JP5140234B2 - Polyolefin resin composition - Google Patents
Polyolefin resin composition Download PDFInfo
- Publication number
- JP5140234B2 JP5140234B2 JP2004380528A JP2004380528A JP5140234B2 JP 5140234 B2 JP5140234 B2 JP 5140234B2 JP 2004380528 A JP2004380528 A JP 2004380528A JP 2004380528 A JP2004380528 A JP 2004380528A JP 5140234 B2 JP5140234 B2 JP 5140234B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- polyolefin resin
- resin composition
- weight
- compound
- 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
- 229920005672 polyolefin resin Polymers 0.000 title claims description 67
- 239000011342 resin composition Substances 0.000 title claims description 63
- -1 nitrogen-containing compound Chemical group 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000003063 flame retardant Substances 0.000 claims description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 33
- 239000003963 antioxidant agent Substances 0.000 claims description 25
- 230000003078 antioxidant effect Effects 0.000 claims description 24
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [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 GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 16
- 229960001545 hydrotalcite Drugs 0.000 claims description 16
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 239000004743 Polypropylene Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 5
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001959 inorganic nitrate Inorganic materials 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 33
- 230000032683 aging Effects 0.000 description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 229920001384 propylene homopolymer Polymers 0.000 description 11
- 150000004703 alkoxides Chemical class 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000011949 solid catalyst Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- CHNUOJQWGUIOLD-NFZZJPOKSA-N epalrestat Chemical compound C=1C=CC=CC=1\C=C(/C)\C=C1/SC(=S)N(CC(O)=O)C1=O CHNUOJQWGUIOLD-NFZZJPOKSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000000020 Nitrocellulose Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 238000009863 impact test Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- APNSGVMLAYLYCT-UHFFFAOYSA-N isobutyl nitrite Chemical compound CC(C)CON=O APNSGVMLAYLYCT-UHFFFAOYSA-N 0.000 description 3
- 229920001220 nitrocellulos Polymers 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Chemical class 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- FDBMBOYIVUGUSL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FDBMBOYIVUGUSL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DQEPEVJAZOOFDV-UHFFFAOYSA-O azanium;lanthanum;nitrate Chemical compound [NH4+].[La].[O-][N+]([O-])=O DQEPEVJAZOOFDV-UHFFFAOYSA-O 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-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
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- LNNXFUZKZLXPOF-UHFFFAOYSA-N 2-methylpropyl nitrate Chemical compound CC(C)CO[N+]([O-])=O LNNXFUZKZLXPOF-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- NTHGIYFSMNNHSC-UHFFFAOYSA-N 3-methylbutyl nitrate Chemical compound CC(C)CCO[N+]([O-])=O NTHGIYFSMNNHSC-UHFFFAOYSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- YQYYFFCLWFBMND-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoate Chemical compound C(C)(C)(C)C=1C(=C(C=C(C=1)C)CCC(=O)OCC(C)(C)C1OCC2(CO1)COC(OC2)C(COC(CCC1=C(C(=CC(=C1)C)C(C)(C)C)O)=O)(C)C)O YQYYFFCLWFBMND-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 238000011276 addition treatment Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- RAESLDWEUUSRLO-UHFFFAOYSA-O aminoazanium;nitrate Chemical compound [NH3+]N.[O-][N+]([O-])=O RAESLDWEUUSRLO-UHFFFAOYSA-O 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 229960003116 amyl nitrite Drugs 0.000 description 1
- GUQAPPPKAMUNSP-UHFFFAOYSA-N aniline;nitric acid Chemical compound O[N+]([O-])=O.NC1=CC=CC=C1 GUQAPPPKAMUNSP-UHFFFAOYSA-N 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere 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
- 230000008901 benefit Effects 0.000 description 1
- QFYNEVKGPDCTIF-UHFFFAOYSA-N benzene;2,6-ditert-butylphenol Chemical compound C1=CC=CC=C1.CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O QFYNEVKGPDCTIF-UHFFFAOYSA-N 0.000 description 1
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical compound N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 description 1
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 1
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QQHZPQUHCAKSOL-UHFFFAOYSA-N butyl nitrate Chemical compound CCCCO[N+]([O-])=O QQHZPQUHCAKSOL-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 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
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- IDNUEBSJWINEMI-UHFFFAOYSA-N ethyl nitrate Chemical compound CCO[N+]([O-])=O IDNUEBSJWINEMI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- CRJZNQFRBUFHTE-UHFFFAOYSA-N hydroxylammonium nitrate Chemical compound O[NH3+].[O-][N+]([O-])=O CRJZNQFRBUFHTE-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- GAPFWGOSHOCNBM-UHFFFAOYSA-N isopropyl nitrate Chemical compound CC(C)O[N+]([O-])=O GAPFWGOSHOCNBM-UHFFFAOYSA-N 0.000 description 1
- SKRDXYBATCVEMS-UHFFFAOYSA-N isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 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
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 description 1
- LRMHVVPPGGOAJQ-UHFFFAOYSA-N methyl nitrate Chemical compound CO[N+]([O-])=O LRMHVVPPGGOAJQ-UHFFFAOYSA-N 0.000 description 1
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- JCZMXVGQBBATMY-UHFFFAOYSA-N nitro acetate Chemical compound CC(=O)O[N+]([O-])=O JCZMXVGQBBATMY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Description
本発明は、ポリオレフィン樹脂組成物に関し、詳しくは難燃性と耐熱老化性に優れた結晶性ポリオレフィン樹脂組成物に関する。 The present invention relates to a polyolefin resin composition, and more particularly to a crystalline polyolefin resin composition excellent in flame retardancy and heat aging resistance.
ポリプロピレン樹脂は、成形加工性、表面外観、機械的性質、耐薬品性に優れることにより電気、電子分野、ＯＡ機器、家電製品、住設機器、車輌分野等広い分野に使用されている。これらの製品において、火災の安全性より、難燃性を付与した材料が多く使用されている。難燃性を付与した材料の多くは、難燃性能の面で、一般的にハロゲン系難燃剤が使用されている。近年これらの製品分野において、環境安全性の面で、ハロゲン系難燃剤を使用しない難燃材料が望まれている。
ハロゲン系難燃剤に替わる難燃剤として、金属水和物、例えば水酸化マグネシウム、水酸化アルミニウムをポリプロピレン樹脂に練り込む方法が提案されている。この方法でハロゲン系難燃剤を使用したのと同レベルの難燃性を得るには、ポリプロピレン樹脂１００重量部に対し水酸化マグネシウム及び／又は水酸化アルミニウムを１００重量部以上もの大量添加をする必要があり、外観不良、機械的強度、特に衝撃強度等の物性低下の問題が生じている。
Polypropylene resins are used in a wide range of fields such as electrical, electronic, OA equipment, home appliances, residential equipment, and vehicle fields due to their excellent moldability, surface appearance, mechanical properties, and chemical resistance. In these products, more materials with flame retardancy than fire safety are used. In many of the materials imparted with flame retardancy, halogen flame retardants are generally used in terms of flame retardancy. In recent years, flame retardant materials that do not use halogen flame retardants are desired in these product fields in terms of environmental safety.
As a flame retardant replacing the halogen flame retardant, a method of kneading a metal hydrate such as magnesium hydroxide or aluminum hydroxide into a polypropylene resin has been proposed. In order to obtain the same level of flame retardancy as the halogen flame retardant used in this method, it is necessary to add a large amount of magnesium hydroxide and / or aluminum hydroxide to 100 parts by weight of polypropylene resin. There are problems of deterioration in physical properties such as poor appearance, mechanical strength, particularly impact strength.
非ハロゲン系難燃剤の添加量を抑えつつ、難燃性と樹脂の諸物性を両立させるものとして、ポリオレフィン樹脂、窒素化合物、金属水酸化物、赤燐とカーボンブラックを含む難燃性樹脂組成物（例えば、特許文献１参照。）が提案されている。かかる発明における樹脂組成物は、黒色以外の着色が困難、赤燐臭が残る、といった問題のほか、引張伸びの低下が生じるなど物性低下の防止が不充分である問題が残り、使用する用途が限定されてしまう。
また、硝酸塩と金属水和化合物（例えば、水酸化アルミニウム、水酸化マグネシウム）からなる非ハロゲン系難燃剤が提案されている（例えば、特許文献２〜４参照。）。かかる難燃剤を添加した樹脂組成物は、難燃剤の添加量が低くても高い難燃性が発現し適度な機械的強度は得られるが、耐熱老化性が著しく低下し、工業部品等耐熱部品用途で求められる耐熱性を充分満足するには到っていない。
Moreover, the non-halogen flame retardant which consists of nitrate and a metal hydration compound (for example, aluminum hydroxide, magnesium hydroxide) is proposed (for example, refer patent documents 2-4). The resin composition to which such a flame retardant is added exhibits high flame retardancy even if the amount of the flame retardant added is low, and an appropriate mechanical strength is obtained, but the heat aging resistance is significantly reduced, and heat resistant parts such as industrial parts The heat resistance required for the application has not been sufficiently satisfied.
本発明は、上記問題点に鑑み、難燃性、衝撃強度に優れ、しかも耐熱性（特に、耐熱老化性）に優れた、幅広い用途に使用できるポリオレフィン樹脂組成物を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a polyolefin resin composition that is excellent in flame retardancy and impact strength and excellent in heat resistance (particularly heat aging resistance) and can be used for a wide range of applications. .
本発明者は、上記課題を解決するために鋭意検討した結果、結晶性ポリオレフィンに含窒素化合物と金属水和化合物を含むノンハロゲン系難燃剤、中和剤、特定の酸化防止剤を、それぞれ特定量配合した樹脂組成物は、難燃性、衝撃強度、耐熱性（特に、耐熱老化性）に優れたノンハロゲン系難燃性ポリオレフィン樹脂組成物となり得ることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a non-halogen flame retardant containing a nitrogen-containing compound and a metal hydrate compound in a crystalline polyolefin, a neutralizing agent, and a specific antioxidant, respectively, in specific amounts. The compounded resin composition was found to be a non-halogen flame retardant polyolefin resin composition excellent in flame retardancy, impact strength, and heat resistance (particularly heat aging resistance), and the present invention was completed.
すなわち、本発明の第１の発明によれば、結晶性ポリオレフィン樹脂（Ａ）１００重量部に対し、金属硝酸塩または有機若しくは無機硝酸化合物から選ばれる少なくとも一種の含窒素化合物と金属水和化合物とを含む難燃剤（Ｂ）２５〜６０重量部、並びに、成分（Ａ）と成分（Ｂ）の混合物１００重量部に対し、ハイドロタルサイトを含む中和剤（Ｃ）０．５〜１０重量部、リン系酸化防止剤（Ｄ）０．０５〜２重量部、及び分子量が８００以下の１，１，３−トリス（２−メチル−４−ハイドロキシ−５−ｔ−ブチルフェニル）ブタン、ｎ−オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ハイドロキシフェニル）−プロピオネート及び３，９−ビス［２−〔３−（３−ｔ−ブチル−４−ハイドロキシ−５−メチルフェニル）プロピオニルオキシ〕−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカンからなる群から選ばれる少なくとも一種のヒンダードフェノール系酸化防止剤（Ｅ）０．０５〜２重量部を含むことを特徴とする結晶性ポリオレフィン樹脂組成物が提供される。 That is, according to the first invention of the present invention, with respect to 100 parts by weight of the crystalline polyolefin resin (A), at least one nitrogen-containing compound selected from a metal nitrate or an organic or inorganic nitrate compound and a metal hydrate compound are added. The flame retardant (B) containing 25-60 parts by weight, and the neutralizing agent (C) 0.5-10 parts by weight containing hydrotalcite with respect to 100 parts by weight of the mixture of the component (A) and the component (B), Phosphorous antioxidant (D) 0.05 to 2 parts by weight, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane having a molecular weight of 800 or less , n-octadecyl -3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate and 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate Niruokishi] -1,1-dimethylethyl] -2,4,8,10-spiro [5.5] at least one hindered phenol antioxidant selected from the group consisting of undecane (E) 0.05 A crystalline polyolefin resin composition comprising ˜2 parts by weight is provided.
また、本発明の第２の発明によれば、第１の発明において、成分（Ｂ）が、水酸化アルミニウム又は水酸化マグネシウムから選ばれる少なくとも一種の金属水酸化物を含むことを特徴とする結晶性ポリオレフィン樹脂組成物が提供される。 According to the second invention of the present invention, in the first invention, the component (B) contains at least one metal hydroxide selected from aluminum hydroxide or magnesium hydroxide. A functional polyolefin resin composition is provided.
また、本発明の第３の発明によれば、第１又は２の発明において、成分（Ｄ）が、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレン−ジフォスフォナイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジフォスファイト、及びビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリロールジフォスファイトからなる群から選ばれる少なくとも一種のリン系酸化防止剤であることを特徴とする結晶性ポリオレフィン樹脂組成物が提供される。 According to the third aspect of the present invention, in the first or second aspect , the component (D) is tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphos. From the group consisting of phonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite There is provided a crystalline polyolefin resin composition, which is at least one selected from the group consisting of phosphorus-based antioxidants.
また、本発明の第４の発明によれば、第１の発明において、成分（Ｃ）が、合成ハイドロタルサイトであることを特徴とする結晶性ポリオレフィン樹脂組成物が提供される。 According to a fourth aspect of the present invention, there is provided a crystalline polyolefin resin composition according to the first aspect, wherein the component (C) is a synthetic hydrotalcite.
また、本発明の第５の発明によれば、第１〜４のいずれかの発明において、成分（Ａ）が、ポリプロピレン樹脂であることを特徴とする結晶性ポリオレフィン樹脂組成物が提供される。 According to a fifth aspect of the present invention, there is provided a crystalline polyolefin resin composition characterized in that in any one of the first to fourth aspects, the component (A) is a polypropylene resin.
本発明のポリオレフィン樹脂組成物は、難燃性、衝撃強度、耐熱性（特に、耐熱老化性）に優れたノンハロゲン系難燃性ポリオレフィン樹脂組成物である。 The polyolefin resin composition of the present invention is a non-halogen flame retardant polyolefin resin composition excellent in flame retardancy, impact strength, and heat resistance (particularly heat aging resistance).
本発明は、結晶性ポリオレフィン樹脂（Ａ）に対し、含窒素化合物と金属水和化合物とを含む難燃剤（Ｂ）、ハイドロタルサイトを含む中和剤（Ｃ）、リン系酸化防止剤（Ｄ）、及び分子量が８００以下のヒンダードフェノール系酸化防止剤（Ｅ）を配合した難燃性結晶性ポリオレフィン樹脂組成物である。以下に本発明の樹脂組成物を構成する成分、組成物の製法等について詳細に説明する。 The present invention relates to a flame retardant (B) containing a nitrogen-containing compound and a metal hydrate compound, a neutralizing agent (C) containing hydrotalcite, and a phosphorus-based antioxidant (D) with respect to the crystalline polyolefin resin (A). ), And a hindered phenol-based antioxidant (E) having a molecular weight of 800 or less. Hereinafter, the components constituting the resin composition of the present invention, the production method of the composition, and the like will be described in detail.
１．ポリオレフィン樹脂組成物の構成成分
（１）結晶性ポリオレフィン樹脂（Ａ）
本発明のポリオレフィン樹脂組成物に用いられる結晶性ポリオレフィン樹脂（Ａ）としては、結晶性プロピレン単独重合体、プロピレンを主成分とし該プロピレンとエチレンもしくはブテン−１、ヘキセン−１、オクテン−１などの炭素数４以上のα−オレフィンとの共重合体、エチレン単独重合体、エチレンを主成分とし該エチレンとプロピレン、ブテン−１、ヘキセン−１、オクテン−１などの炭素数３以上のα−オレフィンとの共重合体、もしくはこれらの２種以上の混合物等が挙げられる。
1. Component of polyolefin resin composition (1) Crystalline polyolefin resin (A)
The crystalline polyolefin resin (A) used in the polyolefin resin composition of the present invention includes a crystalline propylene homopolymer, propylene as a main component, propylene and ethylene or butene-1, hexene-1, octene-1, and the like. Copolymer with α-olefin having 4 or more carbon atoms, ethylene homopolymer, α-olefin having 3 or more carbon atoms such as ethylene and propylene, butene-1, hexene-1, octene-1, etc. Or a mixture of two or more thereof.
本発明で用いられる結晶性ポリオレフィン樹脂のＭＦＲは、０．０１〜１０００ｇ／１０分、好ましくは０．０５〜５００ｇ／１０分、より好ましくは０．１〜２００ｇ／１０分が適当である。射出成形用の樹脂組成物とする場合は、ＭＦＲが１〜６０ｇ／１０分、さらに１〜５０ｇ／１０分が好ましい。ＭＦＲの値が上記下限より低い場合は、成形性が悪くなり、成形品の外観が悪化するとともに、難燃性も低下する。またＭＦＲが上限を超えると機械的強度物性が悪くなり、使用用途が限定されてくるので好ましくない。
ここで、ＭＦＲは、ＪＩＳ Ｋ７２１０に準拠して測定する値である。
The MFR of the crystalline polyolefin resin used in the present invention is 0.01 to 1000 g / 10 minutes, preferably 0.05 to 500 g / 10 minutes, more preferably 0.1 to 200 g / 10 minutes. When the resin composition for injection molding is used, the MFR is preferably 1 to 60 g / 10 minutes, more preferably 1 to 50 g / 10 minutes. When the value of MFR is lower than the above lower limit, the moldability is deteriorated, the appearance of the molded product is deteriorated, and the flame retardancy is also decreased. On the other hand, if the MFR exceeds the upper limit, the mechanical strength properties deteriorate, and the intended use is limited.
Here, MFR is a value measured according to JIS K7210.
また、本発明で用いられる結晶性ポリオレフィン樹脂が立体規則性樹脂の場合には、そのアイソペンタッド分率が０．９７以上、好ましくは０．９８以上が好ましい。アイソペンタッド分率の値が低すぎると剛性が不足し、射出成形体としての適正に欠ける。
立体規則性樹脂としては、結晶性プロピレン単独重合体、プロピレンを主成分とし該プロピレンとエチレンもしくはブテン−１、ヘキセン−１、オクテン−１などの炭素数４以上のα−オレフィンとの共重合体が挙げられる。
ここで、アイソタクチックペンタッド分率は、１３Ｃ−ＮＭＲ（核磁気共鳴法）を用いて測定されるポリプロピレン分子鎖中のペンタッド単位でのアイソタクチックペンタッド分率である。
When the crystalline polyolefin resin used in the present invention is a stereoregular resin, the isopentad fraction is 0.97 or more, preferably 0.98 or more. If the value of the isopentad fraction is too low, the rigidity is insufficient, and it is not suitable as an injection molded article.
As the stereoregular resin, a crystalline propylene homopolymer, a copolymer of propylene as a main component and the propylene and an α-olefin having 4 or more carbon atoms such as ethylene, butene-1, hexene-1, octene-1 or the like Is mentioned.
Here, the isotactic pentad fraction is an isotactic pentad fraction in pentad units in a polypropylene molecular chain measured using 13 C-NMR (nuclear magnetic resonance method).
（２）含窒素化合物と金属水和化合物とを含む難燃剤（Ｂ）
本発明のポリオレフィン樹脂組成物に用いられる含窒素化合物と金属水和化合物とを含む難燃剤（Ｂ）は、下記の（ｉ）金属水和化合物と（ｉｉ）含窒素化合物を含む難燃剤である。
(2) A flame retardant containing a nitrogen-containing compound and a metal hydrate compound (B)
The flame retardant (B) containing a nitrogen-containing compound and a metal hydrate compound used in the polyolefin resin composition of the present invention is a flame retardant containing the following (i) metal hydrate compound and (ii) a nitrogen-containing compound. .
（ｉ）金属水和化合物
本発明の成分（Ｂ）に用いられる金属水和化合物は、一般式：ＭｍＯｎ・ＸＨ２Ｏ（Ｍは金属、ｍ、ｎは金属の原子価によって定まる１以上の整数、Ｘは含有結晶水の数）で表される化合物またはそれを含む複塩である。具体的には、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化亜鉛、水酸化セリウム、水酸化鉄、水酸化銅、水酸化チタン、水酸化バリウム、水酸化ベリリウム、水酸化マンガン、水酸化ストロンチウム、水酸化ジルコニウムおよび水酸化ガリウム等の金属水酸化物、またはその金属水酸化物を含むベーマイト等の鉱物、塩基性炭酸マグネシウム等、カルシウム・アルミネート水和物（３ＣａＯ・Ａｌ２Ｏ３・６Ｈ２Ｏ）、ハイドロタルサイト（Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ）などを例として挙げることができる。これらは、２種以上の混合物であってもよい。なかでも、金属水酸化物が好ましく、水酸化アルミニウムまたは水酸化マグネシウムが高い難燃性を発現する点で好適である。
金属水和化合物は、平均粒径が０．１〜１００μｍの粉末に微粉砕して使用するのが一般的である。
(I) Metal Hydration Compound The metal hydration compound used in the component (B) of the present invention has a general formula: M m O n · XH 2 O (M is a metal, m, n is determined by the valence of the metal 1 The above integer, X is the compound represented by the number of contained crystal water) or a double salt containing it. Specifically, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, cerium hydroxide, iron hydroxide, copper hydroxide, titanium hydroxide, barium hydroxide, beryllium hydroxide, manganese hydroxide, water Metal hydroxides such as strontium oxide, zirconium hydroxide and gallium hydroxide, minerals such as boehmite containing the metal hydroxide, basic magnesium carbonate, calcium aluminate hydrate (3CaO.Al 2 O 3 6H 2 O), hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O) and the like can be mentioned as examples. These may be a mixture of two or more. Of these, metal hydroxides are preferable, and aluminum hydroxide or magnesium hydroxide is preferable in that it exhibits high flame retardancy.
The metal hydrated compound is generally used after being finely pulverized into a powder having an average particle size of 0.1 to 100 μm.
（ｉｉ）含窒素化合物
本発明の成分（Ｂ）に用いられる含窒素化合物としては、硝酸塩、硝酸エステル、硝酸アンモニウム等の有機もしくは無機硝酸化合物を用いることができる。
上記硝酸塩としては、具体的には、硝酸亜鉛六水和物、硝酸ニッケル六水和物、硝酸銅六水和物、硝酸鉄九水和物、硝酸アルミニウム九水和物、硝酸セリウム六水和物、硝酸ランタン、硝酸アンモニウムセリウム、硝酸ランタンアンモニウム等が挙げられる。
また、上記硝酸エステル（ＲＯＮＯ２）としては、具体的には、硝酸メチル（ＣＨ３ＯＮＯ２）、硝酸エチル（Ｃ２Ｈ５ＯＮＯ２）、硝酸ブチル（Ｃ４Ｈ９ＯＮＯ２）、硝酸イソアミル（（ＣＨ３）２ＣＨＣＨ２ＣＨ２ＯＮＯ２）、硝酸イソブチル（（ＣＨ３）２ＣＨＣＨ２ＯＮＯ２）、硝酸イソプロピル（（ＣＨ３）２ＣＨＯＮＯ２）等が挙げられる。
(Ii) Nitrogen-containing compounds As the nitrogen-containing compounds used in the component (B) of the present invention, organic or inorganic nitric acid compounds such as nitrates, nitrates, and ammonium nitrates can be used.
Specific examples of the nitrate include zinc nitrate hexahydrate, nickel nitrate hexahydrate, copper nitrate hexahydrate, iron nitrate nonahydrate, aluminum nitrate nonahydrate, cerium nitrate hexahydrate. Products, lanthanum nitrate, cerium ammonium nitrate, lanthanum ammonium nitrate, and the like.
Specific examples of the nitrate ester (RONO 2 ) include methyl nitrate (CH 3 ONO 2 ), ethyl nitrate (C 2 H 5 ONO 2 ), butyl nitrate (C 4 H 9 ONO 2 ), and isoamyl nitrate. ((CH 3 ) 2 CHCH 2 CH 2 ONO 2 ), isobutyl nitrate ((CH 3 ) 2 CHCH 2 ONO 2 ), isopropyl nitrate ((CH 3 ) 2 CHONO 2 ), and the like.
さらに、硝酸アセチル（Ｃ２Ｈ３ＮＯ４）、硝酸アニリン（Ｃ６Ｈ８Ｎ２Ｏ３）、硝酸アンモニウム（ＮＨ４ＮＯ３）、硝酸グアニジン（ＣＨ６Ｎ４Ｏ３）、硝酸酢酸セルロース（ニトロアセチルセルロース）、硝酸セルロース（ニトロセルロース）、硝酸尿素（ＨＮＯ３・ＣＯ（ＮＨ２）２）、硝酸ヒドラジニウム（Ｎ２Ｈ５ＮＯ３）、硝酸ヒドロキシルアンモニウム（［ＮＨ３ＯＨ］ＮＯ３）、硝酸ベンゼンジアゾニウム（Ｃ６Ｈ５Ｎ３Ｏ３）等も例示することができる。
さらにまた、亜硝酸化合物を用いることも可能で、例えば、亜硝酸アンモニウム（ＮＨ４ＮＯ２）、亜硝酸メチル（ＣＨ３ＯＮＯ）や亜硝酸エチル（Ｃ２Ｈ５ＯＮＯ）や亜硝酸プロピル（Ｃ３Ｈ７ＯＮＯ）や亜硝酸イソプロピル（（ＣＨ３）２ＣＨＯＮＯ）や亜硝酸ブチル（Ｃ４Ｈ９ＯＮＯ）や亜硝酸イソブチル（（ＣＨ３）２ＣＨＣＨ２ＯＮＯ）や亜硝酸イソアミル（亜硝酸アミル）（（ＣＨ３）２ＣＨＣＨ２ＣＨ２ＯＮＯ）等の亜硝酸エステル（ＲＯＮＯ）等を例示することができる。
なお、硝酸化合物、亜硝酸化合物の代替として、次亜硝酸化合物を用いることもできる。
含窒素化合物は、乾燥したものを用いるのが好ましい。乾燥未処理のものは分解温度が低下するため、低温分解成分を含むため、成形性、物性が悪化する場合がある。
中でも、硝酸アンモニウム、硝酸ランタンアンモニウムは、樹脂を着色することが無いこと、分解開始温度も比較的高温であることなどの理由から本発明に用いる含窒素化合物として適している。
Furthermore, acetyl nitrate (C 2 H 3 NO 4 ), aniline nitrate (C 6 H 8 N 2 O 3 ), ammonium nitrate (NH 4 NO 3 ), guanidine nitrate (CH 6 N 4 O 3 ), cellulose nitrate acetate (nitro Acetyl cellulose), cellulose nitrate (nitrocellulose), urea nitrate (HNO 3 .CO (NH 2 ) 2 ), hydrazinium nitrate (N 2 H 5 NO 3 ), hydroxylammonium nitrate ([NH 3 OH] NO 3 ), nitric acid Examples thereof include benzenediazonium (C 6 H 5 N 3 O 3 ).
Furthermore, it is also possible to use a nitrite compound, for example, ammonium nitrite (NH 4 NO 2 ), methyl nitrite (CH 3 ONO), ethyl nitrite (C 2 H 5 ONO), propyl nitrite (C 3 H 7 ONO), isopropyl nitrite ((CH 3 ) 2 CHONO), butyl nitrite (C 4 H 9 ONO), isobutyl nitrite ((CH 3 ) 2 CHCH 2 ONO), isoamyl nitrite (amyl nitrite) Nitrite esters (RONO) such as ((CH 3 ) 2 CHCH 2 CH 2 ONO) can be exemplified.
In addition, a hyponitrous acid compound can also be used as a substitute for a nitric acid compound or a nitrous acid compound.
It is preferable to use a dried nitrogen-containing compound. Since the decomposition temperature of the unprocessed dry product decreases, the low temperature decomposition component is included, so that the moldability and physical properties may deteriorate.
Among them, ammonium nitrate and lanthanum ammonium nitrate are suitable as nitrogen-containing compounds used in the present invention because they do not color the resin and the decomposition start temperature is relatively high.
金属水和化合物および含窒素化合物は、樹脂との親和性、さらには成形性を向上させるための表面処理を施すこともできる。その際には、シランカップリング剤、チタネート系カップリング剤、アルミネート系カップリング剤、脂肪酸系としてステアリン酸、オレイン酸、リノール酸、リノレン酸、エレオステアリン酸、脂肪酸塩として前記各脂肪酸のＣａ塩、Ｚｎ塩、非イオン系界面活性剤としてポリエチレングリコール誘導体、ポリエチレン系またはポリプロピレン系ワックス類、カルボン酸系カップリング剤、リン酸系カップリング剤などの表面処理剤を用いるとよい。 The metal hydrate compound and the nitrogen-containing compound can be subjected to a surface treatment for improving the affinity with the resin and further the moldability. In that case, silane coupling agent, titanate coupling agent, aluminate coupling agent, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, fatty acid salt as fatty acid, Surface treatment agents such as polyethylene glycol derivatives, polyethylene or polypropylene waxes, carboxylic acid coupling agents, and phosphoric acid coupling agents may be used as Ca salts, Zn salts, and nonionic surfactants.
さらに、上記表面処理として具体的には、加熱によりガラス質セラミックスを生ずるガラス前駆体組成物の前記含窒素化合物及び金属水和化合物へのコーティング処理とすることができる。上記ガラス前駆体組成物は、珪素成分及び／又は金属成分と酸素とを含有するものであり、加熱により生ずるガラス質セラミックスは、珪素及び／又は金属の酸化物を主体とするものとすることができる。珪素成分及び／又は金属成分は、加熱により酸化されてガラス質セラミックスを生じやすく、また、生成された珪素及び／又は金属の酸化物を主体とするガラス質セラミックスは耐熱性が高いため、表面処理に係るガラス前駆体組成物として珪素成分及び／又は金属成分と酸素とを含有するものが特に適している。なお、金属成分としては、例えばＴｉ、Ｃｕ、Ａｌ、Ｚｎ、Ｎｉ及びＺｒ、あるいはその他の遷移金属元素の１種又は２種以上を採用することができる。また、上記のようなガラス質セラミックスは、初めから化合物の一部をなすものとして存在していてもよいし、化合物の一部又は全部が加熱されたときにガラス質セラミックスに転化する形態でもよい。 Furthermore, the surface treatment can be specifically a coating treatment of the nitrogen-containing compound and the metal hydrate compound with a glass precursor composition that produces glassy ceramics upon heating. The glass precursor composition contains a silicon component and / or a metal component and oxygen, and the glassy ceramic produced by heating is mainly composed of an oxide of silicon and / or metal. it can. Since the silicon component and / or metal component is easily oxidized by heating to produce glassy ceramics, and the generated glassy ceramics mainly composed of silicon and / or metal oxides have high heat resistance, surface treatment As the glass precursor composition according to the above, one containing a silicon component and / or a metal component and oxygen is particularly suitable. In addition, as a metal component, Ti, Cu, Al, Zn, Ni, Zr, or 1 type, or 2 or more types of other transition metal elements can be employ | adopted, for example. Moreover, the glassy ceramics as described above may exist from the beginning as part of the compound, or may be converted into glassy ceramics when part or all of the compound is heated. .
なお、本発明のポリオレフィン樹脂組成物としては、結晶性ポリオレフィン樹脂中に、含窒素化合物と金属水和化合物とを含む難燃剤（Ｂ）を含んでいればよく、すなわち、含窒素化合物と金属水和化合物とを予め化学処理したもの、予め混合など物理処理をしたものを結晶性ポリオレフィン樹脂に配合しても、含窒素化合物、金属水和化合物を別々に結晶性ポリオレフィン樹脂に配合しても、またはこれらを組み合わせても構わない。
難燃性と衝撃特性の両立の観点からは、含窒素化合物と金属水和化合物とを予め化学処理したものが好ましい。
ここで、予めする化学処理としては、金属水和化合物に対して含窒素化合物を複合化する方法が挙げられる。複合化の方法としては、ゾルゲル法、含浸法、等が例示でき、ゾルゲル法が好ましい。
In addition, as the polyolefin resin composition of the present invention, the crystalline polyolefin resin may contain the flame retardant (B) containing a nitrogen-containing compound and a metal hydrated compound, that is, the nitrogen-containing compound and the metal water. Even if a compound that has been subjected to chemical treatment in advance, a compound that has been subjected to physical treatment such as mixing, is blended with the crystalline polyolefin resin, or a nitrogen-containing compound and a metal hydrate compound are separately blended with the crystalline polyolefin resin, Or these may be combined.
From the viewpoint of achieving both flame retardancy and impact properties, those obtained by previously chemically treating a nitrogen-containing compound and a metal hydrate compound are preferable.
Here, the chemical treatment to be performed in advance includes a method in which a nitrogen-containing compound is combined with a metal hydrate compound. Examples of the composite method include a sol-gel method and an impregnation method, and the sol-gel method is preferable.
本発明の成分（Ｂ）を製造する好ましいゾルゲル法としては、上記含窒素化合物及び／又はＳｉの化合物を溶媒中に分散及び／又は溶解させた溶液（例えば、アルコキシド溶液）から発生するゾル状組成物を上記金属水和化合物と接触させる工程と、前記ゾル状組成物を乾燥させる工程、とを少なくとも含み、前記ゾル状組成物の乾燥により生成するゲル状組成物を前記金属水和化合物と複合化させる方法である。 As a preferable sol-gel method for producing the component (B) of the present invention, a sol-like composition generated from a solution (for example, an alkoxide solution) in which the nitrogen-containing compound and / or Si compound is dispersed and / or dissolved in a solvent. A step of bringing a product into contact with the metal hydrate compound and a step of drying the sol composition, wherein the gel composition produced by drying the sol composition is combined with the metal hydrate compound. It is a method to make it.
上記ゾル状組成物は、含窒素化合物とＳｉのアルコキシドを加水分解することにより製造するのが好ましい。このようなアルコキシドを加水分解させて生成したゾル状組成物は、高熱によりガラス化ないしセラミックス化してポリオレフィン樹脂組成物に高い難燃性を付与する。また、ポリオレフィン樹脂との親和性を向上させ、物性の低下を抑えることが可能となる。
上記ゾル状組成物を作るための溶媒としては、アルコールを用いることができる。アルコールは、比較的低沸点であるため、乾燥工程が短時間で行える利点を備えている。このようなアルコールとしては、例えば、メタノール、エタノール、プロパノール、ブタノール等を用いることができる。その他の溶媒としては、アセトン、アセチルアセトン等のケトン系溶媒、トルエン、キシレン等の芳香族炭化水素系溶媒、シクロヘキサン等の環状炭化水素系溶媒、その他の鎖状炭化水素系溶媒、及びこれらの混合溶媒（アルコールとの混合溶媒も可）を用いることができる。
The sol composition is preferably produced by hydrolyzing a nitrogen-containing compound and an Si alkoxide. A sol-like composition produced by hydrolyzing such an alkoxide is vitrified or ceramicized by high heat to impart high flame retardancy to the polyolefin resin composition. In addition, it is possible to improve the affinity with the polyolefin resin and suppress deterioration of physical properties.
As a solvent for producing the sol composition, alcohol can be used. Since alcohol has a relatively low boiling point, it has an advantage that the drying process can be performed in a short time. As such an alcohol, for example, methanol, ethanol, propanol, butanol and the like can be used. Other solvents include ketone solvents such as acetone and acetylacetone, aromatic hydrocarbon solvents such as toluene and xylene, cyclic hydrocarbon solvents such as cyclohexane, other chain hydrocarbon solvents, and mixed solvents thereof. (A mixed solvent with alcohol is also acceptable).
上記アルコキシドは、Ｓｉ及び／又はＴｉを必須成分とするのがよい。Ｓｉ及び／又はＴｉをアルコキシドの成分として用いると、加水分解されて生成する例えばＳｉＯ２やＴｉＯ２等の酸化物は、高熱によりガラス化ないしセラミックス化し易いため、特に難燃性付与効果が高いものとなる。また、これらＳｉ及び／又はＴｉを含むアルコキシドはゲル化しにくいため、安定した状態のゾル状組成物を得ることが可能である。なかでも、特にＳｉは、生成する酸化物の安定性、ゾル状組成物の安定性等を考慮すると、アルコキシド成分として最も優れている。なお、Ｓｉを用いたアルコキシドとしては、例えばテトラエトキシシラン（Ｓｉ（ＯＣ２Ｈ５）４）等を用いることができ、Ｔｉを用いたアルコキシドとしては、例えばチタンイソプロポキシド（Ｔｉ（ｉｓｏ−ＯＣ３Ｈ７）４）等を用いることができる。また、上記以外の成分としては、例えば、Ｃｕ、Ａｌ、Ｚｎ、Ｎｉ及びＺｒの１種又は２種以上を含有するもの、あるいはその他の遷移元素を含有するもの等を採用することもでき、この場合、例えば、アルミニウムイソプロポキシド（Ａｌ（ＯＣ３Ｈ７）３）等を用いることができる。 The alkoxide preferably contains Si and / or Ti as essential components. When Si and / or Ti is used as an alkoxide component, oxides such as SiO 2 and TiO 2 produced by hydrolysis are easily vitrified or ceramicized due to high heat, and therefore have particularly high flame retardancy imparting effects. It becomes. Moreover, since these alkoxides containing Si and / or Ti are difficult to gel, it is possible to obtain a sol composition in a stable state. Of these, Si is most excellent as an alkoxide component, considering the stability of the oxide to be produced, the stability of the sol composition, and the like. As alkoxide using Si, for example, tetraethoxysilane (Si (OC 2 H 5 ) 4 ) or the like can be used. As alkoxide using Ti, for example, titanium isopropoxide (Ti (iso-OC) is used. 3 H 7 ) 4 ) or the like can be used. Moreover, as a component other than the above, for example, a material containing one or more of Cu, Al, Zn, Ni and Zr, or a material containing other transition elements can be employed. In this case, for example, aluminum isopropoxide (Al (OC 3 H 7 ) 3 ) or the like can be used.
上記ゾルゲル法による製造方法において、上記ゾル状組成物を金属水和化合物と接触させる工程は、金属水和化合物をゾル状組成物に浸漬する方法や、金属水和化合物に対してゾル状組成物を吹き付ける方法等を採用することができる。また、上記乾燥工程としては、加熱乾燥又は真空乾燥、及びそれらの併用により行うことができる。 In the manufacturing method by the sol-gel method, the step of bringing the sol composition into contact with the metal hydrate compound includes a method of immersing the metal hydrate compound in the sol composition, or a sol composition with respect to the metal hydrate compound. A method of spraying can be employed. Moreover, as said drying process, it can carry out by heat drying or vacuum drying, and those combined use.
このような製造方法により得られる難燃剤は、金属水和化合物にゲル状の含窒素化合物及び／又はＳｉの化合物が複合化された構成となる。これを結晶性ポリオレフィン樹脂に配合させると、高熱下に置かれた場合に、その高熱によりポリオレフィン樹脂組成物中の上記無機化合物がガラス化ないしセラミックス化し、そのガラス化ないしセラミックス化した無機化合物が保護膜となって、ポリオレフィン樹脂組成物に高い難燃性を付与することが可能となる。 The flame retardant obtained by such a production method has a structure in which a gel-like nitrogen-containing compound and / or Si compound is combined with a metal hydrate compound. When this is mixed with a crystalline polyolefin resin, when placed under high heat, the inorganic compound in the polyolefin resin composition is vitrified or ceramicized by the high heat, and the vitrified or ceramicized inorganic compound is protected. It becomes a film | membrane and it becomes possible to provide high flame retardance to a polyolefin resin composition.
上記金属水和化合物を担持材料粒子とし、その表面の全面又は一部に前記ゲル状組成物を複合化させて難燃剤を得ることができる。この場合、上記ゾルゲル法によると、金属水和化合物に対してゲル状組成物が均一に分散複合化された難燃剤を得ることが可能で、例えば、金属水和化合物の表面を前記ゲル状組成物の被膜で覆った難燃剤とする場合、そのゲル状組成物の被膜は、例えば０．０１〜１．０μｍ程度の薄くて均一なものとなる。このような難燃剤をポリオレフィン樹脂に配合した場合、金属水和化合物に対して均一かつ薄膜状でゲル状組成物が被膜されているため、その難燃性付与効果は大きく、少量の添加量で十分な難燃性を付与することが可能である。この場合、ポリオレフィン樹脂の物性変化も少なく好ましい。 The metal hydrate compound can be used as support material particles, and the gel composition can be combined on the entire surface or a part of the surface to obtain a flame retardant. In this case, according to the sol-gel method, it is possible to obtain a flame retardant in which the gel-like composition is uniformly dispersed and compounded with respect to the metal hydrate compound. When the flame retardant is covered with a coating of an object, the coating of the gel composition is thin and uniform, for example, about 0.01 to 1.0 μm. When such a flame retardant is blended with a polyolefin resin, the gel composition is coated uniformly and in a thin film with respect to the metal hydrate compound. Sufficient flame retardancy can be imparted. In this case, there is little change in physical properties of the polyolefin resin, which is preferable.
成分（Ｂ）中の含窒素化合物と金属水和化合物との割合は、含窒素化合物が２〜３０重量％、好ましくは４〜２５重量％、より好ましくは７〜２０重量％であり、金属水和化合物が７０〜９８重量％、好ましくは７５〜９６重量％、より好ましくは８０〜９３重量％であることが好ましい。上記範囲を逸脱すると、充分な難燃性が発現しない場合がある。 The ratio of the nitrogen-containing compound and the metal hydrated compound in the component (B) is 2 to 30% by weight of the nitrogen-containing compound, preferably 4 to 25% by weight, more preferably 7 to 20% by weight. It is preferable that the sum compound is 70 to 98% by weight, preferably 75 to 96% by weight, more preferably 80 to 93% by weight. When deviating from the above range, sufficient flame retardancy may not be exhibited.
本発明のポリオレフィン樹脂組成物における成分（Ｂ）の配合量は、成分（Ａ）１００重量部に対し、２５〜６０重量部であり、好ましくは３３〜５５重量である。成分（Ｂ）の配合量が上記下限値より少なくなると、充分な難燃性が得られなくなり好ましくない。また、上限値を超えると、ポリオレフィン樹脂組成物の比重の増加が有るだけでなく機械的強度が低下し好ましくない。 The compounding quantity of the component (B) in the polyolefin resin composition of this invention is 25-60 weight part with respect to 100 weight part of component (A), Preferably it is 33-55 weight. When the amount of component (B) is less than the above lower limit, it is not preferable because sufficient flame retardancy cannot be obtained. On the other hand, when the upper limit is exceeded, not only the specific gravity of the polyolefin resin composition increases but also the mechanical strength decreases, which is not preferable.
（３）中和剤（Ｃ）
本発明のポリオレフィン樹脂組成物に用いられるハイドロタルサイトを含む中和剤（Ｃ）は、一般的にポリオレフィン用の制酸剤として用いられるものであれば、いずれも用いることができる。成分（Ｃ）は、ハイドロタルサイト単独であっても混合物であっても良く、ハイドロタルサイトは、合成品が好ましい。
(3) Neutralizing agent (C)
Any neutralizing agent (C) containing hydrotalcite used in the polyolefin resin composition of the present invention can be used as long as it is generally used as an antacid for polyolefins. Component (C) may be a hydrotalcite alone or a mixture, and the hydrotalcite is preferably a synthetic product.
本発明のポリオレフィン樹脂組成物における成分（Ｃ）の配合量は、成分（Ａ）と成分（Ｂ）の混合物１００重量部に対し、０．５〜１０重量部であり、好ましくは１〜８重量部である。成分（Ｃ）配合量が上記下限値より少ない場合には充分な耐熱性（耐熱老化性）が得られず好ましくない。上限値を超えると樹脂組成物の比重の増加、機械的強度低下及び経済的効果の低下となるので好ましくない。 The compounding quantity of the component (C) in the polyolefin resin composition of this invention is 0.5-10 weight part with respect to 100 weight part of mixtures of a component (A) and a component (B), Preferably it is 1-8 weight. Part. When the amount of component (C) is less than the lower limit, it is not preferable because sufficient heat resistance (heat aging resistance) cannot be obtained. Exceeding the upper limit is not preferable because the specific gravity of the resin composition increases, the mechanical strength decreases, and the economic effect decreases.
（４）リン系酸化防止剤（Ｄ）
本発明のポリオレフィン樹脂組成物に用いられるリン系酸化防止剤（Ｄ）は、一般的にポリオレフィン用のリン系酸化防止剤として用いられるものであれば、いずれも用いることができる。中でも、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレン−ジフォスフォナイト、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジフォスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールジフォスファイト、ジステアリル−ペンタエリスリトールジフォスファイト等が好ましく用いることができ、本発明においては、これらを単独または混合使用することも出来る。
(4) Phosphorous antioxidant (D)
Any phosphorus-based antioxidant (D) used in the polyolefin resin composition of the present invention can be used as long as it is generally used as a phosphorus-based antioxidant for polyolefins. Among them, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphonite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,6- Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl-pentaerythritol diphosphite, etc. are preferably used. In the present invention, these can be used alone or in combination.
本発明のポリオレフィン樹脂組成物における成分（Ｄ）の配合量は、成分（Ａ）と成分（Ｂ）の混合物１００重量部に対し、０．０５〜２重量部であり、好ましくは０．１〜１．５重量部である。成分（Ｄ）の配合量が上記下限より少ない場合は、充分な耐熱性（特に、耐熱老化性）が得られず、また上限値を超える場合には経済性に不利であり好ましくない。 The amount of component (D) in the polyolefin resin composition of the present invention is 0.05 to 2 parts by weight, preferably 0.1 to 100 parts by weight of the mixture of component (A) and component (B). 1.5 parts by weight. When the amount of component (D) is less than the above lower limit, sufficient heat resistance (particularly, heat aging resistance) cannot be obtained, and when it exceeds the upper limit, it is disadvantageous for economy and is not preferable.
（５）ヒンダードフェノール系酸化防止剤（Ｅ）
本発明のポリオレフィン樹脂組成物に用いられるヒンダードフェノール系酸化防止剤（Ｅ）は、ポリオレフィン樹脂組成物を樹脂製品にした場合、高温雰囲気下での耐熱老化における性能を発揮する酸化防止剤をいい、分子量８００以下、好ましくは７５０以下のヒンダードフェノール系酸化防止剤である。成分（Ｅ）の分子量が８００を超えると耐熱老化性に効果が著しく低下し好ましくない。
成分（Ｅ）としては、多環型ヒンダードフェノールであることが好ましい。具体例としては、１，１，３−トリス（２−メチル−４−ハイドロキシ−５−ｔ−ブチルフェニル）ブタン、ｎ−オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ハイドロキシフェニル）プロピオネート、４，４−ブチリデン−ビス−（３−メチル−６−ｔブチルフェノール）、３，９−ビス［２−〔３−（３−ｔ−ブチル−ハイドロキシ−５−メチルフェニル）プロピオニルオキシ〕−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン、等が挙げられ、本発明においては、これらを単独または混合使用することも出来る。
なお、成分（Ｅ）は、構造中にイソシアヌル酸、イオウ、１，３，５−トリメチルベンゼン骨格を有しないことが好ましい。
(5) Hindered phenolic antioxidant (E)
The hindered phenolic antioxidant (E) used in the polyolefin resin composition of the present invention refers to an antioxidant that exhibits performance in heat aging in a high temperature atmosphere when the polyolefin resin composition is made into a resin product. , A hindered phenol antioxidant having a molecular weight of 800 or less, preferably 750 or less. When the molecular weight of component (E) exceeds 800, the effect on heat aging resistance is remarkably lowered, which is not preferable.
The component (E) is preferably a polycyclic hindered phenol. Specific examples include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, 4,4-butylidene-bis- (3-methyl-6-tbutylphenol), 3,9-bis [2- [3- (3-t-butyl-hydroxy-5-methylphenyl) propionyloxy ] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, and the like. In the present invention, these may be used alone or in combination.
In addition, it is preferable that a component (E) does not have isocyanuric acid, sulfur, and a 1,3,5-trimethylbenzene skeleton in a structure.
本発明のポリオレフィン樹脂組成物における成分（Ｅ）の配合量は、成分（Ａ）と成分（Ｂ）の混合物１００重量部に対し、０．０５〜２重量部であり、好ましくは０．１〜１．５重量部である。成分（Ｅ）の配合量が上記下限より少ない場合は、充分な耐熱性（特に耐熱老化性）が得られず、また上限値を超える場合には経済性に不利であり好ましくない。 The amount of component (E) in the polyolefin resin composition of the present invention is 0.05 to 2 parts by weight, preferably 0.1 to 100 parts by weight of the mixture of component (A) and component (B). 1.5 parts by weight. When the amount of component (E) is less than the above lower limit, sufficient heat resistance (particularly heat aging resistance) cannot be obtained.
（６）その他の成分
本発明のプロピレン系樹脂組成物には、更に他の特性を付与するため、または本発明の効果を損なわない範囲で他の添加剤、例えば紫外吸収剤、光安定剤、帯電防止剤、結晶化核剤、滑剤、金属不活性剤、抗菌剤、防カビ剤などの安定剤、着色顔料、各種無機充填剤、ガラス繊維を添加することが出来る。
(6) Other components To the propylene-based resin composition of the present invention, other additives, for example, an ultraviolet absorber, a light stabilizer, and the like, as long as other properties are imparted or the effects of the present invention are not impaired. Antistatic agents, crystallization nucleating agents, lubricants, metal deactivators, antibacterial agents, antifungal agents and other stabilizers, color pigments, various inorganic fillers, and glass fibers can be added.
２．ポリオレフィン樹脂組成物の製造、成形品
本発明のポリオレフィン樹脂組成物を製造する方法としては、特に規定するものではなく公知の樹脂組成物の製造方法を用いることができる。例えば、上記結晶性ポリプロピレン系樹脂（Ａ）、含窒素化合物と金属水和化合物を含む難燃剤（Ｂ）、ハイドロタルサイトを含む中和剤（Ｃ）、リン系酸化防止剤（Ｄ）、及び分子量が８００以下のヒンダードフェノール系酸化防止剤（Ｅ）とを所定量と必要に応じ他の添加剤の所定量を混合装置、例えば、スーパーミキサー、タンブラーミキサー等に入れ１〜５分間混合したのち、得られた混合物を押し出し機、加熱ロール、ニーダーなどにより混練温度１７０℃〜２００℃で溶融混練しペレット化する方法を挙げることができる。その中でも、２軸による押し出し機混練が生産性、難燃特性面で好ましい。
また、各成分のうち一又は二以上の成分をマスターバッチ化して配合することもできる。
2. Production of Polyolefin Resin Composition and Molded Product The method for producing the polyolefin resin composition of the present invention is not particularly defined, and a known method for producing a resin composition can be used. For example, the crystalline polypropylene resin (A), a flame retardant (B) containing a nitrogen-containing compound and a metal hydrate compound, a neutralizing agent (C) containing hydrotalcite, a phosphorus antioxidant (D), and A predetermined amount of a hindered phenol antioxidant (E) having a molecular weight of 800 or less and a predetermined amount of other additives as necessary are mixed in a mixing apparatus such as a super mixer, a tumbler mixer and the like and mixed for 1 to 5 minutes. Thereafter, the obtained mixture can be melt-kneaded at a kneading temperature of 170 ° C. to 200 ° C. by an extruder, a heating roll, a kneader or the like, and pelletized. Among these, twin-screw extruder kneading is preferable in terms of productivity and flame retardancy.
In addition, one or more of the components can be blended in a master batch.
本発明のポリオレフィン樹脂組成物は、射出成形、圧縮成形、トランスファ成形、押出成形、ブロー成形、カレンダ成形、積層成形、シートフォーミングなどの公知の成形方法により、電気・電子部品、ＯＡ機器、家電製品、住設機器、車両部品等の難燃性を特に求められている成形品、特に、複写機部品、便座部品、自動車ヒューズボックス等の成形品とすることができる。 The polyolefin resin composition of the present invention is produced by known molding methods such as injection molding, compression molding, transfer molding, extrusion molding, blow molding, calendar molding, laminate molding, sheet forming, etc. In addition, it can be formed products such as copier parts, toilet seat parts, automobile fuse boxes, etc., which are particularly required to be flame retardant, such as residential equipment and vehicle parts.
本発明を具体的に説明するために、以下に実施例を示すが本発明はこれによって限定されるものではない。
なお、実施例における難燃性、衝撃強度、耐熱性（耐熱老化性）の評価方法、及び用いた樹脂及び難燃剤、添加剤は以下の通りである。
In order to specifically describe the present invention, examples are shown below, but the present invention is not limited thereto.
In addition, the flame retardance in an Example, impact strength, the evaluation method of heat resistance (heat aging resistance), the used resin, a flame retardant, and an additive are as follows.
１．評価方法
（１）難燃性評価：ＵＬ９４Ｖ試験（アンダーライター・ラボラトリーズコーポレイテッド）の「機器の部品用プレスチック材料の燃焼試験」に規定された垂直燃焼試験方法に準拠して、１．５ｍｍ厚（比較例１、２は３ｍｍ厚）の射出成形シートを用いて測定した。
（２）衝撃強度の評価：射出成形機により樹脂温度２００℃、金型冷却温度４０℃、にてＪＩＳ Ｋ７１１０（１９８４年）に記載のアイゾット衝撃試験測定用試験片を作成した。得られた試験片でアイゾット衝撃試験をＪＩＳ Ｋ７１１０試験法に従って測定した。
（３）アイソタクチックペンタッド分率の測定：１３Ｃ−ＮＭＲ（核磁気共鳴法）を用いて測定されるポリプロピレン分子鎖中のペンタッド単位でのアイソタクチックペンタッド分率を、ＦＴ−ＮＭＲの２７０ＭＨｚの装置を用いて行った。
（４）耐熱老化性能の測定：下記の方法により試験片を作成し、ＪＩＳ Ｋ７２１２−Ｂに準拠して、１５０℃（実施例７については１４０℃）で測定した。
温度２００℃で予熱７分、加圧３分、及び冷却温度３０℃で加圧１２ＭＰａ、３分の条件で、２００×２００×０．５ｍｍのシートを作成し、このシートより異常の無く、厚みの均一な個所から幅３５ｍｍ、長さ６５ｍｍの大きさの試験件を切りだし耐熱老化性試験片とした。
なお、耐熱老化試験機（ギアーオーブン）の回転ドラムへ試験片の取りつけには、アルミのクリップを用い直接試験片にアルミが触れないようにガラステープを介して取りつけた。
1. Evaluation Method (1) Flame Retardancy Evaluation: 1.5 mm thickness in accordance with the vertical combustion test method specified in the UL94V test (Underwriters Laboratories) "Plastic material combustion test for equipment parts" Measurement was performed using an injection molded sheet (comparative examples 1 and 2 are 3 mm thick).
(2) Evaluation of impact strength: An Izod impact test measurement specimen described in JIS K7110 (1984) was prepared by an injection molding machine at a resin temperature of 200 ° C. and a mold cooling temperature of 40 ° C. An Izod impact test was measured on the obtained test piece according to the JIS K7110 test method.
(3) Measurement of isotactic pentad fraction: The isotactic pentad fraction in the pentad unit in the polypropylene molecular chain measured using 13 C-NMR (nuclear magnetic resonance method) is calculated using FT-NMR. Using a 270 MHz apparatus.
(4) Measurement of heat aging performance: A test piece was prepared by the following method, and measured at 150 ° C. (140 ° C. for Example 7) in accordance with JIS K7212-B.
A sheet of 200 × 200 × 0.5 mm was prepared under conditions of preheating for 7 minutes at a temperature of 200 ° C., 3 minutes for pressure, and 12 MPa for 3 minutes at a cooling temperature of 30 ° C. A test piece having a size of 35 mm in width and 65 mm in length was cut out from a uniform portion of the sample and used as a heat aging resistance test piece.
For attaching the test piece to the rotating drum of a heat aging tester (gear oven), an aluminum clip was used to attach the test piece directly to the test piece through glass tape so that the aluminum did not touch the test piece.
２．材料
（１）プロピレン重合体（Ａ）
製造例１で得られたプロピレン・エチレンブロック共重合体（ＰＰ−１）、製造例２で得られたプロピレン単独重合体（ＰＰ−２）、製造例３で得られたプロピレンエチレン共重合体（ＰＰ−３）紛状樹脂を用いた。
2. Material (1) Propylene polymer (A)
Propylene / ethylene block copolymer (PP-1) obtained in Production Example 1, propylene homopolymer (PP-2) obtained in Production Example 2, and propylene-ethylene copolymer obtained in Production Example 3 ( PP-3) A powdery resin was used.
（製造例１）
（ｉ）チーグラー触媒の製造
充分に窒素置換した１０Ｌ反応器に、脱水および脱酸素したｎ−ヘプタン４０００ｍｌを導入し、次いでＭｇＣｌ２を８モル、Ｔｉ（Ｏ−ｎ−Ｃ４Ｈ９）４を１６モル導入し、９５℃で２時間反応させた。反応終了後、４０℃に温度を下げ、次いでメチルヒドロポリシロキサン（２０センチストークス）を９６０ｍｌ導入し、３時間反応させた。生成した固体成分をｎ−ヘプタンで洗浄した。次いで、充分に窒素置換した１０Ｌ反応器に、上記と同様に精製したｎ−ヘプタンを１０００ｍｌ導入し、上記で合成した固体成分をＭｇ原子換算で４．８モル導入した。次いでｎ−ヘプタン５００ｍｌにＳｉＣｌ４８モルを混合して３０℃、３０分間でフラスコへ導入し、７０℃で３時間反応させた。反応終了後、ｎ−ヘプタンで洗浄した。次いでｎ−ヘプタン５００ｍｌにフタル酸クロライド０．４８モルを混合して、７０℃、３０分間でフラスコへ導入し、９０℃で１時間反応させた。反応終了後、ｎ−ヘプタンで洗浄した。次いで、ＴｉＣｌ４４００ｍｌを導入して９５℃で６時間反応させた。反応終了後、ｎ−ヘプタンで洗浄した。さらにＳｉＣｌ４２００ｍｌを導入して８０℃で６時間反応させた。反応終了後、ｎ−ヘプタンで充分に洗浄し固体成分を得た。このもののチタン含量は１．７５重量％であった。
(Production Example 1)
(I) Production of Ziegler catalyst Into a fully nitrogen-substituted 10 L reactor, 4000 ml of dehydrated and deoxygenated n-heptane was introduced, and then 8 mol of MgCl 2 and Ti (On-C 4 H 9 ) 4 were introduced. 16 mol was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 960 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane. Next, 1000 ml of n-heptane purified in the same manner as described above was introduced into a 10 L reactor sufficiently purged with nitrogen, and 4.8 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 8 mol of SiCl 4 was mixed with 500 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Subsequently, 0.48 mol of phthalic acid chloride was mixed with 500 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 400 ml of TiCl 4 was introduced and reacted at 95 ° C. for 6 hours. After completion of the reaction, washing with n-heptane was performed. Furthermore, 200 ml of SiCl 4 was introduced and reacted at 80 ° C. for 6 hours. After completion of the reaction, it was sufficiently washed with n-heptane to obtain a solid component. The titanium content of this product was 1.75% by weight.
次いで、充分に窒素置換したフラスコに、上記と同様に精製したｎ−ヘプタンを１０００ｍｌ導入し、上記で合成した固体成分を１００グラム導入し、ビニルトリメチルシラン２５ｍｌ、（ｔ−Ｃ４Ｈ９）Ｓｉ（ＣＨ３）（ＯＣＨ３）２２４ｍｌ、Ａｌ（Ｃ２Ｈ５）３３４グラムを３０℃で２時間接触させた。接触終了後、ｎ−ヘプタンで充分に洗浄し、塩化マグネシウムを主体とする固体触媒成分（１）を得た。このもののチタン含量は１．７０重量％であった。
さらに、トリエチルアルミニウム１７グラムを加えた後、２０℃でプロピレンを１００ｇ１時間かけて導入し、導入終了後３０分継続重合して、予備重合触媒を得た。この予備重合触媒には、触媒１グラム当たり、０．８グラムのポリプロピレンが含まれていた。
Next, 1000 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 100 g of the solid component synthesized above was introduced, and 25 ml of vinyltrimethylsilane, (t-C 4 H 9 ) Si. 24 ml of (CH 3 ) (OCH 3 ) 2 and 34 grams of Al (C 2 H 5 ) 3 were contacted at 30 ° C. for 2 hours. After completion of the contact, the solid catalyst component (1) mainly composed of magnesium chloride was obtained by thoroughly washing with n-heptane. The titanium content of this product was 1.70% by weight.
Furthermore, after adding 17 g of triethylaluminum, propylene was introduced at 20 ° C. over 100 g for 1 hour, followed by continuous polymerization for 30 minutes after the introduction was completed, thereby obtaining a prepolymerized catalyst. This prepolymerized catalyst contained 0.8 grams of polypropylene per gram of catalyst.
（ｉｉ）プロピレン・エチレンブロック共重合体の製造
上記で得た予備重合固体触媒成分及びトリエチルアルミニウムを使用し、第１重合工程として反応部容積２８０Ｌを有する流動床式気相反応器を用い重合温度８５℃、プロピレン分圧１．７５ＭＰａ の条件下、連続的にフィードしつつプロピレン単独重合を連続的に行った。この時、予備重合固体触媒成分は固体触媒成分（１）あたり０．７２ｇ／ｈｒの速度で、またトリエチルアルミニウムを７．８ｇ／ｈｒの速度で連続的に供給した。第１重合工程より抜き出されるパウダーを１９．０５ｋｇ／ｈｒで連続的に第２重合工程として用いる反応部容積２８０Ｌを有する流動床式気相反応器に送り、プロピレンとエチレンの共重合を連続的に行った。第２重合工程から連続的に２３．２ｋｇ／ｈｒのポリマーを抜き出した。各重合工程での水素濃度は１槽目でＨ２／プロピレン＝０．０３５モル比、２槽目でＨ２／（エチレン＋プロピレン）＝０．０１モル比にコントロールすることにより分子量を制御した。ゴム状プロピレン・エチレン共重合体部のエチレン組成は第２重合工程でのプロピレンとエチレンのガス組成をプロピレン／エチレン＝５５／４５モル比にコントロールすることによりプロピレン・エチレンブロック共重合体（ＰＰ−１）を得た。１段重合槽から抜き出したプロピレン単独重合体のアイソタクチックペンタッド分率は０．９８５、ＭＦＲは７４ｇ／１０分、２段目重合槽から抜き出したプロピレン・エチレンブロック共重合体のＭＦＲは２９．５ｇ／１０分であった。
(Ii) Production of propylene / ethylene block copolymer Polymerization temperature using a fluidized bed gas phase reactor having a reaction part volume of 280 L as the first polymerization step using the prepolymerized solid catalyst component obtained above and triethylaluminum. Propylene homopolymerization was continuously carried out while continuously feeding at 85 ° C. and a propylene partial pressure of 1.75 MPa. At this time, the prepolymerized solid catalyst component was continuously supplied at a rate of 0.72 g / hr per solid catalyst component (1) and triethylaluminum at a rate of 7.8 g / hr. The powder extracted from the first polymerization step is continuously fed at 19.05 kg / hr to a fluidized bed gas phase reactor having a reaction part volume of 280 L to be used as the second polymerization step, and the copolymerization of propylene and ethylene is continuously performed. Went to. From the second polymerization step, 23.2 kg / hr of polymer was continuously extracted. Each polymerization hydrogen concentration in step H 2 / propylene = 0.035 mol ratio 1 bath th to control molecular weight by controlling the H 2 / (ethylene + propylene) = 0.01 molar ratio at 2 bath th . The ethylene composition of the rubber-like propylene / ethylene copolymer part was adjusted to a propylene / ethylene block copolymer (PP-) by controlling the propylene / ethylene gas composition in the second polymerization step to a propylene / ethylene = 55/45 molar ratio. 1) was obtained. The isotactic pentad fraction of the propylene homopolymer extracted from the first stage polymerization tank is 0.985, the MFR is 74 g / 10 minutes, and the MFR of the propylene / ethylene block copolymer extracted from the second stage polymerization tank is 29. It was 5 g / 10 minutes.
