping sheets, carpet backing, door panel tarpaulins, mudguards, malls and other automotive applications, wallpaper, furniture, flooring, foamed sheet construction materials, wiring cables, communication cables And cable used for equipment cables, power cords, plugs, fireproof cables, control / instrumentation cables, shrinkable tubes, etc., and adhesives such as adhesive tapes.
以下、実施例により本発明をさらに詳細に説明する。本発明はこれらの例によって何ら制限されるものではない。
尚、実施例および比較例において用いた原料は次の通りである。
Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by these examples.
In addition, the raw material used in the Example and the comparative example is as follows.
（１）ＥＶＡ-a：エチレン−酢酸ビニル共重合体（酢酸ビニル含量：４６質量％、ＭＦＲ：１０５ｇ／１０分）
（２）ＥＶＡ-ｂ：酢酸ビニル−エチレン共重合体（酢酸ビニル含量：７０質量％、ムーニー粘度ＭＬ1+4,１００℃：２７）
（３）ＡＥＭ-a :三井・デュポンポリケミカル社製のエチレン・アクリルゴム（ベイマック（ＤＰ）：商品名）
（４）ＡＥＭ-ｂ :三井・デュポンポリケミカル社製のエチレン・アクリルゴム（ベイマック（ＧＬＳ）：商品名）
（５）ＥＭＡ :三井・デュポンポリケミカル社製のエチレン・アクリルゴム（エチレン・メチルアクリレート共重合体、エルバロイ１１２５ＡＣ：商品名）
（６）ＥＰＤＭ：三井化学社製のエチレン・プロピレン・ジエンゴム（三井ＥＰＴ３０１２Ｐ：商品名）
（７）ＰＶＡｃ：電気化学工業社製のポリ酢酸ビニル樹脂［サクノールＳＮ−１７Ａ（重合度１６５０）：商品名］
（８）パーオキサイドー１：アルキルパーオキシエステル、分子量：２１６．３、活性酸素量：７．１８％、半減期：７７℃（１０Ｈｒ、半減期温度の測定溶剤；ドデカン）
（９）パーオキサイドー２：ジアルキルパーオキサイド、分子量：２７０．４、活性酸素量：５．８０％、半減期：１１７℃（１０Ｈｒ、半減期温度の測定溶剤；デカン）
（１０）酸化防止剤：チバスペシャルティケミカルズ社製（イルガノックス１０１０：商品名）
（１１）難燃剤：協和化学工業社製の水酸化マグネシウム（キスマ５Ｌ：商品名）
(1) EVA-a: ethylene-vinyl acetate copolymer (vinyl acetate content: 46% by mass, MFR: 105 g / 10 min)
(2) EVA-b: vinyl acetate-ethylene copolymer (vinyl acetate content: 70 mass%, Mooney viscosity ML1 + 4, 100 ° C .: 27)
(3) AEM-a: Ethylene acrylic rubber (Baymac (DP): trade name) manufactured by Mitsui DuPont Polychemicals
(4) AEM-b: Ethylene acrylic rubber manufactured by Mitsui DuPont Polychemicals (Baymac (GLS): trade name)
(5) EMA: Ethylene / acrylic rubber (ethylene / methyl acrylate copolymer, Elvalloy 1125AC: trade name) manufactured by Mitsui DuPont Polychemical Co., Ltd.
(6) EPDM: Ethylene / propylene / diene rubber manufactured by Mitsui Chemicals (Mitsui EPT3012P: trade name)
(7) PVAc: polyvinyl acetate resin [Sacnol SN-17A (degree of polymerization 1650): trade name] manufactured by Denki Kagaku Kogyo Co., Ltd.
(8) peroxide 1: alkyl peroxy ester, molecular weight: 216.3, active oxygen content: 7.18%, half-life: 77 ° C. (10 Hr, solvent for measuring half-life temperature; dodecane)
(9) Peroxide-2: Dialkyl peroxide, molecular weight: 270.4, active oxygen content: 5.80%, half-life: 117 ° C. (10 Hr, solvent for measuring half-life temperature; decane)
(10) Antioxidant: Ciba Specialty Chemicals (Irganox 1010: trade name)
(11) Flame retardant: Magnesium hydroxide (Kisuma 5L: trade name) manufactured by Kyowa Chemical Industry Co., Ltd.
