JP2587687B2 - Stabilized polyethylene composition - Google Patents
Stabilized polyethylene compositionInfo
- Publication number
- JP2587687B2 JP2587687B2 JP63203430A JP20343088A JP2587687B2 JP 2587687 B2 JP2587687 B2 JP 2587687B2 JP 63203430 A JP63203430 A JP 63203430A JP 20343088 A JP20343088 A JP 20343088A JP 2587687 B2 JP2587687 B2 JP 2587687B2
- Authority
- JP
- Japan
- Prior art keywords
- butyl
- diphosphite
- pentaerythritol
- compound
- bis
- 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.)
- Expired - Lifetime
Links
- -1 polyethylene Polymers 0.000 title claims description 113
- 239000004698 Polyethylene Substances 0.000 title claims description 48
- 229920000573 polyethylene Polymers 0.000 title claims description 48
- 239000000203 mixture Substances 0.000 title claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 27
- 229940126062 Compound A Drugs 0.000 claims description 21
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- JOYKALXNNJOSEW-UHFFFAOYSA-N [2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)ethyl]-4-methylphenyl] prop-2-enoate Chemical compound C=1C(C)=CC(C(C)(C)C)=C(OC(=O)C=C)C=1C(C)C1=CC(C)=CC(C(C)(C)C)=C1O JOYKALXNNJOSEW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 2
- SUXWHFLDQMZSAV-UHFFFAOYSA-N OP(O)OP(O)O.C1(=CC=CC=C1)C(O)C(CO)(CO)CO Chemical compound OP(O)OP(O)O.C1(=CC=CC=C1)C(O)C(CO)(CO)CO SUXWHFLDQMZSAV-UHFFFAOYSA-N 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 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 description 19
- 238000004040 coloring Methods 0.000 description 19
- 239000003963 antioxidant agent Substances 0.000 description 18
- 239000002530 phenolic antioxidant Substances 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 17
- 239000008188 pellet Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 12
- 238000004898 kneading Methods 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 229920001519 homopolymer Polymers 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000001879 gelation Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 241000251468 Actinopterygii Species 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000003405 preventing effect Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002074 melt spinning Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- SACHYAMVGCBGLW-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(C)CC)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C(C)CC)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(C)CC)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C(C)CC)C(C)(C)C SACHYAMVGCBGLW-UHFFFAOYSA-N 0.000 description 2
- JOKYPIPMUIUEDL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CCCC)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)CCCC)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CCCC)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)CCCC)C(C)(C)C JOKYPIPMUIUEDL-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 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 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 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 1
- ZAHBNGOLTBLVHO-UHFFFAOYSA-N 1,1-bis(2,6-dibutyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(CCC)C1=C(C(=CC(=C1)C)CCCC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1CCCC)C)CCCC ZAHBNGOLTBLVHO-UHFFFAOYSA-N 0.000 description 1
- VHKDMBZLAJXXTJ-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-octylphenyl)-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)CCCCCCCC)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)CCCCCCCC)C(C)(C)C VHKDMBZLAJXXTJ-UHFFFAOYSA-N 0.000 description 1
- WDFWADXIZQJVEX-UHFFFAOYSA-N 1,1-bis[2,6-di(butan-2-yl)-4-methylphenyl]-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(CC)C1=C(C(=CC(=C1)C)C(C)CC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)CC)C)C(C)CC WDFWADXIZQJVEX-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- QPARWRUFFNGOPH-UHFFFAOYSA-N 2-[2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)ethyl]-4-methylphenyl]prop-2-enoic acid Chemical compound C=1C(C)=CC(C(C)(C)C)=C(C(=C)C(O)=O)C=1C(C)C1=CC(C)=CC(C(C)(C)C)=C1O QPARWRUFFNGOPH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VALLALWNAZEWOJ-UHFFFAOYSA-N C(C(=C)C)(=O)OC1=C(C=C(C=C1C(C)C1=C(C(=CC(=C1)C)C(C)(C)C)O)C)C(C)(C)C Chemical compound C(C(=C)C)(=O)OC1=C(C=C(C=C1C(C)C1=C(C(=CC(=C1)C)C(C)(C)C)O)C)C(C)(C)C VALLALWNAZEWOJ-UHFFFAOYSA-N 0.000 description 1
- WKCZWTPMILBZNI-UHFFFAOYSA-N C(C=C)(=O)OC1=C(C=C(C=C1CC1=C(C(=CC(=C1)C)C(C)(C)CC(C)(C)C)O)C)C(C)(C)CC(C)(C)C Chemical compound C(C=C)(=O)OC1=C(C=C(C=C1CC1=C(C(=CC(=C1)C)C(C)(C)CC(C)(C)C)O)C)C(C)(C)CC(C)(C)C WKCZWTPMILBZNI-UHFFFAOYSA-N 0.000 description 1
- BLGRBEQSPNLSGA-UHFFFAOYSA-N CCC(C)C(C=C1C(C)(C)C)=CC(C(C)C2=CC(C(C)CC)=CC(C(C)(C)C)=C2OC(C=C)=O)=C1O Chemical compound CCC(C)C(C=C1C(C)(C)C)=CC(C(C)C2=CC(C(C)CC)=CC(C(C)(C)C)=C2OC(C=C)=O)=C1O BLGRBEQSPNLSGA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- RCZRMCMDNRCJSE-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(C)(C)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(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)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C(C)(C)C)C(C)(C)C RCZRMCMDNRCJSE-UHFFFAOYSA-N 0.000 description 1
- SOHFCLCKXWGBPR-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(C)(C)CC(C)(C)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C(C)(C)CC(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)CC(C)(C)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C(C)(C)CC(C)(C)C)C(C)(C)C SOHFCLCKXWGBPR-UHFFFAOYSA-N 0.000 description 1
- NHWUYWAZWZKMKB-UHFFFAOYSA-N 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=CC=C1C(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(O)(C(CO)(CO)CO)C1=C(C=CC=C1C(C)(C)C)C(C)(C)C NHWUYWAZWZKMKB-UHFFFAOYSA-N 0.000 description 1
- DETBYUFYMNAGAS-UHFFFAOYSA-N OP(O)OP(O)O.C(CC)C1=C(C(=CC(=C1)C)CCC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1CCC)C)CCC Chemical compound OP(O)OP(O)O.C(CC)C1=C(C(=CC(=C1)C)CCC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1CCC)C)CCC DETBYUFYMNAGAS-UHFFFAOYSA-N 0.000 description 1
- SAGLNRIBIWFMKS-UHFFFAOYSA-N OP(O)OP(O)O.C(CCC)C1=C(C(=CC(=C1)CCCC)CCCC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1CCCC)CCCC)CCCC Chemical compound OP(O)OP(O)O.C(CCC)C1=C(C(=CC(=C1)CCCC)CCCC)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1CCCC)CCCC)CCCC SAGLNRIBIWFMKS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- ZVMCTBRFAFJZHQ-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] 2-methylprop-2-enoate Chemical compound C1=C(C)C=C(C(C)(C)C)C(OC(=O)C(=C)C)=C1CC1=CC(C)=CC(C(C)(C)C)=C1O ZVMCTBRFAFJZHQ-UHFFFAOYSA-N 0.000 description 1
- MNSLGKMABZFTBX-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenyl] 2-methylprop-2-enoate Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)OC(=O)C(C)=C)=C1O MNSLGKMABZFTBX-UHFFFAOYSA-N 0.000 description 1
- PFCYRDCICMKDIT-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)OC(=O)C=C)=C1O PFCYRDCICMKDIT-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- CWGBRLKMLXPOIE-UHFFFAOYSA-N [P].C Chemical compound [P].C CWGBRLKMLXPOIE-UHFFFAOYSA-N 0.000 description 1
- PNEOMAJLPNDNPM-UHFFFAOYSA-N [P].P(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C Chemical compound [P].P(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)(OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C)OC1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C PNEOMAJLPNDNPM-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate 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
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
ãçºæã®è©³çŽ°ãªèª¬æã ç£æ¥äžã®å©çšåé æ¬çºæã¯ãå®å®åãããããªãšãã¬ã³çµæç©ã«é¢ã
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å£åé²æ¢æ§ã«åªããããªãšãã¬ã³çµæç©ã«é¢ãããDescription: FIELD OF THE INVENTION The present invention relates to stabilized polyethylene compositions. More specifically, the present invention relates to a polyethylene composition which is excellent in preventing polyethylene from being oxidatively degraded during melt-kneading.
