JPH01193362A - Stabilized synthetic resin composition - Google Patents
Stabilized synthetic resin compositionInfo
- Publication number
- JPH01193362A JPH01193362A JP1865288A JP1865288A JPH01193362A JP H01193362 A JPH01193362 A JP H01193362A JP 1865288 A JP1865288 A JP 1865288A JP 1865288 A JP1865288 A JP 1865288A JP H01193362 A JPH01193362 A JP H01193362A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- formula
- resin composition
- group
- butyl
- 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.)
- Pending
Links
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 16
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- -1 phenol compound Chemical class 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 abstract description 7
- 230000006866 deterioration Effects 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 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 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000463 material 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
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- ZFPOOXOHYITZFO-UHFFFAOYSA-N tetradecyl 3-sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCS ZFPOOXOHYITZFO-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 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 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 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
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical group C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000182067 Fraxinus ornus Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001103 continuous-wave nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- SCKHCCSZFPSHGR-UHFFFAOYSA-N cyanophos Chemical compound COP(=S)(OC)OC1=CC=C(C#N)C=C1 SCKHCCSZFPSHGR-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 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
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 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
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 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
- 239000008188 pellet Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- UMFCIIBZHQXRCJ-NSCUHMNNSA-N trans-anol Chemical compound C\C=C\C1=CC=C(O)C=C1 UMFCIIBZHQXRCJ-NSCUHMNNSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- HBYRZSMDBQVSHO-UHFFFAOYSA-N tris(2-tert-butyl-4-methylphenyl) phosphite Chemical compound CC(C)(C)C1=CC(C)=CC=C1OP(OC=1C(=CC(C)=CC=1)C(C)(C)C)OC1=CC=C(C)C=C1C(C)(C)C HBYRZSMDBQVSHO-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は安定剤を組合せ配合し安定化された合成樹脂組
成物に関する。本発明の組成物は、自動車の外装材、中
空容器、シート成型材料として有用である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a synthetic resin composition stabilized by combining stabilizers. The composition of the present invention is useful as an exterior material for automobiles, a hollow container, and a sheet molding material.
ポリエチレン、ボリプロピレンなどのポリα−オレフィ
ン樹脂、ポリスチレン、耐衝撃性ポリスチレン、ＡＢＳ
などのスチレン系樹脂、ポリアセタール、ポリフェニレ
ンエーテル、ポリアミドなどのエンジニアリングプラス
チック、さらには、ポリウレタンなどの種々の合成樹脂
は各種の分野において広く使用されているが、これらの
合成樹脂はそれ単独で用いた場合、加工時又は、使用時
において熱、光及び酸素の作用によって劣化し、軟ｆヒ
、脆化又は変色などの現象を伴ってその物性が著しく低
下し使用に耐えなくなることが知られている。このよう
な現象を防止するために従来より各種のフェノール系、
燐系、硫黄系などの酸化防止剤が単独もしくは併用で合
成樹脂の製造、加工工程中に添加されている。Polyalpha-olefin resins such as polyethylene and polypropylene, polystyrene, high-impact polystyrene, ABS
Styrenic resins such as polyacetal, polyphenylene ether, engineering plastics such as polyamide, and various synthetic resins such as polyurethane are widely used in various fields, but when used alone, these synthetic resins It is known that during processing or use, the material deteriorates due to the effects of heat, light, and oxygen, resulting in phenomena such as soft fragility, embrittlement, and discoloration, resulting in a significant decrease in its physical properties and rendering it unusable. To prevent this phenomenon, various phenolic,
Phosphorus-based, sulfur-based, and other antioxidants are added alone or in combination during the manufacturing and processing steps of synthetic resins.
しかしながら、これまで使用されている酸化防止剤は、
いずれもその安定化の効果が不十分であり、樹脂に着色
を与えたり、高温加工中に連敗してしまうものが多い。However, the antioxidants used so far are
In either case, the stabilizing effect is insufficient, and many of them cause coloring of the resin or continuous failure during high-temperature processing.
これらの欠点を解決するために数種の酸化防止剤を組み
合わせて用いることも行なわれており、例えば、硫黄系
酸化防止剤とフェノール系酸化防止剤の組合せとして、
特公昭４８−５７８０号公報は、テトラキス（３−（２
−（１クタデシルオキシ力ルボニル）エチルチオ）プロ
ピオニルオキシメチルコメタン等の硫黄系酸化防止剤と
各種フェノール系酸化防止剤との組合せが記載されてい
るが、その効果は未だ充分に満足するほどには至ってい
ない。In order to solve these drawbacks, several types of antioxidants have been used in combination, for example, a combination of a sulfur-based antioxidant and a phenolic antioxidant,
Japanese Patent Publication No. 48-5780 discloses tetrakis (3-(2
Although combinations of sulfur-based antioxidants such as -(1tadecyloxycarbonyl)ethylthio)propionyloxymethylcomethane and various phenolic antioxidants have been described, their effects are still not sufficiently satisfactory. has not yet been reached.
