JP2006249311A - Flame-retardant resin composition - Google Patents
Flame-retardant resin composition Download PDFInfo
- Publication number
- JP2006249311A JP2006249311A JP2005069070A JP2005069070A JP2006249311A JP 2006249311 A JP2006249311 A JP 2006249311A JP 2005069070 A JP2005069070 A JP 2005069070A JP 2005069070 A JP2005069070 A JP 2005069070A JP 2006249311 A JP2006249311 A JP 2006249311A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- weight
- hydrogenated block
- block copolymer
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 36
- 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 abstract description 35
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 229920001400 block copolymer Polymers 0.000 claims abstract description 54
- 229920001577 copolymer Polymers 0.000 claims abstract description 31
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 239000011256 inorganic filler Substances 0.000 claims abstract description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 11
- 229920001038 ethylene copolymer Polymers 0.000 claims description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 238000005984 hydrogenation reaction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 13
- 229920001971 elastomer Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 8
- 150000001993 dienes Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000003679 aging effect Effects 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CBYAPCMTYUIARL-UHFFFAOYSA-N 4-phenylbut-3-en-1-amine Chemical compound NCCC=CC1=CC=CC=C1 CBYAPCMTYUIARL-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 101100389815 Caenorhabditis elegans eva-1 gene Proteins 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 101100185402 Mus musculus Mug1 gene Proteins 0.000 description 1
- 101100185408 Mus musculus Mug2 gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920006361 Polyflon Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 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
- 125000003700 epoxy group Chemical group 0.000 description 1
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- 150000004820 halides Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 229920006285 olefinic elastomer Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical group [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000005068 thioepoxy group Chemical group S(O*)* 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、エチレン系共重合体を用いた非ハロゲンの難燃樹脂組成物に関する。さらに詳しくは、本発明は、エチレン系共重合体、変性水素添加ブロック共重合体および無機充填剤を主成分とした柔軟性に富んだ難燃樹脂組成物に関する。そして、本発明の難燃樹脂組成物は、柔軟性、耐熱性（加熱老化性、加熱変形性等）に優れ、且つ耐寒性に優れることから、電線の被覆材料等をはじめ、軟質塩化ビニル樹脂が使用されている各用途に好適に用いることができる。 The present invention relates to a non-halogen flame retardant resin composition using an ethylene copolymer. More specifically, the present invention relates to a flame retardant resin composition having a high flexibility mainly composed of an ethylene copolymer, a modified hydrogenated block copolymer, and an inorganic filler. And since the flame retardant resin composition of the present invention is excellent in flexibility, heat resistance (heat aging resistance, heat deformability, etc.) and excellent in cold resistance, soft vinyl chloride resin including wire coating materials, etc. Can be suitably used for each application in which is used.
家電部品、自動車部品等の電線の被覆材料として、一般に難燃性に優れた塩化ビニル樹脂が使用されている。軟質塩化ビニル樹脂は、柔軟性があり、且つ耐熱性や耐寒性に優れる。しかしながら、分子中に塩素を多量に含むために環境に対する負荷が懸念され、その代替材料が求められている。
近年、オレフィン系樹脂を中心に非塩化ビニル樹脂系難燃材料の開発が進められており、ポリエチレン等のオレフィン系樹脂に水和金属酸化物を配合した難燃性樹脂組成物（例えば、特許文献１参照）が開示されている。また、熱可塑性エラストマーとポリオレフィンに無機難燃剤を配合した組成物（例えば、特許文献２参照）、オレフィン系エラストマー、変性ポリスチレン、スチレン系エラストマー、プロピレン系樹脂に金属水和物を配合した難燃性樹脂組成物（例えば、特許文献３参照）などが開示されている。
In recent years, development of non-vinyl chloride resin-based flame retardant materials centered on olefin resins has been promoted, and flame retardant resin compositions in which hydrated metal oxides are blended with olefin resins such as polyethylene (for example, patent documents) 1) is disclosed. In addition, a composition in which an inorganic flame retardant is blended with a thermoplastic elastomer and polyolefin (see, for example, Patent Document 2), a flame retardant in which a metal hydrate is blended with an olefin elastomer, modified polystyrene, styrene elastomer, or propylene resin. A resin composition (see, for example, Patent Document 3) is disclosed.
本発明は、優れた難燃性を有するとともに、塩化ビニル樹脂に匹敵する柔軟性と耐熱性、耐寒性を有する難燃樹脂組成物を提供することを課題とする。
前述したオレフィン系樹脂を中心とした非塩化ビニル樹脂系難燃材料は、硬質の樹脂や多量の金属水和物を含有している。そのため、柔軟性に乏しく、耐熱性、耐寒性等が低下した組成物となってしまう。
An object of the present invention is to provide a flame retardant resin composition having excellent flame retardancy and flexibility, heat resistance, and cold resistance comparable to a vinyl chloride resin.
The non-vinyl chloride resin-based flame retardant material centered on the olefin resin described above contains a hard resin and a large amount of metal hydrate. Therefore, the composition is poor in flexibility and has reduced heat resistance, cold resistance and the like.
このような状況下、本発明者らは、上記の問題を解決するために鋭意検討を重ねた。その結果、本発明者らは、エチレン系共重合体と特定の変性水素添加ブロック共重合体と無機充填剤を主成分とした組成物によって、上記課題が解決できることを見いだし、この知見に基づいて本発明を完成した。
すなわち、本発明は、
１．（ａ）エチレン系共重合体１７〜３５重量％、（ｂ）変性水素添加ブロック共重合体３〜１５重量％および（ｃ）無機充填剤５０〜８０重量％を含む難燃樹脂組成物、
２．成分（ｂ）が、ビニル芳香族炭化水素含有量１０重量％以上２０重量％未満である水素添加ブロック共重合体にα、β−不飽和カルボン酸又はその誘導体が結合してなる変性水素添加ブロック共重合体であることを特徴とする上記１に記載の難燃樹脂組成物、
３．成分（ａ）が、エチレン−酢酸ビニル共重合体であることを特徴とする上記１または２のいずれかに記載の難燃樹脂組成物、
４．成分（ｃ）が、金属水酸化物であることを特徴とする上記１〜３のいずれかに記載の難燃樹脂組成物、
５．ＪＩＳＫ６２５１準拠の１００％伸び時の引張弾性率（１００％Ｍｏ）が、１０ＭＰａ以下であることを特徴とする上記１〜４のいずれかに記載の難燃樹脂組成物、
である。
Under such circumstances, the present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above-mentioned problems can be solved by a composition mainly composed of an ethylene-based copolymer, a specific modified hydrogenated block copolymer, and an inorganic filler, and based on this finding The present invention has been completed.
That is, the present invention
1. A flame retardant resin composition comprising (a) 17 to 35% by weight of an ethylene copolymer, (b) 3 to 15% by weight of a modified hydrogenated block copolymer, and (c) 50 to 80% by weight of an inorganic filler,
2. A modified hydrogenated block in which an α, β-unsaturated carboxylic acid or derivative thereof is bonded to a hydrogenated block copolymer in which the component (b) has a vinyl aromatic hydrocarbon content of 10% by weight or more and less than 20% by weight. The flame retardant resin composition according to the above 1, which is a copolymer,
3. The flame retardant resin composition according to any one of the above 1 or 2, wherein the component (a) is an ethylene-vinyl acetate copolymer,
4). The flame retardant resin composition according to any one of the above 1 to 3, wherein the component (c) is a metal hydroxide,
5. The flame retardant resin composition according to any one of the above 1 to 4, wherein a tensile elastic modulus (100% Mo) at 100% elongation according to JISK6251 is 10 MPa or less,
It is.
本発明の難燃樹脂組成物は、難燃性でありながら、柔軟性、耐熱性、耐寒性に優れる。この特性を活かし、電線の被覆材料等をはじめ、軟質塩化ビニル樹脂が使用されている各用途に好適に用いることができる。 The flame retardant resin composition of the present invention is excellent in flexibility, heat resistance, and cold resistance while being flame retardant. Taking advantage of this characteristic, it can be suitably used for various uses in which a soft vinyl chloride resin is used, such as a coating material for electric wires.
以下、本発明について詳細に説明する。
本発明の成分（ａ）はエチレン系共重合体である。本発明に用いることのできるエチレン系共重合体は、エチレンを５０重量％以上含有するエチレンとこれと共重合可能な他のモノマーとの共重合体、例えば、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−エチルアクリレート共重合体、エチレン−メタクリレート共重合体、エチレン−ブチルアクリレート共重合体、エチレン−プロピレン共重合体などが挙げられる。これらは、単独で用いても２種以上を混合して用いてもよい。そして、柔軟性および難燃性の点では、エチレン−酢酸ビニル共重合体が好ましい。また、柔軟性向上という点では酢酸ビニル含有量が２５〜４５重量％のエチレン−酢酸ビニル共重合体が特に好ましい。
Hereinafter, the present invention will be described in detail.
Component (a) of the present invention is an ethylene copolymer. The ethylene-based copolymer that can be used in the present invention is a copolymer of ethylene containing 50% by weight or more of ethylene and another monomer copolymerizable therewith, such as ethylene-vinyl acetate copolymer, ethylene -Acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-propylene copolymer and the like. These may be used alone or in admixture of two or more. And in the point of a softness | flexibility and a flame retardance, an ethylene-vinyl acetate copolymer is preferable. In terms of improving flexibility, an ethylene-vinyl acetate copolymer having a vinyl acetate content of 25 to 45% by weight is particularly preferable.
本発明で用いるエチレン系共重合体のメルトフローレートは加工性、機械的特性の点から０．１〜３０ｇ／１０分が好ましく、０．５〜１５ｇ／１０分がさらに好ましい。
本発明の成分（ｂ）は、官能基を含有する分子単位が結合した変性水素添加ブロック共重合体である。該成分を用いることが、本願の目的である柔軟性、耐熱性、耐寒性を付与するための重要な要素となっている。
官能基を有する分子単位が結合する前のベースとなる水素添加ブロック共重合体は、ビニル芳香族炭化水素−共役ジエンブロック共重合体を水素添加したブロック共重合体である。
はじめに、ベースとなる水素添加ブロック共重合体について説明する。水添ブロック共重合体は、ビニル芳香族炭化水素と共役ジエンとを含む非水添ブロック共重合体を水素添加して得られる。該非水添ブロック共重合体の製造方法については特に制限はなく、公知の方法を用いることができる。例えば、炭化水素溶媒中で有機アルカリ金属化合物等の重合開始剤を用いてアニオンリビング重合により製造することができる。そして、得られた非水添共重合体を水素添加することにより、水添ブロック共重合体が得られる。尚、水添触媒に特に限定はなく、公知の水添触媒を用いることができる。
The melt flow rate of the ethylene copolymer used in the present invention is preferably from 0.1 to 30 g / 10 minutes, more preferably from 0.5 to 15 g / 10 minutes, from the viewpoint of processability and mechanical properties.
Component (b) of the present invention is a modified hydrogenated block copolymer in which molecular units containing functional groups are bonded. Use of this component is an important factor for imparting flexibility, heat resistance, and cold resistance, which are the purposes of the present application.
The hydrogenated block copolymer as a base before the molecular units having a functional group are bonded is a block copolymer obtained by hydrogenating a vinyl aromatic hydrocarbon-conjugated diene block copolymer.
First, the base hydrogenated block copolymer will be described. The hydrogenated block copolymer is obtained by hydrogenating a non-hydrogenated block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene. There is no restriction | limiting in particular about the manufacturing method of this non-hydrogenated block copolymer, A well-known method can be used. For example, it can be produced by anionic living polymerization using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent. And the hydrogenated block copolymer is obtained by hydrogenating the obtained non-hydrogenated copolymer. The hydrogenation catalyst is not particularly limited, and a known hydrogenation catalyst can be used.
本発明のブロック共重合体において、使用するビニル芳香族炭化水素の例として、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ジビニルベンゼン、１，１−ジフェニルエチレン、Ｎ，Ｎ−ジメチル−ｐ−アミノエチルスチレン、Ｎ，Ｎ−ジエチル−ｐ−アミノエチルスチレンなどが挙げられる。これらのうち特に好ましいのはスチレンである。また、使用する共役ジエンは１対の共役二重結合を有するジオレフィンである。共役ジエンの例として、１，３−ブタジエン、２−メチル−１，３−ブタジエン（即ちイソプレン）、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエンが挙げられる。これらのうち特に好ましいのは１，３−ブタジエンである。 Examples of the vinyl aromatic hydrocarbon used in the block copolymer of the present invention include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-. Aminoethyl styrene, N, N-diethyl-p-aminoethyl styrene, etc. are mentioned. Of these, styrene is particularly preferred. The conjugated diene used is a diolefin having a pair of conjugated double bonds. Examples of conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene (ie, isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1, Examples include 3-pentadiene and 1,3-hexadiene. Of these, 1,3-butadiene is particularly preferred.
本発明で用いる水素添加ブロック共重合体の構造に関しては特に限定はなく、いかなる構造のものでも使用できる。水添ブロック共重合体の一態様として、下記式で表されるような構造を有するものが挙げられる。
（Ａ−Ｂ）ｎ+1 、 Ａ−（Ｂ−Ａ）ｎ 、
Ｂ−（Ａ−Ｂ）ｎ+1 、
［（Ａ−Ｂ）ｎ ］ｍ −Ｘ、 ［（Ｂ−Ａ）ｎ−Ｂ］ｍ−Ｘ、
［（Ａ−Ｂ）ｎ−Ａ］ｍ−Ｘ、 ［（Ｂ−Ａ）ｎ+1 ］ｍ−Ｘ
上記式において、各Ａはそれぞれ独立してビニル芳香族炭化水素からなる重合体ブロックを表す。各Ｂはそれぞれ独立して、共役ジエン化合物からなる重合体ブロックを水添して得られる水添重合体ブロックを表す。各ブロックの境界は必ずしも明瞭に区別されていなくてもよい。各ｎはそれぞれ独立して１以上の整数、好ましくは１〜５の整数である。各ｍはそれぞれ独立して２以上の整数、好ましくは２〜１１の整数である。各Ｘはそれぞれ独立してカップリング剤の残基又は多官能開始剤の残基を表す。この中でも、ビニル芳香族ブロックＡを２個以上有する水添ブロック共重合体の変性品を用いた組成物が、耐熱性の点で好ましい。
The structure of the hydrogenated block copolymer used in the present invention is not particularly limited, and any structure can be used. One embodiment of the hydrogenated block copolymer includes one having a structure represented by the following formula.
(AB) n + 1 , A- (BA) n ,
B- (A-B) n + 1 ,
[(AB) n ] m- X, [(BA) n- B] m- X,
[(AB) n- A] m- X, [(BA) n + 1 ] m- X.
In the above formula, each A independently represents a polymer block comprising a vinyl aromatic hydrocarbon. Each B independently represents a hydrogenated polymer block obtained by hydrogenating a polymer block composed of a conjugated diene compound. The boundary of each block does not necessarily have to be clearly distinguished. Each n is independently an integer of 1 or more, preferably an integer of 1 to 5. Each m is independently an integer of 2 or more, preferably an integer of 2 to 11. Each X independently represents a residue of a coupling agent or a residue of a polyfunctional initiator. Among these, a composition using a modified product of a hydrogenated block copolymer having two or more vinyl aromatic blocks A is preferable in terms of heat resistance.
本発明で用いる変性水素添加ブロック共重合体中のビニル芳香族炭化水素含有量は、耐熱性と耐寒性の点から１０重量％以上２０重量％未満が好ましく、１２重量％〜１９重量％がより好ましく、１４重量％〜１８重量％が特に好ましい。
また、本発明で用いる変性水素添加ブロック共重合体において、水添前の共役ジエン化合物重合体ブロック中の共役ジエン単量体単位のビニル結合量（１，２−結合、３，４−結合及び１，４−結合の結合様式で組み込まれている）の中、１，２−結合及び３，４−結合で組み込まれているものの割合は、耐寒性の点で４０％〜８０％が好ましく、４５〜６０％がより好ましい。
The vinyl aromatic hydrocarbon content in the modified hydrogenated block copolymer used in the present invention is preferably 10% by weight or more and less than 20% by weight from the viewpoint of heat resistance and cold resistance, and more preferably 12% by weight to 19% by weight. Preferably, 14% by weight to 18% by weight is particularly preferable.
In the modified hydrogenated block copolymer used in the present invention, the amount of vinyl bonds (1,2-bond, 3,4-bond and conjugated diene monomer unit in the conjugated diene compound polymer block before hydrogenation) The ratio of those incorporated by 1,2-bond and 3,4-bond is preferably 40% to 80% in terms of cold resistance, 45-60% is more preferable.
また、本発明で用いる変性水素添加ブロック共重合体の重量平均分子量は、２万〜３０万が好ましく、３〜２０万がさらに好ましい。重量平均分子量が上記範囲にあることにより、機械的強度と成形加工性とのバランスに優れた組成物が得られる。
また、本発明で用いる変性水素添加ブロック共重合体の該共役ジエン化合物に基づく二重結合の水添率は、７５〜１００％が好ましい。水添率は、耐熱性の点から、好ましくは８０〜１００％、更に好ましくは８５〜１００％、特に好ましくは９０〜１００％である。なお、水添ブロック共重合体におけるビニル芳香族化合物の二重結合の水添率に関しては特に限定はないが、水添率は好ましくは５０％以下、更に好ましくは３０％以下、特に好ましくは２０％以下である。
Further, the weight average molecular weight of the modified hydrogenated block copolymer used in the present invention is preferably 20,000 to 300,000, and more preferably 3 to 200,000. When the weight average molecular weight is in the above range, a composition having an excellent balance between mechanical strength and moldability can be obtained.
Further, the hydrogenation rate of the double bond based on the conjugated diene compound of the modified hydrogenated block copolymer used in the present invention is preferably 75 to 100%. The hydrogenation rate is preferably 80 to 100%, more preferably 85 to 100%, and particularly preferably 90 to 100% from the viewpoint of heat resistance. The hydrogenation rate of the double bond of the vinyl aromatic compound in the hydrogenated block copolymer is not particularly limited, but the hydrogenation rate is preferably 50% or less, more preferably 30% or less, and particularly preferably 20 % Or less.
上記で得られた水添ブロック共重合体を変性することによって、本願発明で使用する変性水素添加ブロック共重合体が得られる。変性方法や変性剤の種類については、特に限定されない。その一例として、α，β−不飽和カルボン酸又はその誘導体、例えばその無水物、エステル化物、アミド化物、イミド化物等の官能基含有化合物でグラフト変性した水素添加ブロック共重合体を挙げることができる。α、β−不飽和カルボン酸又はその誘導体の具体例としては、無水マレイン酸、マレイン酸イミド、アクリル酸又はそのエステル、メタアクリル酸又はそのエステル、エンド−シス−ビシクロ〔２，２，１〕−５−ヘプテン−２，３−ジカルボン酸又はその無水物が挙げられる。 The modified hydrogenated block copolymer used in the present invention is obtained by modifying the hydrogenated block copolymer obtained above. There are no particular limitations on the modification method and the type of the modifier. As an example, there can be mentioned a hydrogenated block copolymer graft-modified with a functional group-containing compound such as an α, β-unsaturated carboxylic acid or a derivative thereof, for example, an anhydride, esterified product, amidated product or imidized product thereof. . Specific examples of α, β-unsaturated carboxylic acid or derivatives thereof include maleic anhydride, maleic imide, acrylic acid or ester thereof, methacrylic acid or ester thereof, endo-cis-bicyclo [2,2,1]. -5-heptene-2,3-dicarboxylic acid or its anhydride.
α、β−不飽和カルボン酸又はその誘導体等の添加量は、水素添加ブロック共重合体１００重量部当たり、通常０．０２〜１０重量部、好ましくは０．１〜５重量部である。グラフト変性する場合の反応温度は、好ましくは１００〜３００℃、より好ましくは１２０〜２８０℃である。グラフト変性する方法の詳細については、例えば、特開昭６２−７９２１１号公報を参照できる。
また、別の例として末端変性した水添ブロック共重合体を挙げることができる。たとえば、有機リチウム化合物を重合触媒として得たベース共重合体のリビング末端に、官能基含有化合物（以後、変性剤とも云う）を反応させることにより変性水添ブロック共重合体が得られる。
The amount of α, β-unsaturated carboxylic acid or its derivative added is usually 0.02 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the hydrogenated block copolymer. The reaction temperature in the case of graft modification is preferably 100 to 300 ° C, more preferably 120 to 280 ° C. For details of the graft modification method, reference can be made to, for example, JP-A No. 62-79211.
Another example is a hydrogenated block copolymer having a terminal modification. For example, a modified hydrogenated block copolymer can be obtained by reacting a functional group-containing compound (hereinafter also referred to as a modifier) with the living terminal of a base copolymer obtained using an organolithium compound as a polymerization catalyst.
官能基含有変性剤基の例として、水酸基、カルボニル基、チオカルボニル基、酸ハロゲン化物基、酸無水物基、カルボキシル基、チオカルボキシル酸基、アルデヒド基、チオアルデヒド基、カルボン酸エステル基、アミド基、スルホン酸基、スルホン酸エステル基、リン酸基、リン酸エステル基、アミノ基、イミノ基、シアノ基、ピリジル基、キノリン基、エポキシ基、チオエポキシ基、スルフィド基、イソシアネート基、イソチオシアネート基、ハロゲン化ケイ素基、シラノール基、アルコキシシラン基、ハロゲン化スズ基、アルコキシスズ基、フェニルスズ基等からなる群より選ばれる少なくとも１種の官能基を有するものが挙げられる。上記の官能基のうち、カルボニル基、カルボキシル基、酸無水物基、水酸基、アミノ基が好ましい。 Examples of functional group-containing modifier groups include hydroxyl groups, carbonyl groups, thiocarbonyl groups, acid halide groups, acid anhydride groups, carboxyl groups, thiocarboxylate groups, aldehyde groups, thioaldehyde groups, carboxylate ester groups, amides Group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, cyano group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group And those having at least one functional group selected from the group consisting of a halogenated silicon group, a silanol group, an alkoxysilane group, a halogenated tin group, an alkoxytin group, a phenyltin group, and the like. Of the above functional groups, a carbonyl group, a carboxyl group, an acid anhydride group, a hydroxyl group, and an amino group are preferable.
変性剤の具体例としては、例えば特公平４−３９４９５号公報（米国特許第５，１１５，０３５号に対応）やＪＰ０３／０２２２２号公報（国際公開）に記載された末端変性処理剤を用いることができる。具体的には、テトラグリシジルメタキシレンジアミン、テトラグリシジル−１，３−ビスアミノメチルシクロヘキサン、ε−カプロラクトン、４−メトキシベンゾフェノン、γ−グリシドキシエチルトリメトキシシラン、γ−グリシドキシブチルトリメトキシシラン、１，３−ジメチル−２−イミダゾリジノン、１，３−ジエチル−２−イミダゾリジノン、Ｎ−メチルピロリドンなどが挙げられる。
尚、エチレン−ブチレン共重合体、エチレン−ヘキセン共重合体、エチレン−オクテン共重合体等のオレフィン系エラストマーを変性した変性オレフィン系エラストマーを用いた難燃樹脂組成物は、耐熱老化性が著しく劣った組成物となる。
As specific examples of the denaturing agent, for example, a terminal denaturing treatment agent described in JP-B-4-39495 (corresponding to US Pat. No. 5,115,035) or JP03 / 02222 (international publication) is used. Can do. Specifically, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, 4-methoxybenzophenone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxybutyltrimethoxy Examples thereof include silane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N-methylpyrrolidone and the like.
In addition, the flame retardant resin composition using a modified olefin elastomer obtained by modifying an olefin elastomer such as an ethylene-butylene copolymer, an ethylene-hexene copolymer, or an ethylene-octene copolymer has extremely poor heat aging resistance. Composition.
本発明の成分（ｃ）は、無機充填剤である。無機充填剤としては、金属水酸化物、金属炭酸化物、金属酸化物、シリカ系無機充填剤等が挙げられる。
この中でも、難燃性の効果の点で特に有用なのが金属水酸化物である。金属水酸化物の例としては、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水和珪酸アルミニウム、水和珪酸マグネシウム、塩基性炭酸マグネシウム、ハイドロタルサイト、水酸化カルシウム、水酸化バリウム、酸化錫の水和物、硼砂等の無機金属化合物の水和物等であり、中でも水酸化マグネシウムが好ましい。また、水酸化マグネシウムでもシランカップリング剤又は脂肪酸等で粒子表面に表面処理したものを用いるとよい。ポリマーへの分散性を高めるためにアミノシランやメタクリロキシシラン等のカップリング剤で表面処理した水酸化マグネシウムが市販されている。具体例としては、キスマ５Ｌ（協和化学工業社）が挙げられる。
Component (c) of the present invention is an inorganic filler. Examples of the inorganic filler include metal hydroxides, metal carbonates, metal oxides, silica-based inorganic fillers, and the like.
Of these, metal hydroxides are particularly useful in terms of flame retardancy. Examples of metal hydroxides include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, tin oxide And hydrates of inorganic metal compounds such as borax, among which magnesium hydroxide is preferred. Further, magnesium hydroxide whose surface is treated with a silane coupling agent or a fatty acid may be used. Magnesium hydroxide surface-treated with a coupling agent such as aminosilane or methacryloxysilane in order to enhance dispersibility in the polymer is commercially available. A specific example is Kisuma 5L (Kyowa Chemical Industry Co., Ltd.).
また、金属炭酸化物としては、炭酸カルシウム、炭酸マグネシウムなどが挙げられる。
また、金属酸化物としては、化学式ＭＸＯＹ（Ｍは金属原子、Ｘ、Ｙはそれぞれ独立して１〜６の整数）を構成単位の主成分とする固体粒子であり、例えばアルミナ、酸化チタン、酸化マグネシウム、酸化亜鉛等が挙げられる。
また、シリカ系無機充填剤は、化学式ＳｉＯ２を構成単位の主成分とする固体粒子であり、例えば、シリカ、クレイ、タルク、カオリン、マイカ、ウォラストナイト、モンモリロナイト、ゼオライト、ガラス繊維等の無機繊維状物質などが挙げられる。
本発明に係わる難燃樹脂組成物において、各成分の配合比率は、成分（ａ）エチレン系共重合体が１７〜３５重量％、成分（ｂ）変性水添ブロック共重合体が３〜１５重量％、成分（ｃ）無機充填剤が５０〜８０重量％である。
Examples of the metal carbonate include calcium carbonate and magnesium carbonate.
Further, the metal oxide is a solid particle whose main component is a chemical unit M X O Y (M is a metal atom, X and Y are each independently an integer of 1 to 6), such as alumina, oxidation, and the like. Examples include titanium, magnesium oxide, and zinc oxide.
Further, silica-based inorganic filler is a solid particle composed mainly of structural units of the formula SiO 2, for example, silica, clay, talc, kaolin, mica, wollastonite, montmorillonite, zeolite, inorganic, such as glass fibers Examples include fibrous materials.
In the flame retardant resin composition according to the present invention, the blending ratio of each component is such that the component (a) ethylene-based copolymer is 17 to 35% by weight, and the component (b) modified hydrogenated block copolymer is 3 to 15% by weight. %, Component (c) inorganic filler is 50 to 80% by weight.
成分（ａ）が１７重量％よりも少ないと、引張強度等の機械的特性が劣る組成物となり、また３５重量％を越えると難燃性に劣る組成物となる。
また、成分（ｂ）は、柔軟性、耐熱性、耐寒性を改良する重要な成分である。その配合量が３重量％よりも少ないと、これらの特性が劣る組成物となり、また１５重量％を越えると加工性に劣る組成物となる。
また、成分（ｃ）が５０重量％よりも少ないと、難燃性に劣る組成物となり、また８０重量％を越えると柔軟性や引張強度等の機械的特性が劣る組成物となる。
本願発明の難燃樹脂組成物は、柔軟性に富むことが特徴である。組成物の引張弾性率（１００％Ｍｏ）が１０Ｍｐａ以下が好ましく、８ＭＰａ以下がより好ましい。
When the component (a) is less than 17% by weight, the composition has poor mechanical properties such as tensile strength, and when it exceeds 35% by weight, the composition has poor flame retardancy.
The component (b) is an important component that improves flexibility, heat resistance, and cold resistance. When the blending amount is less than 3% by weight, these properties are inferior, and when it exceeds 15% by weight, the workability is inferior.
When the amount of component (c) is less than 50% by weight, the composition is inferior in flame retardancy, and when it exceeds 80% by weight, the composition is inferior in mechanical properties such as flexibility and tensile strength.
The flame-retardant resin composition of the present invention is characterized by being rich in flexibility. The tensile elastic modulus (100% Mo) of the composition is preferably 10 Mpa or less, and more preferably 8 MPa or less.
本発明の難燃樹脂組成物は、望むならば、その他の成分、ゴム状重合体、熱可塑性樹脂、添加剤等を含んでいてもよい。
ゴム状重合体の例としては、スチレン−ブタジエンブロック共重合体及びその水添物、スチレン−イソプレンブロック共重合体及びその水添物等のスチレン系エラストマー、１，２−ポリブタジエン、オレフィン系エラストマー、ブチルゴム等が挙げられる。
熱可塑性樹脂の例としては、ポリテトラフルオロエチレン、共役ジエンとビニル芳香族とのブロック共重合樹脂及びその水添物、ポリスチレン、ゴム変性スチレン系樹脂等のスチレン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂等が挙げられる。特にポリテトラフルオロエチレンを配合すると、燃焼時におけるドリップ（滴下）性を改良した組成物が得られる。
The flame retardant resin composition of the present invention may contain other components, a rubber-like polymer, a thermoplastic resin, an additive and the like, if desired.
Examples of rubbery polymers include styrene-butadiene block copolymers and hydrogenated products thereof, styrene-based elastomers such as styrene-isoprene block copolymers and hydrogenated products thereof, 1,2-polybutadiene, olefinic elastomers, Examples include butyl rubber.
Examples of thermoplastic resins include polytetrafluoroethylene, block copolymer resins of conjugated dienes and vinyl aromatics and hydrogenated products thereof, polystyrene, styrene resins such as rubber-modified styrene resins, polyamide resins, polyester resins Examples thereof include resins and polycarbonate resins. In particular, when polytetrafluoroethylene is blended, a composition having improved drip (dripping) properties during combustion can be obtained.
添加剤は、ゴム状重合体等の配合に一般的に配合されるものであれば特に限定はない。添加剤の例として、「ゴム・プラスチック配合薬品」（ラバーダイジェスト社編）などに記載された添加剤が挙げられる。具体例として、硫黄、有機過酸化物等の架橋剤；加硫促進剤；パラフィンオイル、ポリブテン等のゴム用軟化剤；カーボンブラック、酸化鉄等の顔料；ステアリン酸、ベヘニン酸、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸マグネシウム、エチレンビスステアロアミド等の滑剤；離型剤；有機ポリシロキサン、ヒンダードフェノール系酸化防止剤、りん系熱安定剤等の酸化防止剤；ヒンダードアミン系光安定剤；ベンゾトリアゾール系紫外線吸収剤；難燃剤；帯電防止剤、有機繊維、ガラス繊維、炭素繊維、金属ウィスカ等の補強剤；着色剤などである。これらの添加剤は、２種以上を混合して用いてもよい。 The additive is not particularly limited as long as it is generally blended with a rubbery polymer or the like. Examples of the additive include those described in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.). Specific examples include crosslinking agents such as sulfur and organic peroxides; vulcanization accelerators; rubber softeners such as paraffin oil and polybutene; pigments such as carbon black and iron oxide; stearic acid, behenic acid, zinc stearate, Lubricants such as calcium stearate, magnesium stearate, and ethylene bisstearamide; mold release agents; antioxidants such as organic polysiloxanes, hindered phenol antioxidants, and phosphorus heat stabilizers; hindered amine light stabilizers; benzo Examples include triazole ultraviolet absorbers; flame retardants; antistatic agents, reinforcing agents such as organic fibers, glass fibers, carbon fibers, and metal whiskers; and colorants. These additives may be used in combination of two or more.
本発明の難燃樹脂組成物は、その製造方法には特に限定はなく、公知の方法が利用できる。例えば、バンバリーミキサー、単軸スクリュー押出機、２軸スクリュー押出機、コニーダ、多軸スクリュー押出機等の一般的な混和機を用いた溶融混練方法等を用いることができる。
本発明の難燃樹脂組成物を成形品として使用する場合、成形方法としては、押出成形、射出成形、中空成形、圧空成形、真空成形、発泡成形、複層押出成形、複層射出成形、スラッシュ成形及びカレンダー成形などを用いることができる。
また、本発明の難燃樹脂組成物は、難燃性が必要とされる様々な用途に用いることができる。たとえば、家電部品、自動車部品等の電線の被覆材料、電力ケーブル、通信ケーブル、送電用ケーブルなどの被覆用材料や建築材料等に好適に用いることができる。
The method for producing the flame retardant resin composition of the present invention is not particularly limited, and a known method can be used. For example, a melt kneading method using a general blender such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, or a multi-screw extruder can be used.
When the flame retardant resin composition of the present invention is used as a molded product, the molding method may be extrusion molding, injection molding, hollow molding, pressure molding, vacuum molding, foam molding, multilayer extrusion molding, multilayer injection molding, slash Molding and calendering can be used.
Moreover, the flame-retardant resin composition of the present invention can be used in various applications where flame retardancy is required. For example, it can be suitably used for coating materials such as household electrical appliance parts and automobile parts, coating materials such as power cables, communication cables, and power transmission cables, and building materials.
以下、製造例、実施例及び比較例により本発明を具体的に説明するが、本発明はこれら
の例によって何ら限定されるものではない。
Ｉ．変性水素添加ブロック共重合体の作製
使用する変性水素添加ブロック共重合体は、まず非水添共重合体を作製、その後水添、変性反応して得た。この非水添共重合体を、しばしば「ベース非水添共重合体」と称する。
尚、水素添加ブロック共重合体等の特性は次の方法で測定した。
Ｉ−１）スチレン含有量
スチレン含有量は、ベース非水添共重合体を検体として、紫外分光光度計（ＵＶ−２４５０；島津製作所製）を用いて測定した。
Ｉ−２）ジエン部のビニル結合量
ベース非水添共重合体におけるブタジエン重合体ブロックのビニル結合量は、赤外分光光度計（ＦＴ／ＩＲ−２３０；日本分光社製）を用いて測定し、ハンプトン法により算出
した。
Hereinafter, the present invention will be specifically described with reference to production examples, examples, and comparative examples, but the present invention is not limited to these examples.
I. Preparation of modified hydrogenated block copolymer The modified hydrogenated block copolymer to be used was obtained by first preparing a non-hydrogenated copolymer, followed by hydrogenation and modification reaction. This non-hydrogenated copolymer is often referred to as a “base non-hydrogenated copolymer”.
The characteristics of the hydrogenated block copolymer and the like were measured by the following method.
I-1) Styrene content The styrene content was measured using an ultraviolet spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) using the base non-hydrogenated copolymer as a specimen.
I-2) Vinyl Bond Amount of Diene Part The vinyl bond amount of the butadiene polymer block in the base non-hydrogenated copolymer was measured using an infrared spectrophotometer (FT / IR-230; manufactured by JASCO Corporation). Calculated by the Hampton method.
Ｉ−３）重量平均分子量及び分子量分布
水素添加ブロック共重合体の重量平均分子量はベース非水添共重合体の重量平均分子量とほぼ等しいので、水添共重合体の重量平均分子量はベース非水添共重合体の重量平均分子量として求める。ベース非水添共重合体の重量平均分子量は、ＧＰＣにより測定した（米国ウォーターズ社製の装置を用いた）。溶媒としてテトラヒドロフランを用い、温度４０℃で測定した。分子量が既知の市販の標準単分散ポリスチレン系ゲルを用いて作成した検量線を使用し、ＧＰＣクロマトグラムから重量平均分子量を求めた。
また、上記ＧＰＣクロマトグラムから数平均分子量を求めた。
分子量分布は、得られた重量平均分子量（Ｍｗ）の得られた数平均分子量（Ｍｎ）に対
する比として求める。
Ｉ−４）共役ジエン化合物の二重結合の水添率
水添率は、核磁気共鳴装置（ＤＰＸ−４００；ドイツ国ＢＲＵＫＥＲ社製）を用いて測
定した。
Ｉ−５）変性量
無水マレイン酸の付加量は、ナトリウムメチラートによる滴定により求めた。
I-3) Weight average molecular weight and molecular weight distribution Since the weight average molecular weight of the hydrogenated block copolymer is substantially equal to the weight average molecular weight of the base non-hydrogenated copolymer, the weight average molecular weight of the hydrogenated copolymer is the base non-aqueous. The weight average molecular weight of the additive copolymer is determined. The weight average molecular weight of the base non-hydrogenated copolymer was measured by GPC (using an apparatus manufactured by Waters, USA). Tetrahydrofuran was used as a solvent, and measurement was performed at a temperature of 40 ° C. The weight average molecular weight was calculated | required from the GPC chromatogram using the calibration curve created using the commercially available standard monodisperse polystyrene type gel with known molecular weight.
The number average molecular weight was determined from the GPC chromatogram.
The molecular weight distribution is determined as a ratio of the obtained weight average molecular weight (Mw) to the obtained number average molecular weight (Mn).
I-4) Hydrogenation rate of double bond of conjugated diene compound The hydrogenation rate was measured using a nuclear magnetic resonance apparatus (DPX-400; manufactured by BRUKER, Germany).
I-5) Modification Amount The amount of maleic anhydride added was determined by titration with sodium methylate.
製造例１；水素添加ブロック共重合体１の作製
内容積が１００リットルの攪拌装置及びジャケット付き槽型反応器を用いて、共重合を以下の方法で行った。
シクロヘキサン１０重量部を反応器に仕込んで温度７０℃に調整した後、ｎ−ブチルリ
チウムを全モノマー（反応器に投入したブタジエンモノマー及びスチレンモノマーの総量
）の重量に対して０．１１重量％、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン
（以下ＴＭＥＤＡと称する）をｎ−ブチルリチウム１モルに対して０．５モル添加し、そ
の後モノマーとしてスチレン７．５重量部を含有するシクロヘキサン溶液（モノマー濃度２２重量％）を約３分間かけて添加し、反応器内温を約７０℃に調整しながら３０分間反応させた。
Production Example 1 Production of Hydrogenated Block Copolymer 1 Copolymerization was carried out by the following method using a stirrer having an internal volume of 100 liters and a tank reactor with a jacket.
After 10 parts by weight of cyclohexane was charged into the reactor and adjusted to a temperature of 70 ° C., n-butyllithium was 0.11% by weight with respect to the weight of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), N, N, N ′, N′-tetramethylethylenediamine (hereinafter referred to as TMEDA) is added in an amount of 0.5 mol to 1 mol of n-butyllithium, and then cyclohexane solution containing 7.5 parts by weight of styrene as a monomer. (Monomer concentration 22% by weight) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the internal temperature of the reactor to about 70 ° C.
次に、ブタジエン８５重量部を含有するシクロヘキサン溶液（モノマー濃度２２重量％）を６０分間かけて一定速度で連続的に反応器に供給した。この間、反応器内温は約７０℃になるように調整した。
その後、更にモノマーとしてスチレン７．５重量部を含有するシクロヘキサン溶液（モノマー濃度２２重量％）を約３分間かけて添加し、反応器内温を約７０℃に調整しながら３０分間反応させ、ブロック共重合体を得た。得られた共重合体のスチレン含有量は１５重量％であり、ブタジエン部のビニル量は５５％であった。また、共重合体の重量平均分子量は、９．８万、分子量分布は１．１であった。
Next, a cyclohexane solution (monomer concentration: 22% by weight) containing 85 parts by weight of butadiene was continuously fed to the reactor at a constant rate over 60 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C.
Thereafter, a cyclohexane solution containing 7.5 parts by weight of styrene as a monomer (monomer concentration 22% by weight) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the internal temperature of the reactor to about 70 ° C. A copolymer was obtained. The resulting copolymer had a styrene content of 15% by weight and a vinyl content in the butadiene portion of 55%. The copolymer had a weight average molecular weight of 98,000 and a molecular weight distribution of 1.1.
次に、得られたブロック共重合体に、下記水添触媒を共重合体の重量に対してチタンとして１００重量ｐｐｍ添加し、水素圧０．７ＭＰａ、温度６５℃で水添反応を行った。反応終了後にメタノールを添加し、次に安定剤としてオクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートを重合体の重量に対して０．３重量％添加し、水素添加ブロック共重合体１を得た。水添率は９９％であった。
＜水添触媒の調製：窒素置換した反応容器に乾燥、精製したシクロヘキサン１リットルを仕込み、ビス（η5−シクロペンタジエニル）チタニウムジクロリド１００ミリモルを添加し、十分に攪拌しながらトリメチルアルミ二ウム２００ミリモルを含むｎ−ヘキサン溶液を添加して、室温にて約３日間反応させた。＞
Next, 100 wt ppm of the following hydrogenation catalyst as titanium with respect to the weight of the copolymer was added to the obtained block copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. After completion of the reaction, methanol is added, and then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer is added in an amount of 0.3% by weight based on the weight of the polymer. A hydrogenated block copolymer 1 was obtained. The hydrogenation rate was 99%.
<Preparation of hydrogenation catalyst: 1 liter of dried and purified cyclohexane was charged into a nitrogen-substituted reaction vessel, 100 mmol of bis (η 5 -cyclopentadienyl) titanium dichloride was added, and trimethylaluminum was stirred well. An n-hexane solution containing 200 mmol was added and reacted at room temperature for about 3 days. >
製造例２；水素添加ブロック共重合体２の作製
製造例１と同様に共重合を行った。 但し、ＴＭＥＤＡの添加量を０．４モルに、第１ステップで添加するスチレンの量を８．５重量部に、第２ステップで添加するブタジエンの量を８３重量部に、第３ステップで添加するスチレンの量を８．５重量部に変更した。
得られた共重合体のスチレン含有量は１７重量％であり、ブタジエン部のビニル量は４８％であった。また、共重合体の重量平均分子量は、１０．４万、分子量分布は１．１であった。
次に、製造例１と同様の方法で水添反応を行い、水素添加ブロック共重合体２を得た。水添率は９９％であった。
Production Example 2 Production of Hydrogenated Block Copolymer 2 Copolymerization was carried out in the same manner as in Production Example 1. However, the amount of TMEDA added is 0.4 mol, the amount of styrene added in the first step is 8.5 parts by weight, the amount of butadiene added in the second step is 83 parts by weight, and added in the third step. The amount of styrene to be changed was changed to 8.5 parts by weight.
The resulting copolymer had a styrene content of 17% by weight and a vinyl content in the butadiene portion of 48%. The copolymer had a weight average molecular weight of 104,000 and a molecular weight distribution of 1.1.
Next, a hydrogenation reaction was performed in the same manner as in Production Example 1 to obtain a hydrogenated block copolymer 2. The hydrogenation rate was 99%.
製造例３；変性水素添加ブロック共重合体１（ポリマー１）の作製
水添ブロック共重合体１を用い、下記の方法によって変性水素添加ブロック共重合体１（ポリマー１）を作製した。
１００重量部の水素添加ブロック共重合体１に対して、２重量部の無水マレイン酸、０．１重量部のパーヘキサ２５Ｂ＜日本油脂社製＞を均一に混合した後、二軸押出機（装置名；ＰＣＭ−３０＜池貝鉄工社製＞）に供給し、シリンダー温度２４０℃で変性反応を行った。得られた変性水素添加ブロック共重合体から、未反応の無水マレイン酸を加熱減圧除去し、ポリマー１を作製した。尚、ポリマー１の変性量を測定したところ、１．０重量％であった。
製造例４；変性水素添加ブロック共重合体２（ポリマー２）の作製
製造例１と同様にし、水素添加ブロック共重合体２を用いて変性水素添加ブロック共重合体２（ポリマー２）を作製した。ポリマー２の変性量を測定したところ、０．９２重量％であった。
ＩＩ．難燃樹脂組成物の製造
実施例１〜３、比較例１、２において、難燃樹脂組成物を製造した。
Production Example 3 Production of Modified Hydrogenated Block Copolymer 1 (Polymer 1) Using hydrogenated block copolymer 1, modified hydrogenated block copolymer 1 (polymer 1) was produced by the following method.
After 100 parts by weight of the hydrogenated block copolymer 1 were uniformly mixed with 2 parts by weight of maleic anhydride and 0.1 part by weight of Perhexa 25B (manufactured by NOF Corporation), a twin-screw extruder (apparatus Name: PCM-30 (manufactured by Ikekai Tekko Co., Ltd.)), and the modification reaction was performed at a cylinder temperature of 240 ° C. From the resulting modified hydrogenated block copolymer, unreacted maleic anhydride was removed by heating under reduced pressure to prepare polymer 1. The amount of modification of polymer 1 was measured and found to be 1.0% by weight.
Production Example 4 Production of Modified Hydrogenated Block Copolymer 2 (Polymer 2) A modified hydrogenated block copolymer 2 (Polymer 2) was produced using the hydrogenated block copolymer 2 in the same manner as in Production Example 1. . The amount of modification of polymer 2 was measured and found to be 0.92% by weight.
II. Production of flame retardant resin composition In Examples 1 to 3 and Comparative Examples 1 and 2, flame retardant resin compositions were produced.
［実施例１〜３および比較例１、２］
表１に示した配合で各成分を混合、二軸押出機（装置名；ＰＣＭ３０＜池貝鉄工社製＞）で混練し、ペレット化することにより組成物を得た。押出条件は、シリンダー温度が２２０℃、回転数が３００ｒｐｍであった。得られた組成物を圧縮成形して２ｍｍ厚のシートを作成し、このシートを用いて種々の測定を行った。結果を表１に示す。
使用した成分を下記に示す。
（ａ）エチレン系共重合体
・ＥＶＡ−１：エバフレックスＥＶ２７０｛ＶＡ量：２８％、ＭＦＲ：１のエチレン−酢酸ビニル共重合体＜三井・デュポンポリケミカル社製＞｝
・ＥＶＡ−２：エバフレックスＥＶ４０ＬＸ｛ＶＡ量：４１％、ＭＦＲ：２のエチレン−酢酸ビニル共重合体＜三井・デュポンポリケミカル社製＞｝
（ｂ）変性共重合体
ポリマー１：製造例３で作製した変性水素添加ブロック共重合体１を使用
ポリマー２：製造例４で作製した変性水素添加ブロック共重合体２を使用
ポリマー３：タフマーＭＨ５０１０｛無水マレイン酸変性したオレフィン系エラストマー＜三井化学社製＞｝
（ｃ）無機充填剤
水マグ−１：キスマ５Ａ｛ステアリン酸処理した水酸化マグネシウム＜協和化学工業（株）製＞｝
水マグ−２：キスマ５Ｌ｛シランカップリング剤処理した水酸化マグネシウム＜協和化学工業（株）製＞｝
その他成分
ＰＴＦＥ：ポリフロン ＭＰＡ ＦＡ５００｛ポリテトラフルオロエチレン＜ダイキン工業（株）製＞｝
[Examples 1 to 3 and Comparative Examples 1 and 2]
Each component was mixed with the formulation shown in Table 1, kneaded with a twin-screw extruder (device name: PCM30 <manufactured by Ikekai Tekko Co., Ltd.>), and pelletized to obtain a composition. The extrusion conditions were a cylinder temperature of 220 ° C. and a rotation speed of 300 rpm. The obtained composition was compression molded to prepare a sheet having a thickness of 2 mm, and various measurements were performed using this sheet. The results are shown in Table 1.
The components used are shown below.
(A) Ethylene copolymer
EVA-1: EVAFLEX EV270 {VA amount: 28%, MFR: 1 ethylene-vinyl acetate copolymer <Mitsui / DuPont Polychemical Co., Ltd.>}
EVA-2: EVAFLEX EV40LX {VA amount: 41%, MFR: 2 ethylene-vinyl acetate copolymer <Mitsui / DuPont Polychemical Co., Ltd.>}
(B) Modified copolymer Polymer 1: Use modified hydrogenated block copolymer 1 prepared in Production Example 3 Polymer 2: Use modified hydrogenated block copolymer 2 produced in Production Example 4
Polymer 3: Tafmer MH5010 {Maleic anhydride-modified olefin elastomer <Mitsui Chemicals Co., Ltd.}}
(C) Inorganic filler Water mug-1: Kisuma 5A {Stearic acid-treated magnesium hydroxide <Kyowa Chemical Industry Co., Ltd.>}
Water mug-2: Kisuma 5L {magnesium hydroxide treated with silane coupling agent <manufactured by Kyowa Chemical Industry Co., Ltd.>}
Other components PTFE: Polyflon MPA FA500 {Polytetrafluoroethylene <made by Daikin Industries, Ltd.>}
難燃樹脂組成物の物性は次の方法で測定した。
ＩＩ−１）柔軟性(１００％Ｍｏ)、引張強度、伸び
ＪＩＳ Ｋ６２５１に準拠して引張強度と１００％延伸時の応力（１００％Ｍｏ）、破断伸びを測定した。引張速度は５００ｍｍ／ｍｉｎ、測定温度は２３℃であった。１００％Ｍｏは柔軟性の尺度である。１００％Ｍｏが小さいほど柔軟性が良好である。
ＩＩ−２）加熱老化性
サンプル片をオーブンに入れ、１３６℃で１６８時間加熱した。加熱後のサンプルを用い、ＩＩ−１）と同様に引張試験を行った。加熱前の伸びに対する保持率を加熱老化性とした。保持率が１００％に近い程、加熱老化性が優れている。
ＩＩ−３）加熱変形性
ＪＩＳ Ｋ６７２３に準拠して加熱変形試験を行った。条件は、温度１２０℃、荷重１ｋｇ、１時間で行った。変形率（％）が小さい程、加熱変形性が優れる。
ＩＩ−４）耐寒性
シートを−２５℃の条件下に４時間置いた。状態調節後のシートを折り曲げ、耐寒性を割れの有無により判断した。 ・割れない：○
・割れる ：×
ＩＩ−５）難燃性
ＶＷ１に準じた燃焼性試験を行った。
The physical properties of the flame retardant resin composition were measured by the following methods.
II-1) Flexibility (100% Mo), tensile strength, elongation Tensile strength, stress during 100% stretching (100% Mo), and elongation at break were measured according to JIS K6251. The tensile speed was 500 mm / min and the measurement temperature was 23 ° C. 100% Mo is a measure of flexibility. The smaller the 100% Mo, the better the flexibility.
II-2) Heat aging property The sample piece was put into an oven and heated at 136 ° C. for 168 hours. A tensile test was performed in the same manner as II-1) using the sample after heating. The retention with respect to elongation before heating was defined as heat aging property. The closer the retention rate is to 100%, the better the heat aging property.
II-3) Heat Deformability A heat deformation test was performed in accordance with JIS K6723. The conditions were a temperature of 120 ° C., a load of 1 kg, and 1 hour. The smaller the deformation rate (%), the better the heat deformability.
II-4) Cold resistance The sheet was placed under the condition of -25 ° C for 4 hours. The sheet after condition adjustment was bent, and cold resistance was judged by the presence or absence of cracks.・ Do not break: ○
・ Clearance: ×
II-5) Flame retardancy A flammability test according to VW1 was conducted.
本発明の難燃樹脂組成物は、難燃性を有し、且つ柔軟性、耐熱性（加熱老化性、加熱変形性等）、耐寒性に優れる。この特性を活かし、難燃性が必要とされる様々な用途、軟質塩化ビニル樹脂が使用されている各用途に好適に用いることができる。具体的には、家電部品、自動車部品等の電線の被覆材料、電力ケーブル、通信ケーブル、送電用ケーブルなどの被覆用材料や建築材料等に好適に用いることができる。 The flame-retardant resin composition of the present invention has flame retardancy and is excellent in flexibility, heat resistance (heat aging property, heat deformation property, etc.), and cold resistance. Taking advantage of this characteristic, it can be suitably used for various applications where flame retardancy is required and for various applications where a soft vinyl chloride resin is used. Specifically, it can be suitably used as a coating material for electric wires such as home appliance parts and automobile parts, a coating material such as a power cable, a communication cable, and a power transmission cable, a building material, and the like.
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| WO2021241291A1 (en) * | 2020-05-27 | 2021-12-02 | 旭化成株式会社 | Resin composition, method for producing modified hydrogenated block copolymer, and molded object |
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