（ａ）メルトフローレイト（ＭＦＲ）
ＪＩＳ Ｋ ７２１０（１９９９年）法に従い、１９０℃、２，１６０ｇ荷重又は１０ｋｇ荷重で測定した。
(A) Melt flow rate (MFR)
According to the method of JIS K 7210 (1999), the measurement was performed at 190 ° C., 2,160 g load or 10 kg load.
（ｂ）燃焼性
ＵＬ９４垂直燃焼試験法に従った（スガ試験機社製）。尚、試料片の厚みは０．５ｍｍとした。
（ｃ）酢酸ビニル含有量
ＪＩＳ Ｋ ７１９２（１９９９年）法に従って測定した。
(B) Flammability According to UL94 vertical combustion test method (made by Suga Test Instruments Co., Ltd.). The thickness of the sample piece was 0.5 mm.
(C) Vinyl acetate content Measured according to JIS K 7192 (1999) method.
（ｄ）加工性
加圧ニ−ダ−混練槽及びロ−タ−への樹脂付着性を下記の基準で目視評価した。
・付着はほとんど見られない：○
・付着しても簡単に剥ぎ取れる：△
・著しい付着がある：×
(D) Workability The resin adhesion to the pressure kneader kneading tank and the rotor was visually evaluated according to the following criteria.
-Almost no adhesion: ○
-Easy to peel off even if attached: △
・ There is remarkable adhesion: ×
（ｅ）低温特性
組成物の脆化温度を測定し、下記の基準で評価した。
・−１５℃以下：◎
・−１０℃以下〜−１５℃未満：○
・−１０℃未満：×
脆化温度は、以下の方法で測定した。
ＪＩＳ Ｋ７２１６−１９８０（Ａ形）法に従って測定した。
(E) Low temperature characteristics The embrittlement temperature of the composition was measured and evaluated according to the following criteria.
--15 ° C or less: ◎
--10 ° C or lower to lower than -15 ° C: ○
-Less than -10 ° C: ×
The embrittlement temperature was measured by the following method.
It was measured according to JIS K7216-1980 (Type A) method.
（ｆ）耐溶剤性：
アセトンに浸した際のクラック発生状況、溶解、膨潤状況を下記の基準で目視評価した。
・クラックは見られない：○
・小さなクラックが若干見られる（溶解、膨潤なし）：△
・大きなクラックが発生又は溶解する、又は、膨潤する：×
アセトンへの浸漬は、以下の要領で行った。
ビ−カ−にアセトンを注ぎ（室温）、次に試験片（ＪＩＳ Ｋ７２１６−１９８０、Ａ形）を３分間浸して取り出し、外観を目視観察した。
(F) Solvent resistance:
The crack generation state, dissolution, and swelling state when immersed in acetone were visually evaluated according to the following criteria.
・ No cracks are seen: ○
-Some small cracks are seen (no dissolution or swelling): △
Large cracks are generated or dissolved, or swell: x
Immersion in acetone was performed as follows.
Acetone was poured into the beaker (room temperature), and then a test piece (JIS K7216-1980, type A) was immersed for 3 minutes and removed, and the appearance was visually observed.
（調製例１）
上記エチレン−酢酸ビニル共重合体（ＥＶＡ−a）１００質量部、有機過酸化物（パーオキサイドー１）０．２５質量部をヘンシェルミキサーで均一にブレンドした後、単軸押出機（樹脂温度１８０℃）を用いて微架橋ＥＶＡ（樹脂１）を作製した。樹脂１の配合と得られた架橋エチレン−酢酸ビニル共重合体のメルトフローレートを表１に示す。
(Preparation Example 1)
After 100 parts by mass of the ethylene-vinyl acetate copolymer (EVA-a) and 0.25 parts by mass of organic peroxide (Peroxide 1) were uniformly blended with a Henschel mixer, a single screw extruder (resin temperature 180 ° C.) A micro-crosslinked EVA (Resin 1) was prepared using Table 1 shows the blending of resin 1 and the melt flow rate of the obtained crosslinked ethylene-vinyl acetate copolymer.