（製造例２）
製造例１の（ｉ）で得られた予備重合固体触媒成分及びトリエチルアルミニウムを使用し、反応部容積２８０Ｌを有する流動床式気相反応器を用い重合温度８５℃、プロピレン分圧１．７５ＭＰａの条件下、連続的にフィードしつつプロピレン単独重合を連続的に行った。この時、予備重合固体触媒成分は固体触媒成分（１）あたり０．７２ｇ／ｈｒの速度で、またトリエチルアルミニウムを７．８ｇ／ｈｒ、プロピレン３３ｋｇ／ｈｒ、水素をＨ２／プロピレン＝０．０１０モル比で連続的に供給し、目的とするプロピレン単独重合体（ＰＰ−２）パウダーを２５ｋｇ／ｈｒの速度で連続的に製造した。抜き出したプロピレン単独重合体（ＰＰ−２）のアイソタクチックペンタッド分率は０．９８５、ＭＦＲは９．７ｇ／１０分、であった。
(Production Example 2)
Using the prepolymerized solid catalyst component obtained in (i) of Production Example 1 and triethylaluminum, using a fluidized bed gas phase reactor having a reaction part volume of 280 L, a polymerization temperature of 85 ° C. and a propylene partial pressure of 1.75 MPa. Under conditions, propylene homopolymerization was continuously performed while continuously feeding. At this time, the prepolymerized solid catalyst component is at a rate of 0.72 g / hr per solid catalyst component (1), triethylaluminum is 7.8 g / hr, propylene is 33 kg / hr, and hydrogen is H 2 /propylene=0.010. The target propylene homopolymer (PP-2) powder was continuously supplied at a molar ratio of 25 kg / hr. The extracted propylene homopolymer (PP-2) had an isotactic pentad fraction of 0.985 and an MFR of 9.7 g / 10 min.
（製造例３）
製造例２で使用した触媒並び重合方法を用い、上記重合における水素量を、水素／プロピレンのモル比で０．０１６となるように、また、エチレンをエチレン／プロピレンのモル比で０．０２０となるように連続的に供給するように変更し、プロピレン・エチレンランダム共重合体（ＰＰ−３）を製造した。抜き出したプロピレン・エチレンランダム共重合体（ＰＰ−３）のＭＦＲは１０．１ｇ／１０分、エチレン含量２．５％であった。
(Production Example 3)
Using the catalyst and polymerization method used in Production Example 2, the amount of hydrogen in the above polymerization was 0.016 in terms of hydrogen / propylene molar ratio, and ethylene was 0.020 in terms of ethylene / propylene molar ratio. Thus, the propylene / ethylene random copolymer (PP-3) was produced by changing the feed continuously. The extracted propylene / ethylene random copolymer (PP-3) had an MFR of 10.1 g / 10 min and an ethylene content of 2.5%.
（２）難燃剤（Ｂ）
（Ｂ−１）：硝酸塩担持／又は含有金属水和化合物（パイロライザーＨＧ；石塚硝子製）
（Ｂ−２）：水酸化マグネシウム（キスマ−５Ｂ；協和化学工業社製）
（３）中和剤（Ｃ）
（Ｃ−１）：ハイドロタルサイト（ＤＨＴ４Ａ；協和化学工業社製）
（Ｃ−２）：ステアリン酸カルシウム（Ｃａｓｔ；耕正社製）
（４）リン系酸化防止剤（Ｄ）
（Ｄ−１）：テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレン−ジフォスフォナイト（ＰＥＰＱ；チバスペシャリティケミカルズ社製）
（５）ヒンダードフェノール系酸化防止剤（Ｅ）
（Ｅ−１）：１，１，３−トリス（２−メチルー４−ハイドロキシ−５−ｔ−ブチルフェニル）ブタン、分子量５４５（商品名ＡＯ３０；旭電化工業社製）
（Ｅ−２）：ｎ−オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ハイドロキシフェニル）−プロピオネート、分子量５３１（商品名ＡＯ５０；旭電化工業社製）
（Ｅ−３）：３，９−ビス［２−〔３−（３−ｔ−ブチル−４−ハイドロキシ−５−メチルフェニル）プロピオニルオキシ〕−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン、分子量７４１（商品名ＡＯ８０；旭電化工業製）
（Ｅ−４）：ペンタエリスチル−テトラキス〔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、分子量１１７８（商品名イルガノックスＩＲ１０１０；チバスペシャリティケミカルズ社製）
（Ｅ−５）：１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ハイドロキシベンゾール）ベンゼン、分子量７７５（商品名イルガノックスＩＲ１３３０；チバスペシャリティケミカルズ社製）
（Ｅ−６）：トリス（３，５−ジ−ｔ−ブチル−４−ハイドロキシベンゾール）イソシアヌレート、分子量７８４（商品名ＡＯ２０；旭電化工業社製）
(2) Flame retardant (B)
(B-1): Nitrate-supported / containing metal hydrated compound (Pyrolyzer HG; manufactured by Ishizuka Glass)
(B-2): Magnesium hydroxide (Kisuma-5B; manufactured by Kyowa Chemical Industry Co., Ltd.)
(3) Neutralizing agent (C)
(C-1): Hydrotalcite (DHT4A; manufactured by Kyowa Chemical Industry Co., Ltd.)
(C-2): Calcium stearate (Cast; manufactured by Kosho)
(4) Phosphorous antioxidant (D)
(D-1): Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphonite (PEPQ; manufactured by Ciba Specialty Chemicals)
(5) Hindered phenolic antioxidant (E)
(E-1): 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, molecular weight 545 (trade name AO30; manufactured by Asahi Denka Kogyo Co., Ltd.)
(E-2): n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, molecular weight 531 (trade name AO50; manufactured by Asahi Denka Kogyo Co., Ltd.)
(E-3): 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8 , 10-tetraoxaspiro [5,5] undecane, molecular weight 741 (trade name AO80; manufactured by Asahi Denka Kogyo)
(E-4): Pentaerystyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, molecular weight 1178 (trade name Irganox IR1010; manufactured by Ciba Specialty Chemicals)
(E-5): 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzol) benzene, molecular weight 775 (trade name Irganox IR1330; Ciba Specialty) (Chemicals)
(E-6): Tris (3,5-di-t-butyl-4-hydroxybenzole) isocyanurate, molecular weight 784 (trade name AO20; manufactured by Asahi Denka Kogyo Co., Ltd.)
（実施例１）
ポリプロピレン樹脂（Ａ）として（ＰＰ−１）１００重量部、難燃剤（Ｂ）として（Ｂ−１）５０重量部、成分（Ａ）と成分（Ｂ）を混合した混合樹脂１００重量部に対し、中和剤（Ｃ）として（Ｃ−１）を０．５重量部、リン系酸化防止剤（Ｄ）として（Ｄ−１）を０．２重量部、及びヒンダードフェノール系酸化防止剤（Ｅ）として（Ｅ−１）を０．５重量部を加え、スーパーミキサーに入れ、３分間撹拌混合した。得られた混合物を口径３０ｍｍの２軸押し出し機で溶融混練温度２００℃で溶融混練押し出し、ペレット化した。得られたペレットを８０℃で４時間乾燥したのち、型締め圧１００ｔの射出成形機を用い、成型温度２００℃、金型冷却温度４０℃の設定条件下で１．５ｍｍ及び３．０ｍｍ厚みのＵＬ９４Ｖ用試験片を作成した。
また、同条件下でアイゾット衝撃試験用の射出成形試験片を成形し評価した。結果を表１に示す。
Example 1
100 parts by weight of (PP-1) as the polypropylene resin (A), 50 parts by weight of (B-1) as the flame retardant (B), and 100 parts by weight of the mixed resin in which the component (A) and the component (B) are mixed, 0.5 part by weight of (C-1) as neutralizer (C), 0.2 part by weight of (D-1) as phosphorus antioxidant (D), and hindered phenol antioxidant (E ), 0.5 part by weight of (E-1) was added, and the mixture was placed in a supermixer and stirred and mixed for 3 minutes. The obtained mixture was melt-kneaded and extruded at a melt-kneading temperature of 200 ° C. with a biaxial extruder having a diameter of 30 mm, and pelletized. After drying the obtained pellets at 80 ° C. for 4 hours, using an injection molding machine with a mold clamping pressure of 100 t, 1.5 mm and 3.0 mm thicknesses under the setting conditions of a molding temperature of 200 ° C. and a mold cooling temperature of 40 ° C. A test piece for UL94V was prepared.
In addition, an injection molded test piece for an Izod impact test was molded and evaluated under the same conditions. The results are shown in Table 1.
（実施例２）
ヒンダードフェノール系酸化防止剤（Ｅ）の（Ｅ−１）を（Ｅ−２）とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表１に示す。
(Example 2)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1 except that (E-1) of the hindered phenol antioxidant (E) was changed to (E-2). The results are shown in Table 1.
（実施例３）
ヒンダードフェノール系酸化防止剤（Ｅ）の（Ｅ−１）を（Ｅ−３）とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表１に示す。
(Example 3)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1, except that (E-1) of the hindered phenol-based antioxidant (E) was changed to (E-3). The results are shown in Table 1.
（実施例４）
実施例３のヒンダードフェノール系酸化防止剤（Ｅ−３）を１重量部とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表１に示す。
Example 4
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1 except that 1 part by weight of the hindered phenol antioxidant (E-3) of Example 3 was used. The results are shown in Table 1.
（実施例５）
実施例３のハイドロタルサイト（Ｃ−１）を５重量部とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表１に示す。
(Example 5)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1 except that the hydrotalcite (C-1) of Example 3 was changed to 5 parts by weight. The results are shown in Table 1.
（実施例６）
実施例５の（Ｂ−１）を３５重量部とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表１に示す。
(Example 6)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1 except that (B-1) in Example 5 was changed to 35 parts by weight. The results are shown in Table 1.
（実施例７）
実施例４のポリオレフィン（Ａ）の（ＰＰ−１）を、（ＰＰ−２）とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表１に示す。
なお、本実施例においては、耐熱老化試験１５０℃では、（ＰＰ−２）の融点近くなるので、耐熱老化試験温度を１４０℃で行なった。
(Example 7)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1 except that (PP-1) of the polyolefin (A) in Example 4 was changed to (PP-2). The results are shown in Table 1.
In this example, the heat aging test temperature was 140 ° C. because the heat aging test was 150 ° C., which was close to the melting point of (PP-2).
