JPS64982B2 - - Google Patents
Info
- Publication number
- JPS64982B2 JPS64982B2 JP2503182A JP2503182A JPS64982B2 JP S64982 B2 JPS64982 B2 JP S64982B2 JP 2503182 A JP2503182 A JP 2503182A JP 2503182 A JP2503182 A JP 2503182A JP S64982 B2 JPS64982 B2 JP S64982B2
- Authority
- JP
- Japan
- Prior art keywords
- tert
- bis
- butyl
- hydroxy
- butylphenyl
- 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
Links
- -1 phosphite compound Chemical class 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 229920000098 polyolefin Polymers 0.000 claims description 13
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- ZGUBOEMAXMRLON-UHFFFAOYSA-N 4-butan-2-yl-2-[1-(5-butan-2-yl-3-tert-butyl-2-hydroxyphenyl)ethyl]-6-tert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)CC)C(C)(C)C)O)=C1O ZGUBOEMAXMRLON-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- AKHUPODAMHBOMG-UHFFFAOYSA-N 2,3-bis[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methylsulfanyl]terephthalic acid Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CSC1=C(C(O)=O)C=CC(C(O)=O)=C1SCC1=C(C)C=C(C(C)(C)C)C(O)=C1C AKHUPODAMHBOMG-UHFFFAOYSA-N 0.000 claims 1
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 4
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- WBSRIXCTCFFHEF-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinic acid Chemical compound CCOP(O)(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WBSRIXCTCFFHEF-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- IKZVWNHAMKIMSQ-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butylphenyl)methyl]-2,4,6-trimethylbenzene Chemical compound CC1=C(CC=2C=C(C=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 IKZVWNHAMKIMSQ-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- FFJXXTCNNJSZIV-UHFFFAOYSA-N 2,4-ditert-butyl-6-(5-chloro-1H-indol-2-yl)phenol Chemical compound C(C)(C)(C)C=1C(=C(C=C(C=1)C(C)(C)C)C=1NC2=C(C=1)C=C(C=C2)Cl)O FFJXXTCNNJSZIV-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- WQYFETFRIRDUPJ-UHFFFAOYSA-N 2-[2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]sulfanyl-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(SC=2C(=CC=C(C=2)C(C)(C)CC(C)(C)C)O)=C1 WQYFETFRIRDUPJ-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- NMAGCVWUISAHAP-UHFFFAOYSA-N 3,5-ditert-butyl-2-(2,4-ditert-butylphenyl)-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1C1=C(C(O)=O)C=C(C(C)(C)C)C(O)=C1C(C)(C)C NMAGCVWUISAHAP-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 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 1
- KSAQJMKQPSIYHK-UHFFFAOYSA-N CC1(C)C(C(O)=O)C(C)(C)CC(N2CCCCC2)=C1 Chemical class CC1(C)C(C(O)=O)C(C)(C)CC(N2CCCCC2)=C1 KSAQJMKQPSIYHK-UHFFFAOYSA-N 0.000 description 1