（調製例２）
上記エチレン−酢酸ビニル共重合体（ＥＶＡ−ａ）７５質量部、エチレン・アクリルゴム（ＡＥＭ−ｂ）２０質量部、エチレン・メチルアクリレート（ＥＭＡ）５質量部をバンバリ−ミキサ−で溶融混練した後にペレタイズし、次いで有機過酸化物（パーオキサイドー２）０．８質量部をさらに添加してヘンシェルミキサーで均一にブレンドした後、単軸押出機（樹脂温度１８０℃）を用いて微架橋ＥＶＡ（樹脂２）を作製した。樹脂２の配合と得られた微架橋エチレン−酢酸ビニル共重合体のメルトフローレートを表１に示す。
(Preparation Example 2)
After melt-kneading 75 parts by mass of the ethylene-vinyl acetate copolymer (EVA-a), 20 parts by mass of ethylene / acrylic rubber (AEM-b) and 5 parts by mass of ethylene / methyl acrylate (EMA) with a Banbury mixer. After pelletizing, 0.8 parts by weight of organic peroxide (Peroxide 2) was further added and blended uniformly with a Henschel mixer, and then finely crosslinked EVA (resin 2) using a single screw extruder (resin temperature 180 ° C.). ) Was produced. Table 1 shows the blending of resin 2 and the melt flow rate of the resulting micro-crosslinked ethylene-vinyl acetate copolymer.
（調製例３）
上記エチレン・アクリルゴム（ＡＥＭ−a）１００質量部と有機過酸化物（パーオキサイドー２）０．４質量部を、４０℃に設定したゴムロ−ルで均一にブレンドした後、１８０℃に設定したプレスで１５分間架橋させ、さらにペレタイズして微架橋エチレン・アクリルゴム（樹脂３）を作製した。樹脂３の配合と得られた微架橋エチレン・アクリルゴムのメルトフローレートを表１に示す。
(Preparation Example 3)
100 parts by mass of ethylene / acrylic rubber (AEM-a) and 0.4 parts by mass of organic peroxide (Peroxide 2) were uniformly blended with a rubber roll set at 40 ° C., and then set at 180 ° C. For 15 minutes and further pelletized to produce a finely crosslinked ethylene / acrylic rubber (resin 3). Table 1 shows the composition of resin 3 and the melt flow rate of the resulting micro-crosslinked ethylene / acrylic rubber.
（調整例４）
上記エチレン−酢酸ビニル共重合体（ＥＶＡ−a）１００質量部、有機過酸化物（パーオキサイドー１）０．１５質量部をヘンシェルミキサーで均一にブレンドした後、単軸押出機（樹脂温度１８０℃）を用いて微架橋ＥＶＡ（樹脂４）を作製した。樹脂４の配合と得られた架橋エチレン−酢酸ビニル共重合体のメルトフローレートを表１に示す。
(Adjustment example 4)
After 100 parts by mass of the ethylene-vinyl acetate copolymer (EVA-a) and 0.15 parts by mass of organic peroxide (Peroxide 1) were uniformly blended with a Henschel mixer, a single screw extruder (resin temperature 180 ° C.) A micro-crosslinked EVA (resin 4) was prepared using Table 1 shows the formulation of resin 4 and the melt flow rate of the obtained crosslinked ethylene-vinyl acetate copolymer.