本発明は、かかる現状を鑑み、従来技術よりも酸化劣化
に対しきわめて優れた安定性を保つ樹脂組成物る提供せ
んとするものである。In view of the current situation, the present invention aims to provide a resin composition that maintains extremely superior stability against oxidative deterioration compared to the prior art.
本発明は、合成樹脂に一般式（１）
％式％
（式中、ＲＶｉ炭素数８〜２４のアルキル基、Ｘは＋０
ＣＨ２＋ｎＣ＋ＣＨｚＯＨ）＋−ｎ基を表わし、ｉ、ｊ
は１〜３の整数、ｎは１〜４の整数を示す。）
で示される硫黄化合物及び、一般式（Ｉ［）（式中、Ｒ
１＋ Ｒ２は水素原子又はメチル基を、Ｙはへテロ元素
を含む炭化水素基を示す。ｍは２〜４の整数であり、＋
はｔ−ブチル基金表わす。）
で示されるフェノール系化合物を（１） ： （ＩＩ）
＝ ｔ〜１５：１（重量比）の割合で配合してなる安
定化された合成樹脂組成物を提供するものである。The present invention provides synthetic resins with the general formula (1)% formula% (wherein, RVi is an alkyl group having 8 to 24 carbon atoms, and X is +0
CH2+nC+CHzOH)+-n group, i, j
represents an integer of 1 to 3, and n represents an integer of 1 to 4. ) and a sulfur compound represented by the general formula (I[) (wherein R
1+ R2 represents a hydrogen atom or a methyl group, and Y represents a hydrocarbon group containing a hetero element. m is an integer from 2 to 4, +
represents the t-butyl foundation. ) A phenolic compound represented by (1) : (II)
=t to 15:1 (weight ratio) to provide a stabilized synthetic resin composition.
本発明に用いられる上記一般式（１）で示される硫黄化
合物において、Ｒは炭素ａ８〜２４のアルキル基であり
、アルキル基の炭素数が小さい場合には、分子針が低い
ために樹脂成形後、揮赦しやすく、一方、炭素数２４以
上のものは、原料となる高級アルコールが高価であるた
め、実用的でない。In the sulfur compound represented by the above general formula (1) used in the present invention, R is an alkyl group having carbon a8 to a24, and when the number of carbon atoms in the alkyl group is small, the molecular needle is low, so that after resin molding, On the other hand, those having 24 or more carbon atoms are not practical because the higher alcohol used as a raw material is expensive.
Ｘは、ペンタエリスリトールの水酸基の少なくとも１つ
がエステル結合した残基、又は１，３．５−トリアゾー
ル基である。X is a residue in which at least one of the hydroxyl groups of pentaerythritol is ester-bonded, or a 1,3.5-triazole group.
これら硫黄化合物は、例えば、β−メルカグトプロビオ
ン酸の高級アルコー−（炭素数８〜２４）エステルのメ
ルカプト残基を、ペンタエリスリトールの水酸基の少な
くとも１つがアクリロイル化されたエステル化合物、又
は、トリアクリルホルマールなどのアクリル二重結合に
付加させることにより容易に合成することができる。These sulfur compounds are, for example, a mercapto residue of a higher alcohol (8 to 24 carbon atoms) ester of β-mercagutoprobionic acid, an ester compound in which at least one of the hydroxyl groups of pentaerythritol is acryloylated, or It can be easily synthesized by adding it to an acrylic double bond such as acrylic formal.
父、β−メルカプトグプロオン酸に代えてチオクリコー
ル酸やδ−メルカプ）−ｎ−酪酸のエステルを用いたゆ
、さらに、メルカプト残基をモノクロロ酢酸エステルで
置換させたり、メタクリル酸またはクロトン酸エステル
等を付加させることにより、ｌ＠Ｊの異なる硫黄化合物
を合成することができる。In addition, esters of thiocricholic acid or δ-mercap)-n-butyric acid were used in place of β-mercaptogproonic acid, and the mercapto residue was further substituted with monochloroacetic acid ester, or methacrylic acid or crotonic acid ester was used. By adding, etc., sulfur compounds with different l@J can be synthesized.
前記一般式（１）で示される硫黄化合物の代表例の示性
式を次に示す。The representative formula of the sulfur compound represented by the general formula (1) is shown below.
（ｘ口
テトラキス（３−＋２−（テトラデシル乞キシカルボニ
ル）エテルチオ）プロビオニルオキシメチル〕メタン
分子量 １５６０．４０
（煮２）
（Ｃｌ２Ｈ２５−ＱＣ−Ｃｌ−Ｉ２ＣＨ２−５−ＣＨｚ
ＣＨ２−Ｃｏ−ＣＨ２）４− Ｃテトラキス［３−（
ｚ−（ドデシルオキ７カルポニニル）エチルチオ）プロ
ビオニルオキシメチル］メタン
分子量 １４４８．１８
（扁３）
ＣＯＣＨ，ＣＨ！ＳＣＨ，ＣＨ，ＣＯ，Ｃ，、Ｈ，。(x-tetrakis(3-+2-(tetradecyloxycarbonyl)ethylthio)probionyloxymethyl)methane molecular weight 1560.40 (boiled 2) (Cl2H25-QC-Cl-I2CH2-5-CHz
CH2-Co-CH2)4-Ctetrakis[3-(
z-(dodecylox7carponinyl)ethylthio)probionyloxymethyl]methane molecular weight 1448.18 (3) COCH, CH! SCH,CH,CO,C,,H,.
