JP5689599B2 - １，４−シクロヘキサンジメタノールを含むポリエステルを製造する方法 - Google Patents
１，４−シクロヘキサンジメタノールを含むポリエステルを製造する方法 Download PDFInfo
- Publication number
- JP5689599B2 JP5689599B2 JP2009507729A JP2009507729A JP5689599B2 JP 5689599 B2 JP5689599 B2 JP 5689599B2 JP 2009507729 A JP2009507729 A JP 2009507729A JP 2009507729 A JP2009507729 A JP 2009507729A JP 5689599 B2 JP5689599 B2 JP 5689599B2
- Authority
- JP
- Japan
- Prior art keywords
- dibasic acid
- component
- diol
- acid component
- mole percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000728 polyester Polymers 0.000 title claims description 122
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 title claims description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002253 acid Substances 0.000 claims description 251
- 150000002009 diols Chemical class 0.000 claims description 231
- 238000006243 chemical reaction Methods 0.000 claims description 150
- 238000000034 method Methods 0.000 claims description 143
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 126
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 78
- 230000008569 process Effects 0.000 claims description 77
- 229920001169 thermoplastic Polymers 0.000 claims description 38
- 239000004416 thermosoftening plastic Substances 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 description 71
- 238000005886 esterification reaction Methods 0.000 description 70
- 230000032050 esterification Effects 0.000 description 65
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 39
- 229920000642 polymer Polymers 0.000 description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 28
- 239000010936 titanium Substances 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 21
- 229910052719 titanium Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 229920001634 Copolyester Polymers 0.000 description 19
- 150000001991 dicarboxylic acids Chemical class 0.000 description 17
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- -1 sheet Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 239000003086 colorant Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 8
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 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 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- QRMPKOFEUHIBNM-UHFFFAOYSA-N 1,4-dimethylcyclohexane Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- ZVMAGJJPTALGQB-UHFFFAOYSA-N 2-[3-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=CC(OCC(O)=O)=C1 ZVMAGJJPTALGQB-UHFFFAOYSA-N 0.000 description 2
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 2
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 2
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 2
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-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
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 2
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 2
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000033458 reproduction Effects 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/414,466 | 2006-04-28 | ||
| US11/414,466 US7211634B1 (en) | 2006-04-28 | 2006-04-28 | Process for the preparation of polyesters containing 1,4-cyclohexanedimethanol |
| PCT/US2007/009484 WO2007127117A2 (en) | 2006-04-28 | 2007-04-18 | Process for the preparation of polyesters containing 1,4-cyclohexanedimethanol |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2009535450A JP2009535450A (ja) | 2009-10-01 |
| JP2009535450A5 JP2009535450A5 (https=) | 2010-04-22 |
| JP5689599B2 true JP5689599B2 (ja) | 2015-03-25 |
Family
ID=37991420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009507729A Expired - Fee Related JP5689599B2 (ja) | 2006-04-28 | 2007-04-18 | １，４−シクロヘキサンジメタノールを含むポリエステルを製造する方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US7211634B1 (https=) |
| EP (1) | EP2013260B1 (https=) |
| JP (1) | JP5689599B2 (https=) |
| KR (1) | KR101389255B1 (https=) |
| CN (1) | CN101466760B (https=) |
| WO (1) | WO2007127117A2 (https=) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8586701B2 (en) | 2005-10-28 | 2013-11-19 | Eastman Chemical Company | Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
| JP5635411B2 (ja) | 2007-11-21 | 2014-12-03 | イーストマン ケミカル カンパニー | プラスチック製哺乳瓶、他のブロー成形物品及びそれらの製造方法 |
| KR101837793B1 (ko) * | 2010-10-13 | 2018-03-12 | 데이진 가부시키가이샤 | 전선 피복용 수지 조성물 및 그것을 사용한 절연 전선 |
| US20130029068A1 (en) * | 2011-07-28 | 2013-01-31 | Eastman Chemical Company | Extrusion blow molded articles |
| RU2480486C1 (ru) * | 2011-12-16 | 2013-04-27 | Учреждение Российской академии наук Институт катализа им. Г.К. Борескова Сибирского отделения РАН | Способ получения алифатических и алифатически-ароматических полиэфиров |
| KR20140018468A (ko) * | 2012-07-30 | 2014-02-13 | 삼성정밀화학 주식회사 | 방향족 디카르복실산 화합물의 분할 투입에 의한 생분해성 폴리에스테르 공중합체의 제조방법 |
| US10465335B2 (en) | 2015-09-04 | 2019-11-05 | Dic Corporation | Polyester resin, method for producing polyester resin, resin composition, resin-clad fabric, and method for producing resin-clad fabric |
| IT201600078950A1 (it) * | 2016-07-27 | 2018-01-27 | Versalis Spa | Metodo di sintesi regioselettiva di poliesteri da dioli asimmetrici. |
| WO2020131778A1 (en) * | 2018-12-17 | 2020-06-25 | Eastman Chemical Company | Copolyester from terephthalic acid containing low diethylene glycol |
| JP7697369B2 (ja) * | 2020-04-15 | 2025-06-24 | 東洋紡株式会社 | 共重合ポリエステル樹脂、成形品、熱収縮性フィルム、及び繊維 |
| TWI803384B (zh) * | 2022-07-08 | 2023-05-21 | 南亞塑膠工業股份有限公司 | 透明pet材料及其製造方法以及pet產品 |
Family Cites Families (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE592181A (https=) | 1955-12-22 | |||
| US3070575A (en) | 1958-01-27 | 1962-12-25 | Du Pont | Process for the preparation of polyesters from dicarboxylic acids and bis (hydroxy-alkyl) esters |
| US3271370A (en) | 1961-11-10 | 1966-09-06 | Poly(l,x-cyclohexylenedimethylene ter- ephthalate) process using substantial- ly equal proportions of reactants | |
| AT289391B (de) | 1966-12-30 | 1971-04-26 | Alpine Chemische Ag | Verfahren zur Herstellung von Polyestern und Copolyestern |
| US3487049A (en) | 1967-01-04 | 1969-12-30 | Du Pont | Process for producing polyethylene terephthalate |
| US4020049A (en) | 1967-09-14 | 1977-04-26 | The Goodyear Tire & Rubber Company | Process for preparing polyester resin |
| US3551386A (en) | 1968-06-26 | 1970-12-29 | Monsanto Co | Polyester polymerization process,prepolymer and product |
| US3787370A (en) | 1971-03-19 | 1974-01-22 | Teijin Ltd | Process for the preparation of substan-tially linear polyesters of low free carboxyl group content |
| US3984379A (en) | 1971-12-06 | 1976-10-05 | Teijin Limited | Process for preparation of polyesters |
| JPS49117378A (https=) | 1973-03-13 | 1974-11-09 | ||
| JPS539278B2 (https=) * | 1973-06-07 | 1978-04-04 | ||
| US4205157A (en) | 1979-04-02 | 1980-05-27 | The Goodyear Tire & Rubber Company | Method for production of high molecular weight polyester with low catalyst level and low carboxyl content |
| US4238593B1 (en) | 1979-06-12 | 1994-03-22 | Goodyear Tire & Rubber | Method for production of a high molecular weight polyester prepared from a prepolymer polyester having an optional carboxyl content |
| US4442269A (en) | 1982-12-15 | 1984-04-10 | E. I. Du Pont De Nemours & Company | Staged copolymerization of polyesters |
| US4480086A (en) * | 1983-09-09 | 1984-10-30 | Eastman Kodak Company | Radiation-resistant copolyesters |
| US4578453A (en) * | 1984-11-23 | 1986-03-25 | Eastman Kodak Company | High molecular weight polyesters |
| US5039717A (en) | 1985-07-25 | 1991-08-13 | Amoco Corporation | Copolyesters |
| US5239018A (en) | 1989-09-06 | 1993-08-24 | Exxon Chemical Patents Inc. | Liquid polymer and polyol compositions, and process for preparing phenol-functional polymer |
| US5034263A (en) * | 1989-11-27 | 1991-07-23 | Eastman Kodak Company | Film laminate |
| US4983711A (en) | 1989-12-04 | 1991-01-08 | Eastman Kodak Company | Copolyesters and articles extrusion blow-molded therefrom |