（実施例１）
調製例１で得られた微架橋ＥＶＡ（樹脂１）、ＰＶＡｃ、難燃剤および酸化防止剤を、表２に示す配合量（質量部）でヘンシエルミキサーで均一にブレンドした後、加圧ニーダー（樹脂温度１９５℃）で１０分間溶融ブレンドし、ペレタイズした後にプレスシ−ト（１６０℃×予熱５分×加圧５分×冷却５分）を作製した。得られた難燃性樹脂組成物の加工性及び諸物性を表２に示す。
Example 1
The finely crosslinked EVA (resin 1), PVAc, flame retardant and antioxidant obtained in Preparation Example 1 were uniformly blended with a Henschel mixer in the blending amounts (parts by mass) shown in Table 2, and then a pressure kneader ( After melt blending for 10 minutes at a resin temperature of 195 ° C. and pelletizing, a press sheet (160 ° C. × preheating 5 minutes × pressurization 5 minutes × cooling 5 minutes) was produced. Table 2 shows the processability and various physical properties of the obtained flame-retardant resin composition.
（実施例２）
表２に示す実施例１の配合量（質量部）に替えて、調製例１で得られた微架橋ＥＶＡ（樹脂１）、調整例３で得られた微架橋エチレン・アクリルゴム（樹脂３）、ＰＶＡｃ、難燃剤および酸化防止剤を表２に示す配合量（質量部）で配合した以外は実施例１と同様にして、得られた難燃性樹脂組成物の加工性及び諸物性を表２に示す。
(Example 2)
Instead of the blending amount (parts by mass) of Example 1 shown in Table 2, the finely crosslinked EVA obtained in Preparation Example 1 (Resin 1) and the finely crosslinked ethylene / acrylic rubber obtained in Preparation Example 3 (Resin 3) , PVAc, flame retardants and antioxidants were blended in the blending amounts (parts by mass) shown in Table 2 in the same manner as in Example 1 to show the workability and various physical properties of the obtained flame retardant resin composition. It is shown in 2.
（実施例３）
表２に示す実施例１の配合量（質量部）に替えて、調製例２で得られた微架橋ＥＶＡ（樹脂２）、ＰＶＡｃ、難燃剤および酸化防止剤を表２に示す配合量（質量部）で配合した以外は実施例１と同様にして、得られた難燃性樹脂組成物の加工性及び諸物性を表２に示す。
(Example 3)
It replaces with the compounding quantity (mass part) of Example 1 shown in Table 2, The compounding quantity (mass) shown in Table 2 about the micro bridge | crosslinking EVA (resin 2), PVAc, flame retardant, and antioxidant which were obtained by the preparation example 2. Table 2 shows the workability and various physical properties of the obtained flame-retardant resin composition in the same manner as in Example 1 except that the components were blended in (Part).
（実施例４）
表２に示す実施例１の配合量（質量部）に替えて、調製例４で得られた微架橋ＥＶＡ（樹脂４）、ＰＶＡｃ、難燃剤および酸化防止剤を表２に示す配合量（質量部）で配合した以外は実施例１と同様にして、得られた難燃性樹脂組成物の加工性及び諸物性を表２に示す。
Example 4
It replaces with the compounding quantity (mass part) of Example 1 shown in Table 2, The compounding quantity (mass) shown in Table 2 about the micro bridge | crosslinking EVA (resin 4), PVAc, the flame retardant, and antioxidant which were obtained in the preparation example 4. Table 2 shows the workability and various physical properties of the obtained flame-retardant resin composition in the same manner as in Example 1 except that the components were blended in (Part).
（実施例５）
表２に示す実施例１の配合量（質量部）に替えて、調製例１で得られた微架橋ＥＶＡ（樹脂１）、ＡＥＭ−ａ、ＰＶＡｃ、難燃剤および酸化防止剤を表２に示す配合量（質量部）で配合した以外は実施例１と同様にして、得られた難燃性樹脂組成物の加工性及び諸物性を表２に示す。
(Example 5)
Table 2 shows the micro-crosslinked EVA (resin 1), AEM-a, PVAc, flame retardant, and antioxidant obtained in Preparation Example 1 instead of the compounding amount (parts by mass) of Example 1 shown in Table 2. Table 2 shows the workability and various physical properties of the obtained flame-retardant resin composition in the same manner as in Example 1 except that the blending amount (parts by mass) was blended.