１．３．５− ）リス［：２−［２−（テトラデシルオ
キンｈルボニル）エチルチオ）プロピオニル） −１，
３，５−トリアジン−２，４，６−（ＩＨ，３Ｈ，５Ｈ
）−トリオン
分子量 １１５６．８１
（Ａ４）
ＣＯＣ）ｌｔＣＪＳＣＪＣＨｔＣＯ＊Ｃ＋ｓ”−ｖｔ、
３，５−トリスＣ２−＋２−（オクタデシルオキシカル
ボニル）エチルチオ）フロピオニル） −１，３，５−
トリアジン−２，４，６−（ＩＨ，３Ｈ，５Ｈ）−）リ
オン
分子量 １３２５．１３
本発明において、前記一般式（１）で示される硫黄化合
物と組合せ用いられる、一般式（Ｉｔ）で示さレルフェ
ノール系化合物は、ヒドロキシル基のオルン位の２個の
アルキル基の内１個が立体障害を有さないメチル基或は
水素原子であり、ヒドロキシル基の立体障害が緩和され
ている点に特徴を有する。1.3.5- ) Lis[:2-[2-(tetradecyloquinehrbonyl)ethylthio)propionyl) -1,
3,5-triazine-2,4,6-(IH,3H,5H
)-trione molecular weight 1156.81 (A4) COC)ltCJSCJCHtCO*C+s''-vt,
3,5-TrisC2-+2-(octadecyloxycarbonyl)ethylthio)flopionyl) -1,3,5-
Triazine-2,4,6-(IH,3H,5H)-)ion molecular weight 1325.13 In the present invention, the compound represented by the general formula (It) used in combination with the sulfur compound represented by the general formula (1) above Phenol compounds are characterized by the fact that one of the two alkyl groups at the orne position of the hydroxyl group is a methyl group or a hydrogen atom that does not have steric hindrance, and the steric hindrance of the hydroxyl group is alleviated. have
Ｙは、燐、硫黄、窒素、酸素元素 等のへテロ元素を含
む２〜４ ｆｌＬｒｉの炭化水素基であり、具体的には
、
■
ＣＨｚ−
ＯＣＩ（Ｉ ＣＨ３０
＋ＣＩｈＣＩｈＣ０Ｃ）Ｉｚ＋４０ 。Y is a 2 to 4 flLri hydrocarbon group containing a hetero element such as phosphorus, sulfur, nitrogen, or oxygen, and specifically, 1 CHz-OCI (I CH30 + CIhCIhC0C) Iz+40.
ＣＨｚＣ）Ｉ２０ＣＣ）ＬｚＣ＆−
ＩＩ
等の基である。これらの中でも、分子骨格にインシアヌ
ル環或はスピロ環等の耐熱性の優れた構造を有している
ものが熱的に安定で特に好ましい。It is a group such as CHzC)I20CC)LzC&-II. Among these, those having a structure with excellent heat resistance such as an incyanuric ring or a spiro ring in the molecular skeleton are thermally stable and are particularly preferred.
上記一般式（ｎ）で示されるフェノール系化合物の具体
例としては、トリス（４−ｔ−ブチル−２゜６−ジ−メ
チル−３−ヒドロキシベンジル）インシアヌレート（商
品名： Ｃｙａｎｏｘ ｌ ７９０ ）、３゜９−〔
ビス１．１−ジ−メチル−２−（β−（３−ｔ−ブチル
−４−ヒドロキシ−５−メチル７エ二ル）テロピオニル
オキシ）エテル） −２，４，８’、１０−テトラオキ
サスピロ（５，５）ウンデカン（商品名：ＭＡＲＫ
ＡＯ−８０）、等が挙げられる。A specific example of the phenolic compound represented by the above general formula (n) is tris(4-t-butyl-2゜6-di-methyl-3-hydroxybenzyl)in cyanurate (trade name: Cyanox l 790). , 3゜9− [
Bis1,1-di-methyl-2-(β-(3-t-butyl-4-hydroxy-5-methyl7enyl)teropionyloxy)ether) -2,4,8',10- Tetraoxaspiro(5,5)undecane (Product name: MARK
AO-80), etc.
更に１ これらフェノール系化合物は、硫黄系酸化防
止剤との併用効果を充分に発揮させるためには、分子量
が大きいことが必要であり、特に分子量６００以上有し
ているものが好ましい。Furthermore, these phenolic compounds need to have a large molecular weight in order to fully exhibit the effect of combination with the sulfur-based antioxidant, and those having a molecular weight of 600 or more are particularly preferred.
フェノール化合物（ＩＩ）に対する硫黄化合物（１）の
併用重数比は、化合物（■）１に対し、１〜１５である
が好ましくは２〜６である。The combined weight ratio of the sulfur compound (1) to the phenol compound (II) is 1 to 15, but preferably 2 to 6, to 1 of the compound (■).
また、硫黄化合物（Ｉ）とフェノール系化合物（ｎ）の
合成樹脂に対する総添加量は、合成樹脂１００重量部に
たいして通常０．０１〜５重址部であり、好ましくはＯ
，ＯＳ〜１重址部である。The total amount of the sulfur compound (I) and phenolic compound (n) added to the synthetic resin is usually 0.01 to 5 parts by weight per 100 parts by weight of the synthetic resin, preferably O
, OS~1 layer.
本発明により安定化される合成樹脂としては、低密度ポ
リエｔレン、中密度ポリエチレン、リニアー低密度ポリ
エチレン、ポリプロピレン、ボリフ゛テン−１などのポ
リα−オレフィン、エチレン−プロピレンランダムまた
はブロック共重合体。The synthetic resins stabilized by the present invention include low density polyethylene, medium density polyethylene, linear low density polyethylene, polypropylene, polyalpha-olefins such as polyethylene-1, and ethylene-propylene random or block copolymers.
エチレン−ブテン−１ランダム共重合体などのα−オレ
フイン共重重合本無水マレイン酸変性ポリプロピレンな
どのα−オレフィンとビニルモノマーの共重合体及びこ
れらの混合物、ポリ塩化ビニル、メタクリル樹脂、ポリ
スチレン、耐衝撃性ポリスチレン、ＡＢＳ樹脂、ｋＥｓ
樹脂等のスチレン系樹脂、ポリエチレンテレフタレート
、ポリブチレンテレ７タレート等のポリエステル、ポリ
アミド、ポリカーボネート、ポリアセタール、ポリフェ
ニレンエーテル、ポリウレタン、不飽和ポリエステル樹
脂などが挙げられる。α-olefin copolymers such as ethylene-butene-1 random copolymers, copolymers of α-olefins and vinyl monomers such as maleic anhydride-modified polypropylene, and mixtures thereof, polyvinyl chloride, methacrylic resins, polystyrene, resistant High impact polystyrene, ABS resin, kEs
Examples include styrene resins such as resins, polyesters such as polyethylene terephthalate and polybutylene tere-7-thalerate, polyamides, polycarbonates, polyacetals, polyphenylene ethers, polyurethanes, and unsaturated polyester resins.
本発明の合成樹脂組成物には他の添加剤、例えば紫外線
吸収剤、光安定剤、金属不活性剤、金属石鹸類、造核剤
、滑剤、帯電防止剤、難燃剤、顔料、顔料分散剤及び充
填剤などを含有してもよい。The synthetic resin composition of the present invention may contain other additives, such as ultraviolet absorbers, light stabilizers, metal deactivators, metal soaps, nucleating agents, lubricants, antistatic agents, flame retardants, pigments, and pigment dispersants. It may also contain fillers and the like.
とりわけ紫外線吸収剤、ヒンダードアミン系光安定剤な
ど、例えば２−ヒドロキシ−４−メトキシベンゾフェノ
ン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノ
ン、２（２′−ヒドロキシ−５’−メチルフェニル）ベ
ンゾトリアゾール、２（２′−ヒドロキシ−３′−ｔ−
ブチル−５７−メチルフェニル）−ｓ−クロロ−ペンツ
トリアソール、２（２−ヒドロキシル−３′、５′−ジ
−ｔ−ブチルフェニル）−５−クロロ−ベンゾトリアゾ
ール、２（２′−ヒドロキシ−３’＋５’−ジ−アミル
フェニル）ベンゾトリアゾール、（２１２’−チオビス
（４−ｔ−オクチルフェノラート）〕ブチルアミンＮｉ
塩、２．２，６．６−チトラメテルー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、２−（３，５−ジ−ｔ
−フチルー４−ヒドロキシベンジル）−２−ｎ−ブチル
−マロン酸ビス（１，２，２，６，６−ヘンタメテルー
４−ピペリジル）、１−（２−（３−（３，５−シーｔ
−フチルー４−ヒドロキシフェニル）プロピオニルオキ
シ）エチル）−４−（３−（３，ｓ−シーｔ−フチルー
４−ヒドロキシフェニル）プロピオニルオキシ） −２
，２，６，６−チトラメチルピペリジン、コハク酸ジメ
チル・１−（２−ヒドロキシエチル）−４−ヒドロキシ
−２，２，６，６−テトラメチルビペリジン重縮合物な
どを添加することによってその耐光性を改善することが
できる。In particular, ultraviolet absorbers, hindered amine light stabilizers, etc., such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2(2'-hydroxy-5'-methylphenyl)benzotriazole, 2(2'-hydroxy-3'-t-
butyl-57-methylphenyl)-s-chloro-penztriazole, 2(2-hydroxyl-3',5'-di-t-butylphenyl)-5-chloro-benzotriazole, 2(2'-hydroxy- 3'+5'-di-amylphenyl)benzotriazole, (212'-thiobis(4-t-octylphenolate)]butylamine Ni
salt, 2,2,6,6-titramethel-4-piperidinylbenzoate, bis(2,2,6,6-tetramethyl-
4-piperidinyl) sebacate, 2-(3,5-di-t
-phthyl-4-hydroxybenzyl)-2-n-butyl-malonate bis(1,2,2,6,6-hentamether-4-piperidyl), 1-(2-(3-(3,5-sheet
-phthyl-4-hydroxyphenyl)propionyloxy)ethyl)-4-(3-(3,s-t-phthyl-4-hydroxyphenyl)propionyloxy) -2
, 2,6,6-titramethylpiperidine, dimethyl succinate/1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylbiperidine polycondensate, etc. Its light resistance can be improved.
又、本発明の組成物に、燐系酸化防止剤を添加すること
によって、その色相を改善することができる。これら、
４系酸化防止剤としては、例えば、ジステアリルペンタ
エリスリトールジホスファイト、トリス（２，４−ジ−
ｔ−ブチルフェニル）ホスファイト、トリス（２−ｔ−
ブチル−４−メチルフェニル）ホスファイト、ビス（２
，４−シーｔ−ブチルフェニル）ペンタエリスリトール
ジホスファイト、テトラキス（２，４−ジ−ｔ−ブチル
フェニル） ’−４＋４’−ビフェニレンジホスファイ
トなどが挙げられる。Furthermore, by adding a phosphorous antioxidant to the composition of the present invention, its hue can be improved. these,
Examples of 4-based antioxidants include distearyl pentaerythritol diphosphite, tris(2,4-di-
t-butylphenyl) phosphite, tris(2-t-
Butyl-4-methylphenyl)phosphite, bis(2
, 4-sheet-t-butylphenyl) pentaerythritol diphosphite, and tetrakis(2,4-di-t-butylphenyl)'-4+4'-biphenylene diphosphite.
次に、前記一般式（１）で示される硫黄系化合物の合成
例を具体的に説明する。Next, a synthesis example of the sulfur-based compound represented by the general formula (1) will be specifically explained.
く合成例１〉 例示化合物 Ｊ１６１四ツロフラスコ
内に、ミリスチル−３−メルカプトプロピオネート １
１．６ｆ、テトラキス（アクリロイルオキシメチル）メ
タン ３．４５’、テトラ−ｎ−ブチルアンモニウムフ
ルオライド ０．０５２及び、無水テトラヒドロフラン
２０ｄを仕込み、皇累雰囲気下、室温（約２８℃）で１
０時間攪拌した。Synthesis Example 1> Exemplary Compound In a J161 Yotsuro flask, myristyl-3-mercaptopropionate 1
1.6f, tetrakis(acryloyloxymethyl)methane 3.45', tetra-n-butylammonium fluoride 0.052, and anhydrous tetrahydrofuran 20d were charged, and the mixture was heated at room temperature (approximately 28°C) under an atmosphere of 1.
Stirred for 0 hours.
反応終了後、テトラヒドロフランを減圧下にて留去し、
トルエン４０ｍｇを加え、蒸留水２０＋ｔ／で３回洗浄
を行なった。分液後、積木硫酸マグネシウムで脱水し、
溶剤を減圧下で除去した。アセトンより再結晶を行い目
的物 １３．７９を得た。After the reaction, tetrahydrofuran was distilled off under reduced pressure.
40 mg of toluene was added, and washing was performed three times with 20+ tons of distilled water. After liquid separation, dehydrate with block magnesium sulfate,
Solvent was removed under reduced pressure. Recrystallization from acetone yielded the desired product 13.79.
収率 ９２．０（％）
（分析；直）
Ｈｌ−ＮＭＲ吸収スペクトル
［： ＣＤ Ｃｔｓ 、δ（ｐｐｍ） ）０．６０〜１
．８０ （２７Ｈ，ｍ）。Yield 92.0 (%) (Analysis; direct) Hl-NMR absorption spectrum [: CDCts, δ (ppm)) 0.60-1
．． 80 (27H, m).
２．４０〜３．００ （８Ｈ，ｍ）。2.40-3.00 (8H, m).
３．９０〜４．２５ （４Ｈ，ｍ）ＩＲ吸収スペク
トル
〔ＫＢｒ（ｃｒＲ−１）〕
２９４０．１７４０，１３５５，１２４５゜〈合成例２
〉 例示化合物 ＆３
四ツ目フラスコ内に、ミリスチル−３−メルカプトプロ
ピオネート １５．Ｏｆ、１，３．５− トリアクリロ
イルへキサヒドロ−８−トリアジン ４．０？、テトラ
−ｎ−ブチルアンモニウムフルオライド ｏ、ｏ ｓ
を及び、無水テトラヒドロ７ラン４０ｄを仕込み、窒素
雰囲気下、室温（約２８℃）で１０時間攪拌した。3.90-4.25 (4H, m) IR absorption spectrum [KBr (crR-1)] 2940.1740, 1355, 1245° (Synthesis Example 2)
> Exemplary compound &3 In a four-eye flask, myristyl-3-mercaptopropionate 15. Of, 1,3.5-triacryloylhexahydro-8-triazine 4.0? , tetra-n-butylammonium fluoride o, o s
and 40 d of anhydrous tetrahydro 7 run were added, and the mixture was stirred at room temperature (approximately 28°C) for 10 hours under a nitrogen atmosphere.
反応終了後、テトラヒドロフランを減圧下にて留去シ、
トルエン４０−を加え、蒸留水２０ｄで３回洗浄を行な
った。分液後、無水硫酸マグネシウムで脱水し、溶剤を
減圧下で除去した。エタノールより再結晶を行い目的物
１３．９ ｆを得た。After the reaction is complete, tetrahydrofuran is distilled off under reduced pressure.
40 mL of toluene was added, and washing was performed three times with 20 d of distilled water. After separation, the mixture was dehydrated with anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. Recrystallization was performed from ethanol to obtain the desired product 13.9 f.
収率 ７５．０ （％）
（分析値）
Ｈ−ＮＭＲ吸収スペクトル
（ＣＤ Ｃ１ｓ 、 δ（ｐｐｍ））０．７３〜１．
８６ （２７Ｈ，ｍ）。Yield 75.0 (%) (Analytical value) H-NMR absorption spectrum (CDC1s, δ (ppm)) 0.73-1.
86 (27H, m).
２．５３〜２．９３ （８Ｈ，ｍ）。2.53-2.93 (8H, m).
２．０６ （２Ｈ，ｔ ）。2.06 (2H, t).
５．２６ （２Ｈ，５）
ＩＲ吸収スペクトル
（ＫＢｒ （ａｎ−’ ） ）
２９２０．１？３０，１６５０，１４３０゜１２４０．
１１６０
次に、本発明になる合成樹脂組成物の効果を以下の実験
例によって具体的に説明する。5.26 (2H,5) IR absorption spectrum (KBr (an-')) 2920.1?30,1650,1430°1240.
1160 Next, the effects of the synthetic resin composition of the present invention will be specifically explained using the following experimental examples.
しかしながら、これらの実施例は、本発明を単に説明す
るものであり、本発明はこれらの実施例によって同等制
限を受けるものではない。However, these examples are merely illustrative of the invention, and the invention is not equally limited by these examples.
尚、例中の略号は次の通りである。The abbreviations in the examples are as follows.
（硫黄系酸化防止剤）
ＤＭＴＤＰ チオジプロピオン酸シミリスチルＤＬＴ
ＤＰ ｆオシプロピオン酸ジステアリル（フェノール
系酸化防止剤）
１，１，３−）リス−（２−メチル−４−ヒドロキシ−
５−ｔ−ブチルフェニル）ブタン（商品名： ’Ｉ’ｏ
ｐａｎｏｌ ＣＡ ）テトラキス（３−（３，５−ジ
−ｔ−ブチル−４−ヒドロキシフェニル）プロビオニル
オキシメチル〕メタン
（商品名： Ｉｒｇａｎｏｘ １０１０ ）１，３，
５−トリス（４−ｔ−ブチル−２，６−シーメテルー３
−ヒドロキシベンジル）インシアヌレート
（商品名： （ｙａｎｏｘ １７９０ ）３，９−（
ビス１，１−ジ−メチル−２−（β−（３−ｔ−ブチル
−４−ヒドロキシ−５−メチルフェニル）クロピオニル
オキシ）エチル〕−２，４，８，１０−テトラオキサス
ピロ（ｓ、ｓ ）ウンデカン
（商品名：ＭＡＲＫ ＡＯ−８０）
１，３，５−トリス−（３−メチル−５−ｔ−ブチル−
４−ヒドロキシベンジル）インシアヌレート
Ｆ’−４
エチレングリコール−ビス−（３，３−ビス−（３−ｔ
−ブチル−４−ヒドロキシフェニル）ブチレート
（商品名： ）（ｏｓｔａｎｏｘ Ｏ３）〈実施例１
〉
１３５℃テトラリン中で測定した極限粘度が１．９でア
イソタクチックなものが９８％のポリプロピレン粉末１
００重敗部に第１衣に示す各添加剤を配合して、ミキナ
ーで充分混合した。その後シリンダー昌度２６０℃、Ｌ
／Ｄ＝２０．２０口径の押出機によって溶融混練して造
粒した。得られたベレットを２３０℃で厚さ０．５額の
シートに圧縮成型して試験片とし、耐熱老化性及び耐候
性を評価した。(Sulfur-based antioxidant) DMTDP Simiristil thiodipropionate DLT
DP f Distearyl ocipropionate (phenolic antioxidant) 1,1,3-)lis-(2-methyl-4-hydroxy-
5-t-butylphenyl)butane (trade name: 'I'o
panol CA) tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)probionyloxymethyl]methane (trade name: Irganox 1010) 1,3,
5-tris(4-t-butyl-2,6-cymeter-3
-hydroxybenzyl)in cyanurate (trade name: (yanox 1790) 3,9-(
bis1,1-di-methyl-2-(β-(3-t-butyl-4-hydroxy-5-methylphenyl)clopionyloxy)ethyl]-2,4,8,10-tetraoxaspiro( s, s) Undecane (Product name: MARK AO-80) 1,3,5-tris-(3-methyl-5-t-butyl-
4-hydroxybenzyl)in cyanurate F'-4 Ethylene glycol-bis-(3,3-bis-(3-t
-Butyl-4-hydroxyphenyl)butyrate (trade name: ) (ostanox O3) <Example 1
> Polypropylene powder 1 with an intrinsic viscosity of 1.9 measured in tetralin at 135°C and 98% isotactic
Each additive shown in the first batter was added to the 00 heavily defeated part and thoroughly mixed in a mixer. After that, cylinder pressure 260℃, L
/D=20. The mixture was melt-kneaded and granulated using an extruder with a diameter of 20. The obtained pellet was compression molded at 230° C. into a sheet with a thickness of 0.5 mm to obtain a test piece, and the heat aging resistance and weather resistance were evaluated.
（１）耐熱老化性
１５０℃の循環式空気炉中で試験片を加熱して試験片が
酸化劣化によって褐変脆化する迄の所要時間を測定した
。(1) Heat Aging Resistance A test piece was heated in a circulating air oven at 150° C., and the time required for the test piece to brown and become brittle due to oxidative deterioration was measured.
（２）耐候性
アトラス社％６５／ＸＷ−ＷＲ型キセノンウエザオメー
ターを用い、ブラックパネル温度８０℃で試験片に光照
射し、試験片が脆化して１８０度折り曲げたときクラッ
クを発生するまでの所要時間を測定した。(2) Using an Atlas %65/XW-WR xenon weatherometer, the test piece was irradiated with light at a black panel temperature of 80°C until the test piece became brittle and cracked when bent 180 degrees. The required time was measured.
結果は、第１表に示す通りであった。The results were as shown in Table 1.
（以下余白）
第１表
〈実施例２〉
クロロホルムを溶媒として２５℃で測定された極限粘度
が０．４５ｄｔ／ｙのポリ（２，６−ジメチル１．４−
）ユニレン）エーテル粉末１００重量部と第２表に記載
した安定剤の混合物を二軸押出桟により混練してペレッ
ト化し、ついで試験片を成形後、加工安定性及び耐熱老
化性を評価した。(Margins below) Table 1 <Example 2> Poly(2,6-dimethyl 1.4-
) Unilene) A mixture of 100 parts by weight of ether powder and the stabilizer listed in Table 2 was kneaded and pelletized using a twin-screw extrusion bar, and test pieces were then molded and evaluated for processing stability and heat aging resistance.
（１）加工安定性
原点と２８０℃に設定した単軸押出機を３回繰り返して
通過させた後の引張衝撃を比較する方法で加工安定性を
測定した。(1) Processing stability Processing stability was measured by comparing the tensile impact after passing through a single-screw extruder set at 280° C. three times.
（２）耐熱老化性
１２０℃のギアオーブンに引張衝撃試験片を入れ、３０
０時間後、６００時間後の引張衝撃強度を測定した。(2) Heat aging resistance A tensile impact test piece was placed in a gear oven at 120°C.
The tensile impact strength was measured after 0 hours and 600 hours.
尚、引張衝撃強度は、厚み１ｆｉの試験片を用いた。引
張衝撃強度の測定は、ＡＳＴＭ−Ｄ−１８２２の方法で
実施した。Note that a test piece with a thickness of 1 fi was used for the tensile impact strength. The tensile impact strength was measured by the method of ASTM-D-1822.
結果は、第２表に示す通りであった。The results were as shown in Table 2.
Claims (1)
合物と、下記一般式（II）で示されるフェノール系化合
物とを、（ I ）：（II）＝１〜１５：１（重量比）の
割合で配合してなる安定化された合成樹脂組成物。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒは炭素数８〜２４のアルキル基、Ｘは▲数式
、化学式、表等があります▼、 または▲数式、化学式、表等があります▼ 基を表わし、ｉ、ｊは１〜３の整数、ｎは１〜４の整数
を示す。） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿１、Ｒ＿２は水素原子又はメチル基を、Ｙ
はヘテロ元素を含む炭化水素基を示す。ｍは２〜４の整
数であり、＋はｔ−ブチル基を表わす。）(1) A sulfur compound represented by the following general formula (I) and a phenol compound represented by the following general formula (II) are added to a synthetic resin in a weight ratio of (I):(II)=1 to 15:1. ) is a stabilized synthetic resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an alkyl group with 8 to 24 carbon atoms, ▼ Represents a group, where i and j are integers of 1 to 3, and n is an integer of 1 to 4.) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_1 and R_2 are hydrogen atoms Or a methyl group, Y
indicates a hydrocarbon group containing a hetero element. m is an integer of 2 to 4, and + represents a t-butyl group. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1865288A JPH01193362A (en) | 1988-01-29 | 1988-01-29 | Stabilized synthetic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1865288A JPH01193362A (en) | 1988-01-29 | 1988-01-29 | Stabilized synthetic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01193362A true JPH01193362A (en) | 1989-08-03 |
Family
ID=11977547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1865288A Pending JPH01193362A (en) | 1988-01-29 | 1988-01-29 | Stabilized synthetic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01193362A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05262980A (en) * | 1992-03-19 | 1993-10-12 | Mitsui Petrochem Ind Ltd | Thermoplastic resin composition and its molded article |
| JPH0649357A (en) * | 1992-03-19 | 1994-02-22 | Mitsui Petrochem Ind Ltd | Polyamide resin composition and connector |
| US6846866B2 (en) | 2001-06-05 | 2005-01-25 | Invista North America S.A.R.L. | Spandex containing a mixture of phenolic |
| WO2015186617A1 (en) * | 2014-06-04 | 2015-12-10 | 日油株式会社 | Thioether-containing (meth)acrylate derivative and adhesion improver containing same |
| WO2023286616A1 (en) * | 2021-07-15 | 2023-01-19 | 住友化学株式会社 | Phenolic compound, organic material stabilizer, resin composition, and method for stabilizing organic material |
| WO2024150714A1 (en) * | 2023-01-13 | 2024-07-18 | 住友化学株式会社 | Processing stabilizer, resin composition, and organic material stabilizing method |
-
1988
- 1988-01-29 JP JP1865288A patent/JPH01193362A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05262980A (en) * | 1992-03-19 | 1993-10-12 | Mitsui Petrochem Ind Ltd | Thermoplastic resin composition and its molded article |
| JPH0649357A (en) * | 1992-03-19 | 1994-02-22 | Mitsui Petrochem Ind Ltd | Polyamide resin composition and connector |
| US6846866B2 (en) | 2001-06-05 | 2005-01-25 | Invista North America S.A.R.L. | Spandex containing a mixture of phenolic |
| WO2015186617A1 (en) * | 2014-06-04 | 2015-12-10 | 日油株式会社 | Thioether-containing (meth)acrylate derivative and adhesion improver containing same |
| JP2015229642A (en) * | 2014-06-04 | 2015-12-21 | 日油株式会社 | Thioether-containing (meth) acrylate derivative, and adhesion improver comprising the same |
| WO2023286616A1 (en) * | 2021-07-15 | 2023-01-19 | 住友化学株式会社 | Phenolic compound, organic material stabilizer, resin composition, and method for stabilizing organic material |
| WO2024150714A1 (en) * | 2023-01-13 | 2024-07-18 | 住友化学株式会社 | Processing stabilizer, resin composition, and organic material stabilizing method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FI110117B (en) | Flame resistant plastic compression mass with improved stability | |
| EP0070358B1 (en) | Novel light stabilizers for polymers | |
| EP0315162B1 (en) | Polyolefin compositions of high clarity and resistance to oxidation | |
| CA1307613C (en) | Bicyclic phosphate ether, ester, and carbonate intumescent flame retardant compositions | |
| EP0053775B1 (en) | Poly-bis-triazynyl amines, process for their preparation, their use in stabilising synthetic polymers, and polymers stabilised this way | |
| EP0102193A2 (en) | Stabilizers for synthetic resins | |
| US4808650A (en) | High clarity polyolefin compositions and clarifying additive therein | |
| EP0057885B1 (en) | Substituted diazaspirodecanes, their preparation and their use for the stabilisation of organic polymers and these stabilised polymers | |
| JPH01193362A (en) | Stabilized synthetic resin composition | |
| CA1053839A (en) | Polymer compositions containing titanium dioxide having improved visible and ultraviolet and light stability | |
| US3928357A (en) | Substituted piperazine diones and polymeric compositions stabilized thereby | |
| US4617333A (en) | Stabilized polyolefinic compositions and stabilizer compounds suitable to that purpose | |
| EP0106618A2 (en) | Stabilizers for synthetic resins | |
| US5739377A (en) | Phenylalkanoic acid esters and their use as antioxidants | |
| JPS59176256A (en) | Oligomer ester and organic material stabilization | |
| US4293466A (en) | Piperidine phosphite stabilizers for polymers and polymers stabilized thereby | |
| US3895048A (en) | Poly (phosphine oxide) flame-retardants | |
| US4370430A (en) | Hindered amine light stabilizers for polymers | |
| JPS6230134A (en) | Stabilizer for synthetic resin | |
| JPS5927936A (en) | Stabilized polyolefin resin composition | |
| JPS594629A (en) | Stabilized synthetic resin compositon | |
| JPH0525330A (en) | Stabilization of polyolefin | |
| JPS59126439A (en) | Stabilized high polymer material composition | |
| JPS6230135A (en) | Stabilizer for synthetic resin | |
| JPS58168634A (en) | Stabilized synthetic resin composition |