TWI268948B - Polyester compositions of low residual aldehyde content - Google Patents
Polyester compositions of low residual aldehyde content Download PDFInfo
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- TWI268948B TWI268948B TW090132494A TW90132494A TWI268948B TW I268948 B TWI268948 B TW I268948B TW 090132494 A TW090132494 A TW 090132494A TW 90132494 A TW90132494 A TW 90132494A TW I268948 B TWI268948 B TW I268948B
- Authority
- TW
- Taiwan
- Prior art keywords
- tert
- polyester
- butyl
- bis
- composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 229920000728 polyester Polymers 0.000 title claims abstract description 46
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- -1 poly(ethylene terephthalate) Polymers 0.000 claims abstract description 130
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 48
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 48
- 239000000654 additive Substances 0.000 claims abstract description 37
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- 239000005977 Ethylene Substances 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 17
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 12
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 12
- 239000000600 sorbitol Substances 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 11
- 229920002678 cellulose Polymers 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 10
- 238000010128 melt processing Methods 0.000 claims description 10
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000356 contaminant Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 235000000346 sugar Nutrition 0.000 claims description 6
- HBDJFVFTHLOSDW-DNDLZOGFSA-N (2r,3r,4r,5r)-2,3,5,6-tetrahydroxy-4-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyhexanal;hydrate Chemical compound O.O=C[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O HBDJFVFTHLOSDW-DNDLZOGFSA-N 0.000 claims description 5
- BADXJDLPQWRZFL-NZYQVXNASA-N (2r,3r,4s,5s,6r)-2-[(2r,3s,4r,5r,6r)-6-[(2r,3s,4r,5r,6r)-6-[(2r,3s,4r,5r,6r)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,3s,4r,5r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-4,5-dihydroxy-2-(hydrox Chemical compound O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O[C@@H]2[C@H](O[C@H](O[C@@H]3[C@H](O[C@H](O[C@@H]4[C@H](OC(O)[C@H](O)[C@H]4O)CO)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O BADXJDLPQWRZFL-NZYQVXNASA-N 0.000 claims description 5
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 5
- GZCGUPFRVQAUEE-UHFFFAOYSA-N 2,3,4,5,6-pentahydroxyhexanal Chemical compound OCC(O)C(O)C(O)C(O)C=O GZCGUPFRVQAUEE-UHFFFAOYSA-N 0.000 claims description 5
- 229920000858 Cyclodextrin Polymers 0.000 claims description 5
- 229920001353 Dextrin Polymers 0.000 claims description 5
- 239000004375 Dextrin Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 235000019425 dextrin Nutrition 0.000 claims description 5
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 claims description 5
- 239000000845 maltitol Substances 0.000 claims description 5
- 235000010449 maltitol Nutrition 0.000 claims description 5
- 229940035436 maltitol Drugs 0.000 claims description 5
- 229960002160 maltose Drugs 0.000 claims description 5
- 229960003017 maltose monohydrate Drugs 0.000 claims description 5
- 235000010355 mannitol Nutrition 0.000 claims description 5
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- LUEWUZLMQUOBSB-UHFFFAOYSA-N UNPD55895 Natural products OC1C(O)C(O)C(CO)OC1OC1C(CO)OC(OC2C(OC(OC3C(OC(O)C(O)C3O)CO)C(O)C2O)CO)C(O)C1O LUEWUZLMQUOBSB-UHFFFAOYSA-N 0.000 claims description 3
- BNABBHGYYMZMOA-AHIHXIOASA-N alpha-maltoheptaose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)O[C@H](O[C@@H]2[C@H](O[C@H](O[C@@H]3[C@H](O[C@H](O[C@@H]4[C@H](O[C@H](O[C@@H]5[C@H](O[C@H](O[C@@H]6[C@H](O[C@H](O)[C@H](O)[C@H]6O)CO)[C@H](O)[C@H]5O)CO)[C@H](O)[C@H]4O)CO)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O BNABBHGYYMZMOA-AHIHXIOASA-N 0.000 claims description 3
- UYQJCPNSAVWAFU-UHFFFAOYSA-N malto-tetraose Natural products OC1C(O)C(OC(C(O)CO)C(O)C(O)C=O)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(O)C(CO)O2)O)C(CO)O1 UYQJCPNSAVWAFU-UHFFFAOYSA-N 0.000 claims description 3
- LUEWUZLMQUOBSB-OUBHKODOSA-N maltotetraose Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@H](CO)O[C@@H](O[C@@H]2[C@@H](O[C@@H](O[C@@H]3[C@@H](O[C@@H](O)[C@H](O)[C@H]3O)CO)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-OUBHKODOSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims 4
- 239000008121 dextrose Substances 0.000 claims 4
- ILSHEBNQHBZRAD-UHFFFAOYSA-N ethanol propane Chemical compound CCC.CCO.CCO.CCO ILSHEBNQHBZRAD-UHFFFAOYSA-N 0.000 claims 3
- PZUPAGRIHCRVKN-UHFFFAOYSA-N 5-[5-[3,4-dihydroxy-6-[(3,4,5-trihydroxyoxan-2-yl)oxymethyl]-5-[3,4,5-trihydroxy-6-[(3,4,5-trihydroxyoxan-2-yl)oxymethyl]oxan-2-yl]oxyoxan-2-yl]oxy-3,4-dihydroxy-6-[(3,4,5-trihydroxyoxan-2-yl)oxymethyl]oxan-2-yl]oxy-6-(hydroxymethyl)oxane-2,3,4-triol Chemical compound OCC1OC(O)C(O)C(O)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(COC4C(C(O)C(O)CO4)O)O3)O)C(COC3C(C(O)C(O)CO3)O)O2)O)C(COC2C(C(O)C(O)CO2)O)O1 PZUPAGRIHCRVKN-UHFFFAOYSA-N 0.000 claims 2
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000002985 plastic film Substances 0.000 claims 1
- 229920006255 plastic film Polymers 0.000 claims 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 abstract description 45
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 235000013305 food Nutrition 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 6
- 235000013361 beverage Nutrition 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 12
- 239000012964 benzotriazole Substances 0.000 description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229960003742 phenol Drugs 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000000071 blow moulding Methods 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000013772 propylene glycol Nutrition 0.000 description 4
- 229960004063 propylene glycol Drugs 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 3
- 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 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000035558 fertility Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- ZQMPWXFHAUDENN-UHFFFAOYSA-N 1,2-bis[(2-methylphenyl)amino]ethane Natural products CC1=CC=CC=C1NCCNC1=CC=CC=C1C ZQMPWXFHAUDENN-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SLUKQUGVTITNSY-UHFFFAOYSA-N 2,6-di-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SLUKQUGVTITNSY-UHFFFAOYSA-N 0.000 description 2
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- CVVFFUKULYKOJR-UHFFFAOYSA-N n-phenyl-4-propan-2-yloxyaniline Chemical compound C1=CC(OC(C)C)=CC=C1NC1=CC=CC=C1 CVVFFUKULYKOJR-UHFFFAOYSA-N 0.000 description 1
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
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- MQYIQOANLHJLJN-UHFFFAOYSA-N pentane-1,1,5,5-tetrol Chemical compound OC(O)CCCC(O)O MQYIQOANLHJLJN-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
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- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- PRPLPAGUUGVIQN-UHFFFAOYSA-N propane-1,1,3,3-tetrol Chemical compound OC(O)CC(O)O PRPLPAGUUGVIQN-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 description 1
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical class [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
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- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 1
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- 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 1
- 125000002345 steroid group Chemical group 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- 150000003672 ureas Chemical class 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
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- 239000011718 vitamin C Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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- 238000004383 yellowing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Description
1268948 A7 ___ B7______ 五、發明說明(丨) 當聚酯,像聚(對苯二甲酸乙二酯)PET,和一添加劑組 合物的混合物擠出化合時比單獨的PET以同樣方式處理存 在有較低乙醛殘留量。這些添加劑組合物包括選自下列至 少兩組的化合物⑴聚(乙烯醇)或乙烯/乙烯醇共聚物, 多氫醇類和(Hi.)聚丙烯醯胺,聚甲丙烯醯胺或丙烯醯胺或 甲丙烯醯胺的共聚物。本發明關於任何用於製造將用於貯 存消費物質,尤其是食物,飮料,最特別的是水之瓶子或 容器的聚酯。 U.S. 4,361,681揭示含有酐終端覆蓋劑的聚酯具有 減少的乙醛產生率。 U.S.5,459,224揭示一種聚酯,其有4—氧基苯甲叉 終端覆蓋劑,使得其具有改善的耐候性及光穩定性,但沒 有提及乙醛逸出的問題。然而,其中所指出此一聚酯是適 合於食物和飮料的包裝。 聚酯類能以許多此項領域內習知的合成方法,使用各 種的觸媒系統製備而得。EP- A—O 826 713揭示在聚合化 時存在有亞磷酸酯,像雙(2,4-二-叔-丁基苯基)季戊 四醇亞磷酸酯,則在PET共聚合時可產生較低的量的乙醛 〇
U. S. 4,837,115 ; U.S. 5,258,233 ; U.S. 5,266 ,413 ; U.S· 5,340,884 ; U.S. 5,648,032 ; U.S. 5, 650,469 ; WO — A— 93/20147 ; WO—A- 93/23474 ; WO —A- 98/07786和WO—A-98/3幻88揭示使用聚醯胺當作 減少乙醛濃度的手段,即經由一 Schiff-鹼和醛的反廬, ____3_ _ _ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 0--------tr------------------------------- 1268948 A7 _____B7_____ 五、發明說明(/ ) 其在水存在下是不可逆的。 U.S. 5,856,385揭示使用聚醯胺或醯胺一蠟減少當 山梨糖醇一基澄淸劑在聚烯烴中加熱時所產生乙醛的量。 U.S. 5,011,890描述當聚丙嫌醯胺’聚甲丙烯胺 或經選定的丙烯醯胺或甲丙烯醯胺共聚物用於聚乙縮醛中 時抑止乙醛的形成。其條件爲該聚丙烯醯胺或聚甲丙烯醯 胺必須是在聚乙縮醛加工溫度下爲’’非一可熔的”。在此專 利中並沒有揭示在聚酯中使甩聚丙烯醯胺或聚甲丙烯醯胺 ,在熔融混合時,像經由擠出時可減少乙醛的濃度。 U.S. 4,394,470揭示一種聚對苯二甲酸乙二酯模製 組成物,其具有焦糖染色劑。該焦糖染色劑可由單-或二 糖化物衍生而得。 U.S. 5,681,879揭示一種火焰延遲劑聚酯組成物, 包括一聚酯樹脂,一具有不少於3個羥基的多氫醇,一無 機火焰延遲劑和一以鹵素爲基礎的火焰延遲劑。’ WO—Α- 00/66659揭示一種模製組成物,包括PET和 一降低乙醛形成的多氫醇添加劑。 WO — A—01/0〇724揭示使用多元醇減少在PET擠出產 物中形成乙醛。 本發明對於任何其中醛化合物,尤其是乙醛,是在聚 酯熱處理時所形成或逸出的聚酯皆是有用的。PET的熱處 理包括PET合成,用於製造雛形,型杯或瓶子及容器,或 擠出薄膜時的固態聚合化(SSP)的熱曝曬,任何射出模製, 任何射出吹模或拉伸-吹製模製,或任何在PET高於其玻 ___ 4 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) " (請先閱讀背面之注意事項再填寫本頁)
A7 1268948 五、發明說明(j ) 璃轉化溫度及低於其分解溫度間的熔融程序。 本發明於PET水瓶中提供較低量的污染物(如醛類)’ 因此可提供瓶裝水或其它瓶裝飮料在該PET容器中有較佳 的味道。所以在此領域中降低乙醛的量是非常有利的。乙 醛是一種習知聚酯的分解產物,像PET。乙醛對於貯存於 PET瓶中的瓶裝水會產生不欲的氣味,因此長期以來工業 界的目標即在於減少乙醛由PET瓶壁上遷移出而溶入其中 所裝的水或其它飮料中。許多對於製造雛型的擠出器’射 出模製機及製瓶機的工程或設計改變已被嘗試用來減少聚( 對苯二甲酸乙二酯)PET被加工時所形成的乙醛。對於PET 組成物本身已作調整,以降低其熔點或熔融黏度’減少當 PET加工製成雛型或瓶子時嚴重的熱或機械損害。 本發明的特定添加劑組合物對於聚酯組成物提供了不 可預期的優點。這些特定添加劑組合物對於防止熔融加工 時形成酸類具有加乘效果,同時此特定添加劑組合物不可 預期的提供了最佳低色澤,低濁霧及商醒抑止的平衡。“濁 霧,,是一種不欲之可見變灰現象。 本發明關於一種聚酯組成物’其是經穩定抑止在熔融 加工期間形成醒的污染物’包括 (a) —聚酯,及 (b) —有效穩定量的添加劑組合物,其中添加劑是選自 至少兩種不同的族群,這些族群爲 (i.)聚(乙烯基醇)或乙烯/乙烯基醇共聚物,‘ (ii.)多氫醇類和 __5 __ ___ 本紙張尺度適用中國國家標準(CNTS)A4規格(210 X297公釐) (請先閱讀背面之注意事項再填寫本頁) · —訂---------線 A7 1268948 五、發明說明(+ ) (iii.)聚丙烯醯胺,聚甲丙烯醯胺或一丙烯醯胺或和 至少一含乙烯鍵未經取代共單體共聚合之甲丙 烯醯胺共聚物。 較佳地,成份(a)的聚酯是經穩定組成物的95 - 99.9% 重量;和成份(b)的添加劑組合物是經穩定組成物的5至 0.1%重量。每一種選自(i.),(ii.)和(iii·)的添加劑可是較佳 地從1至99%重量(依據成份(b)總共添加劑組合物計算) 〇 本發明成份(b)的添加劑組合物可是兩種成份的組合物 ,例如,一選自⑴的化合物和一選自(Π)的化合物,或一選 自(Π)的化合物和一選自(iii)的化合物。此添加劑組合物也 可爲,例如,一三成份組合物,如,一選自(i.),(ii.)和 化合物的組合物。 , 成份(a)的聚酯具有選自下列組成的二羧酸重覆單元: 具有8至14個碳原子之芳香系的二羧酸,具有'4至12個 碳原子之脂肪系的二羧酸,具有8至12個碳原子^環脂肪 系的二羧酸,和其混合物。 較佳地,此二酸類是對酞酸,異酞酸,〇-酞酸,萘二 羧酸,環己烷二羧酸,環己烷二乙酸,二苯基一4,4,一二 竣酸,丁二酸,順丁烯二酸,戊二酸,己二酸,癸二酸和 其混合物。 尤其佳地是對酞酸,異肽酸和2,6-萘二羧酸。 較佳地,成份(a)聚酯的二醇部份是衍生自下式化合物 HO—R—〇H,其中R是一脂肪系的,環脂肪系的或芳香系 -_________ 6 本紙張中國國家標準(CNS)A4規格(21〇 χ 297公釐) ' " ---I------------------訂 *-------- (請先閱讀背面之注意事項再填寫本頁) 1268948 A7 S- 五、發明說明(<) 的群基,具有2至18個碳原子。 較佳地,此二醇是乙二醇,二乙二醇,三乙二醇,丙 烷一 1,3 —二醇,丙烷—1,2-二醇’ 丁烷一 1 ’ 4一二醇 ,戊烷—1,5-二醇,己;):完—丨,6一二醇,1,4一環己烷 〜二甲醇,3—甲基戊烷一 2,4一二醇,2—甲基戊烷一 1, 4 一二醇,2,二乙基丙烷一 1,3 —二醇,1,4一二一( 羥基乙氧基)苯,2雙(4 一羥基環己基)一丙烷,2,4 —二經基一1,1,3,3 —四一甲基環丁院,2,2—雙一(3 〜羥基乙氧基苯基)丙烷,2,2-雙一(4 一羥基丙氧基苯基 )乙烷和其混合物。 最佳地,此二醇是乙二醇和1,4一環己烷二甲醇。 成份(a)的聚酯較佳地是聚(對苯二甲酸乙二酯)[PET]或 聚(乙撐2,6-萘—2,6-二羧酸酯);最佳地是聚(對苯二 甲酸乙二酯)。 成份(a)的聚酯也能是聚酯混合物,或含有上述成份的 共聚酯。 成份(a)的聚酯能是新生聚合物或是聚合物再生物。除 此之外,其也可能包含80 - 99%重量的聚酯和20 - 1 %重 量的濃縮物,其中此濃縮物包括1〇- 90%重量的聚酯載體 樹脂和90- 10%重量的成份(b)的添加劑組合物。 本發明的新穎的聚酯組成物可用於製造容器或食品的 包裝,像是飮料和食物。由這些聚酯模製得的物品存在有 良好的薄牆剛性,優良的透明度及對溼氣和空氣存在有優 良的貧障性質,特別是對於二氧化碳和氧氣。 __7 ___ 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公爱) ---------------------訂--------1 (請先閱讀背面之注意事項再填寫本頁) A7 1268948 五、發明說明(b ) 本發·明的塑膠容器和薄膜是剛性的或可撓性的單一及 /或多層結構。基本的多層結構具有兩層或多層層板,由 熱成型或多層可撓性薄膜擠出,或瓶子之“雛型,,或“型 枉的擠出,接著再吹製模製此雛型成瓶子。 本發明的多層容器和薄膜可由例如多層聚酯,聚烯烴 ’聚燦經共聚物所形成,像乙撐一乙烯基乙酸酯,聚苯乙 稀’聚(乙烯基氯化物),聚(乙烯叉氯化物),聚醯胺,纖維 素’聚碳酸酯,乙撐一乙烯基醇,聚(乙烯基醇),苯乙烯 -丙烯腈和離子體,但其前提是至少一層包括本發明的聚 酯組成物。 對於薄膜和剛性包裝(瓶子),基本上最外層和接觸內 容物的最內層是由聚酯所組成,像PET或PEN[聚(乙撐萘 酉文酉曰)],I丙細,或聚乙細,像HDPL·。中間層,通常稱作 ‘ 或‘黏著’或‘緊密’層,由一種或多種組合物所形成 ’如PET,PEN,羧酸化的聚乙烯離子體,像,Surlyn®, 乙烯基醇均聚物或共聚物,像聚(乙烯基醇),部份氫化的 聚(乙烯基乙酸酯),聚(乙撐一共一乙烯基醇),像E VOH 或EVAL,尼龍或聚醯胺,像Selar®(DuPont),或以間二甲 苯二胺爲基礎之聚醯胺(有時稱作尼龍MXD - 6),或聚乙 烯叉氯化物(PVDC),或聚氨基甲酸乙酯類。 因此,本發明也關於一種單-或多層塑膠容器或薄膜 ,其是經穩定防此該容器或薄膜在熔融加工時形成醛污染 物,包括至少一含有下列成份的結構層, (a)—聚酯,及 8 ---------!·--------IT---------線丨釋 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) " ^ A7 1268948 五、發明說明() (b)—有效穩定量的添加劑組合物,其中此添加劑是選 自下列成份中的至少兩種 (i.)聚(乙烯基醇)或乙烯/乙烯基醇共聚物’ (Π.)多氫醇類和 (iii.)聚丙烯醯胺,聚甲丙烯醯胺或丙烯醯胺或甲丙 烯醯胺和至少一含乙烯鍵未經取代之共單體形 成的共聚物。 較佳地,此塑膠容器是一剛性瓶子。 剛性容器可由習知的機械程序製得: a) 單步驟吹氣模製,像在Nissei,Aoki,或Uniloy機 上預塑, b) 兩步驟,射出模製的預塑,像在Netstal或Husky 機上,和以吹氣模製將雛型轉化成瓶子(如,雀Sidel ,Corpoplast 和 Krones 機上), c) 層和吹氣模製雛型爲瓶子,像在Sipa,Κηιρρ Kautex,或Husky ISB機上丨喿作的程序,及 d) 拉伸吹氣模製(SBM)的雛型爲瓶子。 雛型在結構上可是單-層或多-層的。所製得的瓶子 可選擇性的後處理,以改變內壁的性質。瓶子可選擇性的 進行外層表面處理,像施覆表面塗覆物。UV吸收劑和其 它習知的穩定劑可加入至該表面塗覆物中。 使用習知的熱固定技藝,特定聚酯的顏色,LV.和熱 扭曲即使在局至約l〇〇°C也是安定的。此安定的特性在此 稱作π熱一充(hot - fill) ”安定。最佳可用於具有“熱—充 __ 9 I紙張尺度適时關家標準(CNS)A4規格(21G X 297公爱)"' - (請先閱讀背面之注意事項再填寫本頁) — · I I I I I I I ·11111111 , 1268948 a7 ___B7_ 五、發明說明() ”安定物品的線性聚酯包括聚(對苯二甲酸乙二酯),聚(對 苯二甲酸乙二酯),其中高至5莫耳百分比的乙二醇殘基已 被由1,4一環己烷二甲醇和聚(乙撐2,6 —萘二羧酸酯)所 衍生的殘基所取代,其中此聚酯是被充份的熱固定,且由 習知方法導向,獲得所期望的結晶度。 族群(i.)的添加劑是聚(乙烯基醇)或一乙烯/乙烯醇共 聚物。 較佳地,族群(i.)的添加劑是一乙烯/乙烯醇共聚物, 其中乙烯和乙烯醇的莫耳比例是99 : 1至1 : 99。尤其佳 的是其中乙烯和乙烯醇莫耳比例是50 : 50至20 : 80的乙 烯/乙烯醇共聚物。 族群⑴的乙烯/乙烯醇共聚物能是散亂或嵌段共聚物 〇 族群(ii)的化合物是下式I的多氫醇類 E-(OH)n (I) 其中 η是2至4000,及 Ε是一烴基。 依據本發明,烴基爲例如一脂肪系的,環脂肪系的, 芳香系的或一單一,二一或聚一糖基。 Ε所定義的烴基可由雜原子所中斷的,例如由一Ο-所 中斷的。 10 ---------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1268948 a7 ___B7__ 五、發明說明(彳) 族群(Π)的多氫醇類可爲例如丙三醇,1,2,3-丁院 三醇,1,2,4一丁烷三醇,赤蘚醇,核糖醇,木糖醇,己 六醇,山梨糖醇,1,2,3 —環己三醇,環己六醇,葡萄糖 ,半乳糖,甘露糖,半乳糖醛酸,木糖,葡糖胺,半乳糖 胺,1,1,2,2 —四一甲醯1環己烷,1,1,1 —三甲醇丙 烷,1,1,2—三甲醯丙烷,1,1,1 —三甲醇丁烷,1,1 ,2—三甲醇丁烷,1,1,1一三甲醇戊烷,1,1,2—三甲 醇戊烷,1,2,2—三甲醇戊烷,三甲醇戊烷,季戊四醇, 二季戊四醇,1,1,3,3—四—羥基丙烷,1,1,5,5 — 四一羥基戊烷,2,2,6,6—四—(羥基甲基)環己烷和2, 2,6,6—四一(羥基甲基)環己醇。 多氫醇爲例如澱粉,纖維素或糖或糖醇。 多氫醇類包括降解的澱粉(糊精和環狀糊精)i麥芽糖 和其衍生物,麥芽糖醇,麥芽五糖水合物,麥芽七糖,麥 芽四糖,麥芽糖單水合物,D,L-葡萄糖,右族糖,蔗糖 和D-甘露醇。 商業化的多氫醇包括三甲醇丙烷,三乙醇丙烷,甘油 ,山梨糖醇,季戊四醇和二季戊四醇。 族群(Π)的聚合物是任何包含一聚合化丙烯醯胺或甲丙 烯醯胺重覆單元的聚合物。丙烯醯胺或甲丙烯醯胺聚合物 的製備一般是習知的。 較佳地,族群(Hi)的聚合物是聚丙烯醯胺,聚甲丙烯 醯胺,或丙烯醯胺或甲丙烯醯胺和另一含乙烯未飽和鍵單 體的共聚物,此含乙烯未飽和鍵單體是丙烯醯胺,甲丙烯 ___ (請先閱讀背面之注意事項再填寫本頁)
本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1268948 a7 _______B7__ 五、發明說明(f〇 醯胺’苯·乙烯,乙烯,烷基丙烯酸酯,烷基甲丙烯酸酯, N-乙烯基一 2—吡咯烷酮或丙烯腈。 其它較佳之族群(iii)的共單體是羥基烷基甲丙烯酸酯 類’羥基烷基丙烯酸酯類或二甲基胺基乙基甲丙烯酸酯。 在這些情況下,結果共聚物包含醛反應性胺基和醛反應基 羥基。 特別有利的族群(iii)之聚合物是丙烯醯胺或甲丙烯醯 胺和另一含乙烯鍵未飽和單體的共聚物,其中該含乙烯鍵 未飽和單體是一羥基烷基甲丙烯酸酯,羥基烷基丙烯酸酯 或二甲基胺乙基甲丙烯酸酯。 最佳地,族群(iii)的聚合物是聚丙烯醯胺(PERCOL® 333,CibaSC)或聚丙烯醯胺(ΡΕΙΙ(:ΟΙ^351,CibaSC)。 族群(iii)的共聚物能是散亂或嵌段共聚物。< 本發明的組成物也可包含其它成份或調整劑像穩定劑 ,分散劑,顏料,染色劑,UV吸收劑,抗氧化劑,粗化 ,核酸劑和塡充劑,這些如描述U.S 5,011,890,其 相關部份在此倂入本發明作爲參考。 本發明也關於一種防止聚酯在熔融加工時形成醛污染 物的方法,包括在該聚酯中加入一有效穩定量的添加劑組 合物,其中此添加劑是選自至少兩種不同的族群,這些族 群爲(i·)聚(乙烯基醇)或乙烯/乙烯基醇共聚物,(ii.)多氫 醇類和(iii·)聚丙烯醯胺,聚甲丙烯醯胺或丙烯醯胺或甲丙 烯醯胺和至少一含乙烯鍵未經取代的共單體形成的共聚物 〇 12 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) " (請先閱讀背面之注意事項再填寫本頁) ·------- 1訂---------線 A7 1268948 五、發明說明(U ) 因此·,本發明的一個較佳實施例爲使用成份(b)防止聚 酯熔融加工時形成醛污染物。 本發明也關於一種形成適合貯存水(礦泉水,天然的 或臭氧處理過的)或其它食物的瓶子雛型或PET瓶或容器 ,其可使水或食物的氣味在其貯存入由本發明聚酯組成物 製成的瓶子或容器後能保持不變。 本發明之以成份(b)化合物穩定的塑膠容器或薄膜也可 選擇性的加入或施用0.01至10%重量;較佳地〇·025至 5%重量,最佳地0.1至3%重量(依據組成物的總共重量 計算)的其它共添加劑,像抗氧化劑,其它UV吸收齊[J, 位阻胺,亞磷酸酯或膦酸酯類,苯並肤喃-2-酮,硫代協 乘劑,聚醯胺穩定劑,金屬硬脂酸鹽類,核酸劑,塡充劑 ,補強劑,潤滑劑,乳化劑,染料,顏料,光學增亮劑, 火焰延遲劑,抗靜電劑,發泡劑及類似物,像以下所列的 物質,或其混合物。 <
1 · 抗氣化齊丨J LJ·烷基化的單酚,例如2, 6-二—叔一丁基〜4一甲基 酌,2—叔一丁基—4,6—二甲基酚,2,6 —二~叔一丁基 —4 一乙基酚,2,6 —二一叔 一丁基—4 一 η — 丁基酣,2,6 —二—叔—丁基—4 一異丁基酚,2,6—二環戊基—4—甲 基酚,2—(α —甲基環己基)一 4,6 —二甲基,2,6—二 -八碳烷基—4—甲基酚,2,4,6 -三環己基酚,2,6一二 -叔-丁基-4-甲氧基甲基酚,壬基酚,其是直鏈或在側 鏈上是含支鏈的,例如2, 6-二一壬基一 4〜甲基·,2 __ 13 本紙張尺度適~用中國國家標準(CNS)A4規格(210 X 297公釐) ' ------ (請先閱讀背面之注意事項再填寫本頁) --------訂·--------. A7 1268948 ______B7__ 五、發明說明( ’4 — 一甲基一 6 —(Γ —甲基十一碳一1,一基)酚,2,4 —二 甲基一 6-(Γ -甲基十七碳一 1丨-基)酚,2,4一二甲基-6 一(Γ 一甲基十三碳一 1’一基)酚和其混合物。 」院基硫代互基酚,例如2,4一二辛基硫代甲基一 6 — 叔—丁基酚,2,4一二辛基硫代甲基一 ό一甲基酚,2,4一 一羊基硫代甲基一 6 -乙基酣,2,6-二一十二碳院基硫代 甲基一 4一壬基·。 '1 ·Hi醌和院基化的氤媪,例如2, 6 —二—叔一 丁基一 4 一甲氧基酚,2,5 —二—叔—丁基氫醌,2,5 —二—叔一 戊基氫醌,2,6-二苯基一 4 —十八碳烷氧基酚,2,6—二 —叔一丁基氫醌,2,5-二一叔—丁基—4一羥基茴香醚, 3,5 —二一叔—丁基一 4 —羥基茴香醚,3,5一二一叔一丁 基—4—羥基苯基硬脂酸酯,雙(3,5 一二一叔—丁,基一4一 羥基苯基)己二酸酯。 I·4:·-生育酉分_,例如α -生育酣,β -生育酸,γ'—生育酉分 ,δ -生育酚和其混合物(維生素Ε)。 1.5·..羥棊化的硫代二茏甚酚観,例如2,2’ —硫代雙(6-叔 一丁基—4 —甲基酚),2,2, 一硫代雙(4 一辛基酚),4,4,一 硫代雙(6 —叔一 丁基一 3 -甲基酣),4,4’ 一硫代雙(6 -叔 一丁基一 2 —甲基酚),4,4, 一硫代雙(3,6 -二—第二一戊 基酚),4,4’一雙(2,ό 一二甲基一 4—羥基苯基)二硫化物 〇 1.6·...烷!曼亂,例如2,2’一甲撐雙(6 —叔一丁基一4一甲 基酚),2,2·—甲撐雙(6一叔一 丁基一 4 一乙基酚),2,2’一 _________ 14 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ··
---訂---------線U A7 1268948 五、發明說明(·、)) 甲撐雙[4_一甲基一 6 —(α —甲基環己基)酉分],2,2’一甲撐 雙(4 一甲基—6—環己基酚),2,2’ —甲撐雙(6—壬基—4 — 甲基酚),2,2’一甲撐雙(4,6—二一叔一 丁基酚),2,2’一 乙叉雙(4,6—二—叔—丁基酚),2,2’一乙叉雙(6-叔一 丁基一 4 一異丁基酚),2, 2’一甲撐雙[6 —(α —甲基苯甲基 )—4 一壬基酚],2, 2’一甲撐雙[6 —(α ,α —二甲基苯甲 基)—4—壬基酚],4, f一甲撐雙(2, 6-二一叔一丁基酚) ·,4,4f —甲撐雙(6 —叔—丁基一 2 -甲基酣),1,1一雙(5 一叔一丁基—4 一羥基—2—甲基苯基)丁烷,2,6-雙(3 -叔一丁基一5—甲基一 2—羥基苯甲基)一 4 一甲基酚,1,1 ,3-二(5 —叔—丁基一 4 一經基一 2 —甲基苯基)丁院,1, 1 —雙(5-叔—丁基一 4 一羥基一 2-甲基苯基)一 3 - η—十 二碳烷基锍基丁烷,乙二醇雙[3,3 —雙(3’一叔一丁基—4’ 一羥基苯基)丁酸酯],雙(3-叔—丁基一 4一羥基一 5 —甲 基一苯基)二環戊二烯,雙[2—(3’一叔一丁基— 2’—羥基— 5’一甲基苯甲基)一 6—叔—丁基一 4 —甲基苯基]對酞酸酯, 1,1一雙一(3,5—二甲基一2-羥基苯基)丁烷,2,2—雙 (3,5 -二一叔—丁基—4一羥基苯基)丙烷,2,2-雙一(5 一叔一丁基—4—羥基2-甲基苯基)—4 一 η-十二碳烷基 锍基丁烷,1,1,5,5—四一(5-叔—丁基一 4一羥基一 2 一甲基苯基)戊烷。 1.7. Ο—,Ν-和S-苯甲基化合物,例如35,3f,5’一 四一叔一 丁基一4,4'—二羥基二苯甲基醚,十八碳烷基一 毫 4一羥基一3,5-二甲基苯甲基锍基乙酸酯,十三碳基一4 ___15_ 本纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) .·--------iii-,---------------------- A7 1268948 —«-_— _ B7_______ 五、發明說明(叭) —羥基一θ,5-二一叔一丁基苯甲基锍基乙酸酯,三(3,5 一二一叔一丁基—4 一羥基苯甲基)胺,雙(4一叔一 丁基一3 —羥基—2,6—二甲基苯甲基)二硫代對肽酸酯,雙(3,5 一一一叔一丁基—4 一羥基苯甲基)硫化物,異辛基一 3,5 一二一叔一 丁基一 4一羥基苯甲基|荒基乙酸酯。 1.8. 羥基苯甲基化的丙二酸酯類,例如二一十八碳烷基一 2,2—雙(3,5 —二一叔—丁基一 2-羥基苯甲基)丙二酸酯 ’一—十八碳院基一 2 -(3-叔一丁基一 4 一經基一 5-甲基 苯甲基)丙二酸酯,二一十二碳烷基锍基乙基—2,2-雙(3 ,5-二一叔—丁基一 4 一羥基苯甲基)丙二酸酯,雙[4—(1 ,:1,3,3 —四一甲基丁基)苯基]—2, 2—雙(3, 5 —二一 叔一丁基一 4 一羥基苯甲基)丙二酸酯。 1.9. 芳香系的羥基苯甲基化合物,例如卜3,5,三(3,5 —二一叔一丁基—4 一羥基苯甲基)—2,4,6-三甲基苯, 1,4—雙(3,5 —二—叔—丁基—4 —羥基苯甲基)一 2,3, 5 ’ 6 —四一甲基苯 ’ 2 ’ 4 ’ 6 —二(3 ’5 — —.—叔一丁基一4 一羥基苯甲基)酚。 1.10. 三嗪化合物,例如2,4一雙(辛基锍基)—6—(3,5 — 二—叔—丁基一 4一羥基苯胺基)一 1,3,5 —三嗪,2 —辛 基锍基一 4,6-雙(3,5-二一叔一丁基一 4一羥基苯胺基) —1,3,5-三嗪,2-辛基锍基一 4,6-雙(3,5 —二—叔 —丁基一 4—羥基苯氧基)—1,3,5-三嗪,2,4,6-三-(3,5 —二一叔一丁基—4 一羥基苯氧基)—1,2,3-三嗪 ,1,3,5-三(3,5 —二-叔一丁基一 4 一羥基苯甲基)異 ____16_ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) .· 訂---------線· A7 1268948 五、發明說明(/ ) 氰尿酸酯.,1,3,5-三(4一叔一丁基—3 —羥基一2,6-二甲基苯甲基)異氰尿酸酯,2,4,6-三(3,5—二一叔— 丁基—4—羥基苯基乙基)—1,3,5 —三嗪,1,3,5 —三 (3,5 —二一叔一丁基一 4 一經基苯基丙醯基)—六氣—1,3 ,5 —三嗪,1,3,5 —三(3,5-二環己基—4—羥基苯甲 基)異氰尿酸酯。 1.11. 苯甲基磷酸酯類,例如二甲基—2,5—二一叔—丁 基—4—羥基苯甲基磷酸酯,二乙基-3,5 —二—叔-丁基 一 4 一羥基苯甲基磷酸酯,二一十八碳烷基一3,5-二一叔 一丁基一 4 一羥基苯甲基磷酸酯,二一十八碳烷基一 5-叔 —丁基一 4 一羥基一 3-甲基苯甲基磷酸酯,3,5 —二—叔 -丁基-4-羥基苯甲基膦酸單乙基酯的鈣鹽。 1.12. 醯基胺基酚,例如4—羥基月桂醯替苯胺,4-羥基 硬脂醯替苯胺,羊基N—(3,5-二一叔一丁基一 4 一經基 苯基)氨基甲酸乙酯。 ’ 1.13. β — (3,5 — —叔—丁基—4 —經基苯基)丙酉爱和單- 或多氫醇類的酯,如和甲醇,乙醇,η-辛醇,i—辛醇, 十八碳醇,1,6—己烷二醇,1,9—壬烷二醇,乙二醇,1 ,2—丙烷二醇,新戊二醇,硫代二乙二醇,二乙二醇,三 乙二醇,季戊四醇,三(羥基乙基)異氰尿酸酯,N,Ν’一雙 (羥基乙基)乙二醯二胺,3 —噻十一碳醇,3-噻十五碳醇 ,三甲基己烷二醇,三甲醇丙烷,4—羥基甲基—1 一膦一2 ,6,7-三氧雜雙環[2.2.2]辛烷。 1.14. β -(5-叔一丁某—4—羥某一 3-甲基苯基)丙酸和m _\1 ___ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) n i n HR n· 一 0、e m n Hi an 11 flu · 線丨 1268948 五、發明說明(4) A7 B7 一或多氫、醇類的酯類,如和甲醇,乙醇,^一辛醇,丨_辛 醇’十八碳醇,1,6 —己院二醇,1,9一壬院二醇,乙二 醇,1,2—丙烷二醇,新戊二醇,硫代二乙二醇,二乙二 醇,三乙二醇,季戊四醇,三(羥基乙基)異氰尿酸酯,Ν, Ν’—雙(羥基乙基)乙二醯二胺,3 一噻十一碳醇,3 一噻十 五碳醇,二甲基己院二醇,三甲醇丙院,4一經基甲基一 ^ 一膦—2,6,7-三氧雜雙環[2·2·2]辛院;3,9 —雙[2 - {3 一(3-叔一丁基一 4 一羥基一 5-甲基苯基)丙醯氧基丨—i, 1 —二甲基乙基]—2,4,8,10—四氧雜螺[5.5]十一碳烷。 1_·ΐ5·β — Π ’ 5-一環己基一4一經基苯基)丙酶和單—或多 氫醇類的酯,如和甲醇,乙醇,辛醇,十八碳醇,1,6 _ 己烷二醇,1,9一壬烷二醇,乙二醇,1,2—丙烷二醇, 新戊二醇,硫代二乙二醇,二乙二醇,三乙二醇,季戊四 醇,三(羥基乙基)異氰尿酸酯,Ν,Ν’一雙(羥基乙基)乙二 醯一胺’ 3-噻十一碳醇,3-噻十五碳醇,三甲基己院二 醇 甲醇丙烷,4一羥基甲基—1 一膦—2,6,7 氧雜 (請先閱讀背面之注意事項再填寫本頁) I · n n n n n n n.^OJI n n n ·ϋ n ϋ ϋ I - 雙環[2.2.2]辛烷。 U6. 3,5—二—叔—丁基一 4 一羥某苯基乙酸和厘一或名 氫醇類的酯,如和甲醇,乙醇,辛醇,十八碳醇,1,6 — 己烷二醇 9一壬烷二醇,乙二醇 2 —丙烷二醇 新戊二醇,硫代二乙二醇,二乙二醇,三乙二醇,季戊四 醇,三(羥基乙基)異氰尿酸酯,Ν,Nf—雙(羥基乙基)乙二 醯二胺,3 —噻十一碳醇,3-噻十五碳醇,三甲基己烷二 醇 甲醇丙烷,4—羥基甲基一 1 —膦—2,6,7—三 18 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) A7 1268948 五、發明說明(ί']) 雙環[2·2·2]辛烷。 1.17. β —(3,5-二一叔一丁基一 4—羥基苯某)丙酸的醯胺 丄如Ν,Ν’一雙(3,5-二一叔一 丁基一 4一羥基苯基丙醯 基)六甲撐二醯胺,Ν,Nf—雙(3,5 —二—叔—丁基—4 一 羥基苯基丙醯基)三甲撐二醯胺,N,Nf-雙(3,5-二一叔 —丁基一 4—羥基苯基丙醯基)肼,Ν,Ν’—雙[2—(3—[3,5 一二一叔一 丁基一4一羥基苯基]丙醯氧基)乙基]乙二醯二胺 (Naugard®XL — 1,由 Uniroyal 提供)。 1.18. 抗壞血酸(維生素C)。 1.19. 胺抗氧化劑,例如Ν,Ν’一二一異丙基一 p—苯撐二 胺,Ν,Ν’一二一第二一 丁基一 ρ—苯撐二胺,Ν,Ν’一雙(1 ,4 —二甲基戊基)—ρ —苯撐一^胺,Ν,Nf—雙(1 —乙基一 3 一甲基戊基)一 P—苯撐二胺,Ν,Ν’一雙(1 一甲基庚基)一 p 一苯撐二胺,Ν,Ν’—二環己基— ρ-苯撐二胺,Ν,Ν’一 雙苯基— ρ—苯撐二胺,Ν,Ν’—雙(2 —萘基)— ρ -苯撐二 胺,Ν—異丙基一 Ν’—苯基—ρ—苯撐二胺,Ν—(1,3 —二 甲基丁基)一 Ν’一苯基一 ρ-苯撐二胺,Ν-(1 一甲基庚基) 一 Ν’ —苯基— ρ—苯撑一胺,Ν-環己基—1ST -苯基一 ρ—苯 擦二胺,4一(ρ-甲苯氨擴醯)二苯基胺,Ν,Ν’一二甲基一 Ν,Ν’ — 一 一第_^^ 一丁基—ρ-苯撑一胺,一苯基胺,Ν — 嫌丙基二苯基胺,4一異丙氧基二苯基胺,Ν-苯基一 1 一 蔡基胺,Ν-(4 一叔—羊基苯基)—1 一蔡基胺,Ν-苯基— 2 —萘基胺,辛基化的二苯基胺,例如p,pf-二—叔一辛 基二苯基胺,4一 η-丁基胺基酚,4一丁醯基胺基酚,4一 ___19^_'__ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) •AW--------訂--------- 1268948 A7 ___ B7___ 五、發明說明(J ) 壬醯基胺基酚,4-十二碳醯基胺基酚,4-十八碳醯基胺 基酣,雙(4一甲氧基苯基)胺,2,6-二—叔—丁基一 4 — 二甲基胺基甲基酚,2,4’一雙胺基二苯基甲烷,4,4’一雙 胺基二苯基甲烷,Ν,Ν,Ν’,Ν’一四甲基一4, 41 一雙胺基 二苯基甲烷,1,2-雙[(2—甲基苯基)胺基]乙烷,1,2 — 雙(苯基胺基)丙烷,(〇-甲苯基)雙胍,雙[4 一(1’,3’一二 甲基丁基)苯基]胺,叔-辛基化的Ν-苯基一 1-萘基胺’ •單-和二烷基化的叔-丁基/叔-辛基二苯基胺的混合物, 單-和二烷基化的壬基二苯基胺的混合物,單-和二烷基 化的十二碳烷基二苯基胺的混合物,單-和二烷基化的異 丙基/異己基二苯基胺的混合物,單-和二烷基化的叔-丁 基二苯基胺的混合物,2,3 —雙氫一 3,3-二甲基一 4Η -1,4-苯並噻嗪,吩噻嗪,單-和二烷基化的叔二丁基/叔 -辛基吩噻嗪的混合物,單-和二烷基化的叔-辛基吩噻 η秦的混合物,Ν —烯丙基吩噻嚷,Ν,Ν,Ν’,Ν’ —四苯基 —1,4 —雙胺基丁一 2-烯。 2. UV吸收劑和光穩定劑 2.1. 2—(2,一羥某茏某)苯並三唑,例如2-(2’—羥基—5f-甲基苯基)苯並三唑,2—(3^ 5, 一二—叔一丁基一 2’—羥基 苯基)苯並三唑,2-(5’-叔-丁基一 2’一羥基苯基)苯並三 口坐,2—(2f —羥基—5’一(1,1,3,3-四甲基丁基)苯基)苯 並三Π坐,2- (3’,5’一二—叔—丁基—2’一羥基苯基)—5 — 氯化苯並三嗖,2-(3’一叔—丁基—2’一經基一 5’一甲基苯 基)—5 —氯化苯並三唑,2-(3, 一第二—丁基— 5f —叔—丁 _20 ___ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公t ) (請先閱讀背面之注意事項再填寫本頁) · 一口,I ϋ 1· n n n n n I n 1— n n n 1 n n n n n n n n 1 I I ί ί ϋ n ' 1268948 μ ___ B7 ___ 五、發明說明(|>| ) 基一 2’ —羥基苯基)苯並三唑,2—(2’一羥基一 41 —辛氧基苯 基)苯並三唑,2-(3,,5’一二一叔—戊基—2’一羥基苯基) 苯並三唑,2—(3’,5f—雙(α ,α —二甲基苯甲基)一 2’ — 羥基苯基)苯並三唑,2—(3’一叔—丁基—2f—羥基— 5’—(2 一辛氧基羰基乙基)苯基)一 5-氯化苯並三唑,2 —(3’一叔 一 丁基一 5’一 [2—(2 —乙基己氧基)羰基乙基]— 2’ —羥基苯 基)—5 —氯化苯並三唑,2-(3’-叔一丁基一 2’ —羥基—5’ 、一(2—甲氧基羰基乙基)苯基)-5—氯化苯並三唑,2-Θ 一叔—丁基一 2’一羥基一 5’一(2-甲氧基羰基乙基)苯基)苯 並三唑,2-(3’一叔一丁基— 2’—羥基一 5’一(2-辛氧基羰 基乙基)苯基)苯並三唑,2-(3, 一叔一丁基一 5’—[2 -(2 — 乙基己氧基)羰基乙基]—2*-羥基苯基)苯並三唑,2-(3’一 十一碳院基一 2f —經基—5’ —甲基苯基)苯並二哇,,2 -(3* -叔一 丁基一 2’一羥基一 5’一(2-異辛氧基羰基乙基)苯基苯 並三唑,2,2’—甲撐雙[4—(1,1,3,3—四甲基丁基)一 6 —苯並三唑一 2-基酚];2—[3’ —叔一 丁基一 5, 一(2—甲氧 基羰基乙基)—2’一羥基苯基]一 2H-苯並三唑和聚二醇300 的酯化產物;[R-CH2CH2-C〇〇-CH2CH2j^,其中R = 3,一叔一 丁基一 4f —羥基— 5’—2H—苯並三唑—2 —基苯基,2—[2’ 一經基一3^—(α ,α —二甲基苯甲基)一 5’一(1,1,3,3 — 四甲基丁基)苯基]苯並三唑;2—[2f—羥基一3’〜(1,1,3 ,3—四甲基丁基)一5’一(α ,α —二甲基苯甲基)苯基]苯 並三唑。 2.2. 2-羥基苯並苯並苯酮,例如4 一羥基,4~甲氧基,4 21 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) " (請先閱讀背面之注意事項再填寫本頁)
--------訂—-------Ί I 1268948 a? -----— B7 ____ 五、發明說明(>-) 一辛氧基,4一癸氧基,4一十二碳烷氧基,4—苯甲氧基, 4 ’ 21,三羥基和2’ —羥基一 4,4’—雙甲氧基的衍生物 〇 2·3.經取代的和未經取代的苹甲酸的酯類,例如4 一叔—丁 基苯基水楊酸酯,苯基水楊酸酯,辛基苯基水楊酸酯,二 苯甲醯間苯二酚,雙(4 一叔一丁基苯甲醯)間苯二酚,苯甲 醯間苯二酚,2,4一二一叔一丁基苯基3,5-二一叔—丁 •基一 4—羥基苯甲酸酯,十六碳烷基3,5-二一叔一丁基 一 4 一羥基苯甲酸酯,十八烷基3,5一二一叔一丁基一4 一羥基苯甲酸酯,2 —甲基一4,6-二一叔一丁基苯基3 ,5 —二一叔一丁基—4—羥基苯甲酸酯。 2.4. 丙烯酸酯,例如乙某α 一氰基一β ,β —雙苯基丙烯 酸酯,異辛基α 一氰基一β ,β 一雙苯基丙烯酸酯,甲基 α —碳甲氧基肉桂酸醋,甲基〇( —氰基一 β —甲基一 p—甲 氧基肉桂酸酯,丁基α —氰基一 β —甲基—ρ二甲氧基肉 桂酸酯,甲基α —碳甲氧基—ρ-甲氧基肉桂酸酯和Ν-( β —碳甲氧基—β —氰基乙稀基)—2-甲基D引卩朵琳。 2.5. 鎳化合物,例如2,2’ —硫代雙[4 一(1,1,3,3—四 甲基丁基)酚]的鎳複合物,像1 : 1或1 : 2複合物,具有 或不具有其它側鏈基像η-丁基胺,三乙醇胺或Ν-環己 基二乙醇胺,二丁基二硫代氨基甲酸乙鎳,單烷基酯類的 鎳鹽,如甲基或乙基酯,4一羥基一3,5-二一叔一丁基苯 甲基膦酸的鎳鹽,酮肟的複合物,如2-羥基-4一甲基苯 基十一碳基酮肟的複合物,1 一苯基一 4 一月桂醯一 5-羥基 ____ 22 ____ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ^OJ· ϋ n n n n n n I n I n n n -ϋ n n n ϋ n n n -ϋ n n n ϋ A7 B7 (2, 2, 6, 6 -四甲基 —2,2 η 1268948 五、發明說明( 吡唑的鎳複合物,具有或不具有其它側鏈基。 立體位姐胺,例如雙(2,2,6,6 —四甲基—4 —呢陡 基)癸二酸酯,雙(2,2,6,6 -四甲基—4 —呢陡基)丁二 酉夂酉曰,雙(1,2,2,6,6 —五甲基—4 —呢B定基)癸二酸醋 ,雙(1 一辛氧基一2,2,6,6-四甲基—4 —呢卩定基)癸二 酸酯,雙(1,2,2,6,6-五甲基—4一呢啶基)n—丁基一 3 ’ 5—二一叔一丁基一 4 一經基苯甲基丙二酸酯,1一(2 -經基乙基)—2,2,6,6 —四甲基—4—羥基派啶和丁二酸 的凝縮產物,Ν,Ν’ 一雙(2,2,6,6 —四甲基—4 一顿卩定基 )六甲撐二胺和4一叔一辛基胺基一2,6-雙氯化一1,3, 5~三嗪的線性或環形凝縮產物 —4一派啶基)氮川三乙酸酯,四(2,2,6,6—四甲基-4 一呢啶基)一 1,2,3,4—丁烷四羧酸酯,1,1’,(1,2_ 乙烷二基)—雙(3,3,5,5—四甲基顿嗪酮),4—苯甲醯 6—四甲基派啶,4一硬脂氧基—2,'2,6,6 四甲基派啶,雙(1,2 ’ 2,6,6—五甲基哌啶基)一2 - η — 丁基一 2-(2 -羥基一 3,5-二一叔一 丁基苯甲基)丙二酸 酯,3 — η—辛基一7,7,9,9一四甲基一1,3,8 —三氮雜 螺[4.5]癸烷一2,4一雙酮,雙(1 —辛氧基一2,2,6,6-四甲基派啶基)癸二酸酯,雙(1 —辛氧基—2,2,6,6—四 甲基顿啶基)丁二酸酯,Ν,Ν’一雙(2,2, 6, 6—四甲基一 4一派啶基)六甲撐二胺和4—嗎咐基一2,6-雙氯化一 1, 3,5 —三嗪的線性或環形凝縮產物,2—氯化一 4,6-雙(4 丁基胺基一2,2,6,6-四甲基哌啶基)一 1,3,5 23 (請先閱讀背面之注意事項再填寫本頁) --訂---------線 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公爱) 1268948 a: _____B7__ 五、發明說明(vV) 三嗪和1·,2-雙(3-胺基丙基胺基)乙烷的凝縮產物,2-氛化—4 ’ 6 — 一 —(4 一 η- 丁 基胺基—1,2,2,6,6 —五 甲基呢啶基)一1,3,5 —三嗪和1,2-雙(3-胺基丙基胺 基)乙烷的凝縮產物,8-乙醯基一 3 —十二碳烷基—7,7, 9, 9 —四甲基一1,3, 8—三氮雜螺[4.5]癸烷一2,4—雙酮 ’ 3 —十一碳院基—1 — (2,2,6,6 —四甲基一 4 一呢;D定基) 卩比略院一 2,5 —雙酮,3 —十二碳院基—1 — (1,2,2,6, •6—五甲基一 4 —派D定基)ρ比略垸—2,5 —雙酮,4—十六碳 烷氧基一和4 —硬脂氧基一2,2,6,6—四甲基顿啶的混 合物,Ν,Nf—雙(2,2,6,6—四甲基—4 一呃啶基)六甲 撐二胺和4—環己基胺基—2,6-雙氯化一 1,3,5 —三嗪 的凝縮產物,1,2 —雙(3 —胺基丙基胺基)乙烷和2,4,6 一三氯化—1,3,5 —三嗪的凝縮產物,以及4—丁基胺基 一2,2,6,6—四甲基呢啶(CAS Reg. No· [136504— 96 — 6]); 1 ’ 6 —己院二胺和2,4,6 —二氯化—1,3,5 —三嗦 的凝縮產物,以及N,N—雙丁基’胺和4—丁基胺基一2,2 ,6,6 —四甲基呢陡(CAS Reg. No. [192268 — 64 — 7]) ; N 一(2 ’ 2,6,6—四甲基—4 —呢Π定基)—η—十二碳院基丁 二醯亞胺,Ν—(1,2,2,6,6—五甲基—4 —派啶基)一 η 一十二碳院基丁二醯亞胺,2—~{--碳基一7,7,9,9一四 甲基一 1 一氧雜—3,8—雙氮雜—4 一氧一螺[4,5]癸烷,7 ,7,9,9 —四甲基一 2 —環-f^一碳基一 1 一氧雜—3,8~雙 氮雜一4一氧螺一 [4,5]癸烷和表氯醇的反應產物,1,i — 雙(1,2,2,6,6—五甲基—4一呢U定氧基羯基)一2-(4~ 24 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱1 " 一 (請先閱讀背面之注意事項再填寫本頁) ·· 訂---------線—康 1268948 a7 ______B7_— ____ 五、發明說明(y)) 甲氧基苯基)乙烯,Ν,Ν’一雙一甲醯基一 N,Nf—雙(2 ’ 2 ,6,6 —四甲基一4 —p欣啶基)六甲撐二胺,4一甲氧基甲撐 丙二酸和1,2,2,6,6-五甲基一 4—羥基派啶的二酯’ 聚[甲基丙基—3 —氧基—4 一(2,2,6,6—四甲基—4一派 啶基)]矽氧烷,順丁烯二酸酐一 α -烯烴共聚物和2 ’ 2 ’ 6 ,6—四甲基一4 —胺基哌啶或1,2,2,6,6-五甲基一4 -胺基呢啶的反應產物。 此立體位阻胺也可是下述化合物之一: GB —Α— 2 301 106 號案中當作成份 I—a),I一 b),I—c),I 一 d),I—e),I—f),I-g),I—h) , I— i),I — j),i—k)或 I 一 1)的化合物,特別是GB —A— 2 301 106號案中第68至 73頁中所列的光穩定劑1一 a—l,l —a-2,1一b—l,l一 c一 1,1 — c—2,1 — d—1,1一d—2,1一d—3,l^-e—l, 1 一 f-卜 1 一g-卜 l-g-2 或 1-k—卜 立體位阻胺也可是下述化合物之一: ’ EP — A- 0 782 994,例如描述於中請專利範圍第10或38 項或實例1 一 12或D- 1至D-5中所述之化合物。 2.7.立體位阻胺,其在N -原子上是由羥某-取代之烷氧 基所取代的,例如像1 一(2-羥基一 2-甲基丙氧基)一4 一 十八碳醯氧基—2,2,6,6-四甲基顿啶,1 —(2—羥基— 2 —甲基丙氧基)—4—十六碳醯氧基一2,2,6,6—四甲基 顿啶,1 —氧基—4—羥基一 2,2,6,6 —四甲基哌啶和一 由t一戊基醇而的碳反應基之反應產物,1一(2-羥基— 2 — 甲基丙氧基)—4一羥基—2,2,6,6—四甲基哌啶,1一(2 25 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)~ ~ ---------------------訂--------I i^w— (請先閱讀背面之注意事項再填寫本頁) 1268948 a7 ^___ B7__ 五、發明說明(舛) 一經基一 2—甲基丙氧基)一4一氧一2,2,6,6—四甲基口飛 啶,雙(1 —(2 —羥基一2-甲基丙氧基)一2,2,6,6—四 甲基派陡一 4一基)癸二酸酯,雙(1 一(2—經基一 2—甲基丙 氧基)一 2,2,6,6—四甲基呢啶一 4一基)己二酸酯,雙(i 一(2-羥基一2—甲基丙氧基)—2, 2, 6, 6—四甲基锨啶 一 4 一基)丁二酸酯,雙(1 一(2-羥基一 2—甲基丙氧基)一 2 ,2,6,6 —四甲基哌啶—4一基)戊二酸酯和2,4 一雙{N 一 [1 一(2 —羥基一2 —甲基丙氧基)一2,2,6,6—四甲基 哌啶一 4一基]—N—丁基胺基} —6-(2—羥基乙基胺基)—s 一三嗪。 gj.乙二醯二胺,例如4,4’ —雙辛氧基草醯替苯胺,2, 2’一雙乙氧基草醯替苯胺,2,2’—雙辛氧基一 5,5,—二— 叔一丁氧醯替苯胺,2,2’一雙十二碳烷氧基一 5,5’一二一 叔一丁氧醯替苯胺,2-乙氧基-2’一乙基草醯替苯胺,N ,Ν’一雙(3—二甲基胺基丙基)乙二醯二胺,2—乙氧基一 5 一叔—丁基—2’一乙氧醯替苯胺和真和2 —乙氧基—2’ —乙 基一 5,4’—二一叔一丁氧醯替苯胺的混合物,〇-和ρ-甲 氧基-二取代的草醯替苯胺的混合物,和〇-和ρ-乙氧基 -雙取代的草醯替苯胺的混合物。 2.9. 2—(2—羥基苯基)—1,3,5 —三嗪,例如2,4,ό — 三(2 —羥基—4—辛氧基苯基)—1,3,5-三嗪,2 —(2 — 羥基一 4一辛氧基苯基)—4,6—雙(2,4—二甲基苯基)一 1 ,3,5-三嗪,2-(2,4—雙羥基苯基)—4,6—雙(2,4 一二甲基苯基)—1,3, 5 —三嗪,2,4一雙(2—羥基—4 — 26_ 本纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) A7 1268948 五、發明說明(/ ) 丙氧基苯基)—6—(2,4 一二甲基苯基)—1,3,5 —三嗪, 2 —(2 —羥基一 4—辛氧基苯基)一 4,6-雙(4 —甲基苯基)一 1,3,5 —二嚷,2-(2 —涇基一 4—十二碳院氧基苯基)—4 ,6 —雙(2,4—二甲基苯基)一1,3,5 —三日秦,2,(2 —經 基一 4一十三碳氧基苯基)一 4,6-雙(2,4一二甲基苯基) 一 1,3,5 — 三曉,2 — [2-羥基一 4—(2—羥基一3 —丁氧 基丙氧基)苯基]—4, 6—雙(2, 4 一二甲基)一1,3,5 —三 P秦,2- [2—經基—4—(2 -經棊一 3 —辛氧基丙氧基)苯基] 一4, 6—雙(2,4—二甲基)一1,3, 5 —三嗪,2- [4—(十 二碳院氧基/十二碳氧基-2-經基丙氧基)- 2-經基苯基] -4,6- 雙(2,4-二甲基苯基)—1,3,5-三嗪,2-[2 一羥基一 4一(2 -羥基一 3-十二碳烷氧基丙氧基)苯基]一 4 ,6—雙(2,4一二甲基苯基)—1,3,5-三嗪,2—(2 —羥 基—4一己氧基)苯基一 4,6-雙苯基一 1,3,5_三嗪,2 一(2 —經基—4 —甲氧基苯基)一 4,6-雙苯基一'1,3,5-三嗪,2,4,6—三[2-羥基—4—(3 —丁氧基一 2-羥基丙 氧基)苯基]一1,3,5—三嗪,2-(2-羥基苯基)—4—(4 — 甲氧基苯基)一6-苯基一1,3,5-三B秦,2-{2 —羥基—4 一 [3 -(2 —乙基己基一 1 一氧基)一 2 —羥基丙氧基]苯基} 一 4 ,6—雙(2,4一二甲基苯基)一 1,3,5-三η秦。 3.金屬去活性蹵[,例如Ν,Ν’一雙苯基乙二醯二胺,Ν_ 水楊醛— Ν’一水楊醯肼,Ν,Ν’一雙(水楊醯)肼,ν,Ν,-雙(3,5 —二一叔一丁基一 4 一羥基苯基丙醯基)肼,3 一水 楊醯胺基—1,2,4—三唑,雙(苯甲叉)乙二醯二肼,草醯 27 本紙張尺度適用中關家標準(CNS)A4規格(21G X 297公爱) ----- (請先閱讀背面之注意事項再填寫本頁)
--------訂·-------I A7 1268948 ___B7__ 五、發明說明(yb ) 替苯胺,裏跃醯二肼,癸二醯雙苯基肼,N,Nf —雙乙酿 基己二醯二肼,N,Ν’一雙(水楊醯)乙二醯二肼,N,Ν’一 雙(水楊醯)硫代丙醯基二胼。 .4.亞磷酸酯和膦酸酯,例如三苯基亞磷酸酯,二苯基烷基 亞磷酸酯,苯基二烷基亞磷酸酯,三(壬基苯基)亞磷酸酯 ,三月桂基亞磷酸酯,三-十八烷基亞磷酸酯,二硬脂基 季戊四醇二亞磷酸酯,三(2,4 一二—叔一丁基苯基)亞磷 酸酯,二異癸基季戊四醇二亞磷酸酯,雙(2,4 一二—叔一 丁基苯基)季戊四醇二亞磷酸酯,雙(2,4-二一枯基苯基) 季戊四醇二亞磷酸酯,雙(2,6-二一叔一 丁基一 4一甲基 苯基)季戊四醇二亞磷酸酯,二異癸氧基季戊四醇二亞磷酸 酯,雙(2,4一二一叔一 丁基一 6-甲基苯基)季戊四醇二亞 磷酸酯,雙(2,4,6-三(叔-丁基苯基)季戊四醇二亞磷 酸酯,三硬脂基山梨糖醇三亞磷酸酯,四(2,4一二一叔一 丁基苯基)4,4’一雙苯撐二膦酸酯,6-異辛氧基一2,4, 8,10—四—叔—丁基一 12Η—雙苯[d,g] — 1,3,2-雙氧 雜磷辛,雙(2,4 一二一叔—丁基一 6-甲基苯基)甲基亞磷 酸酯,雙(2,4—二—叔一 丁基一 6-甲基苯基)乙基亞磷酸 酯,6-氟—2,4,8,10-四—叔一丁基一 12 —甲基一雙 苯[d,g] — 1,3,2_雙氧雜磷辛,2,2’,2"—氮川[三乙 基三(3,,5,5f—四一叔一丁基—1,Γ—二苯基—2,2’ 一二基)亞磷酸酯],2—乙基己基(3,3’,5,5’—四一叔一 丁基—1,Γ一雙基—2,2’一二基)亞磷酸酯,5-丁基—5 一乙基一 2 — (2,4,6 —三一叔一丁基苯氧基)—1 ’ 3 ’ 2- __28____ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ------------·--------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 1268948 A7 B7 五、發明說明(V1' 雙氧雜磷烷。以下的亞磷酸酯是尤其佳的:三(2,4一二-叔-丁基苯基)亞磷酸酯(Irgaf0S®168,Ciba Specialty Chemicals Inc·),三(壬基苯基)亞磷酸酯, (ch3)3c
HX —CH P — F c(ch3)3 • (A)
(CH3)3C
C (ch3)3 (ch3)3c (ch3)3c
p —o — ch2ch2-
(ch3)3c c(ch3)3 N (B) (D) ---------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) c(ch3)3 (ch3)3c
DC
CH3 (e) 29 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) A7 B7
1268948
五、發明說明(J ^H37C~〇—Px ~V~ P—〇-C18 〇—f ^一·〇 5. 苯並呋喃酮和吲盹酮,例如揭示於U.S. 4,325,863 ; U.S. 4,338,244 ; U.S. 5,175,312 ; U.S. 5,216,052 ;U.S· 5,252,643 ; DE-A— 4316611 ; DE— A — 4316622 ; DE—A— 4316876 ; EP—A- 0589839 或 EP—A 一 0591 102的化合物,或3-[4 一(2-乙醯氧基乙氧基)苯 基]—5,7—二一叔—丁基苯並呋喃一 2—酮,5,7-二— 叔—丁基一 3 - [4—(2—硬脂醯氧基乙氧基)苯基]苯並呋喃 一 2- 丽,3,3f —雙[5,7 — 一 —叔—丁基—3 — (4^-[2 —經 基乙氧基]本基)本並咲喃—2 —嗣]’ 5,7 — 一 -叔- 丁某-3 —(4 一乙氧基苯基)苯並呋喃一 2-酮,3 —(4—乙醯氧基 —3,5 —二甲基苯基)—5,7—二一叔一丁基苯並呋喃一 2 —酮,3 —(3,5—二甲基一 4一三甲基乙醯氧基苯基)一 5, 7—二—叔一 丁基苯並呋喃—2—酮,3 —(3,4—二甲基苯 基)—5,7-二—叔—丁基苯並呋喃—2-酮,3 — (2,3-二甲基苯基)—5,7-二一叔一丁基苯並呋喃一 2—酮。 6. 硫代協乘劑,例如二月桂基硫代二丙酸酯或二硬脂基硫 代二丙酸酯。 7. 過氧化物淸潔煙L,例如β -硫代二丙酸的酯,例如月桂 基,硬脂基,十四院基或十三碳基酯,疏基苯咪哇或2- 30 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) #--------1Τ—— 線 A7 1268948 _ B7_ 五、發明說明() 锍基苯咪唑鋅鹽,二丁基二硫代氨基甲酸乙鋅,二-十八 烷基二硫化物,季戊四醇四(β -十二碳烷基锍基)丙酸酯 Ο _ 8.聚醯胺穩定劑,例如銅鹽和碘化物,和/或磷化合物的 組合,及二價錳鹽。 9. 鹼性共-穩定劑,例如蜜胺,聚乙烯基吡咯烷酮,二氰 二醯胺,三烯丙基氰尿酸酯,尿素衍生物,肼衍生物,胺 ,聚醯胺,聚氨基甲酸乙酯,較高脂肪酸的鹼金屬鹽和鹼 土族金屬鹽,例如硬脂酸鈣,硬脂酸鋅,廿二碳酸鎂,硬 脂酸鎂,蓖麻醇酸鈉和棕櫚酸鉀,鄰苯二酚銻或鄰苯二酚 鋅。 10. 親核劑,例如無機物質,像滑石,金屬氧化物,像二 氧化鈦或較佳地是鹼土族金屬的氧化鎂,磷酸鹽,碳酸鹽 或硫酸鹽;有機化合物,像單-或聚羧酸和其鹽,如4-叔一丁基苯甲酸,己二酸,二苯基乙酸,丁二酸鈉或苯甲 酸鈉;聚合物化合物,像離子共聚物(離子體).尤其佳的是 1,3 : 2,4—雙(3,,4,一二甲基苯甲叉)山梨糖醇,1,3 : 2,4—雙(對甲基二苯甲叉)山梨糖醇,及1,3 ·· 2,4 —雙( 苯甲叉)山梨糖醇。 11. 塡充劑和補強劑,例如鈣碳酸鹽,矽酸鹽,玻璃纖維 ,玻璃珠,石棉,滑石,高嶺土,雲母,硫酸鋇,金屬氧 化物和氫氧化物,碳黑,石墨,木材粉和其它天然產物的 粉末或纖維,合成纖維。 12. 分散劑,像聚乙烯氧化物,石鱲或礦物油。 _31 ___ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------------------訂---------^ —^ΟΓ (請先閱讀背面之注意事項再填寫本頁) A7 1268948 〜^___B7_ 五、發明說明(y ) 1其它添加劑,例如增塑劑,潤滑劑,乳化劑,顏料, 染料,流變添加劑,催化劑,流動控制劑,光學增亮劑, 滑動劑,交聯劑,交聯促進劑,鹵素淸潔劑,煙抑止劑, 、防火劑,抗靜電劑,澄淸劑,像經取代的和未經取代的雙 苯甲叉山梨糖醇,苯噁嗪酮UV吸收劑像2,2’一 P—苯撐 ~ 雙(3,1 —苯D惡嗦—4—酮),Cyasorb® 3638(CAS# 18600 ~59—4),和發泡劑。 以下的實例只是作爲說明,並不是要以任何方式限制 本發明。 一般提示-PET瓶子等級的顆粒進行擠出化合,以模 擬當PET熱射出成瓶子雛型,接著再拉伸-吹製成瓶子的 加熱過程。加入添加劑以減少形成乙醛的效果是採用公開 方法後使用熱解附GC _ MS定量分析。每一^天濟出一未經 穩定的PET,以提供一作爲測量乙醛形成的控制聚合物。 擠出-在氮氣及溫度約70°C下,於一烤箱中預先烘烤 PET至溼度約爲30ppm的程度(以一 Mitsubishi VA—06 淫度計測量)。一 Leistritz 18 mm或27 mm共旋轉,非 -交錯雙輥擠出器的各種條件如下:設定溫度=喉部(220 一 23(^0),擠出區和印模(27(TC),實際擠出物熔融溫度是 275 — 280GC,輥旋轉速度100— 11〇 rpm,漏斗餵料器=1〇 —15ppm 〇 PET粒顏色-使用DCI分光計在PET粒上測量包括黃 化指數(YI),和 L*,a*,b* (依據 ASTM D1925,D65 lOdegm 〇 ____ 32 本纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) " (請先閱讀背面之注意事項再填寫本頁) • T • an n «I n n in n J ,镛 MBS M·· MM 言 1268948 A7 ___B7_ 五、發明說明(Ν ) 乙醛分析一乙醛在PET中的濃度使用一熱解附GC〜 MS 方法(B. Nijassen et al·,Packaging Technology 和 Science,i,175(1996) ; S· Yong Lee,SPE ANTEC 1997, pp 857 — 861 ;和 M. Dong et al.,J. Chromatographic Science,11,242(1980))定量測定。實例敘述如下: PET樣品分析(兩次):秤重250毫克的粉狀PET顆 粒(低溫粉碎),置於有5毫升縐摺密封頭部空間的瓶瓿中 '。在一型號5000的Tekmar的靜態頭部空間分析器中以 120 °C加熱樣品瓶瓿1小時。然後該頭部空間氣體(5 cc) 經由一加熱輸送線送至一 Fisons MD- 800 GC —MS系統中 進行乙醛的SIR偵測。乙醛的偵測是由監視其29和44 m/e離子碎片進行。GC - MS的總共離子流(TIC)也於遲滯 區的時間4-8分鐘監視,如此,存在於樣品中的乙醛可由 三個不同偵測器確認。使用一已知含量乙醛値的PET,比 較已知PET樹脂和試驗PET樹脂混合物吸收峰面積的比例 ,則可得試驗混合物中的乙醛含量。 濁霧度— PET混合物使用一 BOY 50M Injection Molder在印模溫度550^(288%)下射出模製成2” x 2” x 60mil的板子。使用BYK—Gardner濁霧計測量濁霧度。“ 濁霧”是不期望的灰化結果。 實例1 :聚(對苯二甲酸乙二酯)(PET)的穩定 使用一未經穩定的商業化PETCCLEARTUF® 7207, Shell)當作控制組PET。數種以下所列的添加劑組合物顯示 一 33 $紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ' " / (請先閱讀背面之注意事項再填寫本頁)
· I I I I 線t----------------------- 1268948 A7 -------B7____ 五、發明說明(γ) 和未經穩定的擠出化合PET比較起來可大幅減少乙醛(ΑΑ) 的量。%ΑΑ減少是和控制組的ΑΑ比較起來的減少量。 控制組PET的總共離子流(TIC)資料操作三次,得到標準偏 .差s = 0.35。每百萬分之一(ppm)添加劑是依據樹脂計算。 配方 添加劑_ A(控制組) 沒有 B 2500 ppm 聚丙烯醯胺,Percol® 333(Ciba)
400 ppm聚(乙烯基醇),PVA C 2500 ppm 聚丙嫌酸胺,perc〇l⑧ 333(Ciba) 1600 ppm cellulose
D 400 ppm聚(乙稀基醇),PVA 1600 ppm纖維素 E 2500 ppm 聚丙烯酸胺,Percol⑧ 351(Ciba)
400 ppm聚(乙烯醇),PVA F 2500 ppm 聚丙烯醯胺,Percor^SSCCiba) 400 ppm聚(乙烯醇),PVA 1600 ppm纖維素 G 750 ppm乙烯/乙烯醇共聚物,40%乙烯 2000 ppm 澱粉 Η 750 ppm乙烯/乙烯醇共聚物,40%乙烯 1000 ppm 激粉 1000 ppm纖維素 使用本發明的添加劑組合物和控制組比較起來可減少 ________34____ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -1 ·1111111 « — III — — — » 1268948 A7 B7 五、發明說明(妁) 乙醛的量·,且提供優良的色澤控制及低濁霧度。 當上述配方中以聚丙烯醯胺,Percol® 333或Percol® 351交換時,可得到良子的醛抑制,低色澤及低濁霧度。 當在上述配方中使用澱粉及纖維素時,可得到優良的醛抑 止,低色澤及低濁霧度。當在上述配方中使用聚(乙烯醇) ,PVA,乙烯/乙烯醇共聚物,40%,38%,32%或27% 乙烯交換時,可得到優良的醛抑止,低色澤和低濁霧度。 35 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公爱 n n n n 1« ϋ n ·ϋ I- I 11 1 I · ϋ n if n I n n 一 ον a n n n n ϋ n ϋ 1 (請先閱讀背面之注意事項再填寫本頁)
Claims (1)
- A8B8C8D8 126894今终^ j^日修(更)正本 六、申請專利範圍 1 · 一種聚酯組成物,其中該聚酯是經穩定抑止在熔 融加工期間形成醛的污染物,包括 (a) —聚酯,及 (b) —有效穩定量的添加劑組合物,其中添加劑是選自 兩種不同的族群,這些族群爲 (ii.)多氫醇類,其是選自澱粉,纖維素’糖 或糖醇,三甲醇丙烷,三乙醇丙烷,丙三醇,山梨糖醇’ 季戊四醇或二季戊四醇,降解的澱粉(糊精和環狀糊精)’ 麥芽糖和其衍生物,麥芽糖醇,麥芽五糖水合物,麥芽七 糖’麥芽四糖,麥芽糖單水合物,D,L一葡萄糖,右旋糖 ,蔗糖和D-甘露醇,和 (出·)聚丙烯醯胺,聚甲丙烯醯胺或一和至少一乙烯 鍵未經取代共單體之丙烯醯胺或或甲丙烯醯胺 共聚物。 2 ·如申請專利範圍第1項之組成物,其中成份(a)的 聚酯是99.9%重量的經穩定組成物;和成份(b)的添加 劑組合物是5至0.1%重量的經穩定組成物。 3 ·如申請專利範圍第1項之組成物,其中成份(a)的 聚酯是聚(對苯二甲酸乙二酯)或聚(乙撐2,6-禁一 2,6-二羧酸酯)。 4 ·如申請專利範圍第1項之組成物,其中族群 (iii·)是聚丙烯醯胺,聚甲丙烯醯胺,或丙烯醯胺或甲丙烯 醯胺和另一含乙烯未飽和鍵單體的共聚物,此含乙烯未飽 和鍵單體是丙烯醯胺,甲丙烯醯胺,苯乙烯,乙烯,烷基 1 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂: 線一 1268948 g D8 六、申請專利範圍 丙烯酸酯,烷基甲丙烯酸酯,N-乙烯基-2—吡咯烷酮或 丙烯腈。 5·—種防止聚酯在熔融加工時形成醛污染物的方法 ’包括在該聚酯中加入一有效穩定量的添加劑組合物,其 中此添加劑是選自兩種不同的族群,這些族群爲(ii.)多氫 醇類’其是選自澱粉,纖維素,糖或糖醇,三甲醇丙院, 三乙醇丙烷,丙三醇,山梨糖醇,季戊四醇或二季戊四醇 ,降解的澱粉(糊精和環狀糊精),麥芽糖和其衍生物,麥 芽糖醇,麥芽五糖水合物,麥芽七糖,麥芽四糖,麥芽糖 單水合物,D,L一葡萄糖,右旋糖,蔗糖和D-甘露醇, 和 (iii·)聚丙烯醯胺,聚甲丙烯醯胺或一和至少一乙 烯鍵未經取代共單體之丙烯醯胺或或甲丙烯醯胺共聚物。 6 · —種單-或多層塑膠容器,其是經穩定防此該容 器在熔融加工時形成醛污染物,包括至少一含有下列成份 的結構層, (a) —聚酯,及 (b) —有效穩定量的添加劑組合物’其中此添加劑是選 自兩種下列的成份 (ii.)多氫醇類,其是選自源粉’纖維素,糖 或糖醇,三甲醇丙烷,三乙醇丙烷,丙三醇, 山梨糖醇,季戊四醇或二季戊四醇,降解的澱 粉(糊精和環狀糊精),麥芽糖和其衍生物,麥 芽糖醇,麥芽五糖水合物’麥芽七糖,麥芽四 糖,麥芽糖單水合物,D,L-葡萄糖,右旋糖 2 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公愛) (請先閲讀背面之注意事項再填寫本頁) 訂 線一 1268948 六、申請專利範圍 ,蔗糖和D-甘露醇,和 (iii.)聚丙烯醯胺,聚甲丙烯醯胺或一和至少一乙烯 鍵未經取代共單體之丙烯醯胺或或甲丙烯醯胺 共聚物。 7 · —種單-或多層塑膠薄膜,其是經穩定防此該 薄膜在熔融加工時形成醛污染物,包括至少一含有下列成 份的結構層, .(a)—聚酯,及 (b) —有效穩定量的添加劑組合物,其中此添加劑是選 自兩種下列的成份 (ii.)多氫醇類,其是選自澱粉,纖維素,糖 或糖醇,三甲醇丙烷,三乙醇丙烷,丙三醇, 山梨糖醇,季戊四醇或二季戊四醇,降解的澱 粉(糊精和環狀糊精),麥芽糖和其衍生物,麥 芽糖醇,麥芽五糖水合物,麥芽七糖,麥芽四 糖,麥芽糖單水合物,D,L-葡萄糖,右旋糖 ,蔗糖和D-甘露醇,和 (iii.)聚丙烯醯胺,聚甲丙烯醯胺或一和至少一乙烯 鍵未經取代共單體之丙烯醯胺或或甲丙烯醯胺 共聚物。 8·如申請專利範圍第6項之單-或多層塑膠容器, 其是一種剛性瓶子。 9 ·如申請專利範圍第1項之組成物,其中成份(b)是 (請先閲讀背面之注意事項再填寫本頁) Tf 、*?*t* 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1268948 § D8 六、申請專利範圍 用於防止一聚酯在熔融加工時形成醛污染物。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)
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| ATE282667T1 (de) * | 1999-09-27 | 2004-12-15 | Ciba Sc Holding Ag | Verfahren zur herstellung einer polyesterzusammensetzung mit niedrigem restaldehydgehalt |
| US6908650B2 (en) * | 2001-03-02 | 2005-06-21 | Ciba Specialty Chemicals Corporation | Polyester and polyamide compositions of low residual aldehyde content |
| CA2435928A1 (en) | 2001-03-28 | 2002-10-10 | Ciba Specialty Chemicals Holding Inc. | Process for preparing a stabilized polyester |
| CA2454399C (en) * | 2001-08-13 | 2010-01-26 | Ciba Specialty Chemicals Holding Inc. | Polyester compositions of low residual aldehyde content |
| US6709746B2 (en) * | 2002-06-05 | 2004-03-23 | Arteva North America S.á.r.l. | Reducing concentration of organic materials with substituted cyclodextrin compound in polyester packaging materials |
| WO2005040261A1 (en) * | 2003-10-15 | 2005-05-06 | Polyone Corporation | Use of tocopherol to scavenge acetaldehyde in polyethylene terephthalate containers |
| EP1838798A2 (en) * | 2004-12-06 | 2007-10-03 | Constar International Inc. | Blends of oxygen scavenging polyamides with polyesters which contain zinc and cobalt |
| PL1824920T3 (pl) * | 2004-12-06 | 2010-02-26 | Eastman Chem Co | Koncentraty kobaltu oparte na poliestrze do kompozycji odtleniających |
| US7375154B2 (en) * | 2004-12-06 | 2008-05-20 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
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-
2001
- 2001-12-19 AT AT01272651T patent/ATE352583T1/de not_active IP Right Cessation
- 2001-12-19 DE DE60126340T patent/DE60126340T2/de not_active Expired - Lifetime
- 2001-12-19 CA CA2433126A patent/CA2433126C/en not_active Expired - Fee Related
- 2001-12-19 WO PCT/EP2001/015011 patent/WO2002053643A1/en not_active Ceased
- 2001-12-19 EP EP01272651A patent/EP1355986B1/en not_active Expired - Lifetime
- 2001-12-19 JP JP2002555161A patent/JP2004517187A/ja active Pending
- 2001-12-19 ES ES01272651T patent/ES2279791T3/es not_active Expired - Lifetime
- 2001-12-20 US US10/034,048 patent/US6790499B2/en not_active Expired - Fee Related
- 2001-12-27 TW TW090132494A patent/TWI268948B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002053643A1 (en) | 2002-07-11 |
| EP1355986B1 (en) | 2007-01-24 |
| DE60126340D1 (de) | 2007-03-15 |
| CA2433126A1 (en) | 2002-07-11 |
| ES2279791T3 (es) | 2007-09-01 |
| ATE352583T1 (de) | 2007-02-15 |
| US20020137856A1 (en) | 2002-09-26 |
| US6790499B2 (en) | 2004-09-14 |
| EP1355986A1 (en) | 2003-10-29 |
| CA2433126C (en) | 2010-04-06 |
| DE60126340T2 (de) | 2007-11-08 |
| JP2004517187A (ja) | 2004-06-10 |
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