（比較例１）
表２に示す実施例１の配合量（質量部）に替えて、調製例１で得られた微架橋ＥＶＡ（樹脂１）、ＰＶＡｃ、難燃剤および酸化防止剤を表３に示す配合量（質量部）で配合した以外は実施例１と同様にして、得られた難燃性樹脂組成物の加工性及び諸物性を表３に示す。
(Comparative Example 1)
It replaces with the compounding quantity (mass part) of Example 1 shown in Table 2, The compounding quantity (mass) shown in Table 3 about the micro bridge | crosslinking EVA (resin 1), PVAc, flame retardant, and antioxidant which were obtained by the preparation example 1. Table 3 shows the workability and various physical properties of the obtained flame-retardant resin composition in the same manner as in Example 1 except that the components were blended in (Part).
（比較例２）
表２に示す実施例１の配合量（質量部）に替えて、調製例１で得られた微架橋ＥＶＡ（樹脂１）、調整例３で得られた微架橋エチレン・アクリルゴム（樹脂３）、難燃剤および酸化防止剤を表３に示す配合量（質量部）で配合した以外は実施例１と同様にして、得られた難燃性樹脂組成物の加工性及び諸物性を表３に示す。
(Comparative Example 2)
Instead of the blending amount (parts by mass) of Example 1 shown in Table 2, the finely crosslinked EVA obtained in Preparation Example 1 (Resin 1) and the finely crosslinked ethylene / acrylic rubber obtained in Preparation Example 3 (Resin 3) Table 3 shows the workability and various physical properties of the obtained flame-retardant resin composition in the same manner as in Example 1 except that the flame retardant and the antioxidant were blended in the blending amounts (parts by mass) shown in Table 3. Show.
（比較例３）
表２に示す実施例１の配合量（質量部）に替えて、ＥＶＡ−ｂ、難燃剤および酸化防止剤を表３に示す配合量（質量部）で配合した以外は実施例１と同様にして、得られた難燃性樹脂組成物の加工性及び諸物性を表３に示す。
(Comparative Example 3)
It replaces with the compounding quantity (mass part) of Example 1 shown in Table 2, and it is the same as that of Example 1 except having mix | blended EVA-b, the flame retardant, and antioxidant with the compounding quantity (mass part) shown in Table 3. Table 3 shows the processability and various physical properties of the obtained flame-retardant resin composition.
（比較例４）
表２に示す実施例１の配合量（質量部）に替えて、ＥＰＤＭ、ＰＶＡ−ｃ、難燃剤および酸化防止剤を表３に示す配合量（質量部）で配合した以外は実施例１と同様にして、得られた難燃性樹脂組成物の加工性及び諸物性を表３に示す。
(Comparative Example 4)
It replaces with the compounding quantity (mass part) of Example 1 shown in Table 2, and is Example 1 except having mix | blended EPDM, PVA-c, a flame retardant, and antioxidant with the compounding quantity (mass part) shown in Table 3. Similarly, Table 3 shows the workability and various physical properties of the obtained flame-retardant resin composition.
本発明により提供される難燃性樹脂組成物は、引っ張り強さ等の機械物性に優れ、しかも柔軟性と難燃性のバランスに優れ、加工性にも優れたエチレン−酢酸ビニル共重合体の微架橋物を含む難燃性樹脂組成物である。
本発明により、エチレン−酢酸ビニル共重合体の本来有する諸物性を実質的に、損なうことなく優れた難燃性が付与された難燃性樹脂組成物が提供される。
本発明により提供される難燃性樹脂組成物は、とくにＵＬ耐炎性試験規格において、薄肉の０．５ｍｍという過酷な条件下でもＶ−１レベルを達成することが可能な難燃性樹脂組成物であり、柔軟性、耐溶剤性も備えているので、各種成形方法によって種々の成形品に加工して使用することができる。
The flame retardant resin composition provided by the present invention is an ethylene-vinyl acetate copolymer having excellent mechanical properties such as tensile strength, excellent balance between flexibility and flame retardancy, and excellent workability. It is a flame retardant resin composition containing a finely crosslinked product.