- XTJYYRKHFBFRJV-UHFFFAOYSA-N CC1(NC(CC(C1)C(C(=O)O)N(C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)(C)C)C Chemical class CC1(NC(CC(C1)C(C(=O)O)N(C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)(C)C)C XTJYYRKHFBFRJV-UHFFFAOYSA-N 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- JVQXFLGVYCKJMV-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2,2,3,3-tetrakis(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C(=O)OCC(CO)(CO)CO)(C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 JVQXFLGVYCKJMV-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical class C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- HIAAVKYLDRCDFQ-UHFFFAOYSA-L calcium;dodecanoate Chemical compound [Ca+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O HIAAVKYLDRCDFQ-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- NYKHQQHUHLNYLW-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,1,1,2-tetracarboxylate Chemical class C1C(C)(C)NC(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(CC)C(=O)OC1CC(C)(C)NC(C)(C)C1 NYKHQQHUHLNYLW-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はポリオレフイン組成物に関し、詳しく
は特定の有機ホスフアイト化合物及び特定のフエ
ノール化合物を含有せしめてなる加工安定性、耐
熱性等の改善されたポリオレフイン組成物に関す
る。
ポリエチレン、ポリプロピレン等のポリオレフ
インは熱、光等の作用により劣化し、着色したり
機械的強度が低下し、使用に耐えなくなることが
知られている。
かかるポリオレフインの劣化を防ぐ目的で、こ
れまで多くの添加剤が単独で、あるいは種々組み
合わせて用いられてきた。これらの添加剤の中で
も、ホスフアイト化合物とフエノール系化合物と
の組み合わせは耐熱性を改善しまた着色を抑制す
る効果が比較的大きいことが知られている。
例えば、特公昭56−5417号公報にはトリス
(2,4−ジ−第3ブチルフエニル)ホスフアイ
ト等のトリアリールホスフアイトとフエノール系
抗酸化剤の組み合わせが記載され、特開昭54−
25951号公報にはビス(2,4−ジ−第3ブチル
フエニル)ペンタエリスリトールジホスフアイト
とフエノール系抗酸化剤を併用することが記載さ
れている。
しかしながら、これらの組み合わせでは、ポリ
オレフインの耐熱性、耐着色性はある程度改善し
得るものの未だ充分ではなく、さらに改善するこ
とが必要とされている。
また、これらの組み合わせを用いた場合は、ポ
リオレフインの加工安定性に難があり、高温での
加工時に、分解あるいは架橋によりポリオレフイ
ンのメルトインデツクスが著るしく変化するとい
う欠点も指摘されている。
本発明者等は、かかる現状から鋭意検討を重ね
た結果、ポリオレフインに対し(a)トリス(2,4
−ジ−第3ブチルフエニル)ホスフアイト及びビ
ス(2,4−ジ−第3ブチルフエニル)ペンタエ
リスリトールジホスフアイトから選ばれたホスフ
アイト化合物の少なくとも一種及び(a)2,2′−エ
チリデンビス(4,6−ジ−第3ブチルフエノー
ル)、2,2′−エチリデンビス(4−第2ブチル
−6−第3ブチルフエノール)、ビス〔2−第3
ブチル−4−メチル−6−(2−ヒドロキシ−3
−第3ブチル−5−メチルベンジル)フエニル〕
テレフタレート及びビス(2,6−ジメチル−3
−ヒドロキシ−4−第3ブチルベンジルチオ)テ
レフタレートから選ばれたフエノール化合物の少
なくとも一種を添加した場合、耐熱性、着色防止
性が満足し得るまで改善され、さらに加工安定性
の極めて優れたポリオレフイン組成物が得られる
ことを見い出した。
本発明で用いられるポリオレフインとしては低
密度ポリエチレン、高密度ポリエチレン、直鎖状
低密度ポリエチレン(エチレン/ブテン−1共重
合体、等のエチレン/α−オレフイン(C3〜C8)
共重合体)、ポリプロピレン、プロピレン/エチ
レン共重合体、ポリブラン−1、ポリー3−メチ
ンブテン、ポリー4−メチルペンテン、エチレ
ン/酢酸ビニル共重合体等のポリ−α−オレフイ
ン及びα−オレフインの共重合体があげられる。
また、本発明で用いられる(a)成分のホスフアイ
ト化合物の添加量はポリオレフイン100重量部に
対し、0.001〜5好ましくは0.01〜3重量部であ
り、(b)成分のフエノール化合物の添加量はポリオ
レフイン100重量部に対して0.001〜5、好ましく
は0.005〜3重量部である。
本発明の組成物に、チオエーテル系抗酸化剤を
含有させることによつて、その抗酸化性をさらに
改良することができる。チオエーテル系抗酸化剤
としては、たとえばジラウリルチオジプロピオネ
ート、ジミリスチルチオジプロピオネート、ジス
テアリルチオジプロピオネート、ペンタエリスリ