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ãŠãã£ãã·ã¥ã¢ã€ãçºçãããšãã£ãåé¡ãããã[Prior Art] In general, polyethylene is relatively inexpensive and has excellent mechanical properties, and is therefore used in the production of various molded products such as injection molded products, hollow molded products, films, sheets, and fibers. However, when polyethylene is molded at a temperature equal to or higher than the melting point of the polyethylene, it undergoes oxidative deterioration due to heat during melt-kneading, and the processability due to crosslinking of the polyethylene, that is, the melt stability is reduced, and the appearance of the molded product is reduced. In addition, coloring and odor problems due to oxidative deterioration occur. In particular, in an extrusion molding method such as melt spinning, a continuous operation for a long time causes the crosslinking of polyethylene to proceed to generate a gelled product, which causes clogging of the screen pack due to the gelled product, resulting in a decrease in discharge amount and Problems such as a remarkable decrease in productivity due to frequent replacement of the screen pack and the like occur. Further, when formed into a film or sheet, there is a problem that fish eyes are generated due to a high molecular weight component due to a gelation reaction.
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å€ãããããåç¬ã«ãŸãã¯äœµçšããŠçšããããŠãããFor this reason, conventionally, various phenolic and phosphorus-based antioxidants are used alone or in combination with each other for the purpose of preventing the thermal oxidation deterioration during melt-kneading of polyethylene and improving the melt stability and the anti-gelling property. Used.
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ãé¡èãšãªããšãã£ãåé¡ç¹ãããã[Problems to be Solved by the Invention] However, conventional phenolic antioxidants, especially low-molecular-weight phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol, are blended in polyethylene. Is excellent in heat-resistant oxidative deterioration during melt-kneading (hereinafter referred to as processing stability, and processing stability means melt stability and anti-gelling properties), but when a molded article is obtained. However, there is a disadvantage that the molded article is colored due to the antioxidant used. Further, a composition obtained by mixing only a high molecular weight phenolic antioxidant with polyethylene has disadvantages in processing stability and coloring property caused by the high molecular weight phenolic antioxidant. Further, a composition comprising the polyethylene in combination with the low-molecular-weight phenolic antioxidant and the high-molecular-weight phenolic antioxidant described above, although the processing stability of the composition is excellent, almost no synergistic effect due to the combination is observed. On the contrary, there is a problem that the coloring of the obtained molded article becomes conspicuous by increasing the amount of the phenolic antioxidant.
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ãããOn the other hand, in the case of a composition obtained by mixing only a phosphorus-based antioxidant with polyethylene, the problem of the coloring property observed in a molded article obtained from the composition obtained by mixing the above-mentioned phenol-based antioxidant is remarkably improved. However, there is a disadvantage that the melt stability, which is the processing stability when subjected to severe heat history due to several times of melt-kneading, is significantly reduced. For this reason, it is conceivable to use a high-molecular-weight phenolic antioxidant having a synergistic action with the phosphorus-based antioxidant in combination. However, such a combined system can improve the processing stability, particularly the melt stability, and the coloring property caused by the used antioxidant, which are problems of the prior art, to some extent, but they are still insufficient. Particularly, in the case of a conventionally used combination system of a high-molecular-weight phenolic antioxidant and a phosphorus-based antioxidant, the effect of preventing gelation of the combined system is recognized to some extent, but is not yet sufficient. At present, in extrusion molding such as melt-spinning which performs continuous operation for a longer time than ever, improvement of gelation prevention among processing stability is strongly desired at present.
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ããã«éæç 究ãããIn order to solve the above-mentioned problems relating to the above-mentioned polyethylene composition, namely, the drawbacks of processing stability and colorability, the present inventors have previously disclosed in JP-A-62-223248 a specific acrylate group-containing phenolic antioxidant. In addition, a polyethylene composition using a phosphorus-based antioxidant comprising a specific phosphite compound or a specific phosphite compound has been proposed, but further studies have been made without satisfaction.
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æãå®æãããAs a result, a phenolic compound represented by the following general formula [I] (hereinafter, referred to as compound A) and a phosphite-based compound represented by the following general formula [II] (hereinafter, referred to as compound B) are respectively specified in polyethylene. The inventors have found that a composition obtained by blending in a large amount can solve the above-mentioned disadvantages of the polyethylene composition, and based on this finding, completed the present invention.
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ãšã§ããã (Wherein, R 1 is hydrogen or an alkyl group having 1 to 3 carbon atoms, R 2 to R 5 are an alkyl group having 1 to 9 carbon atoms, a cyclohexyl group or 1-methylcyclohexyl group, and R 6 is hydrogen or A methyl group, R 7 and R 9 each represent a branched alkyl group having 3 to 9 carbon atoms, and R 8 represents hydrogen or an alkyl group having 1 to 9 carbon atoms.) As apparent from the above description, An object of the present invention is to provide a polyethylene composition which is excellent in processing stability and can obtain a molded article free from coloring caused by an antioxidant used.
課é¡ã解決ããããã®æ段 æ¬çºæã¯ãäžèšã®æ§æãæããã[Means for Solving the Problems] The present invention has the following configurations.
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ç©ãFor 100 parts by weight of polyethylene, the following general formula [I]
(Hereinafter referred to as compound A) and a phosphite compound (hereinafter referred to as compound B) represented by the following general formula [II] are each 0.01.
A stabilized polyethylene composition, which is blended with 1 to 1 part by weight.
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ãç¹ã«å¥œãŸããçšããããã (Wherein, R 1 is hydrogen or an alkyl group having 1 to 3 carbon atoms, R 2 to R 5 are an alkyl group having 1 to 9 carbon atoms, a cyclohexyl group or 1-methylcyclohexyl group, and R 6 is hydrogen or A methyl group, R 7 and R 9 each represent a branched alkyl group having 3 to 9 carbon atoms, and R 8 represents hydrogen or an alkyl group having 1 to 9 carbon atoms.) The polyethylene used in the present invention is a crystal of ethylene. A homopolymer, an ethylene copolymer containing 50% by weight or more of an ethylene component, wherein ethylene and propylene, butene-
1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, etc., with one or more α-olefins, such as a crystalline, low-crystalline or amorphous copolymer, Polyethylene such as a crystalline ethylene-propylene-nonconjugated diene copolymer, a copolymer of ethylene and vinyl acetate or acrylate, a saponified product of the copolymer, a copolymer of ethylene and an unsaturated silane compound, Copolymer of ethylene and unsaturated carboxylic acid or anhydride, reaction product of the copolymer and metal ion compound, modified polyethylene obtained by modifying the above polyethylene with unsaturated carboxylic acid or derivative thereof, polyethylene described above Examples thereof include silane-modified polyethylene modified with an unsaturated silane compound. , It can also be used in combination of two or more polyethylene. In addition, various synthetic rubbers (for example, polybutadiene, polyisoprene,
Polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluoro rubber, styrene-butadiene rubber,
Acrylonitrile-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc. )
Or thermoplastic synthetic resins (for example, polyolefins other than polyethylene such as polypropylene, polybutene-1 and poly-4-methylpentene-1; polystyrene;
Styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, fluororesin, etc.) may be used as a mixture. A crystalline ethylene homopolymer, a crystalline ethylene copolymer containing 50% by weight of an ethylene component, comprising a crystalline ethylene-propylene copolymer, a crystalline ethylene-butene-1 copolymer, and a crystalline ethylene-propylene -Butene-1 terpolymer, crystalline ethylene-pentene-1 copolymer, crystalline ethylene-
Hexene-1 copolymer and a mixture of two or more thereof are particularly preferably used.
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ãå®éçã§ãªãã°ããã§ãªããŸãäžçµæžã§ãããThe compound A used in the present invention includes 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-t
-Butyl-6- (3-t-butyl-2-hydroxy-5
-Ethylbenzyl) -4-ethylphenyl acrylate, 2-nonyl-6- (3-nonyl-2-hydroxy-
5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-nonyl-6- (3,5-di-nonyl-2-hydroxybenzyl) phenyl acrylate, 2-cyclohexyl-6- (3-cyclohexyl- 2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- (1'-methylcyclohexyl) -6- [3
-(1'-methylcyclohexyl) -2-hydroxy-
5-methylbenzyl] -4-methylphenyl acrylate, 2,4-di-methyl-6- [3,5-di-methyl-2-hydroxy (α-propylbenzyl)] phenyl acrylate, 2,4-di- t-butyl-6- (3,5-di-t-butyl-2-hydroxybenzyl) phenyl acrylate,
2-tert-butyl-6- [3-tert-butyl-2-hydroxy-5-methyl (α-methylbenzyl)]-4-methylphenyl acrylate, 2-tert-butyl-6- [3-t
-Butyl-2-hydroxy-5-s-butyl (α-methylbenzyl)]-4-s-butylphenyl acrylate, 2,4-di-t-butyl-6- [3,5-di-t-butyl -2-hydroxy (α-methylbenzyl)] phenyl acrylate, 2-t-octyl-6- (3-t-octyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- (1 Ⲡ-Methylcyclohexyl) -6- [3- (1'-methylcyclohexyl)
-2-hydroxy-5-methyl (α-propylbenzyl)]-4-methylphenyl acrylate, 2,4-di-
Methyl-6- (3,5-di-methyl-2-hydroxybenzyl) phenyl acrylate, 2-tert-butyl-6
(3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl methacrylate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-ethylbenzyl) -4- Ethylphenyl methacrylate,
2-nonyl-6- (3-nonyl-2-hydroxy-5-
Methylbenzyl) -4-methylphenyl methacrylate, 2,4-di-nonyl-6- (3,5-di-nonyl-2-hydroxybenzyl) phenyl methacrylate, 2-cyclohexyl-6- (3-cyclohexyl-2- (Hydroxy-5-methylbenzyl) -4-methylphenyl methacrylate, 2- (1â²-methylcyclohexyl) -6-
[3- (1'-methylcyclohexyl) -2-hydroxy-5-methylbenzyl] -4-methylphenyl methacrylate, 2,4-di-methyl-6- [3,5-di-methyl-
2-hydroxy (α-propylbenzyl)] phenyl methacrylate, 2,4-di-t-butyl-6- (3,5-di-
(tert-butyl-2-hydroxybenzyl) phenyl methacrylate, 2-tert-butyl-6- [3-tert-butyl-2
-Hydroxy-5-methyl (α-methylbenzyl)]-
4-methylphenyl methacrylate, 2-t-butyl-
6- [3-tert-butyl-2-hydroxy-5-s-butyl (α-methylbenzyl)]-4-s-butylphenyl methacrylate, 2,4-di-tert-butyl-6- [3,5 -Di-t-butyl-2-hydroxy (α-methylbenzyl)] phenyl methacrylate, 2-t-octyl-6
-(3-t-octyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl methacrylate, 2-
(1â²-methylcyclohexyl) -6- [3- (1â²-
Methylcyclohexyl) -2-hydroxy-5-methyl (α-propylbenzyl)]-4-methylphenylmethacrylate and 2,4-di-methyl-6- (3,5-di-methyl-2-hydroxybenzyl) phenyl Examples thereof include methacrylate and the like, in particular, 2-t-butyl-6- (3-t
-Butyl-2-hydroxy-5-methylbenzyl) -4
-Methylphenyl acrylate, 2-t-butyl-6-
[3-tert-butyl-2-hydroxy-5-methyl (α-
Methylbenzyl)]-4-methylphenyl acrylate and 2,4-di-t-butyl-6- [3,5-di-t-butyl-2-hydroxy (α-methylbenzyl)] phenyl acrylate are preferred. These compounds A may be used alone, or two or more compounds A may be used in combination. The compounding ratio of the compound A is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of polyethylene. If the amount is less than 0.01 part by weight, the effect of improving the processing stability and the anti-coloring property of the polyethylene composition is not sufficiently exhibited, and the content may exceed 1 part by weight. It is not practical because the improvement effect cannot be expected, and it is uneconomical.
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çã§ãªãã°ããã§ãªããŸãäžçµæžã§ãããAs compound B used in the present invention, bis (2,6-di-i-propyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2-i-propyl-
6-t-butylphenyl) pentaerythritol-diphosphite, bis (2-i-propyl-4-methyl-
6-t-butylphenyl) pentaerythritol-diphosphite, bis (2-i-propyl-4-ethyl-
6-t-butylphenyl) pentaerythritol-diphosphite, bis (2-i-propyl-4,6-di-t
-Butylphenyl) pentaerythritol-diphosphite, bis (2,6-di-i-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,6-di-i-butyl-4-ethyl) Phenyl) pentaerythritol-diphosphite, bis (2,4,6-tri-i-butylphenyl) pentaerythritol-diphosphite, bis (2,6-di-i-butyl-4-t-)
Butylphenyl) pentaerythritol-diphosphite, bis (2,6-di-s-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,6-di-s-butyl-4-ethylphenyl) ) Pentaerythritol-diphosphite, bis (2,4,6-tri-s-butylphenyl) pentaerythritol-diphosphite, bis (2,6-di-s-butyl-4-t-)
Butylphenyl) pentaerythritol-diphosphite, bis (2-s-butyl-4-methyl-6-t-butylphenyl) pentaerythritol-diphosphite, bis (2-s-butyl-4-ethyl-6- t-butylphenyl) pentaerythritol-diphosphite, bis (2-s-butyl-4-i-butyl-6-t-
Butylphenyl) pentaerythritol-diphosphite, bis (2,4-di-s-butyl-6-t-butylphenyl) pentaerythritol-diphosphite, bis (2-s-butyl-4,6-di- t-butylphenyl)
Pentaerythritol diphosphite, bis (2,6
-Di-t-butylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl) -4-ethylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-n-propylphenyl)
Pentaerythritol diphosphite, bis (2,6
-Di-t-butyl-4-i-propylphenyl) pentaerythritol-diphosphite, bis (2,6-di-
t-butyl-4-n-butylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-i-butylphenyl) pentaerythritol-
Diphosphite, bis (2,6-di-t-butyl-4-
(s-butylphenyl) pentaerythritol-diphosphite, bis (2,4,6-tri-t-butylphenyl)
Pentaerythritol diphosphite, bis (2,6
-Di-t-butyl-4-n-amylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t
-Butyl-4-i-amylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-s-amylphenyl) pentaerythritol-diphosphite, bis (2,6-diphenyl) -T-butyl-4-t
-Amylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-n-hexylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4) -N-heptyl)
Pentaerythritol diphosphite, bis (2,6
-Di-t-butyl-4-n-octylphenyl) pentaerythritol-diphosphite, bis (2,6-di-
t-butyl-4-t-octylphenyl) pentaerythritol-diphosphite, bis (2-t-butyl-
4-methyl-6-i-amylphenyl) pentaerythritol-diphosphite, bis (2-t-butyl-4)
-Methyl-6-s-amylphenyl) pentaerythritol-diphosphite, bis (2-tert-butyl-4-)
Methyl-6-t-amylphenyl) pentaerythritol-diphosphite, bis (2-t-butyl-4-methyl-6-t-octylphenyl) pentaerythritol-diphosphite, bis (2-t-butyl- 4-ethyl-6-i-amylphenyl) pentaerythritol diphosphite, bis (2-t-butyl-4-ethyl-6-s-amylphenyl) pentaerythritol-
Diphosphite, bis (2-tert-butyl-4-ethyl-6-tert-amylphenyl) pentaerythritol-diphosphite, bis (2-tert-butyl-4-ethyl-)
6-t-octylphenyl) pentaerythritol-diphosphite, bis (2,4-di-t-butyl-6-t
-Amylphenyl) pentaerythritol-diphosphite and bis (2,4-di-t-butyl-6-t-octylphenyl) pentaerythritol-diphosphite, and especially bis (2,6-di- t-butyl-4-methylphenyl) pentaerythritol-diphosphite and bis (2,6-di-t-butyl-4-s)
-Butylphenyl) pentaerythritol-diphosphite is preferred. These compounds B may be used alone, or two or more compounds B may be used in combination.
The compounding ratio of the compound B is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of polyethylene. If the amount is less than 0.01 part by weight, the effect of improving the processing stability and the anti-coloring property of the polyethylene composition is not sufficiently exhibited, and the content may be more than 1 part by weight, but the processing stability and the anti-coloring property are further increased. It is not practical because the improvement effect cannot be expected, and it is uneconomical.
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䜵çšããããšãã§ãããIn the composition of the present invention, various additives which are usually added to polyethylene, such as phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, heavy metal deactivators (copper harm inhibitors). , Clarifiers, nucleating agents, lubricants, antistatic agents, antifogging agents, antiblocking agents, drip-free agents, flame retardants, flame retardant aids, pigments, radical generators such as peroxides,
Dispersants or neutralizers such as metal soaps, inorganic fillers (for example, talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, zinc oxide , Magnesium oxide, zinc sulfide,
Barium sulfate, calcium silicate, aluminum silicate, glass fiber, potassium titanate, carbon fiber, carbon black, graphite, metal fiber, etc. or coupling agent (for example, silane, titanate, boron, aluminate, zircon) The inorganic filler or the organic filler (for example, wood flour, pulp, waste paper, synthetic fiber, natural fiber, etc.) surface-treated with a surface treating agent such as an aluminate-based agent within a range not to impair the object of the present invention. Can be used together.
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ãããThe composition of the present invention is prepared by adding a predetermined amount of Compound A and Compound B to polyethylene and the above-mentioned various additives usually added to polyethylene by using a conventional mixing device such as a Hensel mixer (trade name), a super mixer, a ribbon blender,
Mixing using a Banbury mixer or the like, and melt-kneading pelletizing at a melt-kneading temperature of 120 ° C to 300 ° C, preferably 180 ° C to 270 ° C using a normal single-screw extruder, a twin-screw extruder, a Brabender or a roll or the like. Can be obtained by The obtained composition is used for production of a target molded article by various molding methods such as an injection molding method, an extrusion molding method, and a blow molding method.
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ãã¹ãçžä¹å¹æãçºæ®ãããã[Action] In the present invention, the action mechanism itself of the combined use of compound A and compound B during melt-kneading of the polyethylene composition is not clear. However, the phenolic antioxidant represented by the compound A is used, for example, in a cylinder of an extruder (a system near an oxygen-free state).
Reported that a radical is added to a double bond of an acrylate group of compound A, and a proton of a hydroxyl group of phenol is transferred to a generated active carbon radical to stabilize as a phenoxy radical. It is generally known that a phosphorus-based antioxidant comprising a phosphite-based compound represented by Compound B acts as a peroxide decomposer. In the present invention, by using the compound A and the compound B together, a surprising synergistic effect which can hardly be predicted from a combination with various conventionally known antioxidants is exhibited.
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ãªããEXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
ãªããå®æœäŸããã³æ¯èŒäŸã§çšããè©äŸ¡æ¹æ³ã¯æ¬¡ã®æ¹
æ³ã«ãã£ããThe evaluation method used in the examples and comparative examples was based on the following method.
ïŒïŒå å·¥å®å®æ§ ïŒïŒ¡ïŒæº¶èå®å®æ§ åŸããããã¬ããã®ã¡ã«ãã€ã³ããã¯ã¹ïŒMIïŒã枬å®
ïŒJIS K 6760ã«æºæ ïŒããããã第1MIãšããããããŠ
åŸããããã¬ãããçšããŠå床溶è混緎枩床270âã«ãŠ
溶èæ··ç·ŽåŠçããŠãã¬ã¿ã€ãºãããããïŒåç¹°ãè¿ã
ããåŸããããã¬ããã®MIã溶èæ··ç·Žã®éœåºŠãå床åèš
ã®æ¹æ³ã§æž¬å®ãããããããããã第2MIã第3MIã第4M
Iã第5MIãšããã1) Processing stability (A) Melt stability The melt index (MI) of the obtained pellet is measured (based on JIS K 6760), and this is defined as the first MI. The obtained pellets were again melt-kneaded at a melt-kneading temperature of 270 ° C. and pelletized, and this was repeated four times. Each time the melt-kneaded MI of the obtained pellets was measured again by the above-described method, and these were respectively measured in the second MI, the third MI, and the fourth MI.
I, 5th MI.
溶èå®å®æ§ã¯æ¬¡åŒã«ããå®çŸ©ãããMIä¿æçã®å€§å°ã
ãè©äŸ¡ãããMelt stability was evaluated based on the magnitude of MI retention as defined by the following equation.
ïŒç¬¬5MIã¯æŒåºæ©ãïŒåééããã®ã¡ã®MIã瀺ããïŒ MIä¿æçã®æ°å€ã1.0ã«è¿ãçšãç¹°ãè¿ãæŒåºæèšã
æãããšæ圢å å·¥æã§ã®å å·¥å®å®æ§ã§ãã溶èå®å®æ§ã
åªããŠããããšã瀺ãã (The 5th MI indicates the MI after five passes through the extruder.) The closer the numerical value of the MI retention rate is to 1.0, the more excellent the melt stability which is the processing stability at the time of repeated extrusion, in other words, the molding process. To indicate that
ïŒïŒ¢ïŒã²ã«åé²æ¢æ§ ã²ã«åé²æ¢æ§ã¯åŸããããã¬ãããçšããŠä»¥äžã®ãã
ããã®æ¹æ³ã«ããè©äŸ¡ããã(B) Anti-gelling property The anti-gelling property was evaluated by any of the following methods using the obtained pellets.
ïŒïœïŒãã£ãã·ã¥ã¢ã€ å£åŸ30mmã®ïŒŽãã€æŒåºæ©ãçšããŠãã·ãªã³ããŒæž©åºŠ19
0âã250âããã€æž©åºŠ250âãæš¹èå§å250kg/cm2Gã§å
ã0.4mmã®ã·ãŒããäœæãããã®ã·ãŒã1000cm2äžã®çŽåŸ
0.3mm以äžã®ãã£ãã·ã¥ã¢ã€ãæ€åºèšæ°ããããã£ãã·
ã¥ã¢ã€ã®å€ãå°ããçšé«ååéæåïŒã²ã«åç©ïŒã®çæ
ãå°ãªãã²ã«åé²æ¢æ§ã«åªããŠããããšã瀺ãã(A) Fish eye Using a T-die extruder with a diameter of 30 mm, the cylinder temperature was 19
0 ° C. to 250 DEG ° C., die temperature 250 ° C., into a sheet having a thickness of 0.4mm in resin pressure 250kg / cm 2 G, the diameter in the sheet 1000 cm 2
Fish eyes of 0.3 mm or more were detected and counted. The smaller the fisheye value is, the less the high molecular weight component (gelled product) is formed, indicating that the gelling prevention property is excellent.
ïŒïœïŒæŒåºç¹æ§ïŒã¹ã¯ãªãŒã³ããã¯ã®ç®è©°ãŸãïŒ å£åŸ20mmã®çŽ¡ç³žæ©ïŒå£åŸ0.5mmã®ããºã«åã50æ¬æã
ããã€ããã³300meshã®ã¹ã¯ãªãŒã³ããã¯ãïŒæ䜿çšïŒ
ãçšããŠãã·ãªã³ããŒæž©åºŠ190âã250âããã€æž©åºŠ250
âãæš¹èå§å30kg/cm2Gã§æº¶è玡糞ãéå§ããæš¹èå§å
ã50kg/cm2GãšãªããŸã§é£ç¶é転ãè¡ããæš¹èå§åã50k
g/cm2Gãšãªã£ãæç¹ïŒæ¥æ°ïŒãã¹ã¯ãªãŒã³ããã¯ã®ç®è©°
ãŸããšããããã®æ¥æ°ã倧ããçšã²ã«åç©ã®çæãå°ãª
ãã²ã«åé²æ¢æ§ã«åªããŠããã(B) Extrusion characteristics (clogging of screen pack) Spinning machine with 20 mm diameter (using a die having 50 nozzle holes with 0.5 mm diameter and three 300mesh screen packs)
Cylinder temperature 190 â ~ 250 â, Die temperature 250
° C., to start the melt-spun at a resin pressure 30kg / cm 2 G, a continuous operation until the resin pressure is 50kg / cm 2 G. 50k resin pressure
The time (days) when g / cm 2 G is reached is regarded as clogging of the screen pack. The larger the number of days, the less the gelled product is formed, and the more excellent the gelation preventing property.
ïŒïŒçè²é²æ¢æ§ åŸããããã¬ããã®YIïŒYellowness IndexïŒã枬å®
ïŒJIS K 7103ã«æºæ ïŒãããã®ãšãã®YIå€ã第1YIãšã
ãããããŠåŸããããã¬ãããçšããŠå床溶è混緎枩床
270âã«ãŠæº¶èæ··ç·ŽåŠçããŠãã¬ã¿ã€ãºãããããïŒå
ç¹°ãè¿ãããåŸããããã¬ããã®YIã溶èæ··ç·Žã®éœåºŠã
å床åèšã®æ¹æ³ã§æž¬å®ãããããããããã第2YIã第3
YIã第4YIã第5YIãšããã2) Anti-coloring property YI (Yellowness Index) of the obtained pellet is measured (based on JIS K 7103), and the YI value at this time is defined as the first YI. Then, using the obtained pellets, melt-kneading temperature again
The mixture was melt-kneaded at 270 ° C. and pelletized, and this was repeated four times. Each time the YI of the obtained pellets is melt-kneaded,
Measured again by the method described above,
These are YI, fourth YI, and fifth YI.
çè²é²æ¢æ§ã¯æ¬¡åŒã«ããå®çŸ©ãããÎYIã®å€§å°ããè©
䟡ãããThe anti-coloring property was evaluated based on the magnitude of ÎYI defined by the following equation.
ÎYIïŒç¬¬5YIâ第1YI ïŒç¬¬5YIã¯æŒåºæ©ãïŒåééããã®ã¡ã®YIã瀺ããïŒ ÎYIã®æ°å€ãå°ããçšãçè²é²æ¢æ§ãåªããŠããããš
ã瀺ããÎYI = 5th YIâ1st YI (5th YI indicates YI after passing through the extruder five times.) The smaller the value of ÎYI, the better the anti-coloring property.
å®æœäŸïŒãïŒãæ¯èŒäŸïŒã15 ããªãšãã¬ã³ãšããŠMIïŒ190âã«ãããè·é2.16kgã
å ããå Žåã®10åéã®æº¶èæš¹èã®ååºéïŒ2.0g/10åã®
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ãšãã¬ã³åç¬éåäœïŒå¯åºŠ0.963g/cm3ïŒ100éééšã«ã
ååç©ïŒ¡ãšããŠïŒâïœâããã«âïŒâïŒïŒâïœâããã«
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èŒäŸïŒã15ãšããŠMIã2.0g/10åã®å®å®åãããŠããªã
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ããŠæº¶èæ··ç·ŽåŠçããŠãã¬ãããåŸããExamples 1 to 6 and Comparative Examples 1 to 15 Unstabilized powdered Ziegler as polyethylene, MI (discharge rate of molten resin for 10 minutes when a load of 2.16 kg at 190 ° C. is applied) of 2.0 g / 10 minutes 100 parts by weight of Natta high-density ethylene homopolymer (density 0.963 g / cm 3 )
As compound A, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-t-butyl-6- [3-t
-Butyl-2-hydroxy-5-methyl (α-methylbenzyl)]-4-methylphenyl acrylate or
2,4-di-t-butyl-6- [3,5-di-t-butyl-2
-Hydroxy (α-methylbenzyl)] phenyl acrylate, compound B as bis (2,6-di-t-butyl-
4-methylphenyl) pentaerythritol-diphosphite or bis (2,6-di-tert-butyl-4-s)
-Butylphenyl) pentaerythritol-diphosphite and other additives in predetermined amounts, respectively,
The mixture was placed in a Henssel mixer (trade name) at the compounding ratio shown in the table, and stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. with a single screw extruder having a diameter of 40 mm to form pellets. As Comparative Examples 1 to 15, 100 parts by weight of an unstabilized powdery Ziegler-Natta type high-density ethylene homopolymer (density 0.963 g / cm 3 ) having an MI of 2.0 g / 10 min are shown in Table 1 below. A predetermined amount of each of the additives described was blended and melt-kneaded according to Examples 1 to 6 to obtain pellets.
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çµæã第ïŒè¡šã«ç€ºãããThe obtained pellets were evaluated for melt stability, gelling inhibitor (fish eye) and anti-coloring properties as processing stability by the test method described above. The results are shown in Table 1.
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00ççŽ ïŒ80ééïŒ
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ãåŸããExamples 7 to 12, Comparative Examples 16 to 30 Unstabilized powdered Ziegler-Natta high-density ethylene-butene-1 copolymer (density 0.948 g / cm 3 , ethyl 0.014 branches / 10
Unstabilized powdery low-density ethylene homopolymer (density 0.918 g / cm 3 ) 10
% By weight and 10% by weight of an unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content: 25% by weight) having a Mooney viscosity of ML1 + 4 (100 ° C.) of 65 A represents 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate;
t-butyl-6- [3-tert-butyl-2-hydroxy-
5-methyl (α-methylbenzyl)]-4-methylphenyl acrylate or 2,4-di-t-butyl-6
[3,5-Di-t-butyl-2-hydroxy (α-methylbenzyl)] phenyl acrylate, compound B as bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite Or screw (2,
A predetermined amount of each of 6-di-t-butyl-4-s-butylphenyl) pentaerythritol-diphosphite and other additives was added to a Hensel mixer (trade name) in a mixing ratio shown in Table 2 below. The mixture was stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. with a single-screw extruder having a mouth diameter of 40 mm to form pellets. In addition, MI was 3.0 g as Comparative Examples 16 to 30.
Powdered Ziegler-Natta high-density ethylene-butene-1 copolymer (density 0.948 g / c)
m 3 , 0.014 ethyl branches / 1000 carbon) 80% by weight, MI 0.5 g
10% by weight of unstabilized powdered low-density ethylene homopolymer (density 0.918 g / cm 3 ) 10% by weight and Mooney viscosity
ML1 + 4 (100 ° C.) is 65 parts of unstabilized powdery amorphous ethylene-propylene random copolymer (propylene content 25% by weight) and 10% by weight. A prescribed amount of each of the additives described was blended and melt-kneaded according to Examples 7 to 12 to obtain pellets.
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çµæã第ïŒè¡šã«ç€ºãããThe obtained pellets were evaluated for melt stability, anti-gelling property (fish eye) and anti-coloring property as processing stability by the test method described above. Table 2 shows the results.
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床ãšãã¬ã³âãããã¬ã³å
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ã«æºæ ããŠæº¶èæ··ç·ŽåŠçããŠãã¬ãããåŸããExamples 13-18, Comparative Examples 31-45 Unstabilized powdered Ziegler-Natta high-density ethylene-propylene copolymer having a MI of 25.0 g / 10 min as polyethylene (density 0.950 g / cm 3 , methyl branch 3.0 Pieces / 1000
Carbon) in 100 parts by weight of compound A as 2-t-butyl-
6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-t-
Butyl-6- [3-tert-butyl-2-hydroxy-5-
Methyl (α-methylbenzyl)]-4-methylphenyl acrylate or 2,4-di-t-butyl-6- [3,5
-Di-t-butyl-2-hydroxy (α-methylbenzyl)] phenyl acrylate, compound B as bis (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite or bis (2,6-di-t-butyl-4-s-butylphenyl) pentaerythritol-diphosphite and other additives Are placed in a Hensel mixer (trade name) at the mixing ratios shown in Table 3 below, and stirred and mixed for 3 minutes.
The mixture was melt-kneaded at 200 ° C. with a single-screw extruder having a diameter of 40 mm to form pellets. Further, as Comparative Examples 31 to 45, an unstabilized powdery Ziegler-Natta high-density ethylene-propylene copolymer having an MI of 25.0 g / 10 min (density 0.950 g / cm 3 , 3.0 methyl branches / 1000 carbons) A predetermined amount of each of the additives described in Table 3 described below was blended with 100 parts by weight, and Examples 13 to 18 were added.
Pellets were obtained by a melt-kneading treatment according to.
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ã®è©äŸ¡ãè¡ã£ãããããã®çµæã第ïŒè¡šã«ç€ºãããThe obtained pellets were evaluated for melt stability, anti-gelling properties (extrusion properties (clogging of screen pack)) and anti-coloring properties as processing stability by the test method described above. The results are shown in Table 3.
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æ·»å å€ã¯äžèšã®éãã§ãããThe compounds and additives according to the present invention shown in Tables 1 to 3 are as follows.
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ãŠé¡èãªçžä¹å¹æãèªããããããšãããããCompound A [I]: 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate Compound A [II]: 2-tert-butyl-6 [3-t-butyl-2-hydroxy-5-methyl (α-methylbenzyl)]-4-methylphenylacrylate Compound A [III]: 2,4-di-t-butyl-6- [3,5- Di-t-butyl-2-hydroxy (α-methylbenzyl)] phenyl acrylate compound B [I]: bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite compound B [ II]: bis (2,6-di-t-butyl-4-s
-Butylphenyl) pentaerythritol-diphosphite phenolic antioxidant 1: 2,6-di-t-butyl-p-
Cresol phenolic antioxidant 2: tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane phosphorus antioxidant 1: tris (2,4-di-t-butylphenyl) phosphite phosphorus antioxidant 2 : Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite phosphorus antioxidant 3: bis (2,4-di-t-butylphenyl) -pentaerythritol -Diphosphite Ca-St: Calcium stearate The examples and comparative examples described in Table 1 are cases where a Ziegler-Natta high density ethylene homopolymer is used as polyethylene. As can be seen from Table 1, Examples 1 to 6 contain the compounds A and B according to the present invention, and Examples 1 to 6 and Comparative Examples 1 to 7 (Compound A and compound according to the present invention) B or other phenolic antioxidants or phosphorus-based antioxidants, each of which was independently compounded.
6 shows that both the processing stability and the coloring prevention property are excellent. In particular, Examples 1 to 6 show almost no decrease in the melt stability even after five heat histories, as is clear from the MI retention rate which indicates the melt stability which is the processing stability in repeated extrusion at high temperatures. Also, it can be seen that the value of fish eye caused by the gelation reaction is small. Comparative Examples 8 to 12 and Examples 1 to 6 which are a combination system of a conventionally known phenolic antioxidant 2 and a phenolic antioxidant 1 or various phosphorus-based antioxidants including compound B.
Compared to Comparative Examples 8 to 12, although the processing stability was improved to some extent by the combined use, the effects were still insufficient, and the effect on the anti-coloring property was not yet sufficient. Furthermore, Comparative Examples 13 to 15 and Examples 1 to 6 in which the compound A according to the present invention was used in combination with various phenolic antioxidants or various phosphorus antioxidants other than the compound B were compared with Comparative Examples 13 to 15.
Although the processing stability and the anti-coloring property are improved as compared with Comparative Example 1 in which Compound A alone is blended, it is still insufficient. Therefore, it can be seen that a remarkable synergistic effect is observed when the compound B is used in combination with the compound A.
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äžè¿°ãšåæ§ã®å¹æã確èªããããTable 2 shows the results obtained by using a mixture of a Ziegler-Natta high-density ethylene-butene-1 copolymer, a low-density ethylene homopolymer and an amorphous ethylene-propylene random copolymer as polyethylene. The same effect as above was confirmed.
ãŸã第ïŒè¡šã¯ãããªãšãã¬ã³ãšããŠããŒã°ã©ãŒã»ãã
ã¿ç³»é«å¯åºŠãšãã¬ã³âãããã¬ã³å
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瀺ãããšãããããTable 3 shows the results obtained by using a Ziegler-Natta high-density ethylene-propylene copolymer as polyethylene, and the same effect as described above was confirmed for this as well. In particular, as is clear from the result of clogging of the screen pack, the composition of the present invention has a remarkable anti-gelling effect.
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ãåªããŠããã[Effects of the Invention] The composition of the present invention has the following advantages: (1) Processing stability at the time of molding processing, compared to a polyethylene composition obtained by using a conventionally known phenolic antioxidant and a phosphorus-based antioxidant alone or in combination. Excellent in properties and anti-coloring properties.
ïŒïŒïŒæ°åã®æº¶èæ··ç·Žã«ããç±å±¥æŽãåãããšãã®å å·¥
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åãšããŠäœ¿çšãããçšéïŒãã£ã«ã ãã·ãŒããªã©ïŒã«æ
å©ã«äœ¿çšã§ããã(2) Since it is remarkably excellent in melt stability, which is processing stability when subjected to heat history due to several times of melt-kneading, it can be advantageously used for applications (films, sheets, etc.) used as recycled products.
ïŒïŒïŒé·æéã®é£ç¶é転ãè¡ã溶è玡糞ã®åŠãæŒåºæ圢
ã«ãããŠãããªãšãã¬ã³ã®ã²ã«åã«èµ·å ããçç£æ§ã®äœ
äžãšãã£ãåé¡ãèãã軜æžãããã(3) In extrusion molding, such as melt spinning, in which continuous operation is performed for a long time, problems such as a decrease in productivity due to gelation of polyethylene are significantly reduced.
âââââââââââââââââââââââââââââââââââââââââââââââââââââ ããã³ãããŒãžã®ç¶ã (51)Int.Cl.6 èå¥èšå· åºå æŽççªå·  æè¡è¡šç€ºç®æ ïŒïŒïŒ« 5:527ïŒ ââââââââââââââââââââââââââââââââââââââââââââââââââç¶ ã Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location C08K 5: 527)
Claims (4)
è¬åŒïŒ»ïŒ©ïŒœã§ç€ºããããã§ããŒã«ç³»ååç©ïŒä»¥äžãåå
ç©ïŒ¡ãšãããïŒããã³äžèšäžè¬åŒïŒ»IIã§ç€ºããããã©
ã¹ãã¡ã€ãç³»ååç©ïŒä»¥äžãååç©ïŒ¢ãšãããïŒããã
ãã0.01ãïŒéééšé åããŠãªãå®å®åãããããªãšã
ã¬ã³çµæç©ã ïŒãã ããåŒäžR1ã¯æ°ŽçŽ ãããã¯ççŽ æ°ïŒãïŒã®ã¢ã«ã
ã«åºããR2ãR5ã¯ççŽ æ°ïŒãïŒã®ã¢ã«ãã«åºãã·ã¯ãã
ãã·ã«åºãããã¯ïŒâã¡ãã«ã·ã¯ãããã·ã«åºããR6ã¯
æ°ŽçŽ ãããã¯ã¡ãã«åºããR7ããã³R9ã¯ççŽ æ°ïŒãïŒã®
åå²éã¢ã«ãã«åºããR8ã¯æ°ŽçŽ ãããã¯ççŽ æ°ïŒãïŒã®
ã¢ã«ãã«åºããããã瀺ããïŒ1. A phenolic compound represented by the following general formula [I] (hereinafter referred to as compound A) and a phosphite compound represented by the following general formula [II] (hereinafter referred to as âcompound Aâ) per 100 parts by weight of polyethylene. (Hereinafter referred to as Compound B) in an amount of 0.01 to 1 part by weight. (Wherein, R 1 is hydrogen or an alkyl group having 1 to 3 carbon atoms, R 2 to R 5 are an alkyl group having 1 to 9 carbon atoms, a cyclohexyl group or 1-methylcyclohexyl group, and R 6 is hydrogen or A methyl group, R 7 and R 9 each represent a branched alkyl group having 3 to 9 carbon atoms, and R 8 represents hydrogen or an alkyl group having 1 to 9 carbon atoms.
ããã³R9ãïœâããã«åºã§ããè«æ±é ïŒïŒïŒèšèŒã®å®å®
åãããããªãšãã¬ã³çµæç©ã2. R 2 , R 5 , R 7 in the general formulas [I] to [II]
The stabilized polyethylene composition according to claim 1, wherein R 9 is a t-butyl group.
ïœâããã«âïŒâããããã·âïŒâã¡ãã«ãã³ãžã«ïŒâ
ïŒâã¡ãã«ãã§ãã«ã¢ã¯ãªã¬ãŒããïŒâïœâããã«âïŒ
âïŒâïœâããã«âïŒâããããã·âïŒâã¡ãã«ïŒÎ±
âã¡ãã«ãã³ãžã«ïŒïŒœâïŒâã¡ãã«ãã§ãã«ã¢ã¯ãªã¬ãŒ
ãã2,4âãžâïœâããã«âïŒâ3,5âãžâïœâããã«
âïŒâããããã·ïŒÎ±âã¡ãã«ãã³ãžã«ïŒïŒœãã§ãã«ã¢
ã¯ãªã¬ãŒããããã¯ãããã®ïŒçš®ä»¥äžã®æ··åç©ã§ããè«
æ±é ïŒïŒïŒèšèŒã®å®å®åãããããªãšãã¬ã³çµæç©ã(3) Compound A is 2-t-butyl-6- (3-
t-butyl-2-hydroxy-5-methylbenzyl)-
4-methylphenyl acrylate, 2-t-butyl-6
-[3-t-butyl-2-hydroxy-5-methyl (α
-Methylbenzyl)]-4-methylphenyl acrylate, 2,4-di-t-butyl-6- [3,5-di-t-butyl-2-hydroxy (α-methylbenzyl)] phenyl acrylate or a mixture thereof The stabilized polyethylene composition according to claim 1, which is a mixture of two or more kinds.
âïŒâã¡ãã«ãã§ãã«ïŒãã³ã¿ãšãªã¹ãªããŒã«âãžãã©
ã¹ãã¡ã€ãããã¹ïŒ2,6âãžâïœâããã«âïŒâïœâã
ãã«ãã§ãã«ïŒãã³ã¿ãšãªã¹ãªããŒã«âãžãã©ã¹ãã¡ã€
ããããã¯ãããã®ïŒçš®ä»¥äžã®æ··åç©ã§ããè«æ±é
ïŒïŒïŒèšèŒã®å®å®åãããããªãšãã¬ã³çµæç©ã4. Compound (B) is bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t-butyl-4-s-butyl) The stabilized polyethylene composition according to claim 1, which is (phenyl) pentaerythritol-diphosphite or a mixture of two or more thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63203430A JP2587687B2 (en) | 1988-08-16 | 1988-08-16 | Stabilized polyethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63203430A JP2587687B2 (en) | 1988-08-16 | 1988-08-16 | Stabilized polyethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02225544A JPH02225544A (en) | 1990-09-07 |
| JP2587687B2 true JP2587687B2 (en) | 1997-03-05 |
Family
ID=16473956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63203430A Expired - Lifetime JP2587687B2 (en) | 1988-08-16 | 1988-08-16 | Stabilized polyethylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2587687B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002080650A (en) * | 2000-09-08 | 2002-03-19 | Sumitomo Chem Co Ltd | Rubber composition and method for producing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62223248A (en) * | 1986-02-10 | 1987-10-01 | Chisso Corp | Stabilized polyethylene composition |
-
1988
- 1988-08-16 JP JP63203430A patent/JP2587687B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02225544A (en) | 1990-09-07 |
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