According to the present invention, there is provided a flame retardant resin composition to which excellent flame retardancy is imparted without substantially impairing various physical properties of an ethylene-vinyl acetate copolymer.
The flame-retardant resin composition provided by the present invention is a flame-retardant resin composition capable of achieving the V-1 level even under severe conditions of 0.5 mm, especially in the UL flame resistance test standard. In addition, since it has flexibility and solvent resistance, it can be processed into various molded products by various molding methods.
Claims (7)
エチレン・アクリルゴム（ａ−２）が、ムーニー粘度（ＭＬ1+4、１００℃）が１０〜７０であり、エチレンと３０〜６５重量％の（メタ）アクリル酸エステルとからなる二元共重合体またはさらに０．３〜７重量％の架橋サイトとなり得るモノマーを含む多元共重合体であって、エチレン−酢酸ビニル共重合体（ａ−１）とエチレン・アクリルゴム（ａ−２）の合計量１００質量部に対し、５０〜５質量部の範囲で含有されており、
ポリ酢酸ビニル（Ｂ）の重合度が６００〜２，０００であり、（Ａ）と（Ｂ）の合計量１００質量部に対し、６０〜１０質量部の範囲にあり、
難燃剤（Ｃ）が水酸化マグネシウムまたは水酸化アルミニウムであって、微架橋エチレン-酢酸ビニル共重合体（Ａ）とポリ酢酸ビニル（Ｂ）の合計量１００質量部に対して７５〜１８０質量部の範囲である難燃性樹脂組成物。Melt flow rate obtained by finely crosslinking an ethylene-vinyl acetate copolymer (a-1) having a vinyl acetate unit content (JIS K7192 method: 1999) of 43 mass% to 47 mass% produced by a high pressure polymerization method (JIS K7210: 1999 method, 190 ° C., weight 2.160 kg) 0.01 to 0.6 g / 10 min of slightly cross-linked ethylene-vinyl acetate copolymer (A) and ethylene / acrylic rubber (a-2) ) Non-crosslinked product or finely crosslinked product, polyvinyl acetate (B) and flame retardant (C),
A binary copolymer of ethylene / acrylic rubber (a-2) having a Mooney viscosity (ML1 + 4, 100 ° C.) of 10 to 70 and comprising ethylene and 30 to 65% by weight of (meth) acrylic acid ester Or a multi-component copolymer containing a monomer capable of becoming a crosslinking site in an amount of 0.3 to 7% by weight, the total amount of the ethylene-vinyl acetate copolymer (a-1) and the ethylene-acrylic rubber (a-2) It is contained in the range of 50 to 5 parts by mass with respect to 100 parts by mass,
The degree of polymerization of polyvinyl acetate (B) is 600 to 2,000, and in the range of 60 to 10 parts by mass with respect to 100 parts by mass of the total amount of (A) and (B) ,
The flame retardant (C) is magnesium hydroxide or aluminum hydroxide, and is 75 to 180 parts by mass with respect to 100 parts by mass of the total amount of the finely crosslinked ethylene-vinyl acetate copolymer (A) and polyvinyl acetate (B). Flame retardant resin composition that is in the range .