（実施例８）
実施例４のポリオレフィン（Ａ）の（ＰＰ−１）を、（ＰＰ−３）とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表１に示す。
(Example 8)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1 except that (PP-1) of the polyolefin (A) in Example 4 was changed to (PP-3). The results are shown in Table 1.
（比較例１）
成分（Ｂ）を、（Ｂ−２）１００重量部、成分（Ｃ）の（Ｃ−１）配合量を０．１重量部、及びヒンダードフェノール系酸化防止剤（Ｅ）を（Ｅ−４）０．１重量部、とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。（Ｂ）成分として含窒素系化合物を含まないため、燃焼してしまう。
(Comparative Example 1)
Component (B), 100 parts by weight of (B-2), 0.1 part by weight of component (C) (C-1), and hindered phenol antioxidant (E) (E-4) ) A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1 except for 0.1 part by weight. The results are shown in Table 2. (B) Since it does not contain a nitrogen-containing compound as a component, it burns.
（比較例２）
比較例１の（Ｂ−２）を１５０重量部とした以外は、比較例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。（Ｂ）成分として含窒素系化合物を含まず、燃焼性を良くしようとして（Ｂ−２）を多くすると燃焼性はよくなるが衝撃強度が更に低くなってしまう。
(Comparative Example 2)
A polyolefin resin composition was obtained and evaluated in the same manner as in Comparative Example 1 except that (B-2) in Comparative Example 1 was changed to 150 parts by weight. The results are shown in Table 2. If the component (B) does not contain a nitrogen-containing compound and increases the amount of (B-2) in order to improve the combustibility, the combustibility is improved, but the impact strength is further lowered.
（比較例３）
実施例１のハイドロタルサイト（Ｃ−１）を０．１重量部、及びヒンダードフェノール系酸化防止剤（Ｅ）を（Ｅ−４）０．１重量部、とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。含窒素系化合物の添加処理をした難燃剤（Ｂ−１）において、ハイドロタルサイト（Ｃ−１）と併用しながら分子量の高い（Ｅ−４）成分では耐熱老化性が出ない。
(Comparative Example 3)
Example 1 except that the hydrotalcite (C-1) of Example 1 was 0.1 part by weight, and the hindered phenol-based antioxidant (E) was (E-4) 0.1 part by weight. Similarly, a polyolefin resin composition was obtained and evaluated. The results are shown in Table 2. In the flame retardant (B-1) subjected to the addition treatment of the nitrogen-containing compound, the heat aging resistance does not appear with the component (E-4) having a high molecular weight while being used in combination with the hydrotalcite (C-1).
（比較例４、５）
実施例１のヒンダードフェノール系酸化防止剤（Ｅ）を（Ｅ−４）０．１重量部（比較例４）、０．５重量部（比較例５）、とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。さらに、ハイドロタルサイト（Ｃ−１）を増量しながら分子量の高い（Ｅ−４）を増量しても耐熱老化性の大きな向上はない。
(Comparative Examples 4 and 5)
Example 1 except that the hindered phenolic antioxidant (E) of Example 1 was changed to (E-4) 0.1 parts by weight (Comparative Example 4) and 0.5 parts by weight (Comparative Example 5). Similarly, a polyolefin resin composition was obtained and evaluated. The results are shown in Table 2. Furthermore, even if the amount of high molecular weight (E-4) is increased while increasing the amount of hydrotalcite (C-1), there is no significant improvement in heat aging resistance.
（比較例６、７）
実施例１のヒンダードフェノール系酸化防止剤（Ｅ）を、（Ｅ−５）０．５重量部（比較例６）、（Ｅ−６）０．５重量部（比較例７）、とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。酸化防止剤（Ｅ）成分の分子量が８００以下であっても、１，３，５−トリメチルベンゼン、イソシアヌル酸、骨格を有していると耐熱老化性がでない。
(Comparative Examples 6 and 7)
The hindered phenol antioxidant (E) of Example 1 was (E-5) 0.5 part by weight (Comparative Example 6) and (E-6) 0.5 part by weight (Comparative Example 7). Except for the above, a polyolefin resin composition was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 2. Even if the molecular weight of the antioxidant (E) component is 800 or less, if it has 1,3,5-trimethylbenzene, isocyanuric acid, or a skeleton, it does not have heat aging resistance.
（比較８、９）
実施例４の成分（Ｂ−１）を２０重量部（比較例８）、７０重量部（比較例９）とした以外は実施例１と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。成分（Ｂ−１）の量が少な過ぎる場合は、耐熱老化性を満足するが燃焼性が満足しなくなる。また、多過ぎる場合は、燃焼性は満足するが衝撃強度、耐熱老化性が満足しなくなってしまう。
(Comparison 8 and 9)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 1 except that the component (B-1) of Example 4 was changed to 20 parts by weight (Comparative Example 8) and 70 parts by weight (Comparative Example 9). The results are shown in Table 2. When the amount of the component (B-1) is too small, the heat aging resistance is satisfied but the combustibility is not satisfied. On the other hand, when the amount is too large, the combustibility is satisfied, but the impact strength and the heat aging resistance are not satisfied.
（比較例１０）
実施例４の成分（Ｃ）を、（Ｃ−１）から（Ｃ−２）に変更した以外は実施例４と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。ハイドロタルサイト（Ｃ−１）に代えて成分（Ｃ−２）にした場合、耐熱老化性が満足出来ない。
(Comparative Example 10)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 4 except that the component (C) of Example 4 was changed from (C-1) to (C-2). The results are shown in Table 2. When the component (C-2) is used instead of the hydrotalcite (C-1), the heat aging resistance cannot be satisfied.
（比較例１１）
実施例４の成分（Ｄ−１）を用いなかった以外は実施例４と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。成分（Ｄ）がない場合、耐熱老化性、衝撃強度、難燃性が良好になるが、耐熱老化性試験前に著しく着色してい色調で満足できない。
(Comparative Example 11)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 4 except that the component (D-1) of Example 4 was not used. The results are shown in Table 2. In the absence of component (D), heat aging resistance, impact strength, and flame retardancy are improved, but the color tone is markedly unsatisfactory before the heat aging test.
（比較例１２）
実施例４の成分（Ｅ）を用いなかった以外は実施例４と同様にしてポリオレフィン樹脂組成物を得、評価した。結果を表２に示す。成分（Ｅ）を用いないと耐熱老化性が著しくでない。
(Comparative Example 12)
A polyolefin resin composition was obtained and evaluated in the same manner as in Example 4 except that the component (E) in Example 4 was not used. The results are shown in Table 2. Unless component (E) is used, the heat aging resistance is not remarkable.
本発明の難燃性ポリプロピレン系樹脂組成物は、従来知られている無機塩坦持／又は含有金属水和化合物の難燃性樹脂組成物より優れた耐熱性、耐熱老化性と難燃性を示し、その工業的価値は極めて大きい。 The flame retardant polypropylene-based resin composition of the present invention has superior heat resistance, heat aging resistance and flame retardancy than the conventionally known flame retardant resin compositions of inorganic salt supported / containing metal hydrate compounds. The industrial value is very large.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004380528A JP5140234B2 (en) | 2004-12-28 | 2004-12-28 | Polyolefin resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004380528A JP5140234B2 (en) | 2004-12-28 | 2004-12-28 | Polyolefin resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006182988A JP2006182988A (en) | 2006-07-13 |
| JP5140234B2 true JP5140234B2 (en) | 2013-02-06 |
Family
ID=36736334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004380528A Active JP5140234B2 (en) | 2004-12-28 | 2004-12-28 | Polyolefin resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5140234B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5137734B2 (en) * | 2008-08-02 | 2013-02-06 | 日本ポリプロ株式会社 | Flame-retardant polypropylene-based resin composition and molded article using the composition |
| JP5467684B2 (en) * | 2010-02-18 | 2014-04-09 | 出光ライオンコンポジット株式会社 | Discoloration-resistant polypropylene resin composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002302612A (en) * | 2001-01-31 | 2002-10-18 | Ishizuka Glass Co Ltd | Flame retardance-imparting composite material, and flame-retardant polymeric composite material |
| JP2003231711A (en) * | 2002-02-08 | 2003-08-19 | Asahi Denka Kogyo Kk | Method for stabilizing polyolefin resin |
| JP3964314B2 (en) * | 2002-11-28 | 2007-08-22 | カルプ工業株式会社 | Method for producing flame retardant resin composition |
-
2004
- 2004-12-28 JP JP2004380528A patent/JP5140234B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006182988A (en) | 2006-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20100087573A1 (en) | Halogen-free flame retardant thermoplastic compositions | |
| TWI752979B (en) | Flame retardant composition and flame retardant synthetic resin composition | |
| CN109206829B (en) | High-yellowing-resistance precipitation-resistance halogen-free flame-retardant thermoplastic elastomer composition and preparation method thereof | |
| JP7158389B2 (en) | Composition and flame-retardant resin composition | |
| US6444736B1 (en) | Flame retardant polyolefin composition | |
| EP3176212B1 (en) | Flame-retardant resin composition and article molded from same | |
| JP5140234B2 (en) | Polyolefin resin composition | |
| KR100814983B1 (en) | Polypropylene resin composition having excellent impact characteristics | |
| JP2018030939A (en) | Flame-retardant resin composition and molding | |
| AU610008B2 (en) | Self-extinguishing polymer composition | |
| JP4721823B2 (en) | Flame retardant resin composition and molded body comprising the same | |
| JP2009035581A (en) | Flame-retardant polypropylene resin composition | |
| JPH10195254A (en) | Flame-retardant polyolefin composition | |
| JPH03207733A (en) | Polyolefin resin composition containing carbon black | |
| JP7479406B2 (en) | Flame-retardant resin composition and molded article thereof | |
| KR102548685B1 (en) | Flame-retardant Polypropylene Resin Composition with Excellent Transparency | |
| JPH09296120A (en) | Flame-retardant resin composition | |
| JP7248457B2 (en) | Polypropylene-based resin composition and molding for automobile interior parts | |
| TW202309254A (en) | Flame retardant agent composition, flame retardant resin composition, and molded article thereof | |
| KR20230150118A (en) | Preparation of polyolefin-based flame-retardant composite composition having flame-retardant and heat-shielding performance | |
| JP2001348489A (en) | Flame-retardant resin composition and its molded article | |
| JP2696558B2 (en) | Flame retardant polyolefin composition | |
| JP2024067493A (en) | Flame-retardant polypropylene resin composition and molded body thereof | |
| CN113195612A (en) | Polymer composition, article comprising said composition and use of said article | |
| JP2022017798A (en) | Method for producing polyolefin resin composition, polyolefin resin composition and molding thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070611 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100408 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100511 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100709 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20100907 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101202 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20101210 |
|
| A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20110121 |
|
| 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: 20121119 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5140234 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151122 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151122 Year of fee payment: 3 |
|
| 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 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |