JPS6123216B2 - - Google Patents
Info
- Publication number
- JPS6123216B2 JPS6123216B2 JP51103173A JP10317376A JPS6123216B2 JP S6123216 B2 JPS6123216 B2 JP S6123216B2 JP 51103173 A JP51103173 A JP 51103173A JP 10317376 A JP10317376 A JP 10317376A JP S6123216 B2 JPS6123216 B2 JP S6123216B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- acid
- acetaldehyde
- molded body
- molding
- 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
Links
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 50
- 229920000728 polyester Polymers 0.000 claims description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 5
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 25
- -1 polyethylene terephthalate Polymers 0.000 description 25
- 238000000465 moulding Methods 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006068 polycondensation reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 230000032050 esterification Effects 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 150000002291 germanium compounds Chemical class 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-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
- 150000003609 titanium compounds Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- HPGJOUYGWKFYQW-UHFFFAOYSA-N diphenyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HPGJOUYGWKFYQW-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 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 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 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
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-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
- 238000007666 vacuum forming Methods 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- UTNSTOOXQPHXJQ-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyethoxy)phenyl]sulfonylphenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1S(=O)(=O)C1=CC=C(OCCO)C=C1 UTNSTOOXQPHXJQ-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- OPNGLLVUIOOVHK-UHFFFAOYSA-N 2-hydroxyethyl dimethyl phosphate Chemical compound COP(=O)(OC)OCCO OPNGLLVUIOOVHK-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- QLIQIXIBZLTPGQ-UHFFFAOYSA-N 4-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=C(C(O)=O)C=C1 QLIQIXIBZLTPGQ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 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
- 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 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は中空成形体又はその前駆成形体作成用
のポリエステルに関する。更に詳しくは、飲食
品、化粧品等の内容物に臭を付けたり、味を変え
たりすることの認められないポリエステル中空成
形体又はその前駆成形体作成用のポリエステルに
関する。
ポリ塩化ビニル容器は、プラスチツク容器とし
て広く知られ、且つ多量に用いられているが、近
年塩化ビニルモノマーの毒性の問題が発生してい
る。しかして、これに代替すべき素材の開発が求
められている。その素材の一つとしてポリエチレ
ンテレフタレートを主たる対象とするポリエステ
ルがある。
しかし、通常のポリエチレンテレフタレートを
用いて成形した容器は、密封保持後にかすかな臭
気を示し、殊に飲食品用容器の場合内容物に臭を
付けたり、味を変えたりする等の不都合を生じ
る。この問題は容器のみならず、例えばフイルム
から真空成形してなる食品包装用品等にも同様の
問題となる。
本発明者は、かかる問題がポリエステル中に含
有されているアセトアルデヒドに起因することを
知見し、更に該アセトアルデヒドの発生の少ない
ポリエステル及びその成形品を得る方法について
鋭意検討した結果、ポリエステル中に含有されて
いるアセトアルデヒド及びその誘導体の濃度を低
下せしめるは末端ヒドロキシル基濃度を低下せし
めることが極めて効果的であること、更に成形時
のアセトアルデヒド及びその誘導体濃度の増加は
成形温度に大きく左右されるが特定の成形温度で
は該アセトアルデヒド及びその誘導体濃度の増加
が殆んど認められないことを知見し、本発明に到
達したものである。
すなわち、本発明は、
中空成形体又はその前駆成形体作成用のエチレ
ンテレフタレートを主たる構成成分とするポリエ
ステルにおいて、該ポリエステルが0.50〜0.75の
固有粘度を有し、その末端ヒドロキシル基濃度が
ポリマー106ｇ当り20ｇ当量未満であり、且つポ
リマーを不活性ガス気流中200℃に１時間加熱し
たときに発生するアセトアルデヒド量が該ポリマ
ーに対し10ppm未満であることを特徴とする中
空成形体又はその前駆成形体作成用のポリエステ
ルに関する。
本発明で云うポリエステル中空成形体として
は、例えばビン、コツプ、袋等が挙げられ、また
前駆成形体とは中空体を２次成形又は加工によつ
て形成することができる成形体であり、例えばフ
イルム、凹凸フイルム、トレイ包装用フイルム、
パツク包装用フイルム、容器の内栓等があげられ
る。
本発明においてエチレンテレフタレートを主た
る構成成分とするポリエステルとしては、ポリエ
チレンテレフタレートを主たる対象とするが、テ
レフタル酸の一部を、例えばイソフタル酸、ナフ
タレンジカルボン酸、ジフミニルジカルボン酸、
ジフエノキシエタンジカルボン酸、ジフエニルエ
ーテルジカルボン酸、ジフエニルスルホンジカル
ボン酸等の如き芳香族ジカルボン酸、ヘキサヒド
ロテレフタル酸、ヘキサヒドロイソフタル酸等の
如き脂環族ジカルボン酸、アジピン酸、セバチン
酸、アゼライン酸等の如き脂肪族ジカルボン酸、
ｐ−β−ヒドロキシエトキシ安息香酸、ε−オキ
シカプロン酸の如きオキシ酸等の二官能性カルボ
ン酸及び／又はエチレングリコールの一部を例え
ばトリメチレングリコール、テトラメチレングリ
コール、ヘキサメチレングリコール、デカメチレ
ングリコール、ネオペンチレングリコール、１，
１−シクロヘキサンジメチロール、１，４−シク
ロヘキサンジメチロール、２，２−ビス（4′−β
−ヒドロキシエトキシフエニル）プロパン、ビス
（4′−β−ヒドロキシエトキシフエニル）スルホ
ン等の如き他のグリコールで置換したポリエステ
ルであつてもよい。またポリエステルは、実質的
に線状である範囲で、例えばペンタエリスリトー
ル、トリメチロールプロパン、トリメリツト酸、
トリメシン酸及びこれらの機能的誘導体等の多官
能化合物の一種以上及び／又はｏ−ベンゾイル安
息香酸、メトキシポリエチレングリコール及びこ
れらの機能的誘導体の如き単官能化合物の一種以
上を共重合せしめたものであつてもよい。
また、かかるポリエステルには安定剤（例えば
熱、紫外線、酸素に対する安定剤）、顔料、離型
剤、核剤等の添加剤を配合してもよいが、これら
の添加剤はできうれば安全性の高いものを使用す
ることが好ましい。
上記ポリエステルは、通常溶融重合法或いは溶
融重合法に引続き、固相重合法を用いる製造方法
によつて製造することができる。この製造方法を
ポリエチレンテレフタレートの製造を例によつて
更に詳しく説明すると、次の通りである。
テレフタル酸又はその低級アルキルエステルと
エチレングリコール又はエチレンオキサイドとを
140〜350℃の温度で触媒の存在又は非存在下にエ
ステル化、エステル交換又は付加反応せしめてビ
ス（β−ヒドロキシエチル）テレフタレート及
び／又はそのオリゴマーを製造し、次いでこれら
を必要に応じて精製した後絶対圧１mmＨｇ以下の
如き高真空下、触媒の存在下250〜350℃の温度で
溶融重縮合反応せしめることによりポリエチレン
テレフタレートを製造する。また必要なら上記で
得られたポリエチレンテレフタレートを粒状また
は粉状等にし、結晶化させた状態で融点以下の温
度で真空または不活性ガス気流中において重合度
を上げる固相重合反応せしめる。
重縮合反応に入る前の反応で最も好ましいのは
直接エステル化法であり、また無触媒で製造する
方法である。エステル化、エステル交換又は付加
反応を触媒の存在下で行なう場合、用いられる触
媒は特に限定されないが、例えば次の如き触媒が
好ましく用いられる。エステル化又はエステル交
換反応の触媒としては、後の重縮合反応に用いる
チタン化合物及び周期律表第族の金属化合物、
更にマグネシウム塩類、カルシウム塩類、マンガ
ン塩類等が好ましく用いられる。殊にマグネシウ
ム化合物が好ましい。これらの使用量は金属がポ
リマーに対して200ppm以下になる様にするのが
好ましい。
また、付加反応においてはアルカリ金属化合物
が好ましく用いられる。しかし、これらの触媒は
反応生成物を精製する場合にはポリマー中に実質
的に含有されなくなるので特にその使用量を問題
とする必要はない。又精製を行なう、行なわない
にかかわらず最も好ましいのは無触媒で反応を行
なうことである。
引続いて行なわれる重縮合反応は実質的に無触
媒又は触媒の存在下に行なわれる。ここで用いら
れる触媒としては、通常ポリエステルの重縮合反
応に用いられる触媒が使用され得る。具体的には
チタン化合物、ゲルマニウム化合物、アンチモン
化合物、スズ化合物等が用いられ、特にチタン化
合物、ゲルマニウム化合物が好ましい。これりら
は金属原子として酸成分に対し１〜200ミリモル
％となる割合で用いるのが好ましい。
前記チタン化合物としては、例えば一般式
XmTi（OR）ｌ，
（Me）nTiF6，
（Ti）ｐ（COCR′）ｑ
〔但し、式中Ｘはハロゲン原子または水素原
子、Ｒはアルキル（炭素数：１〜６），Meは金属
原子またはMH4，R′はカルボキシル基を含むこ
とあるアルキル、アリール、シクロアルキル、ア
ラルキル（炭素数：６〜12），ｍ，ｌは０又は正
の整数（但しｌ又はｍのいずれかは正の整数），
ｎ，ｐ及びｑは正の整数〕
で示される化合物が挙げられ、更に具体的にはテ
トラチチルチタネート、テトラブチルチタネー
ト、四塩化チタン、フツ化チタン酸のリチウム
塩、カリウム塩、マグネシウム塩、修酸チタン、
トリメリツト酸チタン、酢酸チタン、ピロメリツ
ト酸チタン等が例示される。更にこれらの加水分
解物又は誘導体も用いることができる。
更に、ゲルマニウム化合物としては、酸化ゲル
マニウム、ゲルマニウムアルコキシド（例えばメ
トキサイド、ブドキサイド等）、ハロゲン化ゲル
マニウム等が好ましい具体例として挙げられる。
ゲルマニウム化合物はポリエステル中への溶解性
をあげるために種々の方法が提案されているが、
いずれの方法も本発明では用いることができる。
重縮合反応はリン化合物の存在下に実施するこ
ともでき、この際用いられるリン化合物としては
亜リン酸、リン酸等の如きリン酸のアルキルエス
テル、アリールエステル、シクロアルキルエステ
ル等が例示でき、更に具体的にはトリメチルフオ
スフエート、トリエチルフオスフエース、トリフ
エニルフオスフエート、ヒドロキシエチルジメチ
ルフオスフエート、トリメチルフオスフアイト、
トリフエニルフオスフアイト等があげられる。こ
れらのリン化合物はポリマー中に、リン原子とし
て10〜200ppm含有される割合で用いられるのが
好ましい。
これらの重縮合触媒の存在下、エステル化、エ
ステル交換または附加反応の生成物、例えばビス
（β−ヒドロキシエチル）テレフタレート及び／
又はそのオリゴマーを270〜300℃で１mmＨｇ以下
の如き高真空下に0.5〜６時間保つて固有粘度
0.50〜0.75、好ましくは0.60〜0.75のポリエステ
ルとする。しかし、溶融重合のみでかかる固有粘
度にする必要は必ずしもなく、上述した如く固相
重合を併用してもよい。
本発明におけるポリエステルは、末端ヒドロキ
シル基をポリマー106ｇ当り20ｇ当量未満とする
ことが必要であり、好ましくは15ｇ当量未満とす
るのがよい。この末端ヒドロキシル基を減少させ
るには、末端ヒドロキシル基低下剤を使用する方
法を用いる。かかる方法としては、例えば、末端
封鎖剤を使用する方法、末端ヒドロキシル基と反
応する物質を使用する方法等があげられる。この
具体的な方法としては、一価のカルボン酸及び／
又はアルコール或はそれらのエステル形成性誘導
体を添加し、反応せしめる方法、重合反応段階が
ある程度進行した時点で多価のカルボン酸及び／
又はそのエステル形成性誘導体を添加し、反応さ
せる方法、或は酸無水物、有機炭酸エステル等を
添加反応させる方法等があげられる。しかし、本
発明のポリエステルは、これら以外の方法によつ
てその末端ヒドロキシル基を減少させたものも含
むことは当然である。
この末端ヒドロキシル基の減少反応は溶融重合
反応時に行なうのが一般的であるが、重合反応終
了後再溶融して行なつてもよい。上記ポリエステ
ルの末端ヒドロキシル基低下剤の具体例として
は、安息香酸、トリル酸、ナフトエ酸等の如き芳
香族モノカルボン酸、ラウリン酸、ステアリン酸
等の如き脂肪族モノカルボン酸、ステアリルアル
コール、ラウリルアルコール等の如き脂肪族モノ
アルコール、テレフタル酸、イソフタル酸、ナフ
タレンジカルボン酸等の如き芳香族ジカルボン
酸、セバチン酸、ドデカジオン酸、アゼライン酸
等の如き脂肪族ジカルボン酸、ジフエニルカーボ
ネートの如きジアリールカーボネート、ジフエニ
ルテレフタレートの如きジアリールジカルボキシ
レート等が例示される。これら末端ヒドロキシル
基低下剤は沸点が200℃以上、更には250℃以上の
ものが好ましい。
本発明のポリエステルは、更に含有されている
アセトアルデヒド量が10ppm未満である必要が
ある。この含有アセトアルデヒド量は、４メツシ
ユより小さいポリマー粒子を200℃で１時間窒素
の如き不活性ガス気流中で加熱し、該気流中に遊
離、発生したアセトアルデヒドガスを捕集し、該
アセトアルデヒドの量をポリマー重量に対して求
めたのである。
通常の溶融重合法で製造されたポリエチレンテ
レフタレートは、上記の如き方法で測定したアセ
トアルデヒド量が50〜100ppm存在する。この含
有アセトアルデヒド量を10ppm未満にするには
高温で長時間、例えば170℃以上融点以下の温度
で30分〜５時間不活性ガス気流下又は真空下にお
くことによつて達成される。又アセトアルデヒド
を還元たり、酸化したりする試薬で処理すること
も含有アセトアルデヒドを減少させるのに好まし
い方法である。
かくして得られるポリエステルは固有粘度が
0.5〜0.75、好ましくは0.6〜0.75である必要があ
る。これより低い固有粘度のものは得られる成形
物の強度が弱く実用にならない。一方、これより
高い固有粘度のものは、成形の際に発熱したり、
流動性を上げるため、高温の成形温度が必要とな
り、実質上本発明の低アルデヒド化の目的を達成
することが困難となるので好ましくない。
本発明のポリエステルを溶融成形するとアセト
アルデヒド含量の少ない中空成形体又はその前駆
成形体を得ることができるが、この溶融成形温度
を280℃未満とすることにより更にアルデヒド含
量を低減することができる。好ましい成形温度は
220〜280℃である。ここで成形温度とは例えば射
出成形の場合はノズルから出るポリマー温度、ま
た押出成形の場合押出ヘツドから出るポリマーの
温度を言い、他の場合もこれに類する。
ポリエステル中空成形体又はその前駆成形体の
製造には、上述の如き溶融成形法単独でもよく、
また他の成形法と組合せて行なつてもよい。好ま
しい成形法としては、押出し、射出、配向等のブ
ロー成形法、真空成形等の如き成形法が用いられ
る。これらは、いずれも射出成形又は押出成形等
の溶融成形と共に実施される成形法である。溶融
成形を行なう前にポリエステルを十分乾燥するの
は当然であるが、特に本発明の場合、加水分解に
よつてヒドロキシル基が生成するのは好ましくな
いので、水分が0.05％未満、好ましくは0.03％未
満にすることが好ましい。
かくして得られるポリエステル中空成形体又は
その前駆成形体は、ビン、カツプ、袋、フイル
ム、内栓等の形態で食品包装用として、或いは飲
料品又は化粧品の容器として用られる。かかる成
形体はアセトアルデヒド含量が少なく、飲食品と
直接に接触しても該飲食品の味を変えたり、臭を
付けたりすることがなく、また化粧品と直接に接
触しても該化粧品に臭を付けたりすることがな
く、極めて有用である。更に本発明のポリエステ
ルは成形時に悪臭を発することがない利点を有す
る。
以下、実施例を挙げて本発明を更に詳細に説明
する。尚、実施例中の「部」は「重量部」を意味
する。また、ポリエステルの固有粘度（〔η〕）は
オルソクロロフエノール中1.2ｇ／ｄの濃度で
35℃において測定して求めた。
実施例 １
テレフタル酸428部及びエチレングリコール262
部を加圧下加熱してエステル化反応を行ない、理
論量の約95％の水を除去した。得られたエステル
化物を重合槽に移し、二酸化ゲルマニウム0.376
部をエチレングリコールスラリーとして添加した
後、減圧下285℃で常法により固有粘度〔η〕が
0.644になる迄重合した。ここで反応系を窒素ガ
スで常圧に戻し、ジフエニルカーボネート（以下
DPCと略称する）22部を添加してから、更に常
圧窒素雰囲気下20分間反応させ、次いで徐々に減
圧にし１mmＨｇ以下の減圧下に30分間保つたのち
吐出した。得られたポリエステルのチツプは
〔η〕が0.678であり、ヒドロキシル基濃度は13当
量／106ｇであつた。このチツプを窒素気流下220
℃で２時間処理した後のチツプは〔η〕＝0.672、
ヒドロキシル基濃度12当量／106ｇ、アセトアル
デヒド含量2ppmであつた。
得られた熱処理チツプをシリンダー温度255℃
で射出成形し、ボトル成形用プリフオームを得
た。このときの樹脂温度は275℃であつた。得ら
れたプリフオームを180℃で１分間加熱した後吹
込成形を行なつた。得られたボトルを密栓し、１
週間放置した後栓を開いて臭をかいだが全く臭い
はなかつた。また、該ボトルを粉砕し、アセトア
ルデヒド含量を測定したところ2.5ppmであつ
た。
比較例 １
実施例１で得られたポリエステルチツプをシリ
ンダー温度280℃でプリフオームを成形した。こ
のときのポリマー温度は290℃であつた。このプ
リフオームを実施例１と同様に成形したところ、
得られたボトルとアセトアルデヒド含量は
15ppmであり、密封後１週間放置してから開封
し、ボトル中の臭をかいだところ臭いがわずかで
はあるが感じられた。
比較例 ２〜５
DPCの量を下表に示すように変化させる以外
は実施例１と同様に行なつてポリエステルを製造
し、次いで該ポリエステルを用いて実施例１と同
様に行なつてボトルを得た。その結果を下表に示
す。
The present invention relates to a polyester for producing a hollow molded body or a precursor molded body thereof. More specifically, the present invention relates to a polyester for producing a polyester hollow molded article or a precursor molded article thereof, which does not add odor or change the taste of the contents of foods, drinks, cosmetics, etc. Polyvinyl chloride containers are widely known as plastic containers and are used in large quantities, but in recent years a problem has arisen regarding the toxicity of vinyl chloride monomers. Therefore, there is a need to develop materials that can replace this. One such material is polyester, which is mainly made of polyethylene terephthalate. However, containers molded using ordinary polyethylene terephthalate exhibit a faint odor after being kept sealed, and in the case of containers for food and beverages in particular, this causes problems such as imparting an odor to the contents or changing the taste. This problem occurs not only in containers, but also in food packaging products made by vacuum forming a film, for example. The inventor of the present invention discovered that this problem is caused by acetaldehyde contained in polyester, and as a result of intensive study on methods for obtaining polyester and molded products thereof that generate less acetaldehyde, the inventor found that the problem is caused by acetaldehyde contained in polyester. In order to reduce the concentration of acetaldehyde and its derivatives, it is extremely effective to reduce the concentration of terminal hydroxyl groups.Furthermore, the increase in the concentration of acetaldehyde and its derivatives during molding is greatly influenced by the molding temperature, but there are certain The present invention was achieved based on the finding that the concentration of acetaldehyde and its derivatives hardly increases at the molding temperature. That is, the present invention provides a polyester containing ethylene terephthalate as a main component for producing a hollow molded body or a precursor molded body thereof, wherein the polyester has an intrinsic viscosity of 0.50 to 0.75, and the terminal hydroxyl group concentration is 10 6 A hollow molded article or its precursor molding, characterized in that the amount of acetaldehyde is less than 20 g equivalent per gram, and the amount of acetaldehyde generated when the polymer is heated at 200°C for 1 hour in an inert gas stream is less than 10 ppm based on the polymer. Concerning polyester for body construction. Examples of the polyester hollow molded body referred to in the present invention include bottles, cups, bags, etc., and the precursor molded body is a molded body that can be formed from a hollow body by secondary molding or processing, for example. Film, textured film, tray packaging film,
Examples include packaging films and inner stoppers for containers. In the present invention, the polyester containing ethylene terephthalate as a main component is mainly polyethylene terephthalate, but a part of terephthalic acid can be used, for example, isophthalic acid, naphthalene dicarboxylic acid, difuminyl dicarboxylic acid,
Aromatic dicarboxylic acids such as diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, etc., alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, etc., adipic acid, sebacic acid, aliphatic dicarboxylic acids such as azelaic acid,
Bifunctional carboxylic acids such as oxyacids such as p-β-hydroxyethoxybenzoic acid and ε-oxycaproic acid and/or a portion of ethylene glycol, such as trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol , neopentylene glycol, 1,
1-Cyclohexanedimethylol, 1,4-cyclohexanedimethylol, 2,2-bis(4'-β
Polyesters substituted with other glycols such as -hydroxyethoxyphenyl)propane, bis(4'-β-hydroxyethoxyphenyl)sulfone, and the like may also be used. In addition, the polyester may be substantially linear, for example, pentaerythritol, trimethylolpropane, trimellitic acid,
Copolymerized with one or more polyfunctional compounds such as trimesic acid and functional derivatives thereof and/or one or more monofunctional compounds such as o-benzoylbenzoic acid, methoxypolyethylene glycol and functional derivatives thereof. It's okay. In addition, additives such as stabilizers (for example, stabilizers against heat, ultraviolet rays, and oxygen), pigments, mold release agents, and nucleating agents may be added to such polyesters, but these additives are preferably safe. It is preferable to use one with a high The above-mentioned polyester can be produced by a production method that usually uses a melt polymerization method or a melt polymerization method followed by a solid phase polymerization method. This production method will be explained in more detail using the production of polyethylene terephthalate as an example. Terephthalic acid or its lower alkyl ester and ethylene glycol or ethylene oxide
Bis(β-hydroxyethyl) terephthalate and/or its oligomers are produced by esterification, transesterification or addition reaction in the presence or absence of a catalyst at a temperature of 140 to 350°C, and then purified as necessary. Thereafter, polyethylene terephthalate is produced by carrying out a melt polycondensation reaction at a temperature of 250 to 350° C. in the presence of a catalyst under a high vacuum such as an absolute pressure of 1 mmHg or less. If necessary, the polyethylene terephthalate obtained above is made into granules or powder, and the crystallized state is subjected to a solid phase polymerization reaction to increase the degree of polymerization in a vacuum or in an inert gas stream at a temperature below the melting point. The most preferable reaction before starting the polycondensation reaction is a direct esterification method, and a method of producing without a catalyst. When esterification, transesterification or addition reaction is carried out in the presence of a catalyst, the catalyst used is not particularly limited, but for example, the following catalysts are preferably used. As catalysts for esterification or transesterification reactions, titanium compounds and metal compounds from group 3 of the periodic table used in the subsequent polycondensation reaction,
Furthermore, magnesium salts, calcium salts, manganese salts, etc. are preferably used. Especially preferred are magnesium compounds. The amount of these metals used is preferably 200 ppm or less relative to the polymer. Moreover, an alkali metal compound is preferably used in the addition reaction. However, when the reaction product is purified, these catalysts are substantially no longer contained in the polymer, so there is no particular need to worry about the amount used. Moreover, regardless of whether purification is performed or not, it is most preferable to carry out the reaction without a catalyst. The subsequent polycondensation reaction is carried out substantially without a catalyst or in the presence of a catalyst. As the catalyst used here, a catalyst normally used in polyester polycondensation reactions can be used. Specifically, titanium compounds, germanium compounds, antimony compounds, tin compounds, etc. are used, and titanium compounds and germanium compounds are particularly preferred. These metal atoms are preferably used in a proportion of 1 to 200 mmol % based on the acid component. The titanium compound has, for example, the general formula: XmTi(OR)l, (Me)nTiF 6 , (Ti)p(COCR')q [wherein, 1 to 6), Me is a metal atom or MH 4 , R' is alkyl, aryl, cycloalkyl, aralkyl (carbon number: 6 to 12) that may contain a carboxyl group, m and l are 0 or a positive integer (however, Either l or m is a positive integer),
n, p and q are positive integers] Examples include compounds represented by: tetratityl titanate, tetrabutyl titanate, titanium tetrachloride, lithium salts, potassium salts, magnesium salts of titanate fluoride, titanium oxalate,
Examples include titanium trimellitate, titanium acetate, titanium pyromellitate, and the like. Furthermore, these hydrolysates or derivatives can also be used. Furthermore, as the germanium compound, germanium oxide, germanium alkoxide (for example, methoxide, budoxide, etc.), germanium halide, etc. can be mentioned as preferable examples.
Various methods have been proposed to increase the solubility of germanium compounds in polyester.
Either method can be used in the present invention. The polycondensation reaction can also be carried out in the presence of a phosphorus compound, and examples of the phosphorus compound used in this case include alkyl esters, aryl esters, and cycloalkyl esters of phosphoric acid such as phosphorous acid and phosphoric acid. More specifically, trimethyl phosphate, triethyl phosphace, triphenyl phosphate, hydroxyethyl dimethyl phosphate, trimethyl phosphite,
Examples include triphenylphosphite. These phosphorus compounds are preferably used in a proportion of 10 to 200 ppm as phosphorus atoms in the polymer. In the presence of these polycondensation catalysts, the products of the esterification, transesterification or addition reactions, such as bis(β-hydroxyethyl) terephthalate and/or
Or keep the oligomer under high vacuum such as 1 mmHg or less at 270-300℃ for 0.5-6 hours to determine the intrinsic viscosity.
The polyester has a weight of 0.50 to 0.75, preferably 0.60 to 0.75. However, it is not necessarily necessary to achieve such an intrinsic viscosity only by melt polymerization, and solid phase polymerization may be used in combination as described above. The polyester used in the present invention needs to have a terminal hydroxyl group of less than 20 g equivalent per 10 6 g of polymer, preferably less than 15 g equivalent. In order to reduce this terminal hydroxyl group, a method using a terminal hydroxyl group reducing agent is used. Such methods include, for example, a method using a terminal capping agent, a method using a substance that reacts with the terminal hydroxyl group, and the like. This specific method includes monovalent carboxylic acid and/or
Alternatively, a method in which alcohol or an ester-forming derivative thereof is added and reacted, and when the polymerization reaction step has progressed to a certain extent, polyhydric carboxylic acid and/or
or a method of adding and reacting an ester-forming derivative thereof, or a method of adding and reacting an acid anhydride, an organic carbonate, etc. However, it goes without saying that the polyester of the present invention also includes those whose terminal hydroxyl groups have been reduced by methods other than these. This reaction for reducing the terminal hydroxyl group is generally carried out during the melt polymerization reaction, but it may also be carried out by remelting the material after the polymerization reaction is completed. Specific examples of the terminal hydroxyl group lowering agent for the polyester include aromatic monocarboxylic acids such as benzoic acid, tolylic acid, and naphthoic acid, aliphatic monocarboxylic acids such as lauric acid and stearic acid, stearyl alcohol, and lauryl alcohol. aliphatic monoalcohols such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid etc., aliphatic dicarboxylic acids such as sebacic acid, dodecadionic acid, azelaic acid etc., diaryl carbonates such as diphenyl carbonate, diphenyl carbonates, etc. Examples include diaryl dicarboxylate such as enyl terephthalate. These terminal hydroxyl group lowering agents preferably have a boiling point of 200°C or higher, more preferably 250°C or higher. The polyester of the present invention further needs to contain less than 10 ppm of acetaldehyde. The amount of acetaldehyde contained can be determined by heating polymer particles smaller than 4 meshes at 200°C for 1 hour in a stream of inert gas such as nitrogen, and collecting the acetaldehyde gas liberated and generated in the stream. It was calculated based on the weight of the polymer. Polyethylene terephthalate produced by a conventional melt polymerization method contains 50 to 100 ppm of acetaldehyde as measured by the method described above. The content of acetaldehyde can be reduced to less than 10 ppm by keeping the product under an inert gas stream or under vacuum for a long time at a high temperature, for example, at a temperature of 170°C or higher and lower than the melting point for 30 minutes to 5 hours. Treatment with a reagent that reduces or oxidizes acetaldehyde is also a preferred method for reducing the acetaldehyde content. The polyester thus obtained has an intrinsic viscosity of
It should be between 0.5 and 0.75, preferably between 0.6 and 0.75. If the intrinsic viscosity is lower than this, the strength of the resulting molded product is too low to be of practical use. On the other hand, those with higher intrinsic viscosity may generate heat during molding,
In order to increase the fluidity, a high molding temperature is required, which is not preferable because it becomes difficult to substantially achieve the object of the present invention of reducing aldehyde. When the polyester of the present invention is melt-molded, a hollow molded article or its precursor molded article with a low acetaldehyde content can be obtained, but the aldehyde content can be further reduced by setting the melt-molding temperature to less than 280°C. The preferred molding temperature is
The temperature is 220-280℃. Here, the molding temperature refers to, for example, the temperature of the polymer exiting from a nozzle in the case of injection molding, or the temperature of the polymer exiting from the extrusion head in the case of extrusion molding, and is similar in other cases. The above-mentioned melt molding method alone may be used to produce the polyester hollow molded body or its precursor molded body,
It may also be carried out in combination with other molding methods. Preferred molding methods include blow molding methods such as extrusion, injection, and orientation, and molding methods such as vacuum forming. These are all molding methods that are carried out together with melt molding such as injection molding or extrusion molding. It goes without saying that the polyester should be sufficiently dried before melt molding, but especially in the case of the present invention, it is undesirable for hydroxyl groups to be generated by hydrolysis, so the moisture content is less than 0.05%, preferably 0.03%. It is preferable to keep it below. The thus obtained polyester hollow molded product or its precursor molded product is used for food packaging in the form of bottles, cups, bags, films, inner stoppers, etc., or as containers for beverages or cosmetics. Such a molded product has a low acetaldehyde content, so even if it comes into direct contact with food or drinks, it will not change the taste or add odor to the food or drink, and even if it comes into direct contact with cosmetics, it will not impart an odor to the cosmetics. It is extremely useful as there is no need to attach anything. Furthermore, the polyester of the present invention has the advantage of not emitting any bad odor during molding. Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that "parts" in the examples mean "parts by weight." In addition, the intrinsic viscosity ([η]) of polyester is at a concentration of 1.2 g/d in orthochlorophenol.
It was determined by measuring at 35°C. Example 1 428 parts of terephthalic acid and 262 parts of ethylene glycol
The esterification reaction was carried out by heating under pressure to remove about 95% of the theoretical amount of water. The obtained esterified product was transferred to a polymerization tank, and germanium dioxide 0.376
% as an ethylene glycol slurry, and then the intrinsic viscosity [η] was determined by a conventional method at 285°C under reduced pressure.
It was polymerized until it reached 0.644. Here, the reaction system is returned to normal pressure with nitrogen gas, and diphenyl carbonate (hereinafter referred to as
After adding 22 parts of DPC (abbreviated as DPC), the mixture was further reacted for 20 minutes under a nitrogen atmosphere at normal pressure, and then the pressure was gradually reduced to 1 mmHg or less and maintained for 30 minutes before being discharged. The obtained polyester chips had a [η] of 0.678 and a hydroxyl group concentration of 13 equivalents/10 6 g. This chip was heated under a nitrogen stream for 220 min.
After 2 hours of treatment at °C, the chips were [η] = 0.672,
The hydroxyl group concentration was 12 equivalents/10 6 g, and the acetaldehyde content was 2 ppm. The resulting heat-treated chips were heated to a cylinder temperature of 255°C.
A preform for bottle molding was obtained by injection molding. The resin temperature at this time was 275°C. The obtained preform was heated at 180° C. for 1 minute and then blow molded. Seal the resulting bottle and add 1
After leaving it for a week, I opened the bottle and smelled it, but there was no odor at all. In addition, the bottle was crushed and the acetaldehyde content was measured and found to be 2.5 ppm. Comparative Example 1 The polyester chips obtained in Example 1 were molded into a preform at a cylinder temperature of 280°C. The polymer temperature at this time was 290°C. When this preform was molded in the same manner as in Example 1,
The resulting bottle and acetaldehyde content are
The concentration was 15 ppm, and when I opened the bottle after leaving it for a week after sealing and sniffed the inside of the bottle, I could sense a slight odor. Comparative Examples 2 to 5 A polyester was produced in the same manner as in Example 1 except that the amount of DPC was changed as shown in the table below, and then a bottle was produced in the same manner as in Example 1 using the polyester. Obtained. The results are shown in the table below.
【表】
但し、成形は比較例５のみシリンダー温度270
℃（樹脂温度295℃）にしないと成形できなかつ
た。
実施例 ２
ジメチルテレフタレート50部、ネオペンチルグ
リコール3.5部、エチレングリコール31部及び
0.02部の酢酸マンガンをエステル交換反応釜に仕
込み、反応を行なつた。理論量のメタノールが留
出したところで0.011ｇの酸化ゲルマニウムと
0.014ｇのトリメチルホスフエートを加えた後反
応液は重縮合反応釜に移した。エステル交換反応
中の温度は110℃より始まり最終的に220℃で示
し、反応時間は約４時間であつた。
重縮合反応槽に移した反応液は徐々に真空を高
めると同時に昇温を始め、60分後に270℃に達
し、真空度は0.3mm／Ｈｇであつた。この状態を
80分保つた後、一旦反応系を常圧に返し、ジフエ
ニルテレフタレート3.2部を添加した。添加前の
ポリマーの〔η〕は0.681であつた。ジフエニル
テレフタレートを添加後25分間常圧に保ち、続い
て0.3mm／Ｈｇに真空度で30分間反応した。得ら
れたポリエステルのチツプは〔η〕0.68であつ
た。
このチツプを220℃で２時間窒素気流下に熱処
理して、アセトアルデヒド濃度2ppm、末端ヒド
ロキシル基濃度13当量／106ｇ、且つ〔η〕が
0.67の熱処理ポリエステルチツプを得た。このチ
ツプを実施例１と同様に成形した結果、樹脂温度
は277℃であり、ボトル中のアセトアルデヒド濃
度は3ppmであつた。更に１週間密封状態で放置
後もアセトアルデヒドの臭は感じられなかつた。
実施例 ３
実施例１と同様にして得られたポリエステルチ
ツプは窒素雰囲気中220℃で２時間熱処理し、
〔η〕＝0.672、ヒドロキシル基濃度12当量／106
ｇ、アセトアルデヒド含量2ppmの熱処理チツプ
を得た。
この熱処理チツプをシリンダー温度255℃でフ
イルム状に押出し、60℃の回転ドラムに接触させ
て急速に冷却した。得られたフイルムを更に100
℃の熱風雰囲気中で軸方向に3.0倍、横方向に3.8
倍延伸してから120℃に加熱された凹凸状の金型
ではさみ凹凸状のフイルムを得た。この凹凸状の
フイルムはアセトアルデヒド含量が2ppmであつ
た。[Table] However, only Comparative Example 5 was molded at a cylinder temperature of 270
℃ (resin temperature 295℃), it could not be molded. Example 2 50 parts of dimethyl terephthalate, 3.5 parts of neopentyl glycol, 31 parts of ethylene glycol, and
0.02 part of manganese acetate was charged into a transesterification reactor and a reaction was carried out. When the theoretical amount of methanol is distilled out, 0.011g of germanium oxide and
After adding 0.014 g of trimethyl phosphate, the reaction solution was transferred to a polycondensation reactor. The temperature during the transesterification reaction started at 110°C and ended at 220°C, and the reaction time was about 4 hours. The temperature of the reaction solution transferred to the polycondensation reactor began to increase as the vacuum was gradually increased, reaching 270° C. after 60 minutes, and the degree of vacuum was 0.3 mm/Hg. this state
After being maintained for 80 minutes, the reaction system was once returned to normal pressure, and 3.2 parts of diphenyl terephthalate was added. [η] of the polymer before addition was 0.681. After adding diphenyl terephthalate, the pressure was kept at normal pressure for 25 minutes, and then the reaction was carried out at a vacuum level of 0.3 mm/Hg for 30 minutes. The polyester chips obtained had a [η] of 0.68. This chip was heat-treated at 220°C for 2 hours under a nitrogen stream to obtain an acetaldehyde concentration of 2 ppm, a terminal hydroxyl group concentration of 13 equivalents/10 6 g, and [η].
0.67 heat treated polyester chips were obtained. When this chip was molded in the same manner as in Example 1, the resin temperature was 277°C and the acetaldehyde concentration in the bottle was 3 ppm. Furthermore, even after being left in a sealed state for one week, no acetaldehyde odor was detected. Example 3 Polyester chips obtained in the same manner as in Example 1 were heat-treated at 220°C for 2 hours in a nitrogen atmosphere.
[η] = 0.672, hydroxyl group concentration 12 equivalents/10 6
A heat-treated chip with an acetaldehyde content of 2 ppm was obtained. This heat-treated chip was extruded into a film at a cylinder temperature of 255°C, and rapidly cooled by contacting with a rotating drum at 60°C. 100 more of the obtained film
3.0 times axially and 3.8 times laterally in hot air atmosphere at ℃
After stretching the film twice, it was held in an uneven mold heated to 120°C to obtain an uneven film. This uneven film had an acetaldehyde content of 2 ppm.
Claims (1)
レンテレフタレートを主たる構成成分とするポリ
エステルにおいて、該ポリエステルの固有粘度が
0.50〜0.75であり、末端ヒドロキシル基が末端ヒ
ドロキシル基低下剤を用いてポリマー106ｇ当り
20ｇ当量未満に低減されており、且つポリマーを
不活性ガス気流中200℃に１時間加熱したときに
発生するアセトアルデヒド量が該ポリマーに対し
10ppm未満であることを特徴とする中空成形体
又はその前駆成形体作成用のポリエステル。1. In a polyester whose main constituent is ethylene terephthalate for producing a hollow molded body or its precursor molded body, the intrinsic viscosity of the polyester is
0.50 to 0.75, and the terminal hydroxyl group is reduced per 10 6 g of polymer using a terminal hydroxyl group reducing agent.
The amount of acetaldehyde generated when the polymer is heated to 200°C for 1 hour in an inert gas stream is reduced to less than 20g equivalent.
A polyester for producing a hollow molded body or a precursor molded body thereof, characterized in that the content is less than 10 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10317376A JPS5328693A (en) | 1976-08-31 | 1976-08-31 | Polyester polyestier rlow molded articles or other preliminary molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10317376A JPS5328693A (en) | 1976-08-31 | 1976-08-31 | Polyester polyestier rlow molded articles or other preliminary molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5328693A JPS5328693A (en) | 1978-03-17 |
| JPS6123216B2 true JPS6123216B2 (en) | 1986-06-04 |
Family
ID=14347104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10317376A Granted JPS5328693A (en) | 1976-08-31 | 1976-08-31 | Polyester polyestier rlow molded articles or other preliminary molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5328693A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6360212U (en) * | 1986-10-07 | 1988-04-21 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS553426A (en) * | 1978-06-23 | 1980-01-11 | Toray Ind Inc | Hollow molded polyester article having improved transparency |
| JPH0631143B2 (en) * | 1986-04-04 | 1994-04-27 | 三菱電機株式会社 | Elevator safety device |
| JPH066911Y2 (en) * | 1988-06-14 | 1994-02-23 | 東洋製罐株式会社 | Polyester container |
-
1976
- 1976-08-31 JP JP10317376A patent/JPS5328693A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6360212U (en) * | 1986-10-07 | 1988-04-21 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5328693A (en) | 1978-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5288676B2 (en) | Catalyst for producing polyester, method for producing polyester, and polyester | |
| KR840000282B1 (en) | Method for the production of a high molecular weight polyester prepared from a prepolymer polyester having an optimal carboxyl content | |
| US5594092A (en) | Process for manufacturing polyester copolymers | |
| JPS5964658A (en) | Polyester melt blend with high gas barrier properties | |
| JP3717392B2 (en) | Polyester resin | |
| JP3690255B2 (en) | Polyester resin production method and polyester resin obtained thereby | |
| JP5598162B2 (en) | Copolyester molded product | |
| JPH06322082A (en) | Polyester and hollow container made using the same | |
| JP3685042B2 (en) | Production method of polyester resin | |
| JP3679264B2 (en) | Production method of polyester resin | |
| JPS6123216B2 (en) | ||
| JPS6252766B2 (en) | ||
| US3462395A (en) | Method for preparing esters using imidazoles as catalysts | |
| JP4159237B2 (en) | Production method of polyester resin | |
| JPS6055536B2 (en) | Method for producing polyester hollow molded body or its precursor molded body | |
| JP2008274071A (en) | Production method of polyester polycondensation catalyst and polyester production method using the catalyst | |
| JP3331719B2 (en) | Copolyester for direct blow bottle | |
| US5942596A (en) | Process for the production of clear copolyesters of terephthalic acid, napthalenedicarboxylic acid and ethylene glycol | |
| JP2000219730A (en) | Polyester resin | |
| JP2004307597A (en) | Method for producing polyethylene terephthalate | |
| JPS6134451B2 (en) | ||
| JP3136743B2 (en) | Copolyester and molded product thereof | |
| JP2000226445A (en) | Polyester resin | |
| US4196279A (en) | Process for producing polyesters having a high degree of polymerization | |
| JP4624590B2 (en) | Method for producing metal compound-containing polyester resin composition, preform for hollow molded article, and method for producing hollow molded article |