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007077440 | 2007-03-23 | ||
| JP2007077440 | 2007-03-23 | ||
| JP2007309242 | 2007-11-29 | ||
| JP2007309242 | 2007-11-29 | ||
| PCT/JP2008/055381 WO2008123177A1 (en) | 2007-03-23 | 2008-03-24 | Flame-retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP4425346B2 true JP4425346B2 (en) | 2010-03-03 |
| JPWO2008123177A1 JPWO2008123177A1 (en) | 2010-07-15 |
Family
ID=39830674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009509088A Active JP4425346B2 (en) | 2007-03-23 | 2008-03-24 | Flame retardant resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4425346B2 (en) |
| WO (1) | WO2008123177A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2012023174A1 (en) * | 2010-08-17 | 2013-10-28 | 住江織物株式会社 | Waterproof sheet with excellent flame resistance |
| JP6782222B2 (en) * | 2017-12-27 | 2020-11-11 | 古河電気工業株式会社 | Silane-crosslinked acrylic rubber molded article and its manufacturing method, silane-crosslinked acrylic rubber composition, and oil-resistant products |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6326906A (en) * | 1986-07-18 | 1988-02-04 | 日立電線株式会社 | Flame resisting electrically insulating composition |
| DE3875781D1 (en) * | 1987-04-24 | 1992-12-17 | Bayer Ag | FLAME-RESISTANT, HALOGEN-FREE THERMOPLASTIC POLYMER. |
| JPS63289717A (en) * | 1987-05-21 | 1988-11-28 | Hitachi Cable Ltd | Nonflammable electrical insulating composition |
| JP3815315B2 (en) * | 2001-12-05 | 2006-08-30 | 東ソー株式会社 | Microcrosslinkable ethylene-vinyl acetate copolymer and process for producing the same |
| JP4737362B2 (en) * | 2003-12-24 | 2011-07-27 | 東ソー株式会社 | Ethylene-vinyl acetate copolymer and flame retardant resin composition |
| JP2006089603A (en) * | 2004-09-24 | 2006-04-06 | Dainippon Ink & Chem Inc | Resin composition for coating and insulated wire produced by using the same |
| JP5030083B2 (en) * | 2006-08-30 | 2012-09-19 | 三井・デュポンポリケミカル株式会社 | Crosslinked ethylene-vinyl acetate copolymer |
-
2008
- 2008-03-24 JP JP2009509088A patent/JP4425346B2/en active Active
- 2008-03-24 WO PCT/JP2008/055381 patent/WO2008123177A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2008123177A1 (en) | 2010-07-15 |
| WO2008123177A1 (en) | 2008-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5005349B2 (en) | Flame retardant, halogen-free composition | |
| JP2014028967A (en) | Thermoplastic halogen-free flame-retardant formulations | |
| JP2006131720A (en) | Flame retardant resin composition for mixing with silane-crosslinkable polyolefin and molding thereof | |
| JPWO2018180689A1 (en) | Flame-retardant crosslinked resin molded article and method for producing the same, silane masterbatch, masterbatch mixture and molded article thereof, and flame-retardant product | |
| JPWO2007026735A1 (en) | Flame retardant resin composition | |
| WO2000040651A1 (en) | Halogen-free flame-retardant resin composition | |
| JP2007277530A (en) | Flame-retardant resin composition and insulated wire coated with the resin composition | |
| JP5030083B2 (en) | Crosslinked ethylene-vinyl acetate copolymer | |
| JP2008239901A (en) | Flame-retardant resin composition and insulated electric wire coated with the resin composition | |
| JP5275547B2 (en) | Method for producing flame retardant resin composition | |
| JP2005298807A (en) | Flame retardant resin composition | |
| JP2978524B2 (en) | Flame retardant foam composition | |
| JP4425346B2 (en) | Flame retardant resin composition | |
| CN101328294B (en) | Plastic for low-smoke halogen-free high flame-retardant electric wire and cable | |
| JP2004156026A (en) | Flame-retardant resin composition | |
| JP2005002245A (en) | Silane-crosslinked flame retardant resin molded product | |
| JP4737362B2 (en) | Ethylene-vinyl acetate copolymer and flame retardant resin composition | |
| JP2003012864A (en) | Method for producing flame-retardant polymer composition and flame-retardant polymer composition | |
| JP2003160704A (en) | Flame-retardant resin composition and wiring material using the same | |
| JPH03269029A (en) | Flame retardant expandable composition, flame retardant foam and production thereof | |
| WO2008038709A1 (en) | Flame-retardant resin composition | |
| JPH0423854A (en) | Resin composition for covering electric wire | |
| JP2007302907A (en) | Crosslinkable thermoplastic resin composition, method for producing the same and molded product therefrom | |
| JP2006182875A (en) | Flame-retardant thermoplastic resin composition | |
| JP2006083322A (en) | Crosslinked thermoplastic flame-retardant resin composition, method for producing the same and its molded article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20091208 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20091208 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4425346 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121218 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121218 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131218 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |