TWI586730B - An antistatic composition, a resin composition, and a molded article using the same - Google Patents
An antistatic composition, a resin composition, and a molded article using the same Download PDFInfo
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- TWI586730B TWI586730B TW102118398A TW102118398A TWI586730B TW I586730 B TWI586730 B TW I586730B TW 102118398 A TW102118398 A TW 102118398A TW 102118398 A TW102118398 A TW 102118398A TW I586730 B TWI586730 B TW I586730B
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- mass
- carbon atoms
- compound represented
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- 239000000203 mixture Substances 0.000 title claims description 116
- 239000011342 resin composition Substances 0.000 title description 10
- -1 diester compound Chemical class 0.000 claims description 159
- 150000001875 compounds Chemical class 0.000 claims description 105
- 125000000217 alkyl group Chemical group 0.000 claims description 63
- 229920003002 synthetic resin Polymers 0.000 claims description 50
- 239000000057 synthetic resin Substances 0.000 claims description 50
- 125000004432 carbon atom Chemical group C* 0.000 claims description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 31
- 239000012760 heat stabilizer Substances 0.000 claims description 27
- 239000003017 thermal stabilizer Substances 0.000 claims description 27
- 125000003342 alkenyl group Chemical group 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 125000004434 sulfur atom Chemical group 0.000 claims description 22
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 21
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 229920005672 polyolefin resin Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004455 differential thermal analysis Methods 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 description 37
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- 230000000694 effects Effects 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005086 pumping Methods 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 14
- 235000006708 antioxidants Nutrition 0.000 description 14
- 150000005690 diesters Chemical class 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 230000006641 stabilisation Effects 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 8
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 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 7
- 229930185605 Bisphenol Natural products 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000002216 antistatic agent Substances 0.000 description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000002530 phenolic antioxidant Substances 0.000 description 7
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 150000003568 thioethers Chemical class 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000012748 slip agent Substances 0.000 description 6
- 241000208340 Araliaceae Species 0.000 description 5
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 5
- 235000003140 Panax quinquefolius Nutrition 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 5
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 235000008434 ginseng Nutrition 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002667 nucleating agent Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 229960000956 coumarin Drugs 0.000 description 4
- 235000001671 coumarin Nutrition 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 4
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 150000001540 azides Chemical class 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- MQQKTNDBASEZSD-UHFFFAOYSA-N 1-(octadecyldisulfanyl)octadecane Chemical compound CCCCCCCCCCCCCCCCCCSSCCCCCCCCCCCCCCCCCC MQQKTNDBASEZSD-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
- MFZAXZRJGHLULL-UHFFFAOYSA-N 2,4-ditert-butyl-6-[2-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CCC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O MFZAXZRJGHLULL-UHFFFAOYSA-N 0.000 description 2
- VVFNNEKHSFZNKA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-ene Chemical compound CC(C)(C)OOC(C)(C)C=CC(C)(C)OOC(C)(C)C VVFNNEKHSFZNKA-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- NGEDIUKJODFHJJ-UHFFFAOYSA-N 2-[1,4-dioxo-1,4-di(tridecoxy)butan-2-yl]butanedioic acid Chemical compound CCCCCCCCCCCCCOC(=O)CC(C(CC(=O)O)C(=O)O)C(=O)OCCCCCCCCCCCCC NGEDIUKJODFHJJ-UHFFFAOYSA-N 0.000 description 2
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 2
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 244000291564 Allium cepa Species 0.000 description 2
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- BUAIYNOXVIVNLG-UHFFFAOYSA-N bis(ethenoxy)phosphorylbenzene Chemical compound C=COP(=O)(OC=C)C1=CC=CC=C1 BUAIYNOXVIVNLG-UHFFFAOYSA-N 0.000 description 1
- YSRMRWIQPVDQBV-UHFFFAOYSA-N bis(prop-2-enoxy)phosphorylbenzene Chemical compound C=CCOP(=O)(OCC=C)C1=CC=CC=C1 YSRMRWIQPVDQBV-UHFFFAOYSA-N 0.000 description 1
- FLAJFZXTYPQIBY-CLFAGFIQSA-N bis[(z)-octadec-9-enyl] hydrogen phosphite Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(O)OCCCCCCCC\C=C/CCCCCCCC FLAJFZXTYPQIBY-CLFAGFIQSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical class Br* 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
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 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
- JRZBPELLUMBLQU-UHFFFAOYSA-N carbonazidic acid Chemical compound OC(=O)N=[N+]=[N-] JRZBPELLUMBLQU-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- IEJNAGSUKYCWCR-UHFFFAOYSA-N chloroethene;1,1-dichloroethene;ethenyl acetate Chemical compound ClC=C.ClC(Cl)=C.CC(=O)OC=C IEJNAGSUKYCWCR-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- DXGPLGPVXNBIQZ-UHFFFAOYSA-L copper;2-hydroxybenzoate;methyl n-(1h-benzimidazol-2-yl)carbamate;6-methyl-n-phenyl-2,3-dihydro-1,4-oxathiine-5-carboxamide;quinolin-8-olate Chemical class [Cu+2].OC1=CC=CC=C1C([O-])=O.C1=CN=C2C([O-])=CC=CC2=C1.C1=CC=C2NC(NC(=O)OC)=NC2=C1.S1CCOC(C)=C1C(=O)NC1=CC=CC=C1 DXGPLGPVXNBIQZ-UHFFFAOYSA-L 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KSCAZGPKPGSMTR-UHFFFAOYSA-N decyl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCC KSCAZGPKPGSMTR-UHFFFAOYSA-N 0.000 description 1
- SWUYLUYFFADSNR-UHFFFAOYSA-N decyl phenyl hydrogen phosphite Chemical compound CCCCCCCCCCOP(O)OC1=CC=CC=C1 SWUYLUYFFADSNR-UHFFFAOYSA-N 0.000 description 1
- ZVHINFYXDXKLLA-UHFFFAOYSA-N decylazanium;octadecanoate Chemical compound CCCCCCCCCC[NH3+].CCCCCCCCCCCCCCCCCC([O-])=O ZVHINFYXDXKLLA-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- DYHSBBDFFBVQSS-UHFFFAOYSA-J dicalcium;2,6-ditert-butyl-4-(1-phosphonatopropyl)phenol Chemical compound [Ca+2].[Ca+2].CCC(P([O-])([O-])=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CCC(P([O-])([O-])=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DYHSBBDFFBVQSS-UHFFFAOYSA-J 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 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
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical class CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 1
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- VOWPVJACXJNHBC-UHFFFAOYSA-N methyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OC)OC1=CC=CC=C1 VOWPVJACXJNHBC-UHFFFAOYSA-N 0.000 description 1
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- ACMVLJBSYFHILY-UHFFFAOYSA-N oxo-di(tridecoxy)phosphanium Chemical compound CCCCCCCCCCCCCO[P+](=O)OCCCCCCCCCCCCC ACMVLJBSYFHILY-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
- 239000002245 particle Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 description 1
- 239000001601 sodium adipate Substances 0.000 description 1
- 235000011049 sodium adipate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- SNAQARSCIHDMGI-UHFFFAOYSA-M sodium;bis(4-tert-butylphenyl) phosphate Chemical compound [Na+].C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 SNAQARSCIHDMGI-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- DECPGQLXYYCNEZ-UHFFFAOYSA-N tris(6-methylheptyl) phosphite Chemical compound CC(C)CCCCCOP(OCCCCCC(C)C)OCCCCCC(C)C DECPGQLXYYCNEZ-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical group C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen
- C09K15/14—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen containing a phenol or quinone moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本發明係關於一種安定劑組成物、樹脂組成物及使用此之成形品,詳而言之,即使在低溫環境下固形物亦不析出,而處理性良好的安定劑組成物、樹脂組成物及使用此之成形品、以及不含固形物而優異的耐熱性與低黏性且處理性良好的合成樹脂用之安定劑組成物、合成樹脂組成物、及使用此之成形品。
至今,由雙酚硫醚之烷基氫硫基羧酸的單酯體及二酯體所構成的安定劑組成物係已知對於聚氯乙烯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚丁烯樹脂、聚對苯二甲酸丁二酯樹脂、聚碳酸酯樹脂、ABS樹脂、尼龍6、尼龍66、乙烯-醋酸乙烯酯共聚物、石油樹脂、香豆素樹脂等之各種合成樹脂而賦予優異的安定化效果(專利文獻1~4)。
又,以往,雙酚硫醚之烷基氫硫基羧酸的單酯體化合物、其二酯體化合物、及硫二烷基羧酸二烷基酯化合物係已知有聚氯乙烯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚丁烯樹脂、聚對苯二甲酸丁二酯樹脂、聚碳酸酯樹脂、ABS樹
脂、尼龍6、尼龍66、乙烯-醋酸乙烯酯共聚物、石油樹脂、香豆素樹脂等之各種合成樹脂而賦予優異的安定化效果(專利文獻1~4)。
專利文獻1:特開昭51-70192號公報
專利文獻2:特開昭52-154851號公報
專利文獻3:特開昭54-083950號公報
專利文獻4:特開昭55-149338號公報
然而,含有雙酚硫醚之烷基氫硫基羧酸的單酯體及二酯體的安定劑組成物係在25℃左右的常溫環境下有關保存性之問題無特別,但冬場或低溫倉庫等、在低溫環境下長期保管時,有安定劑組成物固形化而處理性困難之問題,尋求改善。在專利文獻1~4中係記載有關如此之安定劑組成物優異的安定化效果,但對於長期保管安定劑組成物時之保存性的問題係未特別提及,其解決方法亦未被暗示。
又,含有雙酚硫醚之烷基氫硫基羧酸的單酯體化合物及其二酯體化合物的熱安定劑組成物之黏性高,有摻合於
合成樹脂時可使用的泵浦受限定等的問題。若摻混黏性低之化合物,上述問題可被改善,但此時,產生層分離,或於熱安定劑組成物產生混濁或固形物,而於品質管理上產生問題。進一步,於熱安定劑組成物所含有的羥基具有阻礙合成樹脂尤其聚乙烯、乙烯-醋酸乙烯酯、乙烯-乙基丙烯酸酯、乙烯-丙烯、乙烯-丙烯-丁二烯等之共聚物交聯的問題。
因此,本發明之目的係提供一種含有雙酚硫醚之烷基氫硫基羧酸的單酯體及二酯體的安定劑組成物,即使在低溫環境下固形物亦未析出,而可維持處理性的安定劑組成物、樹脂組成物及使用此之成形品、以及不含固形物而優異的耐熱性與低黏性且處理性良好的合成樹脂用之熱安定劑組成物、合成樹脂組成物、及使用此之成形品。
亦即,本發明之安定劑組成物係含有以下述通式(1)、
(式中,R1、R2及R3係分別獨立地表示氫原子、碳原子數1~18的烷基、碳原子數3~18的環烷基、或可被烷基、烷氧基、烯基、烯氧基或羥基取代之碳原子數6~30的芳基,R4及R5係分別獨立地表示可被烷氧基、烯基、烯氧基、羥基或氰基取代之碳原子數3~30的直鏈或分枝烷基
)所示的二酯體、及、以下述通式(2)、
(式中,R1、R2及R3係分別獨立地表示氫原子、碳原子數1~18的烷基、碳原子數3~18的環烷基、或可被烷基、烷氧基、烯基、烯氧基或羥基取代之碳原子數6~30的芳基,R6係表示可被烷氧基、烯基、烯氧基、羥基或氰基取代之碳原子數3~30的直鏈或分枝烷基)所示的單酯體;以前述式(1)所示之二酯體與以前述式(2)所示之單酯體的合計100質量份中,以前述式(1)所示之二酯體的含量多於65質量份且未達80質量份。
本發明之安定劑組成物,宜黏度為6000mPa.s以下。使用泵浦而將本發明之安定劑組成物饋入於合成樹脂等之時,可使用齒輪泵浦、隔膜泵浦、旋轉泵浦、螺桿泵浦、Waukesha泵浦、Sine泵浦、Hose泵浦等公知的泵浦而饋入,但若安定劑組成物之黏度超過6000mPa.s,必須為特殊之泵浦,或有時安定劑組成物附著於泵浦或配管內壁而損失變多,故宜為6000mPa.s以下。使本發明之安定劑組成物的黏度低於6000mPa.s以下係必須將以上述通式(1)所示之二酯體與以上述通式(2)所示之單酯體調整成上述特定之組成比。
本發明之安定劑組成物宜前述通式(1)中之R4、R5及前述通式(2)中之R6為全部相同之烷基。
本發明之樹脂組成物其特徵係將上述任何之安定劑組成物摻合於合成樹脂中。
本發明之成形品其特徵係使如上述之樹脂組成物成形而成。
本發明人等為解決上述課題經專心研究之結果,發現可得到一種使具有特定構造之二酯體化合物、單酯體化合物、及硫二烷基羧酸二烷基酯化合物混合特定量,而解決上述課題之熱安定劑組成物,終完成本發明。
亦即本發明之熱安定劑組成物係含有以下述通式(3)、
(式中,R11~R18係分別獨立地表示氫原子、可被氧原子或硫原子中斷之碳原子數1~18的烷基、碳原子數3~18的環烷基、或可被氧原子或硫原子中斷之烷基、烷氧基、烯基、烯氧基或羥基所取代之碳原子數6~30的芳基,R19及R20係分別獨立地表示可被烷氧基、烯基、烯氧基、羥基或氰基取代,又,亦可被氧原子或硫原子中斷之碳原子數3~30的直鏈或分枝烷基)所示的二酯體化合物、及、以下述通式(4)、
(式中,R11~R18係分別獨立地表示氫原子、可被氧原子
或硫原子中斷之碳原子數1~18的烷基、碳原子數3~18的環烷基、或亦可被氧原子或硫原子中斷之烷基、烷氧基、烯基、烯氧基或羥基所取代之碳原子數6~30的芳基,R11係亦可被烷氧基、烯基、烯氧基、羥基或氰基取代,亦可被氧原子或硫原子中斷之碳原子數3~30的直鏈或分枝烷基)所示的單酯體化合物;以下述通式(5)、
(式中,R22係可被烷氧基、烯基、烯氧基、羥基或氰基取代,亦可被氧原子或硫原子中斷之碳原子數3~30的直鏈或分枝烷基,A係表示可被烷氧基、烯基、烯氧基、羥基或氰基取代之碳原子數1~8的直鏈或分枝伸烷基)所示之硫二烷基羧酸二烷基酯化合物的熱安定劑組成物,其特徵係使前述通式(3)所示之二酯體化合物、與前述通式(4)所示之單酯體化合物之合計100質量份中,以前述通式(3)所示之二酯體化合物的含量多於65質量份,且以前述通式(3)所示之二酯體化合物與前述通式(4)所示之單酯體化合物之合計與以前述通式(5)所示之硫二烷基羧酸二烷基酯化合物的質量比為{(3)+(4)}/(5)=95/5~50/50的範圍內。
本發明之熱安定劑組成物中,宜在25℃之黏度為3000mPa.s以下。又本發明之熱安定劑組成物中,宜使用微分熱分析(TG-DTA),在氮氣下,以10℃/分的昇溫速
度之條件從室溫加熱時,質量減少5%之溫度為240℃以上。
本發明之合成樹脂組成物,其特徵係相對於合成樹脂100質量份,摻合上述本發明之熱安定劑組成物0.01~5質量份而成。
本發明之合成樹脂組成物中,前述合成樹脂適宜為聚烯烴樹脂。
進一步本發明之成形品,其特徵係上述本發明之合成樹脂組成物成形而成。
若依本發明,可提供一種即使在低溫環境下固形物亦未析出,而處理性良好之安定劑組成物、樹脂組成物及使用此之成形品、以及不含固形物而優異的耐熱性與低黏性且處理性良好的合成樹脂用之安定劑組成物、合成樹脂組成物、及使用此之成形品。
首先,詳細說明有關即使在本發明之低溫環境下固形物亦未析出,而處理性良好之安定劑組成物。
本發明之安定劑組成物其特徵係含有以上述通式(1)所示之雙酚硫醚之烷基氫硫基羧酸二酯及以通式(2)所示之雙酚硫醚之烷基氫硫基羧酸單酯者,式(1)之化合物與式(2)之化合物的合計量100質量份中,以通式
(1)所示之化合物的含量多於65質量份且未達80質量份。本發明之安定劑組成物係處理性良好的低黏度液狀,即使在低溫下,例如5℃之環境下保存,亦可抑制固形分之析出。黏度宜為6000mPa.s以下。黏度係在25℃之黏度,可藉由例如B型黏度計測定。
本發明之安定劑組成物係適宜本質上為由以上述通式(1)所示之二酯體與以上述通式(2)所示之單酯體所構成者,但只要不損及本發明之效果,於如下述之樹脂中亦可含有一般所使用的添加劑等其他成分。含有其他成分時,在本發明之安定劑組成物中的主成分係以上述通式(1)所示之化合物與以上述通式(2)所示之化合物,故其他之含量係相對於以上述通式(1)所示之二酯體與以上述通式(2)所示之單酯體之合計100質量份,宜為1000質量份以下。
前述通式(1)中之R4、R5及通式(2)中之R6所示的可被取代之碳原子數3~30的直鏈或分枝烷基,可舉例如丙基、異丙基、丁基、異丁基、第三丁基、第二丁基、戊基、異戊基、新戊基、己基、2-乙基己基、異己基、庚基、辛基、異辛基、壬基、癸基、異癸基、月桂基、十四碳基、十六碳基、十三碳基、十四碳基、十五碳基、十六碳基、十七碳基、十八碳基、二十碳基、二十四碳基、二十八碳基等。
上述烷基係可被烯基、烷氧基、羥基、或氰基取代,又亦可被氧原子、或硫原子中斷。又,此等之中斷或取代
係可被組合。烷基之碳原子數少於3之化合物係有時於成形品表面滲出或起霧而損及成形品之外觀。若烷基之碳數超過30,有時無法得到必需的安定化效果。在本發明中,含有R4、R5及R6全部為同一烷基之化合物的安定劑組成物係比較低黏度,熱安定性良好,故較宜使用。
前述通式(1)及(2)中之以R1、R2及R3所示的碳原子數1~18的烷基,可舉例如與以上述烷基記載者相同。
前述通式(1)及(2)中之以R1、R2及R3所示的碳原子數3~18的環烷基,可舉例如環丙基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基等,環烷基中之氫原子亦可被烷基、烯基、烯氧基、羥基、或氰基取代,該烷基亦可被氧原子、或硫原子中斷。可舉例如環戊基、環己基、環辛基、環十二碳基、4-甲基環己基等。
前述通式(1)及(2)中之以R1、R2及R3所示的烷基、烷氧基、烯基、烯氧基或羥基取代之碳原子數6~30的芳基,可舉例如苯基、甲基苯基、丁基苯基、辛基苯基、4-羥基苯基、3,4,5-三甲氧基苯基、4-第三丁基苯基、聯苯基、萘基、甲基萘基、蔥基、菲基、苯甲基、苯基乙基、1-苯基-1-甲基乙基等。又,芳基中之氫原子亦可被烷基、烯基、烯氧基、羥基、或氰基取代,該烷基亦可被氧原子、或硫原子中斷。
以上述通式(1)所示的二酯體宜為以下述通式(1’)所示者。
又,以上述通式(2)所示的單酯體宜為以下述通式(2’)所示者。
以上述通式(1)所示之化合物的具體構造可舉例如下述之化合物。但,本發明係不受以下之化合物限制。
以上述通式(2)所示之化合物的具體構造可舉例如下述之化合物。但,本發明係不受以下之化合物限制。
藉由本發明之安定劑組成物而安定化之合成樹脂,可舉例如聚丙烯、高密度聚乙烯、低密度聚乙烯、直鏈低密度聚乙烯、聚丁烯-1、聚-4-甲基戊烯等之α-烯烴聚合物或乙烯-醋酸乙烯酯共聚物、乙烯-丙烯共聚物等之聚烯烴及此等之共聚物、聚氯乙烯、聚偏氯乙烯、氯化橡膠、氯乙烯-醋酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-偏氯乙烯共聚物、氯乙烯-偏氯乙烯-醋酸乙烯酯三元共聚物、氯乙烯-丙烯酸酯共聚物、氯乙烯-馬來酸酯共聚物、氯乙烯-環己基馬來醯亞胺共聚物等之含鹵素樹脂、石油樹脂、香豆素樹脂、聚苯乙烯、聚醋酸乙烯酯、丙烯酸樹脂
、苯乙烯及/或α-甲基苯乙烯與其他之單體(例如馬來酸酐、苯基馬來醯亞胺、甲基丙烯酸甲酯、丁二烯、丙烯腈等)之共聚物(例如AS樹脂、ABS樹脂、MBS樹脂、耐熱ABS樹脂等)、聚甲基丙烯酸甲酯、聚乙烯醇、聚乙烯醇縮甲醛、聚乙烯醇縮丁醛、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚對苯二甲酸四亞甲基酯等之直鏈聚酯、聚苯氧、聚己內醯胺及聚六亞甲基己二醯胺等之聚醯胺、聚碳酸酯、分枝聚碳酸酯、聚乙縮醛、聚苯硫醚、聚胺基甲酸酯、纖維素系樹脂等之熱塑性樹脂、及此等之混合物、或、酚樹脂、脲樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯樹脂等之熱硬化性樹脂。進一步,可為異戊二烯橡膠、丁二烯橡膠、丙烯腈-丁二烯共聚合橡膠、苯乙烯-丁二烯共聚合橡膠等之彈性體,亦可為於上述樹脂中含有者。又,本發明之安定劑組成物係亦可良好地使用藉過氧化物或放射線等所製造之交聯用合成樹脂、發泡聚苯乙烯等之發泡樹脂。交聯用合成樹脂係可舉例如聚乙烯或乙烯-醋酸乙烯酯、乙烯-乙基丙烯酸酯、乙烯-丙烯、乙烯-丙烯-丁二烯等之共聚物。
又,可使用於合成樹脂之交聯劑可舉例如過氧化苯甲醯基、過氧化二-第三丁基、過氧化異丙苯基、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、2,5-二甲基-2,5-二(第三丁基過氧化)己烯、1,3-雙(第三丁基過氧化異丙基)苯、氫過氧化第三丁基、氫過氧化異丙基苯、聚碸疊氮、疊氮甲酸酯、四甲基異酞醯基二-第三丁基雙過氧化物
、四甲基異酞醯基二-異丙苯基雙過氧化物、二乙醇胺、三乙醇胺等之醇胺、六亞甲基二胺、4,4’-二胺基二苯基甲烷等。
上述合成樹脂之中,聚乙烯、聚丙烯、乙烯-丙烯共聚合樹脂等之聚烯烴系樹脂係以本案發明之安定劑組成物所產生的安定化效果優,故較宜使用。亦即,本發明之安定劑組成物係適宜作為聚烯烴系樹脂用安定劑。
於本發明之安定劑組成物係如上述般,亦可摻合以上述通式(1)所示的化合物及以上述通式(2)所示的化合物以外之其他的成分。其他之成分可舉例如一般對合成樹脂所使用之添加劑。又,其他之成分係亦可添加於摻合有本發明之安定劑組成物的樹脂組成物。添加劑可舉例如酚系抗氧化劑、磷系抗氧化劑、硫醚系抗氧化劑、紫外線吸收劑、阻胺化合物、耐燃劑、造核劑、填充劑、滑劑、抗靜電劑、重金屬惰性化劑、金屬皂、水滑石、顏料、染料、可塑劑等。
上述酚系抗氧化劑係亦可為與以上述通式(1)所示者相同,亦可為相異者。上述酚系抗氧化劑係可舉例如2,6-二第三丁基4-乙基酚、2-第三丁基4,6-二甲基酚、苯乙烯化酚、2,2’-亞甲基雙(4-乙基-6-第三丁基酚)、2,2’-硫雙-(6-第三丁基4-甲基酚)、2,2’-硫二乙烯雙[3-(3,5-二第三丁基4-羥基苯基)丙酸酯]、2-甲基-4,6-雙(辛基磺醯基甲基)酚、2,2’-異亞丁基雙(4,6-二甲基酚)、異-辛基-3-(3,5-二-第三丁基4-羥基苯基)丙酸酯、
N,N’-己烷-1,6-二基雙[3-(3,5-二-第三丁基4-羥基苯基)丙醯胺]、2,2’-草醯胺-雙[乙基-3-(3,5-二-第三丁基4-羥基苯基)丙酸酯]、2-乙基己基-3-(3’,5’-二-第三丁基4’-羥基苯基)丙酸酯、2,2’-亞乙基雙(4,6-二-第三丁基酚)、3,5-雙(1,1-二甲基乙基)-4-羥基-苯丙酸及C13~15烷基之酯、2,5-二-第三戊基氫醌、阻酚之聚合物(ADEKA PALMARORE公司製商品名AO.OH 998)、2,2’-亞甲基雙[6-(1-甲基環己基)-對甲酚]、2-第三丁基6-(3-第三丁基2-羥基-5-甲基苯甲基)-4-甲基苯基丙烯酸酯、2-[1-(2-羥基-3,5-二第三戊基苯基)乙基]-4,6-二第三戊基苯基丙烯酸酯、6-[3-(3-第三丁基4-羥基-5-甲基)丙氧基]-2,4,8,10-四-第三丁基苯並[d,f][1,3,2]-二噁磷雜庚英(dioxaphosphepin)、六亞甲基雙[3-(3,5-二-第三丁基4-羥基苯基)丙酸酯]、雙[單乙基(3,5-二第三丁基4-羥基苯甲基)膦酸酯]鈣鹽、5,7-雙(1,1-二甲基乙基)-3-羥基-2(3H)-苯並呋喃酮、與鄰二甲苯之反應生成物、2,6-二-第三丁基4-(4,6-雙(辛基硫)-1,3,5-三嗪-2-基胺基)酚、DL-α-兒茶酚(維生素E)、2,6-雙(α-甲基苯甲基)-4-甲基酚、雙[3,3-雙-(4’-羥基-3’-第三丁基苯基)丁酸]甘醇酯、2,6-二-第三丁基對甲酚、2,6-二苯基-4-十八碳氧基酚、硬脂基(3,5-二-第三丁基4-羥基苯基)丙酸酯、二硬脂基(3,5-二-第三丁基4-羥基苯甲基)膦酸酯、十三碳基-3,5-二-第三丁基4-羥基苯甲基硫乙酸酯、硫二乙烯雙[(3,5-二-第三丁基4-羥基苯基)丙酸酯]
、4,4’-硫雙(6-第三丁基間甲酚)、2-辛基硫-4,6-二(3,5-二-第三丁基4-羥基苯氧基)-s-三嗪、2,2’-亞甲基雙(4-甲基-6-第三丁基酚)、雙[3,3-雙(4-羥基-3-第三丁基苯基)丁酸]甘醇酯、4,4’-亞丁基雙(2,6-二-第三丁基酚)、4,4’-亞丁基雙(6-第三丁基3-甲基酚)、2,2’-亞乙基雙(4,6-二-第三丁基酚)、1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷、雙[2-第三丁基4-甲基-6-(2-羥基-3-第三丁基5-甲基苯甲基)苯基]對酞酸酯、1,3,5-參(2,6-二甲基-3-羥基-4-第三丁基苯甲基)三聚異氰酸酯、1,3,5-參(3,5-二-第三丁基4-羥基苯甲基)三聚異氰酸酯、1,3,5-參(3,5-二-第三丁基4-羥基苯甲基)-2,4,6-三甲基苯、1,3,5-參[(3,5-二-第三丁基4-羥基苯基)丙醯基氧乙基]三聚異氰酸酯、肆[亞甲基-3-(3’,5’-二-第三丁基4’-羥基苯基)丙酸酯]甲烷、2-第三丁基4-甲基-6-(2-丙烯醯氧-3-第三丁基5-甲基苯甲基)酚、3,9-雙[2-(3-第三丁基4-羥基-5-甲基氫肉桂醯氧)-1,1-二甲基乙基]-2,4,8,10-四氧螺[5.5]十一烷、三乙二醇雙[β-(3-第三丁基4-羥基-5-甲基苯基)丙酸酯]及以前述通式(1)所示之酚系抗氧化劑,但尤其肆[亞甲基-3-(3’,5’-二-第三丁基4’-羥基苯基)丙酸酯]甲烷比較廉價,成本效益佳,故較宜使用。
上述磷系抗氧化劑可舉例如三苯基亞磷酸酯、二異辛基亞磷酸酯、庚三亞磷酸酯、三異癸基亞磷酸酯、二苯基異辛基亞磷酸酯、二異辛基苯基亞磷酸酯、二苯基十三碳
基亞磷酸酯、三異辛基亞磷酸酯、三月桂基亞磷酸酯、二苯基亞磷酸酯、參(二丙二醇)亞磷酸酯、二異癸基季戊四醇二亞磷酸酯、二油基氫亞磷酸酯、三月桂基三硫亞磷酸酯、雙(十三碳基)亞磷酸酯、參(異癸基)亞磷酸酯、參(十三碳基)亞磷酸酯、二苯基癸基亞磷酸酯、二壬基苯基雙(壬基苯基)亞磷酸酯、聚(二丙二醇)苯基亞磷酸酯、四苯基二丙二醇二亞磷酸酯、參壬基苯基亞磷酸酯、參(2,4-二第三丁基苯基)亞磷酸酯、參(2,4-二-第三丁基5-甲基苯基)亞磷酸酯、參[2-第三丁基4-(3-第三丁基4-羥基-5-甲基苯基硫)-5-甲基苯基]亞磷酸酯、十三碳基亞磷酸酯、辛基二苯基亞磷酸酯、二(癸基)單苯基亞磷酸酯、二硬脂基季戊四醇二亞磷酸酯、二硬脂基季戊四醇與硬脂酸鈣鹽之混合物、烷基(C10)雙酚A亞磷酸酯、二(十三碳基)季戊四醇二亞磷酸酯、二(壬基苯基)季戊四醇二亞磷酸酯、雙(2,6-二第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,4-二第三丁基4-甲基苯基)季戊四醇二亞磷酸酯、雙(2,4,6-三第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,4-二枯基苯基)季戊四醇二亞磷酸酯、四苯基-四(十三碳基)季戊四醇四亞磷酸酯、雙(2,4-二第三丁基6-甲基苯基)乙基亞磷酸酯、肆(十三碳基)異亞丙基二酚二亞磷酸酯、肆(十三碳基)-4,4’-正亞丁基雙(2-第三丁基5-甲基酚)二亞磷酸酯、六(十三碳基)-1,1,3-參(2-甲基-4-羥基-5-第三丁基苯基)丁烷三亞磷酸酯、肆(2,4-二第三丁基苯基)聯伸苯基二膦酸
酯、9,10-二氫-9-氧-10-膦菲-10-氧化物、(1-甲基-1-丙基-3-亞基)參(2-1,1-二甲基乙基)-5-甲基-4,1-伸苯基)陸十三碳基亞磷酸酯、2,2’-亞甲基雙(4,6-第三丁基苯基)-2-乙基己基亞磷酸酯、2,2’-亞甲基雙(4,6-二-第三丁基苯基)-十八碳基亞磷酸酯、2,2’-亞乙基雙(4,6-二-第三丁基苯基)氟亞磷酸酯、4,4’-亞丁基雙(3-甲基-6-第三丁基苯基貳十三碳基)亞磷酸酯、參(2-[(2,4,8,10-肆-第三丁基二苯並[d,f][1,3,2]二噁磷雜庚英(dioxaphosphepin)-6-基)氧]乙基)胺、3,9-雙(4-壬基苯氧基)-2,4,8,10-四噁-3,9-二磷螺[5,5]十一碳烷、2,4,6-三-第三丁基苯基-2-丁基-2乙基-1,3-丙烷二醇亞磷酸酯、聚4,4’-異亞丙基二酚C12-15醇亞磷酸酯、2-乙基-2-丁基丙二醇與2,4,6-三-第三丁基酚之亞磷酸酯等。
上述硫醚系抗氧化劑可舉例如肆[亞甲基-3-(月桂基硫)丙酸酯]甲烷、雙(甲基-4-[3-正烷基(C12/C14)硫丙酸基氧]5-第三丁基苯基)硫醚、貳十三碳基-3,3’-硫二丙酸酯、二月桂基-3,3’-硫二丙酸酯、二肉豆蔻基-3,3’-硫二丙酸酯、二硬脂基-3,3’-硫二丙酸酯、月桂基/硬脂基硫二丙酸酯、4,4’-硫雙(6-第三丁基間甲酚)、2,2’-硫雙(6-第三丁基對甲酚)、二硬脂基-二硫醚。
上述紫外線吸收劑可舉例如2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、5,5’-亞甲基雙(2-羥基-4-甲氧基二苯甲酮)等之2-羥基二苯甲酮類;2-(2-羥基-5-甲基苯基)苯並三唑、2-(2-
羥基-5-第三辛基苯基)苯並三唑、2-(2-羥基-3,5-二第三丁基苯基)-5-氯苯並三唑、2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯並三唑、2-(2-羥基-3,5-二枯基苯基)氯苯並三唑、2,2’-亞甲基雙(4-第三辛基-6-苯並三唑基酚)、2-(2-羥基-3-第三丁基-5-羧基苯基)苯並三唑之聚乙二醇酯、2-[2-羥基-3-(2-丙烯醯氧乙基)-5-甲基苯基]苯並三唑、2-[2-羥基-3-(2-甲基丙烯醯氧乙基)-5-甲基苯基]苯並三唑、2-[2-羥基-3-(2-甲基丙烯醯氧乙基)-5-第三辛基苯基]苯並三唑、2-[2-羥基-3-(2-甲基丙烯醯氧乙基)-5-第三丁基苯基]-5-氯苯並三唑、2-[2-羥基-5-(2-甲基丙烯醯氧乙基)苯基]苯並三唑、2-[2-羥基-3-第三丁基-5-(2-甲基丙烯醯氧乙基)苯基]苯並三唑、2-[2-羥基-3-第三戊基-5-(2-甲基丙烯醯氧乙基)苯基]苯並三唑、2-[2-羥基-3-第三丁基-5-(3-甲基丙烯醯氧丙基)苯基]-5-氯苯並三唑、2-[2-羥基-4-(2-甲基丙烯醯氧甲基)苯基]苯並三唑、2-[2-羥基-4-(3-甲基丙烯醯氧-2-羥基-丙基)苯基]苯並三唑、2-[2-羥基-4-(3-甲基丙烯醯氧丙基)苯基]苯並三唑等之2-(2-羥基苯基)苯並三唑類;2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪、2-(2-羥基-4-己氧基苯基)-4,6-二苯基-1,3,5-三嗪、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-(3-C12~13混合烷氧基-2-羥基丙氧基)苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-(2-丙烯醯氧乙氧基)苯基)-4,6-雙(4-甲基苯基)-1,3,5-三
嗪、2-(2,4-二羥基-3-烯丙基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2,4,6-參(2-羥基-3-甲基-4-己氧基苯基)-1,3,5-三嗪等之2-(2-羥基苯基)-4,6-二芳基-1,3,5-三嗪類;苯基水楊酸酯、間二甲酚單苯甲酸酯、2,4-二第三丁基苯基-3,5-二第三丁基-4-羥基苯甲酸酯、辛基(3,5-二第三丁基-4-羥基)苯甲酸酯、十二碳基(3,5-二第三丁基-4-羥基)苯甲酸酯、十四碳基(3,5-二第三丁基-4-羥基)苯甲酸酯、十六碳基(3,5-二第三丁基-4-羥基)苯甲酸酯、十八碳基(3,5-二第三丁基-4-羥基)苯甲酸酯、二十碳基(3,5-二第三丁基-4-羥基)苯甲酸酯等之苯甲酸酯類;2-乙基-2’-乙氧基草醯苯胺、2-乙氧基-4’-十二碳基草醯苯胺等之取代草醯苯胺類;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(對甲氧基苯基)丙烯酸酯等之氰基丙烯酸酯類;各種之金屬鹽、或金屬螯合物,尤其鎳、鉻之鹽、或螯合物類等。
上述阻胺化合物可舉例如2,2,6,6-四甲基-4-六氫吡啶基硬脂酸酯、1,2,2,6,6-五甲基-4-六氫吡啶基硬脂酸酯、2,2,6,6-四甲基-4-六氫吡啶基苯甲酸酯、雙(2,2,6,6-四甲基-4-六氫吡啶基)癸二酸酯、肆(2,2,6,6-四甲基-4-六氫吡啶基)-1,2,3,4-丁烷四羧酸酯、肆(1,2,2,6,6-五甲基-4-六氫吡啶基)-1,2,3,4-丁烷四羧酸酯、雙(2,2,6,6-四甲基-4-六氫吡啶基).二(十三碳基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,6,6-五甲基-4-六氫吡啶基).二(十三碳基)-1,2,3,4-丁烷四羧酸酯、雙(1,2,2,4,4-五甲基-4-六氫
吡啶基)-2-丁基-2-(3,5-二第三丁基-4-羥基苯甲基)丙二酸酯、1-(2-羥乙基)-2,2,6,6-四甲基-4-六氫吡啶醇/琥珀酸二乙酯聚縮合物、1,6-雙(2,2,6,6-四甲基-4-六氫吡啶基胺基)己烷/2,4-二氯-6-嗎啉基-s-三嗪聚縮合物、1,6-雙(2,2,6,6-四甲基-4-六氫吡啶基胺基)己烷/2,4-二氯-6-第三辛基胺基-s-三嗪聚縮合物、1,5,8,12-肆[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-六氫吡啶基)胺基)-s-三嗪-6-基]-1,5,8,12-四偶氮十二碳烷、1,5,8,12-肆[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-六氫吡啶基)胺基)-s-三嗪-6-基]-1,5,8,12-四偶氮十二碳烷、1,6,11-參[2,4-雙(N-丁基-N-(2,2,6,6-四甲基-4-六氫吡啶基)胺基)-s-三嗪-6-基]胺基十一碳烷、1,6,11-參[2,4-雙(N-丁基-N-(1,2,2,6,6-五甲基-4-六氫吡啶基)胺基)-s-三嗪-6-基]胺基十一碳烷、雙{4-(1-辛基氧-2,2,6,6-四甲基)六氫吡啶基}癸烷二醇酯、雙{4-(2,2,6,6-四甲基-1-十一碳氧)六氫吡啶基}碳酸酯等。此等之中,與六氫吡啶基之1位的位置連結者宜為N-氧烷基或N-甲基之化合物。
上述耐燃劑係可舉例如三苯基磷酸酯、三甲酚基磷酸酯、三二甲苯基磷酸酯、甲酚基二苯基磷酸酯、甲酚基-2,6-二甲酚基磷酸酯及間二甲酚雙(二苯基磷酸酯)等之芳香族磷酸酯、苯基膦酸二乙烯酯、苯基膦酸二烯丙基及苯基膦酸(1-丁烯基)等之膦酸酯、二苯基磷酸苯基酯、二苯基磷酸甲酯、9,10-二氫-9-噁-10-磷菲-10-氧化物衍生物等之磷酸酯、雙(2-烯丙基苯氧基)膦氮烯、二甲酚基
膦氮烯等之膦氮烯化合物、磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸蜜白胺、聚磷酸銨、含磷乙烯基之苯甲基化合物及紅磷等之磷系耐燃劑、氫氧化鎂、氫氧化鎂等之金屬氫氧化物、溴化雙酚A型環氧樹脂、溴化酚酚醛清漆型環氧樹脂、六溴苯、五溴甲苯、乙烯雙(五溴苯基)、乙烯雙四溴酞醯亞胺、1,2-二溴-4-(1,2-二溴乙基)環己烷、四溴環辛烷、六溴環十二碳烷、雙(三溴苯氧基)乙烷、溴化聚苯醚、溴化聚苯乙烯及2,4,6-參(三溴苯氧基)-1,3,5-三嗪、三溴苯基馬來醯亞胺、三溴苯基丙烯酸酯、三溴苯基甲基丙烯酸酯、四溴雙酚A型二甲基丙烯酸酯、五溴苯甲基丙烯酸酯、及、溴化苯乙烯等之溴系耐燃劑等。
上述造核劑係可舉例如安息香酸鈉、4-第三丁基安息香酸鋁鹽、己二酸鈉及2鈉聯環[2.2.1]庚烷-2,3-二羧酸酯等之羧酸金屬鹽、鈉雙(4-第三丁基苯基)磷酸酯、鈉-2,2’-亞甲基雙(4,6-二第三丁基苯基)磷酸酯及鋰-2,2’-亞甲基雙(4,6-二第三丁基苯基)磷酸酯等之磷酸酯金屬鹽、二亞苄基山梨糖醇、雙(甲基亞苄基)山梨糖醇、雙(對-乙基亞苄基)山梨糖醇、及雙(二甲基亞苄基)山梨糖醇等之多元醇衍生物、N,N’,N”-參[2-甲基環己基]-1,2,3-丙烷三羧醯胺(RIKACLEAR PC1)、N,N’,N”-三環己基-1,3,5-苯三羧醯胺、N,N’-二環己基-萘二羧醯胺、1,3,5-三(二甲基異丙醯胺基)苯等之醯胺化合物等。
上述填充劑係宜為例如滑石、雲母、碳酸鈣、氧化鈣
、氫氧化鈣、碳酸鎂、氫氧化鎂、氧化鎂、硫酸鎂、氫氧化鋁、硫酸鋇、玻璃粉末、玻璃纖維、泥土、白雲石、雲母、氧化矽、氧化鋁、鈦酸鉀晶鬚、鈣矽石、纖維狀鎂氧硫酸鹽等。在此等之填充劑中,宜平均粒徑(球狀乃至平板狀者)或平均纖維徑(針狀乃至纖維狀者)為5μm以下者。
上述滑劑係可就對成形體表面賦予滑性並提高防止刮傷效果的目的所添加。滑劑係可舉例如油酸醯胺、芥酸醯胺等之不飽和脂肪酸醯胺;山萮酸醯胺、硬脂酸醯胺等之飽和脂肪酸醯胺等。此等係可1種單獨使用,亦可併用2種以上而使用。
上述抗靜電劑係就成形品的帶電性之降低化、或防止帶電所造成的塵埃附著之目的所添加。抗靜電劑係可舉例如陽離子系、陰離子系、非離子系等。較佳之例係可舉例如聚氧乙烯烷基胺或聚氧乙烯烷基醯胺乃至其等之脂肪酸酯、甘油之脂肪酸酯等。
在本發明所使用的其他添加劑較佳的使用量範圍係從效果顯現之量看不到添加效果的提昇之範圍。各添加劑之使用量係相對於合成樹脂100質量份,可塑劑為0.1~20質量份,填充劑為1~50質量份,表面處理劑為0.001~1質量份,酚系抗氧化劑為0.001~10質量份,磷系抗氧化劑為0.001~10質量份,硫醚系抗氧化劑0.001~10質量份,紫外線吸收劑0.001~5質量份,阻胺化合物為0.01~1質量份,耐燃劑為1~50質量份,滑劑為0.03~2質量份,
抗靜電劑為0.03~2質量份,造核劑為0.01~10質量份。又,此等添加劑係可1種單獨使用,亦可併用2種以上而使用。
本發明之樹脂組成物其特徵係相對於上述合成樹脂摻合上述本發明之安定劑組成物而成。本發明之安定劑組成物的摻合量係宜相對於合成樹脂100質量份,0.01~5.0質量份,更宜為0.1~1.0質量份。
又,本發明之成形品係以押出成形、射出成形、中空成形、壓縮成形等之公知的成形方法成形本發明之樹脂組成物者。本發明之成形品的用途、形態可舉例如汽車內外裝品、食品用容器、化粧品、衣料用容器、食品用瓶、飲料用瓶、食用油瓶、調味料瓶等之瓶、食品用包裝材、摩擦材、輸送用包裝材等之包裝材料、電子材料之保護膜、電化製品的保護片等之片、膜、纖維、日用雜貨、玩具等。
其次,詳細說明有關不包含本發明之固形物而優異的耐熱性與低黏性、處理性良好之合成樹脂用的熱安定劑組成物。
本發明之熱安定劑組成物係含有以下述通式(3)所示之二酯體化合物及以下述通式(4)所示之單酯體化合物、及以下述通式(5)所示之硫二烷基羧酸二烷基酯化合物者。
在本發明之熱安定劑組成物中,以上述通式(3)所示之二酯體化合物及以上述通式(4)所示之單酯體化合物的比率係相對於以上述通式(3)所示之二酯體化合物及以上述通式(4)所示之單酯體化合物之合計量100質量份,以上述通式(3)所示之二酯體化合物為65質量份以上,宜為70~90質量份,更佳係70~85質量份。以上述通式(3)所示之二酯體化合物少於65質量份時,有時熱安定劑組成物之黏性變高。
又,在本發明之熱安定劑組成物中,以上述通式(3)所示之二酯體化合物及以上述通式(4)所示之單酯體化合物之合計量與以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物之質量比為{(3)+(4)}/(5)=95/5~50/50之範圍內,較佳係90/10~70/30之範圍內。以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物的比率未達5時,有時熱安定劑組成物之黏性變高,以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物的比率多於50時,有時熱安定劑組成物之耐熱性不足。
本發明之熱安定劑組成物係不含有固形物,為處理性良好之低黏度的液狀,不阻礙摻合之合成樹脂的交聯。黏度較佳係3000mPa.s以下。黏度超過3000mPa.s時,有時可使用於熱安定劑組成物之配送的泵浦受限制,於處理性造成障礙。又,在本發明之黏度為25℃中的黏度,例如可藉由B型黏度計而測定。
本發明之熱安定劑組成物係適宜由上述通式(3)所示之二酯體化合物、以上述通式(4)所示之單酯體化合物及以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物所構成者,但只要不損及本發明之效果,對於合成樹脂,亦可含有一般所使用之成分等的其他成分。含有其他之成分時,本發明之熱安定劑組成物中的主成分係上述通式(3)所示之二酯體化合物、以上述通式(4)所示之單酯體化合物及以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物,其他之成分的含量相對於上述通式(3)所示之二酯體化合物、以上述通式(4)所示之單酯體化合物及以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物之合計100質量份,宜為1000質量份以下。
上述通式(3)及(4)中之以R11~R18所示的碳原子數1~18的烷基,係可舉例如甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、第二丁基、戊基、異戊基、新戊基、己基、2-乙基己基、異己基、庚基、辛基、異辛基、壬基、癸基、異癸基、月桂基、十三碳基、十四碳基、十六碳基、十八碳基等。此烷基係亦可在氧原子或硫原
子中斷。
上述通式(3)及(4)中之以R11~R18所示的碳原子數3~18的環烷基係亦可以環丙基、環戊基、環己基、環庚基、環辛基、環壬基、環癸基、環十二碳基、4-甲基環己基等,環烷基中之氫原子係亦可被烷基、烷氧基、烯基、烯氧基、羥基、或氰基取代,此烷基係亦可在氧原子或硫原子中斷。
上述通式(3)及(4)中之以R11~R18所示的烷基、烷氧基、烯基、烯氧基或羥基取代之碳原子數6~30的芳基,係可舉例如苯基、甲基苯基、丁基苯基、辛基苯基、4-羥基苯基、3,4,5-三甲氧基苯基、4-第三丁基苯基、聯苯基、萘基、甲基萘基、蔥基、菲基、苯甲基、苯基乙基、1-苯基-1-甲基乙基等。又,芳基中之氫原子亦可被烷基、烯基、烯氧基、羥基、或氰基取代,烷基係亦可在氧原子或硫原子中斷。
以上述通式(3)中之R19、R20、以通式(4)中之R21、及以通式(5)中之R22所示的亦可被取代的碳原子數3~30的直鏈或分枝烷基係可舉例如丙基、異丙基、丁基、異丁基、第三丁基、第二丁基、戊基、異戊基、新戊基、己基、2-乙基己基、異己基、庚基、辛基、異辛基、壬基、癸基、異癸基、月桂基、十三碳基、十四碳基、十六碳基、十八碳基、二十碳基、二十四碳基、二十八碳基等。
上述烷基係亦可被烷氧基、烯基、烯氧基、羥基、或
氰基取代,又亦可在氧原子或硫原子中斷。又,此等之中斷或取代係亦可被組合。烷基之碳原子數少於3之化合物係有時於成形品表面滲出或起霧而損及成形品的外觀。若烷基之碳數超過30,有時無法得到必要之安定化效果。
以上述通式(5)中之A所示的烷氧基、烯基、烯氧基、羥基、或氰基取代的碳原子數1~8的直鏈或分枝伸烷基係可舉例如亞甲基、亞乙基、亞丙基、丙烷-2,2-二基、亞丁基、異亞丁基、亞己基、亞庚基等。伸烷基係亦可在氧原子或硫原子中斷。
以上述通式(3)所示的二酯體化合物宜為以下述通式(3’)所示的化合物。又,式中,R11~R20係分別表示與通式(3)同樣者。
以上述通式(4)所示的單酯體化合物宜為以下述通式(4’)所示的化合物。式中,R11~R18及R21係分別表示與通式(4)同樣者。
以上述通式(5)所示的硫二烷基羧酸二烷基酯化合物宜為以下述通式(5’)所示的化合物。式中,R22係表示與通式(5)同樣者。
以上述通式(3)所示的二酯體化合物之具體構造係可舉例如下述之化合物No.3-1~3-14的化合物。但,本發明係並非受以下之化合物限制。又,式(3)中之R19及R20為C12~14混合烷基之化合物係表示式(3)中之R19及R20為碳原子數12的烷基之化合物、及、碳原子數14的烷基之化合物的混合物。
以上述通式(4)所示的單酯體化合物之具體構造係可舉例如下述之化合物No.4-1~4-13的化合物。但,本發明係並非受以下之化合物限制。又,式(4)中之R21為C12~14混合烷基之化合物係表示式(4)中之R21為碳原子數12的烷基之化合物、及、碳原子數14的烷基之化合物的混合物。式(4)中之R21為具有C24~28混合烷基之化合物係表示式(22)中之R21為碳原子數24~28的烷基之化合物的混合物。
以上述通式(5)所示的硫二烷基羧酸二烷基酯化合物之具體構造係可舉例如二月桂基-3,3’-硫二丙酸酯、貳十三碳基-3,3’-硫二丙酸酯、二肉豆蔻基-3,3’-硫二丙酸酯、二硬脂基-3,3’-硫二丙酸酯、月桂基/硬脂基混合-3,3’-硫二丙酸酯、二(2-乙基己基)-3,3’-硫二丙酸酯等。但,本發明係不受上述之化合物限制。
本發明之熱安定劑組成物係如上述般,在25℃之黏度宜為3000mPa.s以下。使用泵浦而將本發明之熱安定劑組成物潰入於合成樹脂時,可使用齒輪泵浦、隔膜泵浦、旋轉泵浦、螺桿泵浦、Waukesha泵浦、Sine泵浦、Hose泵浦、化學泵浦、空壓泵浦等公知的泵浦而饋入,但若熱安定劑組成物之黏度超過3000mPa.s,必須為特殊之泵浦
,或有時附著於泵浦或配管內壁而損失變多。使本發明之熱安定劑組成物的黏度低於3000mPa.s以下係必須將上述通式(3)所示之二酯體化合物、以上述通式(4)所示之單酯體化合物及以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物調整成上述特定之組成比。
本發明之熱安定劑組成物係宜於熱安定劑組成物所含有的羥基為熱安定劑組成物之1質量%以下者,更佳係0.65質量%以下。羥基之比率高於1.0質量%時,有時阻礙聚乙烯或乙烯-醋酸乙烯酯、乙烯-乙基丙烯酸酯、乙烯-丙烯、乙烯-丙烯-丁二烯等之共聚物的交聯。
本發明之熱安定劑組成物係使用微分熱分析(TG-DTA),以氮氣下、10℃/分之昇溫速度的條件從室溫加熱時,質量減少5%之溫度,宜為240℃以上。未達240℃時,對於摻合有本發明之熱安定劑組成物的合成樹脂而無法賦予充分的安定化效果。
於本發明之熱安定劑組成物中係無損本發明之所期望的效果之範圍,以上述通式(3)~(5)所示的化合物以外,亦可摻合其他之成分。
上述成分係可舉例如酚系抗氧化劑、磷系抗氧化劑、以通式(3)~(5)所示的化合物以外之硫醚系抗氧化劑、紫外線吸收劑、阻胺化合物、耐燃劑、造核劑、填充劑、滑劑、抗靜電劑、重金屬惰性化劑、金屬皂、水滑石、顏料、染料、可塑劑等。
上述酚系抗氧化劑、磷系抗氧化劑、紫外線吸收劑、
阻胺化合物、耐燃劑、造核劑、填充劑、滑劑、抗靜電劑係可使用與前述者相同者。
以通式(3)~(5)所示之化合物以外的硫醚系抗氧化劑係可舉例如肆[亞甲基-3-(月桂基硫)丙酸酯]甲烷、雙(甲基-4-[3-正烷基(C12/C14)硫丙醯氧]5-第三丁基苯基)硫醚、4,4’-硫雙(6-第三丁基-間甲酚)、2,2’-硫雙(6-第三丁基-對甲酚)、二硬脂基-二硫醚。
在本發明所使用的其他成分較佳的使用量範圍係從效果顯現之量看不到添加效果的提昇之範圍。各成分之使用量係相對於合成樹脂100質量份,可塑劑為0.1~20質量份,填充劑為1~50質量份,表面處理劑為0.001~1質量份,酚系抗氧化劑為0.001~10質量份,磷系抗氧化劑為0.001~10質量份,硫醚系抗氧化劑0.001~10質量份,紫外線吸收劑0.001~5質量份,阻胺化合物為0.01~1質量份,耐燃劑為1~50質量份,滑劑為0.03~2質量份,抗靜電劑為0.03~2質量份。又,此等成分係可1種單獨使用,亦可併用2種以上而使用。
其次,說明有關本發明之合成樹脂組成物。
本發明之合成樹脂組成物係相對於合成樹脂100質量份,摻合上述本發明之熱安定劑組成物0.01~5質量份而成者。藉由本發明之熱安定劑組成物而安定化的合成樹脂,係可舉例如聚丙烯、高密度聚乙烯、低密度聚乙烯、直鏈低密度聚乙烯、聚丁烯-1、聚-4-甲基戊烯等之α-烯烴聚合物或乙烯-醋酸乙烯酯共聚物、乙烯-丙烯共聚物等之
聚烯烴及此等之共聚物、聚氯乙烯、聚偏氯乙烯、氯化橡膠、氯乙烯-醋酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-偏氯乙烯共聚物、氯乙烯-偏氯乙烯-醋酸乙烯酯三元共聚物、氯乙烯-丙烯酸酯共聚物、氯乙烯-馬來酸酯共聚物、氯乙烯-環己基馬來醯亞胺共聚物等之含鹵素樹脂、石油樹脂、香豆素樹脂、聚苯乙烯、聚醋酸乙烯酯、丙烯酸樹脂、苯乙烯及/或α-甲基苯乙烯與其他之單體(例如馬來酸酐、苯基馬來醯亞胺、甲基丙烯酸甲酯、丁二烯、丙烯腈等)之共聚物(例如AS樹脂、ABS樹脂、MBS樹脂、耐熱ABS樹脂等)、聚甲基丙烯酸甲酯、聚乙烯醇、聚乙烯基甲醛、聚乙烯基丁醛、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚對苯二甲酸四亞甲基酯等之直鏈聚酯、聚苯氧、聚己內醯胺及聚六亞甲基己二醯胺等之聚醯胺、聚碳酸酯、分枝聚碳酸酯、聚乙縮醛、聚苯硫醚、聚胺基甲酸酯、纖維素系樹脂等之熱塑性樹脂、及此等之混合物、或、酚樹脂、脲樹脂、三聚氰胺樹脂、環氧樹脂、不飽和聚酯樹脂等之熱硬化性樹脂。進一步,亦可為異戊二烯橡膠、丁二烯橡膠、丙烯腈-丁二烯共合聚橡膠、苯乙烯-丁二烯共聚合橡膠等之彈性體,亦可為於上述樹脂含有者。
上述合成樹脂之中,聚乙烯、聚丙烯、乙烯-丙烯共聚合樹脂等之聚烯烴樹脂係本發明之熱安定劑組成物所產生的安定化效果優異,故較宜使用。
又,本發明之熱安定劑組成物係亦可適宜使用於藉過
氧化物或放射線等所製造的交聯用合成樹脂、發泡聚苯乙烯等之發泡樹脂。交聯用合成樹脂係可舉例如聚乙烯或乙烯-醋酸乙烯酯、乙烯-乙基丙烯酸酯、乙烯-丙烯、乙烯-丙烯-丁二烯等之共聚物。
又,可使用於合成樹脂組成物之交聯劑係可舉例如過氧化苯甲醯基、過氧化二-第三丁基、過氧化二異丙苯基、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、2,5-二甲基-2,5-二(第三丁基過氧化)己烯、1,3-雙(第三丁基過氧化異丙基)苯-第三丁基-氫過氧化物、氫過氧化異丙苯、聚碸疊氮、疊氮甲酸酯、四甲基異酞醯基二-第三丁基雙過氧化物、四甲基異酞醯基二異丙苯基雙過氧化物、二乙醇胺、三乙醇胺等之烷醇胺、六亞甲基二胺、4,4’-二胺基二苯基甲烷等。
於本發明之合成樹脂組成物中係與上述本發明之熱安定劑組成物同樣,在無損本發明之所期望的效果之範圍,亦可摻合其他之成分。其他之成分係可使用與上述本發明之熱安定劑組成物同樣者。
其次,說明有關本發明之成形品。本發明之成形品係使上述本發明之合成樹脂組成物成形而成者。本發明之成形品係可以押出成形、射出成形、中空成形、壓縮成形等公知的成形方法成形。本發明之成形品係可舉例如汽車內外裝品、食品用容器、化粧品、衣料用容器、食品用瓶、飲料用瓶、食用油瓶、調味料瓶等之瓶、食品用包裝材、摩擦材、輸送用包裝材等之包裝材料、電子材料之保護膜
、電線等之被覆材料、電化製品的保護片等之片、膜、纖維、日用雜貨、玩具等。
以下舉出參考例、實施例及比較例。更具體地說明本發明,但本發明係不受以下之實施例等任何限制。
以通式(1)所示之二酯體,上述通式(1’)中,R1~R3為氫原子,R4及R5分別記載於表中之取代基的化合物、及以通式(2)所示之單酯體,上述通式(2’)中,R1~R3為氫原子,R6為記載於表中之取代基的化合物分別加入於試藥玻璃瓶中,充分攪拌後密封而靜置於5℃之恆溫器內。對於此等之試料進行以下之評估。
有關表1之比較例1-1的試料係不使用5℃之恆溫器,而在常溫(25℃)下放置,進行以下之評估。
每一週目視觀察試料之狀態。評估係以如下之方法進行。
-:為液狀看不出固形物。
A:固形物稍析出。
B:很大的固形物析出,但一半以上為液狀。
C:一半以上以固形物析出。
D:全量形成固形物而析出。
對於經過5個月之試料,以(B型黏度計/4號轉子/25℃/60rpm)之條件測定黏度。
將試料置入於100g燒瓶中,在25℃(常溫)下將燒瓶翻轉過來而測定至試料97g掉落至接受皿之燒杯的時間。評估97g掉落之時間為5分以內時為○,經過5分鐘後8分以內之時為Δ,超過8分鐘時為×。有關此等之結果表示於表1。
從比較例1-1,可確認出相對於以通式(1)及通式(2)所示的化合物之合計量100質量份,以式(1)所示的化合物之比率為80質量份以上時,在低溫環境下的保存性惡化,若經過2個月,產生固形物。又,從比較例2,相對於以通式(1)及通式(2)所示的化合物之合計量100質量份,以式(1)所示的化合物之比率為65質量份以下時,可確認出成為6000mPa.s以上之高黏度。又,從參考例1-1,以式(1)所示的化合物之比率超過80質量份,在常溫下亦可保存時係不產生固形物。
然而,從實施例1-1~1-5,可確認出相對於以通式(1)及(2)所示的化合物之合計量100質量份,以式(1)所示的化合物之比率超過65質量份而未達80質量份之範圍內的本發明之安定劑組成物係可得到即使在低溫環境下亦不產生固形物,在6000mPa.s以下的低黏度且處理性優異之液狀安定劑。
就以通式(3)所示之二酯體化合物,為上述通式(3’)中之R11及R17為第三丁基、R13及R16為甲基、R12、R14、R16、R18為氫原子,R19及R20為分別記載於表中之取代基的化合物;就以通式(4)所示之單酯體化合物,為以通式(4’)中,R11及R17為第三丁基、R13及R15為甲基、R12、R14、R16、R18為氫原子,R21為記載於表中之取代基的化合物;及就以通式(5)所示之硫二烷基羧酸二烷基酯化合物,為上述通式(5’)中,R22為記載於表中之取代基的化合物;將以上分別加入於試藥玻璃瓶中,充分攪拌後,密封而靜置一夜。
在比較例2-2中,使用2-甲基-4,6-雙[(辛基硫)甲基)酚取代以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物以外,其餘係與比較例2-2同樣地做法而評估。
在實施例2-3中,使用2-甲基-4,6-雙[(辛基硫)甲基)酚取代以上述通式(5)所示之硫二烷基羧酸二烷基酯化合物以外,其餘係與實施例2-3同樣地做法而評估。
對於實施例2-1~2-7及比較例2-1~2-7之各別的熱安定劑組成物,進行以下之評估。
以(B型黏度計/4號轉子/25℃/60rpm)之條件測定黏度。將所得到之結果一併記載於表2及3。
將試料以微分掃描熱量測定機(Thermoglass TG8120;(股)Rigaku製),氮氣環境下(20m1/分)、10℃/分之昇溫條件加熱,測定試料之質量已減少5%的溫度。將所得到之結果一併記載於表2及3。
以目視觀察,確認出混濁或固形狀者之時評估為×,為透明時評估為○。將所得到之結果一併記載於表2及3。
求出羥基對熱安定劑組成物所含有的各別化合物之分子量的比率,算出熱安定劑組成物所含有的羥基之比率。將所得到之結果一併記載於表2及3。
從比較例2-1及比較例2-4,不含有以通式(5)所示之硫二烷基羧酸二烷基酯化合物時,可確認出3000mPa.s以上之高黏度。從比較例2-2,以通式(5)所示之硫二烷基羧酸二烷基酯化合物單獨時,可確認出缺乏耐熱性。又,從比較例2-3,以通式(3)所示的二酯體化合物與以通式(4)所示的單酯體化合物之合計與以通式(5)所
示之硫二烷基羧酸二烷基酯化合物之質量比({(3)+(4)}/(5))中,以通式(5)所示之硫二烷基羧酸二烷基酯化合物之比率多於50時,可確認出耐熱性不充分。
又,從比較例2-6,併用與以通式(5)所示之硫二烷基羧酸二烷基酯化合物相異之硫醚抗氧化劑時,可確認出於熱安定劑組成物產生固形狀的沉澱。又,從比較例2-7,以通式(3)所示的二酯體化合物與以通式(4)所示的單酯體化合物之合計100質量份中,以通式(3)所示的二酯體化合物之含量少於65質量份時,可確認出變成3000mPa.s以上的高黏度。
然而,從實施例2-1~2-7,以通式(3)所示的二酯體化合物與以通式(4)所示的單酯體化合物之合計100質量份中,以通式(3)所示的二酯體化合物之含量多於65質量份,以通式(3)所示的二酯體化合物與以通式(4)所示的單酯體化合物之合計與以通式(5)所示之硫二烷基羧酸二烷基酯化合物的質量比為{(3)+(4)}/(5)=95/5~50/50的範圍內之本發明的熱安定劑組成物係可確認出可得到低密度且處理性優異,且良好的耐熱性及無固形物之優異液狀的熱安定劑組成物。又,本發明之熱安定劑組成物係因熱安定劑組成物所含有的羥基少,故可得到不阻礙摻合本發明之熱安定劑組成物的合成樹脂組成物之交聯的效果。
為看到本發明之熱安定劑組成物對於合成樹脂之優異安定化效果,對於本發明之熱安定劑組成物的安定化效果進行研究。將未安定之低密度聚乙烯(NUC-8000;日本Unika股份公司製)100質量份、作為交聯劑之過氧化二異丙基苯2質量份、以通式(3)所示的二酯體化合物與以通式(4)所示的單酯體化合物及以通式(5)所示之硫二烷基羧酸二烷基酯化合物以表3所記載的質量比0.3質量份以120℃、20rpm之條件、混合輥輪混練6分30秒鐘,然後,以120℃、9.8MPa之條件進行壓縮成形5分鐘,製作厚2mm之薄片。進一步,使厚2mm之薄片以170℃、9.8MPa之條件壓縮成形20分鐘,促進聚乙烯之交聯反應,製作厚1mm之薄片。將此厚1mm之薄片。切成170×130mm之大小,將此試料在150℃之齒輪泵浦中、空氣環境下進行熱劣化試驗。評估方法係在552小時後取出的試驗片中,對於試驗片之面積,以未變色成紅褐色之處的面積之比率作為未燃燒率而算出,評估安定化效果。對於此等之結果,表示於下述表4。
從表4之實施例3-1~3-3、及比較例3-1~3-3可確認出本發明外之熱安定劑組成物係缺乏安定化效果,但本案發明之熱安定劑組成物係對於合成樹脂賦予優異之安定化效果。
Claims (6)
- 一種熱安定劑組成物,其特徵係含有以下述通式(3)所示的二酯體化合物、以下述通式(4)所示的單酯體化合物,及以下述通式(5)所示之硫二烷基羧酸二烷基酯化合物,且使前述通式(3)所示之二酯體化合物與前述通式(4)所示之單酯體化合物之合計100質量份中,以前述通式(3)所示之二酯體化合物的含量多於65質量份,且以前述通式(3)所示之二酯體化合物與前述通式(4)所示之單酯體化合物之合計與以前述通式(5)所示之硫二烷基羧酸二烷基酯化合物的質量比為{(3)+(4)}/(5)=95/5~50/50的範圍內;
- 如申請專利範圍第1項之熱安定劑組成物,其中在25℃之黏度為3000mPa.s以下。
- 如申請專利範圍第1項之熱安定劑組成物,其係使用微分熱分析(TG-DTA),在氮氣下,以10℃/分的昇溫速度之條件從室溫加熱時,質量減少5%之溫度為240℃以上。
- 一種合成樹脂組成物,其特徵係相對於合成樹脂100質量份,摻合如申請專利範圍第1項之熱安定劑組成物0.01~5質量份而成。
- 如申請專利範圍第4項之合成樹脂組成物,其中前述合成樹脂為聚烯烴樹脂。
- 一種成形品,係如申請專利範圍第5項之合成樹脂組成物成形而成。
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