JPH10512006A - 生分解可能なポリマー、その製法並びに生分解可能な成形体の製造のためのその使用 - Google Patents
生分解可能なポリマー、その製法並びに生分解可能な成形体の製造のためのその使用Info
- Publication number
- JPH10512006A JPH10512006A JP52138696A JP52138696A JPH10512006A JP H10512006 A JPH10512006 A JP H10512006A JP 52138696 A JP52138696 A JP 52138696A JP 52138696 A JP52138696 A JP 52138696A JP H10512006 A JPH10512006 A JP H10512006A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- biodegradable
- weight
- polyesteramide
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 52
- 229920002988 biodegradable polymer Polymers 0.000 title claims abstract description 28
- 239000004621 biodegradable polymer Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims abstract description 99
- 239000000203 mixture Substances 0.000 claims abstract description 92
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 37
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 32
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001361 adipic acid Substances 0.000 claims abstract description 18
- 150000001408 amides Chemical class 0.000 claims abstract description 18
- 239000012778 molding material Substances 0.000 claims abstract description 18
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 17
- 230000008018 melting Effects 0.000 claims abstract description 17
- 238000009757 thermoplastic moulding Methods 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 10
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims abstract description 8
- 239000008107 starch Substances 0.000 claims abstract description 8
- 235000019698 starch Nutrition 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- -1 Phenyl Chemical group 0.000 claims description 34
- 125000005442 diisocyanate group Chemical group 0.000 claims description 20
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229920000229 biodegradable polyester Polymers 0.000 claims description 14
- 239000004622 biodegradable polyester Substances 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000002361 compost Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920000765 poly(2-oxazolines) Polymers 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000009264 composting Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 238000010137 moulding (plastic) Methods 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 8
- 150000002009 diols Chemical class 0.000 abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000002253 acid Substances 0.000 description 21