トールテトラ(β−ドデシルチオプロピオネー
ト)などがあげられる。
本発明の組成物に、カルシウムステアレート、
カルシウムラウレート、亜鉛ステアレート、バリ
ウムステアレート、マグネシウムステアレート等
の族金属の高級脂肪酸塩を添加しその加工性、
耐熱性をさらに改善することもできる。
本発明の組成物に光安定剤を添加することによ
つてその耐光性を改善することができる。これら
の光安定剤としてはたとえば、2−ヒドロキシ−
4−メトキシベンゾフエノン、2−ヒドロキシ−
4−n−オクトキシベンゾフエノン、2,2′−ジ
−ヒドロキシ−4−メトキシベンゾフエノン、
2,4−ジヒドロキシベンゾフエノン等のヒドロ
キシベンゾフエノン類、2−(2′−ヒドロキシ−
3′−t−ブチル−5′−メチルフエニル)−5−ク
ロロベンゾトリアゾール、2−(2′−ヒドロキシ
−3′,5′−ジ−t−ブチルフエニル)−5クロロ
ベンゾアゾール、2−(2′−ヒドロキシ−5′−メ
チルフエニル)ベンゾトリアゾール、2−(2′−
ヒドロキシ−3′,5′−ジ−t−アミルフエニル)
ベンゾトリアゾール等のベンゾトリアゾール類、
フエニルサリシレート、p−t−ブチルフエニル
サリシレート、2,4−ジ−t−ブチルフエニル
−3,5−ジ−t−ブチル−4−ヒドロキシベン
ゾエート等のベンゾエート類、2,2′−チオビス
(4−t−オクチルフエノール)Ni塩、〔2,2′−
チオビス(4−t−オクチルフエノラート)〕−n
−ブチルアミンNi塩、(3,5−ジ−t−ブチル
−4−ヒドロキシベンジル)ホスホン酸モノエチ
ルエステルNi塩等のニツケル化合物類、置換ア
クリロニトリル類及び2,2,6,6−テトラメ
チル−4−ピペリジニルベンゾエート、ビス
(2,2,6,6−テトラメチル−4−ピペリジ
ニル)セバケート、トリス(2,2,6,6−テ
トラメチル−4−ピペリジニル)ニトリロトリア
セテート、テトラキス(2,2,6,6−テトラ
メチル−4−ピペリジニル)ブタンテトラカルボ
キシレート等のピペリジン系化合物類等があげら
れる。
本発明の組成物に、必要に応じ2,6−ジ−第
3ブチル−p−クレゾール、アテアリル−(3,
5−ジ−第3ブチル−4−ヒドロキシフエニル)
プロピオネート、トリス(3,5−ジ−第3ブチ
ル−4−ヒドロキシベンジル)イソシアヌレー
ト、トリス(2,6−ジメチル−3−ヒドロキシ
−4−第3ブチルベンジル)イソシアヌレート、
1,3,5−トリス(3,5−ジ−第3ブチルベ
ンジル)−2,4,6−トリメチルベンゼン、ペ
ンタエリスリトールテトラ(3,5−ジ−第3ブ
チル−4−ヒドロキシフエニル)プロピオネート
等の他のフエノール系抗酸化剤を配合し、その抗
酸化性をさらに改善することもできる。
その他必要に応じて、重金属不活性化剤、造核
剤、可塑剤、エポキシ化合物、顔料、充填剤、発
泡剤、帯電防止剤、難燃剤等を包含させることが
できる。
次に本発明を実施例によつてさらに詳細に説明
する。しかしながら本発明は以下の実施例によつ
て限定されるものではない。
実施例 1
下記配合物を擂潰機で5分間混合した後、250
℃で押し出し加工を行なつた。次いで250℃で射
出成型し、厚さ1mmの試験片を作成した。この試
験片を用いて160℃のギヤーオーブン中での熱安
定性試験を行なつた。また、着色防止性をみるた
めに試験片の黄色度をハンター比色計を用いて測
定した。さらに、加工安定性をみるために250℃
で押し出しを5回くり返した場合のメルトインデ
ツクス(MI)(230℃、荷重2160g)の変化を測
定した。その結果を表−1に示す。
配 合
ポリプロピレン(Profax6501) 100重量部
カルシウムステアレート 0.15
ジラウリルチオジプロピオネート 0.2
トリス(2,4−ジ−第3ブチルフエニル)ホ
スフアイト 0.1
フエノール化合物 0.1
The present invention relates to a polyolefin composition, and more particularly to a polyolefin composition containing a specific organic phosphite compound and a specific phenol compound and having improved processing stability, heat resistance, etc. It is known that polyolefins such as polyethylene and polypropylene deteriorate due to the effects of heat, light, etc., becoming colored and having reduced mechanical strength, making them unusable. For the purpose of preventing such deterioration of polyolefins, many additives have been used singly or in various combinations. Among these additives, the combination of a phosphite compound and a phenol compound is known to have a relatively large effect of improving heat resistance and suppressing coloration. For example, Japanese Patent Publication No. 5417/1989 describes a combination of a triarylphosphite such as tris(2,4-di-tert-butylphenyl) phosphite and a phenolic antioxidant;
Publication No. 25951 describes the combined use of bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite and a phenolic antioxidant. However, although these combinations can improve the heat resistance and coloring resistance of polyolefins to some extent, they are still not sufficient, and further improvements are required. Furthermore, when a combination of these is used, it has been pointed out that there is a problem in the processing stability of the polyolefin, and that the melt index of the polyolefin changes significantly due to decomposition or crosslinking during processing at high temperatures. The inventors of the present invention have conducted intensive studies based on the current situation, and have determined that (a) Tris (2,4
-di-tert-butylphenyl) phosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; and (a) 2,2'-ethylidene bis(4,6 -di-tert-butylphenol), 2,2'-ethylidene bis(4-sec-butyl-6-tert-butylphenol), bis[2-tert-butylphenol),
Butyl-4-methyl-6-(2-hydroxy-3
-tert-butyl-5-methylbenzyl)phenyl]
Terephthalate and bis(2,6-dimethyl-3
- When at least one phenol compound selected from -hydroxy-4-tert-butylbenzylthio) terephthalate is added, the heat resistance and discoloration prevention properties are improved to a satisfactory level, and the polyolefin composition has extremely excellent processing stability. I discovered that things can be obtained. The polyolefins used in the present invention include ethylene/α-olefins (C 3 to C 8 ) such as low density polyethylene, high density polyethylene, and linear low density polyethylene (ethylene/butene-1 copolymer).
copolymers of poly-α-olefins and α-olefins such as polypropylene, propylene/ethylene copolymers, polybran-1, poly-3-methinebutene, poly-4-methylpentene, and ethylene/vinyl acetate copolymers Combination can be mentioned. Further, the amount of the phosphite compound (a) used in the present invention is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the polyolefin, and the amount of the phenol compound (b) added is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, per 100 parts by weight of the polyolefin. The amount is 0.001 to 5, preferably 0.005 to 3 parts by weight per 100 parts by weight. By incorporating a thioether antioxidant into the composition of the present invention, its antioxidative properties can be further improved. Examples of thioether antioxidants include dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythritol tetra (β-dodecylthiopropionate), and the like. The composition of the present invention includes calcium stearate,
Addition of higher fatty acid salts of group metals such as calcium laurate, zinc stearate, barium stearate, and magnesium stearate improves processability.
Heat resistance can also be further improved. By adding a light stabilizer to the composition of the invention, its light resistance can be improved. Examples of these light stabilizers include 2-hydroxy-
4-methoxybenzophenone, 2-hydroxy-
4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone,
Hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-(2'-hydroxy-
3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5chlorobenzazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole,2-(2'-
hydroxy-3',5'-di-t-amyl phenyl)
Benzotriazoles such as benzotriazole,
Benzoates such as phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,2'-thiobis(4 -t-octylphenol) Ni salt, [2,2'-
Thiobis(4-t-octylphenolate)]-n
-Nickel compounds such as butylamine Ni salt, (3,5-di-t-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester Ni salt, substituted acrylonitriles, and 2,2,6,6-tetramethyl-4 -piperidinylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, tris(2,2,6,6-tetramethyl-4-piperidinyl)nitrilotriacetate, tetrakis(2,2 , 6,6-tetramethyl-4-piperidinyl) butane tetracarboxylate and other piperidine compounds. 2,6-di-tert-butyl-p-cresol, atearyl-(3,
5-di-tert-butyl-4-hydroxyphenyl)
Propionate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate,
1,3,5-tris(3,5-di-tert-butylbenzyl)-2,4,6-trimethylbenzene, pentaerythritol tetra(3,5-di-tert-butyl-4-hydroxyphenyl)propionate It is also possible to further improve the antioxidative properties by adding other phenolic antioxidants such as. In addition, heavy metal deactivators, nucleating agents, plasticizers, epoxy compounds, pigments, fillers, blowing agents, antistatic agents, flame retardants, etc. can be included as necessary. Next, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to the following examples. Example 1 After mixing the following formulation in a grinder for 5 minutes,
Extrusion processing was carried out at ℃. Next, injection molding was performed at 250°C to prepare a test piece with a thickness of 1 mm. Using this test piece, a thermal stability test was conducted in a gear oven at 160°C. Further, in order to check the coloring prevention property, the yellowness of the test piece was measured using a Hunter colorimeter. Furthermore, in order to check the processing stability,
The change in melt index (MI) (230°C, load 2160g) was measured when extrusion was repeated 5 times. The results are shown in Table-1. Blend Polypropylene (Profax6501) 100 parts by weight Calcium stearate 0.15 Dilauryl thiodipropionate 0.2 Tris(2,4-di-tert-butylphenyl) phosphite 0.1 Phenol compound 0.1
【表】
実施例 2
次の配合により実施例1と同様な試験を行なつ
た。その結果を表−2に示す。
配 合
ポリプロピレン(Profax6501) 100重量部
カルシウムステアレート 0.15
ジラウリルチオジプロピオネート 0.2
ビス(2,4−ジ−第3ブチルフエニル)ペン
タエリスリトールジホスフアイト 0.1
フエノール化合物 0.05[Table] Example 2 A test similar to Example 1 was conducted using the following formulation. The results are shown in Table-2. Blend Polypropylene (Profax6501) 100 parts by weight Calcium stearate 0.15 Dilauryl thiodipropionate 0.2 Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite 0.1 Phenol compound 0.05
【表】
実施例 3
次の配合物を150℃の温度で5分間ミキシング
ロールで混練し、次いで150℃の温度、180Kg/cm2
の条件で5分間圧縮成型を行い、厚さ1.2mmのシ
ートを作成した。このシートを10×20mmの試験片
としてアルミ箔上、150℃の温度で空気中に於け
るギヤーオーブン加熱劣化試験を行なつた。な
お、同一サンプルに10枚の試片を用い5枚以上が
変色、ワツクス状化した時点を劣化時間とした。
また、同じ配合物を230℃で押し出し加工した
後、メルトインデクサー中に290℃で滞留させた
時のメルトインデツクスの変化を測定した。その
結果を表−3に示す。
配 合
高密度ポリエチレン(ハイゼツクス;三井石油
化学社製) 100重量部
ジラウリルチオジプロピオネート 0.15
添加剤 0.1[Table] Example 3 The following formulation was kneaded with a mixing roll at a temperature of 150°C for 5 minutes, and then at a temperature of 150°C and 180Kg/cm 2
Compression molding was performed for 5 minutes under the following conditions to create a sheet with a thickness of 1.2 mm. This sheet was used as a 10 x 20 mm test piece and subjected to a gear oven heating deterioration test in air at a temperature of 150°C on aluminum foil. Note that 10 specimens were used for the same sample, and the time when 5 or more specimens became discolored or waxy was defined as the deterioration time. Furthermore, after extruding the same formulation at 230°C, the change in melt index was measured when it was allowed to stay in a melt indexer at 290°C. The results are shown in Table-3. Blend High-density polyethylene (HIZEX; manufactured by Mitsui Petrochemicals) 100 parts by weight Dilauryl thiodipropionate 0.15 Additives 0.1
【表】
実施例 4
直鎖状低密度ポリエチレンの加工安定性をみる
ために次の配合物を用い、ブラベンダープラスト
グラフ(230℃、80rpm)により、経時的にトル
クの変化を測定した。また、耐熱性をみるために
樹脂の着色をハンター比色計で測定し黄色度
(%)で示した。結果を表−4に示す。
配 合
直鎖状低密度ポリエチレン(Unipol;ユニオ
ンカーバイド社製) 100重量部
添加剤 0.05[Table] Example 4 To examine the processing stability of linear low-density polyethylene, the following formulation was used and changes in torque over time were measured using a Brabender plastograph (230°C, 80 rpm). Furthermore, in order to examine heat resistance, the coloration of the resin was measured using a Hunter colorimeter and expressed as yellowness (%). The results are shown in Table 4. Blend Linear low-density polyethylene (Unipol; manufactured by Union Carbide) 100 parts by weight Additives 0.05
Claims (1)
−第3ブチルフエニル)ホスフアイト及びビス
(2,4−ジ−第3ブチルフエニル)ペンタエリ
スリトールジホスフアイトから選ばれたホスフア
イト化合物の少なくとも一種及びb2,2′−エチリ
デンビス(4,6−ジ−第3ブチルフエノール)、
2,2′−エチリデンビス(4−第2ブチル−6−
第3ブチルフエノール)、ビス〔2−第3ブチル
−4−メチル−6−(2−ヒドロキシ−3−第3
ブチル−5−メチルベンジル)フエニル〕テレフ
タレート及びビス(2,6−ジメチル−3−ヒド
ロキシ−4−第3ブチルベンジルチオ)テレフタ
レートから選ばれたフエノール化合物の少なくと
も一種を含有せしめてなるポリオレフイン組成
物。[Claims] 1. For polyolefins, (a) a phosphite compound selected from tris(2,4-di-tert-butylphenyl) phosphite and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite; at least one of the following and b2,2'-ethylidene bis(4,6-di-tert-butylphenol),
2,2'-ethylidene bis(4-sec-butyl-6-
tert-butylphenol), bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert.
A polyolefin composition comprising at least one phenol compound selected from butyl-5-methylbenzyl)phenyl]terephthalate and bis(2,6-dimethyl-3-hydroxy-4-tert-butylbenzylthio)terephthalate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2503182A JPS58142924A (en) | 1982-02-18 | 1982-02-18 | Polyolefin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2503182A JPS58142924A (en) | 1982-02-18 | 1982-02-18 | Polyolefin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58142924A JPS58142924A (en) | 1983-08-25 |
JPS64982B2 true JPS64982B2 (en) | 1989-01-10 |
Family
ID=12154537
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2503182A Granted JPS58142924A (en) | 1982-02-18 | 1982-02-18 | Polyolefin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58142924A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6169811A (en) * | 1984-09-12 | 1986-04-10 | Mitsubishi Chem Ind Ltd | High-molecular weight 3-methylbutene-1 polymer containing stabilizer |
GB8710171D0 (en) * | 1987-04-29 | 1987-06-03 | Shell Int Research | Copolymer composition |
IT1215943B (en) * | 1988-02-24 | 1990-02-22 | Enichem Sintesi | STABILIZING COMPOSITION FOR ORGANIC POLYMERS. |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5625935B2 (en) * | 1973-08-27 | 1981-06-16 | ||
JPS5521457A (en) * | 1978-08-04 | 1980-02-15 | Toa Nenryo Kogyo Kk | Heat-stabilized poly-alpha-olefin composition |
-
1982
- 1982-02-18 JP JP2503182A patent/JPS58142924A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS58142924A (en) | 1983-08-25 |
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