| DE4137841C2 (de) | 1991-11-16 | 2003-08-28 | Zimmer Ag | Diskontinuierliches Verfahren zur Polykondensation von Terephthalsäure und 1,4-Bis-(hydroxymethyl)-cyclohexan |
| DE4137842A1 (de) * | 1991-11-16 | 1993-05-19 | Zimmer Ag | Verfahren zur kontinuierlichen polykondensation von terephthalsaeure und 1,4-bis-(hydroxymethyl)-cyclohexan |
| US5385773A (en) | 1993-04-27 | 1995-01-31 | Eastman Chemical Company | Copolyester of cyclohexanenedimethanol and process for producing such polyester |
| US5340907A (en) | 1993-06-28 | 1994-08-23 | Eastman Chemical Company | Copolyester of cyclohexanedimethanol and process for producing such polyester |
| US5616404A (en) * | 1995-10-10 | 1997-04-01 | Eastman Chemical Company | Orientable, heat setable semi-crystalline copolyesters |
| US5608031A (en) * | 1995-11-30 | 1997-03-04 | Eastman Chemical Company | Polyesters modified with 1,4-cyclohexaned imethanol having high clarity prepared utilizing an antimony containing catalyst/stabilizer system |
| TW381104B (en) | 1996-02-20 | 2000-02-01 | Eastman Chem Co | Process for preparing copolyesters of terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol |
| US5656715A (en) * | 1996-06-26 | 1997-08-12 | Eastman Chemical Company | Copolyesters based on 1,4-cyclohexanedimethanol having improved stability |
| US6103859A (en) * | 1997-04-09 | 2000-08-15 | Eastman Chemical Company | Late addition of supplemental ethylene glycol in the preparation of copolyesters |
| CN1146679C (zh) * | 1997-08-28 | 2004-04-21 | 伊斯曼化学公司 | 改良的共聚物粘合纤维 |
| US5986040A (en) | 1998-09-03 | 1999-11-16 | General Electric Company | Crystalline polyester resins and process for their preparation |
| JP3693831B2 (ja) | 1998-12-18 | 2005-09-14 | 三菱化学株式会社 | ポリシクロヘキサンジメチレンテレフタレートの製造方法 |
| JP3696741B2 (ja) | 1998-12-18 | 2005-09-21 | 三菱化学株式会社 | ポリシクロヘキサンジメチレンテレフタレート |
| IT1304797B1 (it) | 1998-12-23 | 2001-03-29 | Sinco Ricerche Spa | Procedimento per la preparazione di resine poliestere (mg33). |
| US6084055A (en) | 1999-03-30 | 2000-07-04 | General Electric Company | Method for preparing poly(1,4-cyclohexanedicarboxylates) |
| DE60028342T2 (de) | 1999-10-19 | 2007-05-24 | Aies Co., Ltd. | Verfahren zur polymerisation von deionisiertem bis-beta-hydroxyethylterephthalat |
| KR100366483B1 (ko) | 1999-12-17 | 2003-01-14 | 주식회사 이래화학 | 코폴리에스테르 수지 조성물 및 그 제조방법 |
| TWI235754B (en) | 1999-12-27 | 2005-07-11 | Ind Tech Res Inst | Composition and process for preparing a high molecular weight polyester |
| JP3209336B1 (ja) * | 2000-05-17 | 2001-09-17 | エスケー ケミカルズ カンパニー リミテッド | １，４−シクロヘキサンジメタノールが共重合されたポリエステル樹脂の製造方法 |
| JP4649709B2 (ja) * | 2000-07-25 | 2011-03-16 | 東亞合成株式会社 | 共重合ポリエステルの製造方法 |
| BR0113999A (pt) | 2000-09-21 | 2003-08-12 | Rohm & Haas | Processo para preparar uma dispersão polimérica aquosa nanocompósita de argila, dispersão nanocompósita aquosa, espessador, dispersante, aglutinante, composição de tinta flexográfica, verniz de sobre impressão, modificador de pó de cimento seco, semente polimérica nanocompósita de argila, composição polimérica nanocompósita de argila, e, método para preparar uma pluralidade de partìculas poliméricas nanocompósitas de argila ocas |
| US6458915B1 (en) | 2000-10-13 | 2002-10-01 | Eastman Chemical Company | Process for producing poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate) and the reactor grade polyester therefrom |
| US6455664B1 (en) | 2000-11-20 | 2002-09-24 | General Electric Company | Crystalline polyester resins and process for their preparation |
| US6429278B1 (en) * | 2001-01-22 | 2002-08-06 | Eastman Chemical Company | Process for manufacture of polyesters based on 1,4-cyclohexanedimethanol and isophthalic acid |
| US6740377B2 (en) * | 2001-09-14 | 2004-05-25 | Eastman Chemical Company | Polyester having improved crystallization behavior and extrusion blow molded articles made therefrom |
| ITMI20021293A1 (it) | 2002-06-12 | 2003-12-12 | Gen Electric | Metodo per preparare poli(cicloesan-1,4-dicarbossilato) (i) da acido cicloesan-1,4-bicarbossilico e composizione |