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 20
- 238000005259 measurement Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000005809 transesterification reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 102000004190 Enzymes Human genes 0.000 description 10
- 108090000790 Enzymes Proteins 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229920001634 Copolyester Polymers 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 229920000747 poly(lactic acid) Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000001384 succinic acid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 5
- 239000011135 tin Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 4
- 230000007515 enzymatic degradation Effects 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-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
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- 241000196324 Embryophyta Species 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Nonanedioid acid Natural products OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
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- 239000002585 base Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- PVBLJPCMWKGTOH-UHFFFAOYSA-N 1-aminocyclohexan-1-ol Chemical compound NC1(O)CCCCC1 PVBLJPCMWKGTOH-UHFFFAOYSA-N 0.000 description 1
- BVJYDVKFDDPCAW-UHFFFAOYSA-N 1-aminocyclopentan-1-ol Chemical compound NC1(O)CCCC1 BVJYDVKFDDPCAW-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
- C08G18/606—Polyester-amides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Biological Depolymerization Polymers (AREA)
- Materials For Medical Uses (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1. 生分解可能なポリエステルアミドP1において、主に次の成分: (a1) 主に次の成分からなる混合物: アジピン酸又はそのエステル形成誘導体又はその混合物 35〜95 モル%、 テレフタル酸又はそのエステル形成誘導体又はその混合物 5〜65 モル%及び スルホネート基含有化合物 0〜5モル%(ここで、個々のモル%表 示の合計は、100モル%である)及び (a2) 主に次の成分からなる混合物: (a21) C2〜C6−アルカンジオール及びC5〜C10−シクロアル カンジオールからなる群から選択されるジヒドロキシ化合物99.5〜0.5モ ル%、 (a22) アミノ−C2〜C12−アルカノール又はアミノ−C5〜C10 −シクロアルカノール 0.5〜99.5モル%及び (a23) ジアミノ−C1〜C8−アルカン 0〜50モル% (a24) 一般式I: [式中、R1は、単結合、(CH2)q−アルキレン基(q=2、3又は4) 又はフェニレン基を表す]の2,2′−ビスオキサゾリン 0〜50モル%(ここ で、個々のモル%表示の合計は、100モル%であり、かつ(a1)と(a1) とのモル比は、0.4:1〜1.5:1の範囲で選択される) からなる混合物を反応させることにより得られるが、但し、このポリエステルア ミドP1は、4000〜40000g/モルの範囲の分子量(Mn)、30〜3 50g/mlの範囲の粘度数(o−ジクロルベンゼン/フェノール(重量比50 /50)中で、ポリエステルアミドP1 0.5重量%の濃度で、25℃で測定 )及び50〜220℃の範囲の融点を有し、更に、使用成分(a1)のモル量に 対して、少なくとも3個のエステル形成可能な基を有する化合物D0〜5モル% を、ポリエステルアミドP1の製造のために使用することを特徴とする、生分解 可能なポリエステルアミドP1。 2. 生分解可能なポリエステルアミドP2において、主に、次の成分: (b1) 主に次の成分からなる混合物: アジピン酸又はそのエステル形成誘導体又はそれらの混合物 35〜 95モル%、 テレフタル酸又はそのエステル形成誘導体又はそれらの混合物 5〜 65モル%及び スルホネート基含有化合物 0〜5モル%(この際、個々のモル% 表示の合計は、100モル%である)、 (b2) 混合物(a2)、(この際、(b1)と(b2)とのモル比は、0. 4:1〜1.5:1の範囲から選択する) (b3) アミノカルボン酸B1 0.01〜40重量%(成分(b1)に対し て)及び (b4) 化合物D 0〜5モル%(成分b1に対して) からなる混合物を反応させることにより得られ、その際、 アミノカルボン酸B1は、天然アミノ酸、最高18000g/モルの分子量を 有し、4〜6個のC−原子を有するジカルボン酸及び4〜10個のC−原子を有 するジアミンとの重縮合により得られるポリアミド及び式IIa又はIIb: [式中、pは、1〜1500の整数を、かつrは、1〜 4の整数を表し、かつGは、フェニレン、−(CH2)n−(ここで、nは、1〜1 2の整数を表す)、−C(R2)H−及び−C(R2)HCH2(ここで、R2は、メチ ル又はエチルである)からなる群から選択されている基である]により定義される 化合物並びに繰り返し単位III: [式中、R3は、水素、C1〜C6−アルキル、C5〜C8−シクロアルキル、未置換 か、又はC1〜C4−アルキル基で3回まで置換されたフェニル又はテトラヒドロ フリルである]を有するポリオキサゾリンからなる群から選択されており、その 際、ポリエステルアミドP2は、4000〜40000g/モルの範囲の分子量 (Mn)、30〜450g/mlの範囲の粘度数(o−ジクロルベンゼン/フェ ノール(重量比50/50)中、ポリエステルアミドP2 0.5重量%の濃度 、25℃の温度で測定)及び50〜255℃の範囲の融点を有する、生分解可能 なポリエステルアミドP2。 3. 生分解可能なポリエステルアミドQ1において、主に次の成分: (c1) ポリエステルアミドP1、 (c2) アミノカルボン酸B1 0.01〜50重量%((c1)に対して) 及び (c3) 化合物D 0〜5モル%(P1の製造に由来する成分(a1)に対し て) からなる混合物を反応させることにより得られ、その際、このポリエステルアミ ドQ1は、5000〜50000g/モルの範囲の分子量(Mn)、30〜45 0g/mlの範囲の粘度数(o−ジクロルベンゼン/フェノール(50/50重 量%)中、ポリエステルアミドQ1 0.5重量%の濃度、25℃の温度で測定 )及び50〜255℃の範囲の融点を有する、生分解可能なポリエステルアミド Q1。 4. 5000〜50000g/モルの範囲の分子量(Mn)、30〜450 g/mlの範囲の粘度数(o−ジクロルベンゼン/フェノール(50/50重量 %)中、ポリエステルアミドQ2 0.5重量%の濃度、25℃の温度で測定) 及び50〜220℃の範囲の融点を有する生分解可能なポリエステルアミドQ2 において、主に次の成分: (d1) ポリエステルアミドP1 95〜99.9 重量%、 (d2) ジイソシアネートC1 0.1〜5重量%及び (d3) 化合物D 0〜5モル%(P1の製造に由来する成分(a1)に対し て)からなる混合物を反応させることにより得られる、生分解可能なポリエステ ルアミドQ2。 5. 6000〜50000g/モルの範囲の分子量(Mn)、30〜450 g/mlの範囲の粘度数(o−ジクロルベンゼン/フェノール(重量比50/5 0)中、ポリマーT1 0.5重量%の濃度、25℃の温度で測定)及び50〜 255℃の範囲の融点を有する生分解可能なポリマーT1において、 請求項3に記載のポリエステルアミドQ1と、 (e1) ジイソシアネートC1 0.1〜5重量%(ポリエステルアミドQ1 に対して)並びに (e2) 化合物D 0〜5モル%(ポリエステルアミドP1を介してのポリエ ステルアミドQ1の製造に由来する成分(a1)に対して) とを反応させることにより得られる、生分解可能なポリマーT1。 6. 6000〜50000g/モルの範囲の分子量(Mn)、30〜450 g/mlの範囲の粘度数(o−ジクロルベンゼン/フェノール(重量比50/5 0)中、ポリマーT2 0.5重量%の濃度、25℃の温度で測定)及び50〜 255℃の範囲の融点を有する生分解可能なポリマーT2において、 ポリエステルアミドQ2と、 (f1) アミノカルボン酸B1 0.01〜50重量%(ポリエステルアミド Q2に対して)並びに (f2) 化合物D 0〜5モル%(ポリエステルア ミドP1を介してのポリエステルアミドQ2の製造に由来する成分(a1)に対 して) とを反応させることにより得られる、生分解可能なポリマーT2。 7. 6000〜50000g/モルの範囲の分子量(Mn)、30〜450 g/mlの範囲の粘度数(o−ジクロルベンゼン/フェノール(重量比50/5 0)中、ポリマーT3 0.5重量%の濃度、25℃の温度で測定)及び50〜 255℃の範囲の融点を有する生分解可能なポリマーT3において、 (g1) ポリエステルアミドP2又は (g2) 主にポリエステルアミドP1及びアミノカルボン酸B1 0.01〜 50重量%(ポリエステルアミドP1に対して)からなる混合物又は (g3) 主に、相互に種々異なる組成を有するポリエステルアミドP1からな る混合物と、 ジイソシアネートC1 0.1〜5重量%(使用ポリエステルアミドの量に対 して)並びに 化合物D 0〜5モル%(使用ポリエステルアミド(g1)〜(g3)の製造 のために使用された成分(a1)のそれぞれのモル量に対して)とを反応させる ことにより得られる、生分解可能なポリマーT3。 8. 生分解可能な熱可塑性成形材料T4において、 (h1) P1、P2、Q2及びT3からなる群から選択されるポリマー 99 .5〜0.5重量%と、 (h2) 一般式IVa又はIVb: [式中、xは1〜1500の整数を、かつyは、1〜4の整数を表し、 かつMは、フェニレン、−(CH2)z−(ここで、zは、1〜5の整数を表す)、 −C(R2)H−及び−C(R2)HCH2(ここで、R2は、メチル又はエチルである) からなる群から選択される1個の基である]のヒドロキシカルボン酸H1 0.5 〜99.5重量%とを 自体公知の方法で混合することにより得られる、生分解可能な熱可塑性成形材料 T4。 9. 請求項1に記載の生分解可能なポリエステルアミドP1を、自体公知の 方法で製造する方法において、主に次の成分: (a1) 主に次の成分からなる混合物: アジピン酸又はそのエステル形成誘導体又はその混合物 35〜95 モル%、 テレフタル酸又はそのエステル形成誘導体又はその混合物 5〜65 モル%及び スルホネート基含有化合物 0〜5モル%(ここで、個々のモル%表 示の合計は、100モル%である)及び (a2) 主に次の成分からなる混合物: (a21) C2〜C6−アルカンジオール及びC5〜C10−シクロアル カンジオールからなる群から選択されるジヒドロキシ化合物99.5〜0.5モ ル%、 (a22) アミノ−C2〜C12−アルカノール又はアミノ−C5〜C10 −シクロアルカノール 0.5〜99.5モル%及び (a23) ジアミノ−C1〜C8−アルカン 0〜50モル% (a24) 一般式I: [式中、R1は、単結合、(CH2)q−アルキレン基(q=2、3又は4) 又はフェニレン基を表す]の2,2′−ビスオキサゾリン 0〜50モル%(ここ で、個々のモル%表示の合計は、100モル%である) からなり、(a1)と(a2)とのモル比が、0.4:1〜1.5:1の範囲か ら選択される混合物及び少なくとも3個のエステル形成可能な基を有する化合物 D0〜5モル%(使用成分(a1)のモル量に対して)を反応させることを特徴 とする、請求項1に記載の生分解可能なポリエステルアミドP1の製法。 10. 請求項2に記載の生分解可能なポリエステルアミドP2を、自体公知 の方法で製造する方法において、主に、次の成分: (b1) 主に次の成分からなる混合物: アジピン酸又はそのエステル形成誘導体又はそれらの混合物 20〜 95モル%、 テレフタル酸又はそのエステル形成誘導体又はそれらの混合物 5〜 80モル%及び スルホネート基含有化合物 0〜5モル%(この際、個々のモル%表 示の合計は、100モル%である)、 (b2) 混合物(a2)、(この際、(b1)と(b2)とのモル比は、0. 4:1〜1.5:1の範囲から選択する) (b3) アミノカルボン酸B1 0.01〜40重量%(成分(b1)に対し て)及び (b4) 化合物D 0〜5モル%(成分b1に対して) からなる混合物を反応させることを特徴とする、請求項2に記載の生分解可能な ポリエステルアミドP2の製法。 11. 請求項3に記載の生分解可能なポリエステルアミドQ1を自体公知の 方法で製造する方法において、主に次の成分: (c1) ポリエステルアミドP1、 (c2) アミノカルボン酸B1 0.01〜50重量%((c1)に対して) 及び (c3) 化合物D 0〜5モル%(P1の製造に由来する成分(a1)に対し て) からなる混合物を反応させることを特徴とする、請求項3に記載の生分解可能な ポリエステルアミドQ1の製法。 12. 請求項4に記載の生分解可能なポリエステルアミドQ2を、自体公知 の方法で製造する方法において、主に次の成分: (d1) ポリエステルアミドP1 95〜99.9重量%、 (d2) ジイソシアネートC1 0.1〜5重量%及び (d3) 化合物D 0〜5モル%(P1の製造に由来する成分(a1)に対し て) からなる混合物を反応させることを特徴とする、請求項4に記載の生分解可能な ポリエステルアミドQ2の製法。 13. 請求項5に記載の生分解可能なポリマーT1を、自体公知の方法で製 造する方法において、請求 項3に記載のポリエステルアミドQ1と、 (e1) ジイソシアネートC1 0.1〜5重量%(ポリエステルアミドQ1 に対して)並びに、 (e2) 化合物D 0〜5モル%(ポリエステルアミドP1を介してのポリエ ステルアミドQ1の製造に由来する成分(a1)に対して) とを反応させることを特徴とする、請求項5に記載の生分解可能なポリマーT1 の製法。 14. 請求項6に記載の生分解可能なポリマーT2を、自体公知の方法で製 造する方法において、ポリエステルアミドQ2と、 (f1) アミノカルボン酸B1 0.01〜50重量%(ポリエステルアミド Q2に対して)並びに (f2) 化合物D 0〜5モル%(ポリエステルアミドP1を介してポリエス テルアミドQ2の製造に由来する成分(a1)に対して) とを反応させることを特徴とする、請求項6に記載の生分解可能なポリマーT2 の製法。 15. 請求項7に記載の生分解可能なポリマーT3を、自体公知の方法で製 造する方法において、 (g1) ポリエステルアミドP2又は (g2) 主にポリエステルアミドP1及びアミノカルボン酸B1 0.01〜 50重量%(ポリ エステルアミドP1に対して)からなる混合物又は (g3) 主に、相互に種々異なる組成を有するポリエステルアミドP1からな る混合物と、 ジイソシアネートC1 0.1〜5重量%(使用ポリエステルアミドの量に対 して)並びに化合物D0〜5モル%(使用ポリエステルアミド(g1)〜(g3 )の製造のために使用された成分(a1)のそれぞれのモル量に対して)とを反 応させることを特徴とする、請求項7に記載の生分解可能なポリマーT3の製法 。 16. 請求項8に記載の生分解可能な熱可塑性成形材料T4を、自体公知の 方法で製造する方法において、 P1、P2、Q2及びT3からなる群から選択されるポリマー 99.5〜0 .5重量%と、 ヒドロキシカルボン酸H1 0.5〜99.5重量%とを 混合することを特徴とする、請求項8に記載の生分解可能な熱可塑性成形材料 T4の製法。 17. 請求項1から7に記載の生分解可能なポリマー又は請求項8に記載の 、又は請求項9から16の記載により製造された熱可塑性成形材料を、たい肥に なりうる成形体を製造するために使用すること。 18. 請求項1から7に記載の生分解可能なポリ マー又は請求項8に記載の、又は請求項9から16の記載により製造された熱可 塑性成形材料を、接着剤を製造するために使用すること。 19. 請求項17に記載の使用により得られる、たい肥になりうる成形体。 20. 請求項18に記載の使用により得られる、接着剤。 21. 請求項1から7に記載の生分解可能なポリマー又は請求項8に記載の 、又は請求項9から16の記載により製造された熱可塑性成形材料を、主に、本 発明のポリマー及びデンプンを含有する生分解可能なブレンドを製造するために 使用すること。 22. 請求項21に記載の使用により得られる、生分解可能なブレンド。 23. 請求項22に記載の生分解可能なブレンドを自体公知の方法で製造す る方法において、デンプンと本発明のポリマーを混合することを特徴とする、請 求項22に記載の生分解可能なブレンドの製法。 24. 請求項1から7に記載の生分解可能なポリマー又は請求項8に記載の 、又は請求項9から16の記載により製造された熱可塑性成形材料を、生分解可 能なフォームを製造するために使用すること。 25. 請求項24に記載の使用により得られる、生分解可能なフォーム。
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| Application Number | Priority Date | Filing Date | Title |
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| DE19500757.3 | 1995-01-13 | ||
| DE19500757A DE19500757A1 (de) | 1995-01-13 | 1995-01-13 | Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper |
| PCT/EP1995/002493 WO1996021689A2 (de) | 1995-01-13 | 1995-06-27 | Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper |
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| JP (1) | JP3471809B2 (ja) |
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| AT (1) | ATE170890T1 (ja) |
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| JP3179177B2 (ja) * | 1992-04-10 | 2001-06-25 | 昭和高分子株式会社 | ウレタン結合を含む脂肪族ポリエステル |
| DE19500754A1 (de) | 1995-01-13 | 1996-07-18 | Basf Ag | Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper |
| DE19500755A1 (de) | 1995-01-13 | 1996-07-18 | Basf Ag | Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper |
| US5661193A (en) | 1996-05-10 | 1997-08-26 | Eastman Chemical Company | Biodegradable foamable co-polyester compositions |
-
1995
- 1995-01-13 DE DE19500757A patent/DE19500757A1/de not_active Withdrawn
- 1995-06-27 PL PL32129795A patent/PL321297A1/xx unknown
- 1995-06-27 EP EP95925769A patent/EP0802939B1/de not_active Expired - Lifetime
- 1995-06-27 JP JP52138696A patent/JP3471809B2/ja not_active Expired - Fee Related
- 1995-06-27 DE DE59503552T patent/DE59503552D1/de not_active Expired - Lifetime
- 1995-06-27 DK DK95925769T patent/DK0802939T3/da active
- 1995-06-27 HU HU9800040A patent/HU223825B1/hu not_active IP Right Cessation
- 1995-06-27 AU AU29782/95A patent/AU710607B2/en not_active Ceased
- 1995-06-27 NZ NZ289824A patent/NZ289824A/en not_active IP Right Cessation
- 1995-06-27 WO PCT/EP1995/002493 patent/WO1996021689A2/de not_active Ceased
- 1995-06-27 CZ CZ19972089A patent/CZ292656B6/cs not_active IP Right Cessation
- 1995-06-27 KR KR1019970704783A patent/KR100342144B1/ko not_active Expired - Fee Related
- 1995-06-27 CA CA 2209495 patent/CA2209495C/en not_active Expired - Fee Related
- 1995-06-27 CN CN95197314A patent/CN1070879C/zh not_active Expired - Fee Related
- 1995-06-27 AT AT95925769T patent/ATE170890T1/de not_active IP Right Cessation
- 1995-06-27 BR BR9510193A patent/BR9510193A/pt not_active Application Discontinuation
- 1995-06-27 US US08/860,755 patent/US6353084B1/en not_active Expired - Lifetime
- 1995-06-27 ES ES95925769T patent/ES2120759T3/es not_active Expired - Lifetime
-
1997
- 1997-07-11 NO NO19973228A patent/NO311032B1/no not_active IP Right Cessation
- 1997-07-11 FI FI972963A patent/FI116842B/fi active IP Right Grant
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6521717B1 (en) | 1999-10-05 | 2003-02-18 | Nippon Shokubai Co., Ltd. | Biodegradable polyester resin composition and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| NO973228D0 (no) | 1997-07-11 |
| FI116842B (fi) | 2006-03-15 |
| HU223825B1 (hu) | 2005-02-28 |
| EP0802939A2 (de) | 1997-10-29 |
| US6353084B1 (en) | 2002-03-05 |
| NO973228L (no) | 1997-09-11 |
| ES2120759T3 (es) | 1998-11-01 |
| CZ292656B6 (cs) | 2003-11-12 |
| HUT77457A (hu) | 1998-04-28 |
| ATE170890T1 (de) | 1998-09-15 |
| JP3471809B2 (ja) | 2003-12-02 |
| NO311032B1 (no) | 2001-10-01 |
| MX9704806A (es) | 1997-10-31 |
| FI972963A7 (fi) | 1997-07-11 |
| WO1996021689A2 (de) | 1996-07-18 |
| CZ208997A3 (cs) | 1998-04-15 |
| WO1996021689A3 (de) | 1996-09-06 |
| NZ289824A (en) | 1998-11-25 |
| EP0802939B1 (de) | 1998-09-09 |
| PL321297A1 (en) | 1997-12-08 |
| AU2978295A (en) | 1996-07-31 |
| FI972963A0 (fi) | 1997-07-11 |
| DK0802939T3 (da) | 1999-06-07 |
| AU710607B2 (en) | 1999-09-23 |
| KR100342144B1 (ko) | 2002-08-22 |
| CA2209495A1 (en) | 1996-07-18 |
| KR19980701394A (ko) | 1998-05-15 |
| BR9510193A (pt) | 1997-12-23 |
| CN1173190A (zh) | 1998-02-11 |
| DE59503552D1 (de) | 1998-10-15 |
| CN1070879C (zh) | 2001-09-12 |
| DE19500757A1 (de) | 1996-07-18 |
| CA2209495C (en) | 2006-08-01 |
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