| US6828410B2 (en) | 2002-07-10 | 2004-12-07 | General Electric Company | Method for preparing poly(cyclohexane-1,4-dicarboxylate)s from cyclohexane-1,4-dicarboxylic acid, and composition |
| US6924349B2 (en) * | 2003-06-23 | 2005-08-02 | Sk Chemicals Co., Ltd. | Copolyester resin and articles using the same |
-
2006
- 2006-04-28 US US11/414,466 patent/US7211634B1/en not_active Expired - Lifetime
-
2007
- 2007-02-20 US US11/708,244 patent/US20070255020A1/en not_active Abandoned
- 2007-04-18 EP EP07775690.6A patent/EP2013260B1/en not_active Not-in-force
- 2007-04-18 KR KR1020087026292A patent/KR101389255B1/ko not_active Expired - Fee Related
- 2007-04-18 JP JP2009507729A patent/JP5689599B2/ja not_active Expired - Fee Related
- 2007-04-18 CN CN200780021818XA patent/CN101466760B/zh not_active Expired - Fee Related
- 2007-04-18 WO PCT/US2007/009484 patent/WO2007127117A2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007127117A3 (en) | 2008-02-07 |
| US7211634B1 (en) | 2007-05-01 |
| EP2013260B1 (en) | 2016-04-06 |
| CN101466760A (zh) | 2009-06-24 |
| KR101389255B1 (ko) | 2014-04-24 |
| JP2009535450A (ja) | 2009-10-01 |
| KR20080112341A (ko) | 2008-12-24 |
| EP2013260A2 (en) | 2009-01-14 |
| WO2007127117A2 (en) | 2007-11-08 |
| US20070255020A1 (en) | 2007-11-01 |
| CN101466760B (zh) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5689599B2 (ja) | １，４−シクロヘキサンジメタノールを含むポリエステルを製造する方法 | |
| KR101543043B1 (ko) | 2,2,4,4-테트라메틸-1,3-사이클로뷰탄다이올 및 1,4-사이클로헥산다이메탄올을 기제로 한 코폴리에스터의 제조 방법 | |
| US8586701B2 (en) | Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol | |
| US5959066A (en) | Polyesters including isosorbide as a comonomer and methods for making same | |
| JP4571910B2 (ja) | エステル変性ジカルボキシレートポリマー | |
| US6063464A (en) | Isosorbide containing polyesters and methods for making same | |
| US5681918A (en) | Process for preparing copolyesters of terephthalic acid ethylene glycol and 1 4-cyclohexanedimethanol exhibiting a neutral hue high clarity and increased brightness | |
| JP5711667B2 (ja) | イソソルビドが共重合されたポリエステル樹脂の製造方法 | |
| JP2003501532A (ja) | 高ガラス転移温度、低溶融粘度の非晶質コポリエステル | |
| JP7369178B2 (ja) | ポリエステル樹脂およびその製造方法 | |
| KR101514786B1 (ko) | 바이오 매스 유래 성분을 포함한 폴리에스테르 수지 및 이의 제조 방법 | |
| EP0496404B1 (en) | Process for the preparation of aromatic polyesters | |
| JPS5921889B2 (ja) | ポリエステルの製造方法 | |
| JP2002293906A (ja) | ポリエステル樹脂の製造方法 | |
| JPH0790066A (ja) | 共重合ポリエステル | |
| JPS63210127A (ja) | 芳香族コポリエステル | |
| JPS62212429A (ja) | コポリエステル | |
| MXPA00010288A (en) | Polyesters including isosorbide as a comonomer and methods for making same | |
| JPH0813880B2 (ja) | 液晶性ブロックコポリエステル | |
| JPH0211623A (ja) | サーモトロピック液晶性コポリエステル | |
| JP2003231756A (ja) | ポリオルガノシロキサン化合物のスラリー化法 | |
| HK1036813B (en) | Polyesters including isosorbide as a comonomer and methods for making same | |
| MXPA98006719A (en) | Process to prepare copolysteres of tereftal acid, ethylenglycol, and 1,4-cyclohexandimethanol that exhibit neutral color, high clarity and brightness increment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100303 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100303 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120912 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121002 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20121220 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20121228 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130401 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131217 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20140317 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20140325 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140409 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20140729 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141121 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20141202 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150106 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150129 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5689599 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |