JP2006176627A - Catalyst for polyester polymerization, polyester obtained using the same and its manufacturing method - Google Patents
Catalyst for polyester polymerization, polyester obtained using the same and its manufacturing method Download PDFInfo
- Publication number
- JP2006176627A JP2006176627A JP2004370882A JP2004370882A JP2006176627A JP 2006176627 A JP2006176627 A JP 2006176627A JP 2004370882 A JP2004370882 A JP 2004370882A JP 2004370882 A JP2004370882 A JP 2004370882A JP 2006176627 A JP2006176627 A JP 2006176627A
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- JP
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- Prior art keywords
- solution
- polyester
- acid
- compound
- color adjusting
- 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.)
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- 229920000728 polyester Polymers 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 89
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 54
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 238000010521 absorption reaction Methods 0.000 claims abstract description 20
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 15
- 239000002685 polymerization catalyst Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 238000000862 absorption spectrum Methods 0.000 claims description 12
- 238000002835 absorbance Methods 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 10
- 230000031700 light absorption Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 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 claims description 3
- NMYFVWYGKGVPIW-UHFFFAOYSA-N 3,7-dioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical compound O=C1OCCCOC(=O)C2=CC=C1C=C2 NMYFVWYGKGVPIW-UHFFFAOYSA-N 0.000 claims description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 6
- 229920001634 Copolyester Polymers 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 20
- 238000006068 polycondensation reaction Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 6
- 150000001463 antimony compounds Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 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
- 238000005259 measurement Methods 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005452 bending 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
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 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
- 238000004451 qualitative analysis Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- LLJFNWVJKMVHIL-UHFFFAOYSA-N (2-methoxy-2-oxoethyl)phosphonic acid Chemical compound COC(=O)CP(O)(O)=O LLJFNWVJKMVHIL-UHFFFAOYSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- QOSTVEDABRQTSU-UHFFFAOYSA-N 1,4-bis(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC)=CC=C2NC QOSTVEDABRQTSU-UHFFFAOYSA-N 0.000 description 1
- ZKIVUFFTMWIBCO-UHFFFAOYSA-N 1,5-bis(4-methylanilino)anthracene-9,10-dione Chemical compound C1=CC(C)=CC=C1NC1=CC=CC2=C1C(=O)C1=CC=CC(NC=3C=CC(C)=CC=3)=C1C2=O ZKIVUFFTMWIBCO-UHFFFAOYSA-N 0.000 description 1
- BWQIGAJDKXZJTG-UHFFFAOYSA-N 1-(cyclohexylamino)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1CCCCC1 BWQIGAJDKXZJTG-UHFFFAOYSA-N 0.000 description 1
- GBAJQXFGDKEDBM-UHFFFAOYSA-N 1-(methylamino)-4-(3-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=CC(C)=C1 GBAJQXFGDKEDBM-UHFFFAOYSA-N 0.000 description 1
- ITYXXSSJBOAGAR-UHFFFAOYSA-N 1-(methylamino)-4-(4-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=C(C)C=C1 ITYXXSSJBOAGAR-UHFFFAOYSA-N 0.000 description 1
- NIDFGXDXQKPZMA-UHFFFAOYSA-N 14h-benz[4,5]isoquino[2,1-a]perimidin-14-one Chemical compound C1=CC(N2C(=O)C=3C4=C(C2=N2)C=CC=C4C=CC=3)=C3C2=CC=CC3=C1 NIDFGXDXQKPZMA-UHFFFAOYSA-N 0.000 description 1
- ZPSZXWVBMOMXED-UHFFFAOYSA-N 2-(2-bromo-5-chlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC(Cl)=CC=C1Br ZPSZXWVBMOMXED-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- UBZVRROHBDDCQY-UHFFFAOYSA-N 20749-68-2 Chemical compound C1=CC(N2C(=O)C3=C(C(=C(Cl)C(Cl)=C3C2=N2)Cl)Cl)=C3C2=CC=CC3=C1 UBZVRROHBDDCQY-UHFFFAOYSA-N 0.000 description 1
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 1
- BFWNTVZEALLTGQ-UHFFFAOYSA-N 3-methoxy-3-oxo-2-phenyl-2-phosphonopropanoic acid Chemical compound COC(=O)C(C(O)=O)(P(O)(O)=O)C1=CC=CC=C1 BFWNTVZEALLTGQ-UHFFFAOYSA-N 0.000 description 1
- AMPCGOAFZFKBGH-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]-n,n-dimethylaniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 AMPCGOAFZFKBGH-UHFFFAOYSA-N 0.000 description 1
- TYFJTEPDESMEHE-UHFFFAOYSA-N 6,8-dihydroxy-3-[2-(4-methoxyphenyl)ethyl]-3,4-dihydroisochromen-1-one Chemical compound C1=CC(OC)=CC=C1CCC1OC(=O)C2=C(O)C=C(O)C=C2C1 TYFJTEPDESMEHE-UHFFFAOYSA-N 0.000 description 1
- NMZURKQNORVXSV-UHFFFAOYSA-N 6-methyl-2-phenylquinoline Chemical compound C1=CC2=CC(C)=CC=C2N=C1C1=CC=CC=C1 NMZURKQNORVXSV-UHFFFAOYSA-N 0.000 description 1
- VJUKWPOWHJITTP-UHFFFAOYSA-N 81-39-0 Chemical compound C1=CC(C)=CC=C1NC1=CC=C2C3=C1C(=O)C1=CC=CC=C1C3=CC(=O)N2C VJUKWPOWHJITTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OGBVRMYSNSKIEF-UHFFFAOYSA-N Benzylphosphonic acid Chemical compound OP(O)(=O)CC1=CC=CC=C1 OGBVRMYSNSKIEF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HLNMYBZPLZNJPZ-UHFFFAOYSA-N N-cyclohexylcyclohexanamine 7-hydroxy-8-[(4-phenyldiazenylphenyl)diazenyl]naphthalene-1,3-disulfonic acid Chemical compound C1CCC(CC1)NC1CCCCC1.Oc1ccc2cc(cc(c2c1N=Nc1ccc(cc1)N=Nc1ccccc1)S(O)(=O)=O)S(O)(=O)=O HLNMYBZPLZNJPZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPGIHFRTRXVWOY-UHFFFAOYSA-N Oil red O Chemical compound Cc1ccc(C)c(c1)N=Nc1cc(C)c(cc1C)N=Nc1c(O)ccc2ccccc12 NPGIHFRTRXVWOY-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-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
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- PHIBEYMUALDAQI-UHFFFAOYSA-N benzylphosphinic acid Chemical compound OP(=O)CC1=CC=CC=C1 PHIBEYMUALDAQI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- NHXXLZBKTKNTEF-UHFFFAOYSA-N chembl1997306 Chemical compound CC1=CC=CC(N=NC=2C(=CC(=CC=2)N=NC=2C3=CC=CC=C3C=CC=2O)C)=C1 NHXXLZBKTKNTEF-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- SVTDYSXXLJYUTM-UHFFFAOYSA-N disperse red 9 Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC SVTDYSXXLJYUTM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- RCTGMCJBQGBLKT-PAMTUDGESA-N scarlet red Chemical compound CC1=CC=CC=C1\N=N\C(C=C1C)=CC=C1\N=N\C1=C(O)C=CC2=CC=CC=C12 RCTGMCJBQGBLKT-PAMTUDGESA-N 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940033816 solvent red 27 Drugs 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- 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 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
本発明はポリエステル重合用触媒、それを用いたポリエステル及びその製造方法に関する。さらに詳しくは、真比重５．０以上の金属元素、特にアンチモン、ゲルマニウムの含有量が極めて少なく、色相に優れ、繊維やフィルム製造時の成形性に優れているという性能を有したポリエステル重合用触媒、それを用いたポリエステル及びその製造方法に関する。 The present invention relates to a catalyst for polyester polymerization, a polyester using the same, and a method for producing the same. More specifically, the polyester polymerization catalyst has the performance that the content of a metal element having a true specific gravity of 5.0 or more, particularly antimony and germanium, is extremely small, excellent in hue, and excellent in moldability during fiber and film production. And a polyester using the same and a method for producing the same.
ポリエステル、特にポリエチレンテレフタレート、ポリエチレンナフタレート、ポリトリメチレンテレフタレート及びポリテトラメチレンテレフタレートは、その機械的、物理的、化学的性能が優れているため、繊維、フィルム、又はその他の成形物に広く利用されている。 Polyesters, especially polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate are widely used in fibers, films or other molded products because of their excellent mechanical, physical and chemical performance. ing.
その中で例えばポリエチレンテレフタレートは、次のような２段階の工程で製造されている。通常まずテレフタル酸とエチレングリコールとを直接エステル化反応させるか、テレフタル酸ジメチルのようなテレフタル酸の低級アルキルエステルとエチレングリコールとをエステル交換反応させるか、又はテレフタル酸とエチレンオキサイドとを反応さて、テレフタル酸のエチレングリコールエステル及び／又はその低重合体を生成させる。次いでこの反応生成物を重縮合触媒の存在下で減圧加熱して所定の重合度になるまで重縮合反応させることによって、ポリエチレンテレフタレートが製造されている。 Among them, for example, polyethylene terephthalate is manufactured by the following two-stage process. Usually, terephthalic acid and ethylene glycol are first esterified directly, terephthalic acid lower alkyl ester such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene oxide are reacted, An ethylene glycol ester of terephthalic acid and / or a low polymer thereof is produced. Next, polyethylene terephthalate is produced by heating the reaction product under reduced pressure in the presence of a polycondensation catalyst to carry out a polycondensation reaction until a predetermined polymerization degree is reached.
これらのポリエステルにおいては、重縮合反応段階で使用する触媒の種類によって、反応速度及び得られるポリエステルの品質が大きく左右されることはよく知られている。この点について従来から検討の結果、ポリエチレンテレフタレートの重縮合触媒としては、優れた重縮合触媒性能を有し、かつ色相の良好なポリエステルが得られるなどの理由からアンチモン化合物が最も広く使用されている。 In these polyesters, it is well known that the reaction rate and the quality of the resulting polyester greatly depend on the type of catalyst used in the polycondensation reaction stage. As a result of conventional studies on this point, as a polycondensation catalyst for polyethylene terephthalate, an antimony compound is most widely used because it has excellent polycondensation catalyst performance and a polyester having a good hue. .
しかしながら、アンチモン化合物を重縮合触媒として使用したポリエステルを例えば長時間にわたって連続的に溶融紡糸し繊維化しようとした場合、口金孔周辺に異物（以下、単に口金異物と称することがある。）が付着堆積し、溶融ポリマー流れの曲がり現象（ベンディング）が発生することがある。するとこれが原因となって紡糸、延伸工程において毛羽及び／又は断糸などを発生するという成形性の問題がある。 However, when a polyester using an antimony compound as a polycondensation catalyst is continuously melt-spun for a long time, for example, to make a fiber, foreign matter (hereinafter, sometimes referred to simply as a base foreign matter) adheres to the periphery of the base hole. Accumulation and bending of the molten polymer flow (bending) may occur. As a result, there is a problem of formability that fluff and / or yarn breakage occurs in the spinning and drawing processes.
またペットボトル用などのポリエステル触媒としては、一般的にゲルマニウム化合物が使用されているが、ゲルマニウムは稀少金属であり、高価な為、得られる製品の価格が高くなってしまうことが問題となっている。 In addition, germanium compounds are generally used as polyester catalysts for PET bottles, but germanium is a rare metal and is expensive, so the price of the resulting product becomes high. Yes.
このようなアンチモン化合物やゲルマニウム化合物以外の重縮合触媒として、チタンテトラブトキシドのようなチタン化合物を用いることも提案されている。このようなチタン化合物を使用した場合、上記のような口金異物の堆積に起因する成形性の問題は解決できる。しかし、得られたポリエステル自身が黄色く着色されており、また溶融熱安定性も不良であるという新たな問題が発生する。この着色問題を解決するために、コバルト化合物をポリエステルに添加して黄味を抑えることが一般的に行われている。確かにコバルト化合物を添加することによってポリエステルの色相（ｂ＊値）は改善することができるが、コバルト化合物を添加することによってポリエステルの溶融熱安定性がさらに低下し、ポリマーの分解も起こりやすくなるという問題がある。 It has also been proposed to use a titanium compound such as titanium tetrabutoxide as a polycondensation catalyst other than such antimony compounds and germanium compounds. When such a titanium compound is used, the above-described problem of formability due to the accumulation of foreign matter in the die can be solved. However, there is a new problem that the obtained polyester itself is colored yellow and that the heat stability of the melt is poor. In order to solve this coloring problem, it is a common practice to suppress yellowishness by adding a cobalt compound to polyester. Certainly, the hue (b * value) of the polyester can be improved by adding a cobalt compound. However, the addition of a cobalt compound further lowers the melt heat stability of the polyester and tends to cause degradation of the polymer. There is a problem.
また、他のチタン化合物として、水酸化チタン、又はα−チタン酸をポリエステル製造用触媒として使用することが開示されている（それぞれ例えば特許文献１、特許文献２参照。）。しかしながら、前者の方法では水酸化チタンの粉末化が容易でなく、一方後者の方法ではα−チタン酸が変質し易いため、その保存、取扱いが容易でない。したがっていずれも工業的に採用するには適当ではなく、さらに、良好な色相（ｂ＊値）のポリマーを得ることも困難である。 In addition, it is disclosed that titanium hydroxide or α-titanic acid is used as a polyester production catalyst as another titanium compound (see, for example, Patent Document 1 and Patent Document 2). However, in the former method, powdering of titanium hydroxide is not easy, whereas in the latter method, α-titanic acid is likely to be altered, so that storage and handling are not easy. Accordingly, none of them are suitable for industrial use, and it is also difficult to obtain a polymer having a good hue (b * value).
このような問題を解決する為に、チタン化合物と特定のリン化合物とを反応させて得られた生成物を（例えば特許文献３及び特許文献４参照。）、またチタン化合物と特定のリン化合物の未反応混合物あるいは反応生成物を（例えば特許文献５参照。）、それぞれポリエステル製造用触媒として使用することが開示されている。確かにこの方法によればポリエステルの溶融熱安定性は向上し、得られるポリマーの色相も大きく改善されるが、これらの方法ではポリエステル製造時の重合反応速度が遅い為、ポリエステルの生産性がやや劣ってしまう問題を有している。 In order to solve such a problem, a product obtained by reacting a titanium compound with a specific phosphorus compound (see, for example, Patent Document 3 and Patent Document 4), a titanium compound and a specific phosphorus compound It is disclosed that an unreacted mixture or a reaction product (see, for example, Patent Document 5) is used as a catalyst for polyester production. Certainly, this method improves the melt heat stability of the polyester and greatly improves the hue of the resulting polymer. However, in these methods, the polymerization reaction rate during the production of the polyester is slow, so that the productivity of the polyester is slightly higher. Has the problem of being inferior.
ポリエステルの安定成形性を向上させるには、前記のように触媒としてアンチモン化合物を使用しないことが有効な手段であるが、アンチモン化合物を使用しない方法では、糸のカラー（色相）が低下してしまうため、従来は使用に供することができなかった。したがって触媒としてアンチモン化合物を使用せず、かつ色相に優れたポリエステルが求められていた。 In order to improve the stable moldability of polyester, it is an effective means not to use an antimony compound as a catalyst as described above, but in the method not using an antimony compound, the color (hue) of the thread is lowered. Therefore, it could not be used in the past. Accordingly, there has been a demand for a polyester that does not use an antimony compound as a catalyst and is excellent in hue.
一方ポリエステルの色相を改善する試みとしては染料を混練したポリエステルが開示されているが（例えば特許文献６〜１０参照。）、色相改善のレベルとしてはまだ十分なものではなかった。 On the other hand, a polyester kneaded with a dye has been disclosed as an attempt to improve the hue of the polyester (see, for example, Patent Documents 6 to 10), but the level of hue improvement has not been sufficient.
本発明の目的は色相に優れ、長時間連続的に紡糸しても、口金への付着物の発生量が非常に少なく、優れた成形性を有するポリエステルを製造する為の触媒、ポリエステル及びその製造方法を提供することにある。 An object of the present invention is a catalyst for producing a polyester having excellent hue, having a very small amount of deposits on the die even when continuously spun for a long time, and having excellent moldability, and the production thereof It is to provide a method.
本発明者らは上記従来技術に鑑み鋭意検討を重ねた結果、本発明を完成するに至った。
すなわち本発明は、ポリエステル重合用の触媒であり、有機チタン化合物を溶解させたアルキレングリコール溶液からなる溶液Ａと、波長３８０〜７８０ｎｍ領域において可視・紫外分光光度計によって測定された最大吸収波長領域が５２０〜６４０ｎｍの範囲にある有機系整色剤を溶解又は分散させたアルキレングリコール溶液からなる溶液Ｂからなる、ポリエステル重合用触媒であり、このポリエステル重合用触媒を用いて溶融重合された、真比重５．０以上の金属元素の含有量が０〜１０質量ｐｐｍ以下であるポリエステルによって上記の課題が解決できる。
As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention.
That is, the present invention is a catalyst for polyester polymerization, and has a solution A comprising an alkylene glycol solution in which an organic titanium compound is dissolved, and a maximum absorption wavelength region measured by a visible / ultraviolet spectrophotometer in a wavelength region of 380 to 780 nm. A polyester polymerization catalyst comprising a solution B consisting of an alkylene glycol solution in which an organic color adjusting agent in the range of 520 to 640 nm is dissolved or dispersed. The true specific gravity obtained by melt polymerization using the polyester polymerization catalyst Said problem can be solved by the polyester whose content of the metal element of 5.0 or more is 0-10 mass ppm or less.
本発明によればポリエステルの優れた特性を保持しながら、アンチモンやゲルマニウム触媒を使用しないポリエステルの欠点であった色相の悪化を解消することができる。また、口金への付着物の発生量が非常に少なく、優れた成形性を有するポリエステルを提供することが出来る。 According to the present invention, it is possible to eliminate the deterioration of the hue, which is a defect of the polyester not using antimony or germanium catalyst, while maintaining the excellent characteristics of the polyester. Further, it is possible to provide a polyester having a very small amount of deposits on the die and having excellent moldability.
以下本発明を詳しく説明する。
本発明のポリエステル重合用触媒とは、有機チタン化合物を溶解させたアルキレングリコール溶液からなる溶液Ａと、波長３８０〜７８０ｎｍ領域において可視・紫外分光光度計によって測定された最大吸収波長領域が５２０〜６４０ｎｍの範囲にある有機系整色剤を溶解又は分散させたアルキレングリコール溶液からなる溶液Ｂからなる、ポリエステル重合用触媒である。ここでアルキレングリコールについては特に限定は無いが、通常ポリエステルの重合に用いられる炭素数２〜１０のアルキレングリコールが好ましく、特に直鎖型のアルキレングリコールが特に好ましい。更に、該アルキレングリコールとしては、エチレングリコール、トリメチレングリコール、テトラメチレングリコールのいずれか１種以上が５０質量％以上含まれていることが好ましく、エチレングリコールが９０質量％以上であることが最も好ましい。
The present invention will be described in detail below.
The polyester polymerization catalyst of the present invention is a solution A composed of an alkylene glycol solution in which an organic titanium compound is dissolved, and a maximum absorption wavelength region measured by a visible / ultraviolet spectrophotometer in a wavelength range of 380 to 780 nm is 520 to 640 nm. A polyester polymerization catalyst comprising a solution B comprising an alkylene glycol solution in which an organic color adjusting agent in the range of 1 is dissolved or dispersed. Here, the alkylene glycol is not particularly limited, but an alkylene glycol having 2 to 10 carbon atoms that is usually used for polymerization of a polyester is preferable, and a linear alkylene glycol is particularly preferable. Further, as the alkylene glycol, it is preferable that at least one of ethylene glycol, trimethylene glycol, and tetramethylene glycol is contained in an amount of 50% by mass or more, and ethylene glycol is most preferably 90% by mass or more. .
本発明の溶液Ａに使用する有機チタン化合物とは、ポリエステルの重縮合触媒として一般的なチタン化合物、例えば、酢酸チタンやテトラアルコキシチタンなどが挙げられ、酸化チタンなどのような無機粒子のチタン化合物は含まれない。更に、有機チタン化合物としては下記一般式（Ｉ）で表される化合物、又は下記一般式（Ｉ）で表される化合物と１分子中のカルボキシル基数が１〜４個であるカルボン酸化合物を予め反応させた化合物であることが好ましい。 The organic titanium compound used in the solution A of the present invention is a general titanium compound as a polyester polycondensation catalyst, such as titanium acetate or tetraalkoxytitanium, and a titanium compound of inorganic particles such as titanium oxide. Is not included. Further, as the organic titanium compound, a compound represented by the following general formula (I), or a compound represented by the following general formula (I) and a carboxylic acid compound having 1 to 4 carboxyl groups in one molecule are previously used. A reacted compound is preferable.
ここで、一般式（Ｉ）の化合物としては、テトラメトキシシチタン、テトラエトキシチタン、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラ−ｎ−ブトキシチタン、テトラフェノキシチタン、あるいはこれらのダイマー、トリマー、テトラマー等が例示される。また、１分子中のカルボキシル基数が１〜４個であるカルボン酸化合物としては、安息香酸、フタル酸、無水フタル酸、テレフタル酸、イソフタル酸、トリメリット酸、無水トリメリット酸、ピロメリット酸、無水ピロメリット酸、シュウ酸、コハク酸、無水コハク酸、アジピン酸、セバシン酸、乳酸等が例示され、これらの中でもフタル酸、無水フタル酸、テレフタル酸、イソフタル酸、トリメリット酸、無水トリメリット酸などの芳香族ジカルボン酸若しくは芳香族トリカルボン酸、又はこれらの酸無水物化合物が特に好ましい。上記チタン化合物とカルボン酸化合物とを反応させる場合には、溶媒にカルボン酸化合物を溶解又は分散させ、これにチタン化合物を滴下して、０〜２００℃の温度で少なくとも３０分間反応させれば良く、溶媒としては上述したアルキレングリコール、特にエチレングリコールが好ましい。 Here, as the compound of the general formula (I), tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetraphenoxy titanium, or a dimer thereof, A trimer, a tetramer, etc. are illustrated. Moreover, as a carboxylic acid compound having 1 to 4 carboxyl groups in one molecule, benzoic acid, phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, Examples include pyromellitic anhydride, oxalic acid, succinic acid, succinic anhydride, adipic acid, sebacic acid, lactic acid, etc. Among these, phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, trimellitic acid, trimellitic anhydride Aromatic dicarboxylic acids or aromatic tricarboxylic acids such as acids, or acid anhydride compounds thereof are particularly preferred. When the titanium compound and the carboxylic acid compound are reacted, the carboxylic acid compound may be dissolved or dispersed in a solvent, and the titanium compound may be dropped into the solvent and reacted at a temperature of 0 to 200 ° C. for at least 30 minutes. The solvent is preferably the above-described alkylene glycol, particularly ethylene glycol.
本発明の溶液Ｂに使用する有機系整色剤とは、波長３８０〜７８０ｎｍ領域において可視・紫外分光光度計によって測定された最大吸収波長領域が５２０〜６４０ｎｍの範囲にある有機化合物であることが必要であり、有機の多芳香族環系染料又は顔料であることが好ましい。これらの化学構造について限定はないが、ポリエステルに添加する場合の変色を低減するべく、ハロゲン元素は含んでいない方が好ましい。また、化合物としては単独でもよく、２種類以上の混合物であってもよい。ここで、整色剤溶液の吸収スペクトルの最大吸収波長が５２０ｎｍ未満の場合は得られるポリエステルの赤味が強くなり、また６４０ｎｍを超える場合は得られるポリエステルの青味が強くなる為好ましくない。最大吸収波長の範囲は５３０〜６３０ｎｍの範囲が好ましく、５４０〜６２０ｎｍの範囲が更に好ましい。また、該有機系整色剤は、濃度２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて可視・紫外分光光度計によって測定された波長３８０〜７８０ｎｍ領域の可視光吸収スペクトルを測定したとき、最大吸収波長における吸光度に対する各波長での吸光度の割合が下記数式（１）〜（４）のすべてを満たしていることが好ましい。
０．００≦Ａ４００／Ａｍａｘ≦０．２０ （１）
０．１０≦Ａ５００／Ａｍａｘ≦０．７０ （２）
０．５５≦Ａ６００／Ａｍａｘ≦１．００ （３）
０．００≦Ａ７００／Ａｍａｘ≦０．０５ （４）
［上記数式中、Ａ４００、Ａ５００、Ａ６００及びＡ７００はそれぞれ波長４００ｎｍ、５００ｎｍ、６００ｎｍ及び７００ｎｍでの可視光吸収スペクトルにおける吸光度を、Ａｍａｘは最大吸収波長での可視光吸収スペクトルにおける吸光度を表す。］
The organic color adjusting agent used for the solution B of the present invention is an organic compound having a maximum absorption wavelength range measured by a visible / ultraviolet spectrophotometer in a wavelength range of 380 to 780 nm in a range of 520 to 640 nm. It is necessary and is preferably an organic polyaromatic ring dye or pigment. Although there is no limitation on these chemical structures, it is preferable not to contain a halogen element in order to reduce discoloration when added to polyester. Moreover, as a compound, it may be individual and a 2 or more types of mixture may be sufficient. Here, when the maximum absorption wavelength of the absorption spectrum of the color adjusting agent solution is less than 520 nm, the redness of the obtained polyester becomes strong, and when it exceeds 640 nm, the blueness of the obtained polyester becomes strong. The range of the maximum absorption wavelength is preferably in the range of 530 to 630 nm, and more preferably in the range of 540 to 620 nm. The organic color adjusting agent has a maximum absorption wavelength when a visible light absorption spectrum in a wavelength range of 380 to 780 nm measured with a visible / ultraviolet spectrophotometer at an optical path length of 1 cm for a chloroform solution having a concentration of 20 mg / L is measured. It is preferable that the ratio of the absorbance at each wavelength with respect to the absorbance in the formula satisfies all of the following formulas (1) to (4).
0.00 ≦ A 400 / A max ≦ 0.20 (1)
0.10 ≦ A 500 / A max ≦ 0.70 (2)
0.55 ≦ A 600 / A max ≦ 1.00 (3)
0.00 ≦ A 700 / A max ≦ 0.05 (4)
[In the above formula, A 400 , A 500 , A 600 and A 700 are the absorbance in the visible light absorption spectrum at wavelengths of 400 nm, 500 nm, 600 nm and 700 nm, respectively, and A max is the absorbance in the visible light absorption spectrum at the maximum absorption wavelength. Represents. ]
更に該有機系整色剤は、窒素雰囲気下中、昇温速度１０℃／分の条件で熱天秤にて測定したときの質量減少開始温度が２５０℃以上である整色用色素から選ばれることが好ましい。ここで、熱天秤で測定したときの質量減少開始温度とは、ＪＩＳ Ｋ−７１２０に記載の質量減少開始温度（Ｔ１）のことであり、整色剤が有している耐熱性の指標となる。該質量減少開始温度が２５０℃未満である場合、整色剤の耐熱性が不十分であることから最終的に得られるポリエステルの着色の原因となり好ましくない。該質量減少開始温度は３００℃以上であることが更に好ましい。 Further, the organic color adjusting agent is selected from color adjusting dyes having a mass decrease starting temperature of 250 ° C. or higher when measured with a thermobalance in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. Is preferred. Here, the mass decrease start temperature when measured with a thermobalance is the mass decrease start temperature (T 1 ) described in JIS K-7120, and is a heat resistance index possessed by the color adjuster. Become. When the mass decrease starting temperature is less than 250 ° C., the heat resistance of the color adjusting agent is insufficient, which is not preferable because it causes coloring of the finally obtained polyester. The mass decrease starting temperature is more preferably 300 ° C. or higher.
本発明に使用する有機系整色剤としては、青色系整色用色素と紫色系整色用色素を質量比９０：１０〜４０：６０の範囲で併用すること、又は青色系整色用色素と赤色系又は橙色系整色用色素を質量比９８：２〜８０：２０の範囲で併用することが好ましい。ここで青色系整色用色素とは、一般に市販されている整色用色素の中で「Ｂｌｕｅ」と表記されているものであって、具体的には溶液中の可視光吸収スペクトルにおける最大吸収波長が５８０〜６２０ｎｍ程度にあるものを示す。同様に紫色系整色用色素とは市販されている整色用色素の中で「Ｖｉｏｌｅｔ」と表記されているものであって、具体的には溶液中の可視光吸収スペクトルにおける最大吸収波長が５６０〜５８０ｎｍ程度にあるものを示す。赤色系整色用色素とは市販されている整色用色素の中で「Ｒｅｄ」と表記されているものであって、具体的には溶液中の可視光吸収スペクトルにおける最大吸収波長が４８０〜５２０ｎｍ程度にあるものである。橙色系系整色用色素とは市販されている整色用色素の中で「Ｏｒａｎｇｅ」と表記されているものである。 As the organic color adjusting agent used in the present invention, a blue color adjusting dye and a purple color adjusting dye are used in a mass ratio of 90:10 to 40:60, or a blue color adjusting dye. It is preferable to use red and orange color adjusting pigments in a mass ratio of 98: 2 to 80:20. Here, the blue color-modifying dye is generally indicated as “Blue” among commercially available color-adjusting dyes, and specifically, the maximum absorption in the visible light absorption spectrum in the solution. The wavelength is about 580 to 620 nm. Similarly, the purple color-modifying dye is the one described as “Violet” among commercially available color-adjusting dyes. Specifically, the maximum absorption wavelength in the visible light absorption spectrum in the solution is The thing in about 560-580 nm is shown. The red color-modifying dyes are those listed as “Red” among commercially available color-adjusting dyes. Specifically, the maximum absorption wavelength in the visible light absorption spectrum in the solution is 480 to 480. It is about 520 nm. The orange-based color-adjusting colorant is the one described as “Orange” among commercially available color-adjusting colorants.
これらの整色用色素としては油溶染料が特に好ましく、具体的な例としては、青色系整色用色素には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ １１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ３５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ３６、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ４５ （Ｔｅｌａｓｏｌ Ｂｌｕｅ ＲＬＳ）、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ５５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ６３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ７８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ８３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ８７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ９４等が挙げられる。紫色系整色用色素には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ １３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ １４、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ３６等が挙げられる。赤色系整色用色素には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２４、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ３０、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ４９、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ５２、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １００、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １０９、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １１１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １２１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １３５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １６８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １７９等が例示される。橙色系整色用色素には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｏｒａｎｇｅ ６０等が挙げられる。 As these color adjusting dyes, oil-soluble dyes are particularly preferable. As specific examples, blue color adjusting dyes include C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 45 (Telasol Blue RLS), C.I. I. Solvent Blue 55, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I. I. Solvent Blue 87, C.I. I. Solvent Blue 94 and the like. Examples of purple color adjusting pigments include C.I. I. Solvent Violet 8, C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Violet 21, C.I. I. Solvent Violet 27, C.I. I. Solvent Violet 28, C.I. I. Solvent Violet 36 etc. are mentioned. Examples of red color adjusting pigments include C.I. I. Solvent Red 24, C.I. I. Solvent Red 25, C.I. I. Solvent Red 27, C.I. I. Solvent Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Solvent Red 100, C.I. I. Solvent Red 109, C.I. I. Solvent Red 111, C.I. I. Solvent Red 121, C.I. I. Solvent Red 135, C.I. I. Solvent Red 168, C.I. I. Solvent Red 179 etc. are illustrated. Examples of the orange color adjusting dye include C.I. I. Solvent Orange 60 etc. are mentioned.
ここで青色系整色用色素と紫色系整色用色素を併用する場合、質量比９０：１０より青色系整色用色素の質量比が大きい場合は、得られるポリエステルのカラーａ＊値が小さくなって緑色を呈し、４０：６０より青色整色用色素の質量比が小さい場合は、カラーａ＊値が大きくなって赤色を呈してくる為好ましくない。同様に青色系整色用色素と赤色系又は橙色系整色用色素を併用する場合、質量比９８：２より青色系整色用色素の質量比が大きい場合は、得られるポリエステルのカラーａ＊値が小さくなって緑色を呈し、８０：２０より青色整色用色素の質量比が小さい場合は、カラーａ＊値が大きくなって赤色を呈してくる為好ましくない。該整色用色素は、青色系整色用色素と紫色系整色用色素を質量比８０：２０〜５０：５０の範囲で併用すること、あるいは青色系整色用色素と赤色系又は橙色系整色用色素を質量比９５：５〜９０：１０の範囲で併用することが更に好ましい。 Here, when the blue color adjusting dye and the purple color adjusting dye are used in combination, when the mass ratio of the blue color adjusting dye is larger than the mass ratio 90:10, the color a * value of the obtained polyester is small. If the mass ratio of the blue color adjusting dye is smaller than 40:60, the color a * value increases and a red color is exhibited, which is not preferable. Similarly, in the case where a blue color adjusting dye and a red or orange color adjusting dye are used in combination, when the mass ratio of the blue color adjusting dye is larger than 98: 2, the color a * of the obtained polyester If the value is small and green, and the mass ratio of the blue color adjusting pigment is smaller than 80:20, the color a * value becomes large and red is not preferable. The color adjusting dye is a combination of a blue color adjusting dye and a purple color adjusting dye in a mass ratio of 80:20 to 50:50, or a blue color adjusting dye and a red or orange color. It is more preferable to use the color adjusting dye in a mass ratio of 95: 5 to 90:10.
本発明のポリエステル重合用触媒は、上述した溶液Ａ及び溶液Ｂに、更にリン化合物を溶解させたアルキレングリコール溶液からなる溶液Ｃを組合せた溶液であることが好ましい。ここでアルキレングリコールとしては上述した溶液Ａ、溶液Ｂと同じグリコールであることが好ましく、エチレングリコールであることが特に好ましい。リン化合物としては特に限定はないが、リン酸、亜リン酸、ホスホン酸、ホスフィン酸系化合物、あるいはこれらのエステル化合物であることが好ましい。具体的にはリン酸、亜リン酸、メチルホスホン酸、エチルホスホン酸、フェニルホスホン酸、ベンジルホスホン酸、メチルホスフィン酸、エチルホスフィン酸、フェニルホスフィン酸、ベンジルホスフィン酸、カルボメトキシメタンホスホン酸、カルボエトキシメタンホスホン酸、カルボプロポキシメタンホスホン酸、カルボブトキシメタンホスホン酸、カルボメトキシ−ホスホノ−フェニル酢酸、カルボエトキシ−ホスホノ−フェニル酢酸、カルボプロポキシ−ホスホノ−フェニル酢酸、カルボブトキシ−ホスホノ−フェニル酢酸、[｛３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル｝メチル]ホスホン酸若しくは[｛３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル｝エチル]ホスホン酸、又はこれらのメチルエステル、エチルエステル、プロピルエステル、ブチルエステル若しくはフェニルエステル等が例示される。 The polyester polymerization catalyst of the present invention is preferably a solution in which the solution A and the solution B described above are combined with a solution C made of an alkylene glycol solution in which a phosphorus compound is further dissolved. Here, the alkylene glycol is preferably the same glycol as the solution A and the solution B described above, and particularly preferably ethylene glycol. Although it does not specifically limit as a phosphorus compound, It is preferable that they are phosphoric acid, phosphorous acid, phosphonic acid, a phosphinic acid type compound, or these ester compounds. Specifically, phosphoric acid, phosphorous acid, methylphosphonic acid, ethylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, methylphosphinic acid, ethylphosphinic acid, phenylphosphinic acid, benzylphosphinic acid, carbomethoxymethanephosphonic acid, carboethoxy Methanephosphonic acid, carbopropoxymethanephosphonic acid, carbobutoxymethanephosphonic acid, carbomethoxy-phosphono-phenylacetic acid, carboethoxy-phosphono-phenylacetic acid, carbopropoxy-phosphono-phenylacetic acid, carbobutoxy-phosphono-phenylacetic acid, [{ 3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] phosphonic acid or [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} ethyl] phosphonic acid, Or these Examples thereof include methyl ester, ethyl ester, propyl ester, butyl ester, and phenyl ester.
本発明のポリエステル重合用触媒に使用する溶液Ａ、溶液Ｂ及び溶液Ｃは通常、それぞれ単独で調製されて別々に添加されるが、これらのいずれか２種以上を予め混合させておいてもよい。 The solution A, solution B and solution C used in the polyester polymerization catalyst of the present invention are usually prepared individually and added separately, but any two or more of these may be mixed in advance. .
本発明のポリエステル重合用触媒に使用する溶液Ａ、溶液Ｂ及び溶液Ｃの濃度、温度は特に限定は無いが、溶液Ａ、Ｃの濃度については０．１〜５０質量％程度の範囲が好ましく、溶液Ｂの濃度については０．０１％〜５質量％の範囲が好ましい。温度は１０℃〜１００℃の範囲で保持しておくことが好ましい。 The concentration and temperature of solution A, solution B and solution C used for the polyester polymerization catalyst of the present invention are not particularly limited, but the concentration of solutions A and C is preferably in the range of about 0.1 to 50% by mass, About the density | concentration of the solution B, the range of 0.01%-5 mass% is preferable. The temperature is preferably maintained in the range of 10 ° C to 100 ° C.
本発明のポリエステルは、上述したポリエステル重合用触媒を用いて溶融重合された、真比重５．０以上の金属元素の含有量が０〜１０質量ｐｐｍ以下であるポリエステルであり、ここでいうポリエステルとは、テレフタル酸やナフタレンジカルボン酸、あるいはこれらのエステル形成性誘導体に代表されるジカルボン酸成分と、エチレングリコールやテトラメチレングリコール等に代表されるグリコール成分を重縮合反応せしめて得られるポリエステルのことである。このポリエステルは、共重合ポリエステルであってもよいが、好ましくは、ポリエステルの繰り返し単位が、エチレンテレフタレート、トリメチレンテレフタレート、テトラメチレンテレフタレート、エチレン−２，６−ナフタレート、トリメチレン−２，６−ナフタレート、テトラメチレン−２，６−ナフタレートのいずれか５０モル％以上であることが好ましく、９０モル％以上であることが更に好ましい。 The polyester of the present invention is a polyester having a content of a metal element having a true specific gravity of 5.0 or more and melt-polymerized using the above-described polyester polymerization catalyst, which is 0 to 10 ppm by mass or less. Is a polyester obtained by polycondensation reaction of a dicarboxylic acid component typified by terephthalic acid, naphthalenedicarboxylic acid or an ester-forming derivative thereof and a glycol component typified by ethylene glycol or tetramethylene glycol. is there. The polyester may be a copolyester, but preferably the polyester repeating unit is ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, ethylene-2,6-naphthalate, trimethylene-2,6-naphthalate, It is preferably 50 mol% or more of tetramethylene-2,6-naphthalate, and more preferably 90 mol% or more.
本発明における真比重５．０以上の金属元素とは通常ポリエステル中に含有される触媒や金属系の整色剤、艶消剤等に含有されている金属化合物に由来するものである。具体的には、アンチモン、ゲルマニウム、マンガン、コバルト、セリウム、錫、亜鉛、鉛又はカドミウム等が該当する。これらに対し、チタン、アルミニウム、カルシウム、マグネシウム、ナトリウム又はカリウム等はここでいう真比重５．０以上の金属には該当しない。 The metal element having a true specific gravity of 5.0 or more in the present invention is derived from a metal compound usually contained in a catalyst, a metal color adjuster, a matting agent and the like contained in a polyester. Specifically, antimony, germanium, manganese, cobalt, cerium, tin, zinc, lead, cadmium, and the like are applicable. On the other hand, titanium, aluminum, calcium, magnesium, sodium, potassium, and the like do not correspond to metals having a true specific gravity of 5.0 or more.
本発明のポリエステルは真比重５．０以上の金属元素の含有量が０〜１０質量ｐｐｍ以下であることが必要である。含有される金属の種類によってその特徴、特性は変わるが、例えばアンチモン金属含有量が１０質量ｐｐｍより多い場合、溶融紡糸時やフィルムの製膜時に異物となって口金やダイ周辺に付着し、長期間の連続成形性に悪影響を与える。ゲルマニウム金属の場合は、それ自体が高価な為、含有量が多くなると得られるポリエステルの価格が上昇してしまい好ましくない。また、鉛、カドミウムなどの金属の場合は金属元素そのものに毒性がある為、ポリエステル中に多量に含有していることは好ましくない。該真比重５．０以上の金属元素の含有量は０〜７質量ｐｐｍ以下であることが好ましく、０〜５質量ｐｐｍ以下であることが更に好ましい。 In the polyester of the present invention, the content of a metal element having a true specific gravity of 5.0 or more needs to be 0 to 10 ppm by mass or less. The characteristics and properties vary depending on the type of metal contained. For example, when the content of antimony metal is more than 10 ppm by mass, it becomes a foreign substance during melt spinning or film formation and adheres to the periphery of the die or die. This will adversely affect the continuous formability of the period. In the case of germanium metal, since it is expensive per se, the price of the resulting polyester is undesirably increased as the content increases. Further, in the case of metals such as lead and cadmium, since the metal element itself is toxic, it is not preferable to contain a large amount in the polyester. The content of the metal element having a true specific gravity of 5.0 or more is preferably 0 to 7 mass ppm or less, and more preferably 0 to 5 mass ppm or less.
本発明のポリエステルの固有粘度（溶媒：オルトクロロフェノール、測定温度：３５℃）は特に制限は無いが、繊維やフィルム、ボトル等の樹脂成形品において通常使用することが出来る範囲であることが好ましく、具体的には０．４０〜１．００の範囲にあることが好ましい。また、該ポリエステルは固相重合によって固有粘度を高めることも好ましく実施される。 The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the polyester of the present invention is not particularly limited, but is preferably within a range that can be normally used in resin molded products such as fibers, films, and bottles. Specifically, it is preferably in the range of 0.40 to 1.00. The polyester is also preferably increased in intrinsic viscosity by solid phase polymerization.
本発明のポリエステルの色相は特に厳密な制限はないが、本発明に使用されるべきポリエステル重合用触媒、特に溶液Ｃが添加されていないと、得られるポリエステルの色相が黄色味を帯びた色相となり好ましくない。該ポリエステルの色相は用途や添加剤の種類によって異なるが、１４０℃、２時間の熱処理により結晶化を進めた後のＬ＊ａ＊ｂ＊表色系におけるカラーａ＊値が−９〜０、カラーｂ＊値が−２〜１０の範囲にあることが好ましい。該カラー値は、カラーａ＊値が−９より小さい場合緑色味が強くなり、０より大きい場合は赤味が強くなり好ましくない。またカラーｂ＊値が−２より小さい場合青味が強くなり、１０より大きい場合は黄色味が強くなるため好ましくない。 The hue of the polyester of the present invention is not particularly limited, but if the polyester polymerization catalyst to be used in the present invention, in particular, the solution C is not added, the hue of the resulting polyester becomes a yellowish hue. It is not preferable. The hue of the polyester varies depending on the use and the kind of the additive, but the color a * value in the L * a * b * color system after proceeding crystallization by heat treatment at 140 ° C. for 2 hours is −9 to 0, The color b * value is preferably in the range of −2 to 10. When the color a * value is smaller than −9, the color value is unfavorably greenish, and when the color value is larger than 0, the redness becomes strong. Further, when the color b * value is less than −2, the bluish color becomes strong, and when it is larger than 10, the yellow color becomes strong, which is not preferable.
また本発明におけるポリエステルは、必要に応じて少量の添加剤、例えば酸化防止剤、固相重合促進剤、蛍光増白剤、帯電防止剤、抗菌剤、紫外線吸収剤、光安定剤、熱安定剤、遮光剤又は艶消剤等を含んでいてもよい。特に繊維用途に使用する場合は艶消剤として酸化チタンが好ましく添加される。 Further, the polyester in the present invention contains a small amount of additives as necessary, for example, an antioxidant, a solid phase polymerization accelerator, a fluorescent whitening agent, an antistatic agent, an antibacterial agent, an ultraviolet absorber, a light stabilizer, and a heat stabilizer. Further, it may contain a light-shielding agent or a matting agent. In particular, when used for textile applications, titanium oxide is preferably added as a matting agent.
本発明のポリエステル重合用触媒を用いてポリエステルを重合する場合の溶液Ａ、溶液Ｂ及び溶液Ｃの添加量は各溶液の濃度、製造するポリエステルの種類によって異なる。 When the polyester is polymerized using the polyester polymerization catalyst of the present invention, the amount of solution A, solution B and solution C added varies depending on the concentration of each solution and the type of polyester to be produced.
溶液Ａについては得られるポリエステル中に含有されるチタン元素量がポリエステルの全繰り返し単位に対して、１〜５０ミリモル％の範囲になるように添加することが好ましい。含有量が１ミリモル％未満の場合、ポリエステルを重合する為の反応性が不十分となり、５０ミリモル％を超えると、ポリエステルの耐熱性が低下し、着色が大きくなる為好ましくない。ポリエステル中に含有されるチタン元素量は、ポリエステルがポリエチレンテレフタレートあるいはポリエチレン−２，６−ナフタレートを主たる構成成分とする場合は２〜２０ミリモル％の範囲となるように添加することが更に好ましく、ポリエステルがポリトリメチレンテレフタレート、ポリテトラメチレンテレフタレート、ポリトリメチレン−２，６−ナフタレート、ポリテトラメチレン−２，６−ナフタレートを主たる構成成分とする場合は、５〜４０ミリモル％の範囲となるように添加することが更に好ましい。 About the solution A, it is preferable to add so that the amount of titanium elements contained in the obtained polyester may be in the range of 1 to 50 mmol% with respect to all the repeating units of the polyester. When the content is less than 1 mmol%, the reactivity for polymerizing the polyester is insufficient, and when it exceeds 50 mmol%, the heat resistance of the polyester is lowered and coloring is unfavorable. The amount of titanium element contained in the polyester is more preferably 2-20 mmol% when the polyester is mainly composed of polyethylene terephthalate or polyethylene-2,6-naphthalate. When the main component is polytrimethylene terephthalate, polytetramethylene terephthalate, polytrimethylene-2,6-naphthalate, polytetramethylene-2,6-naphthalate, it is in the range of 5 to 40 mmol%. More preferably, it is added.
溶液Ｂについては、得られるポリエステルの全質量を基準として有機系整色剤を０．１〜１０質量ｐｐｍ含有するように添加することが好ましい。ポリエステル中の該有機系整色剤の含有量が、０．１質量ｐｐｍ未満の場合、ポリエステルの黄色味が強くなる。一方、１０質量ｐｐｍを超える場合、明度が弱くなり見た目に黒味が強くなる為好ましくない。該整色剤の含有量は０．４〜８質量ｐｐｍの範囲にあることが更に好ましい。 About the solution B, it is preferable to add so that 0.1-10 mass ppm of organic type color adjusting agents may be contained on the basis of the total mass of the polyester obtained. When the content of the organic color adjusting agent in the polyester is less than 0.1 mass ppm, the yellowness of the polyester becomes strong. On the other hand, if it exceeds 10 ppm by mass, the brightness becomes weak and the blackness becomes strong visually, which is not preferable. The content of the color adjusting agent is more preferably in the range of 0.4 to 8 mass ppm.
溶液Ｃについては得られるポリエステル中に含有されるリン元素量がポリエステルの全繰り返し単位に対して、０〜１００ミリモル％の範囲になるように添加することが好ましい。１００ミリモル％を超えるとポリエステルを重合する為の反応性が不十分となり好ましくない。該リン元素量は、ポリエステルを製造するプロセスや使用する触媒によっても異なるが、３〜３０ミリモル％の範囲になるように添加することが更に好ましい。 About the solution C, it is preferable to add so that the amount of phosphorus elements contained in the obtained polyester may be in the range of 0 to 100 mmol% with respect to all repeating units of the polyester. If it exceeds 100 mmol%, the reactivity for polymerizing polyester is insufficient, which is not preferable. The amount of the phosphorus element varies depending on the process for producing the polyester and the catalyst used, but it is more preferable to add it in a range of 3 to 30 mmol%.
本発明のポリエステルの製造方法は、通常知られているポリエステルの製造方法が用いられる。すなわち、まずテレフタル酸の如きジカルボン酸とエチレングリコールの如きグリコールとを直接エステル化反応させる、又はテレフタル酸ジメチル（以下ＤＭＴと称することがある。）の如きジカルボン酸成分の低級アルキルエステルとエチレングリコールの如きグリコールとをエステル交換反応させ、ジカルボン酸のグリコールエステル及び／又はその低重合体を製造する。次いでこの反応生成物を重縮合触媒の存在下で減圧加熱して所定の重合度になるまで重縮合反応させることによって目的とするポリエステルが製造される。 As a method for producing the polyester of the present invention, a conventionally known polyester production method is used. That is, first, a dicarboxylic acid such as terephthalic acid is directly esterified with a glycol such as ethylene glycol, or a lower alkyl ester of a dicarboxylic acid component such as dimethyl terephthalate (hereinafter sometimes referred to as DMT) and ethylene glycol. A glycol ester of dicarboxylic acid and / or a low polymer thereof is produced by transesterification with such a glycol. The reaction product is then heated under reduced pressure in the presence of a polycondensation catalyst to cause a polycondensation reaction until a predetermined degree of polymerization is obtained, thereby producing the desired polyester.
ここで、本発明のポリエステルの製造方法において使用するポリエステル重合用触媒は、エステル交換反応法の場合は、まず前述した溶液Ａをエステル交換反応触媒としてエステル交換反応を実施した後、溶液Ｂ、若しくは溶液Ｂ及び溶液Ｃを反応系内に添加して、重縮合反応せしめることが好ましく選択される。また、直接エステル化法の場合はジカルボン酸とグリコールのエステル化反応が終了するまでのいずれかの段階でポリエステルオリゴマーに溶液Ａを添加した後、溶液Ｂ、若しくは溶液Ｂ及び溶液Ｃを反応系内に添加して、重縮合反応せしめることが好ましく選択される。いずれの製造方法の場合においても、溶液Ｂと溶液Ｃを併用する場合は、これらを別々に添加してもよく、混合して添加してもよい。また、溶液Ｂと溶液Ｃの添加順序は順不同でよい。一方、いずれの製造方法の場合においても、溶液Ａは溶液Ｂを添加する前に反応系内に添加しておくことが好ましい。溶液Ｂを溶液Ａより早い段階で反応系内に添加した場合、あるいは溶液Ａと溶液Ｂを混合、あるいは別々に同時期に添加した場合は、得られるポリエステルの色相がやや黄色味を帯び、好ましくない。また、これら溶液Ａ、溶液Ｂ、溶液Ｃを反応系内に添加する際の温度は特に限定はないが、２６０℃以下の温度で添加することが好ましい。 Here, in the case of the transesterification method, the polyester polymerization catalyst used in the method for producing a polyester of the present invention is first subjected to the transesterification reaction using the above-mentioned solution A as the transesterification reaction catalyst, and then the solution B, or It is preferable to add the solution B and the solution C to the reaction system to cause polycondensation reaction. In the case of the direct esterification method, after adding the solution A to the polyester oligomer at any stage until the esterification reaction of the dicarboxylic acid and the glycol is completed, the solution B or the solution B and the solution C are added to the reaction system. It is preferably selected to be added to the polycondensation reaction. In any of the production methods, when the solution B and the solution C are used in combination, they may be added separately or mixed and added. Further, the order of adding the solution B and the solution C may be in any order. On the other hand, in any production method, it is preferable that the solution A is added to the reaction system before the solution B is added. When the solution B is added to the reaction system at an earlier stage than the solution A, or when the solution A and the solution B are mixed or added separately at the same time, the hue of the obtained polyester is slightly yellowish, Absent. Moreover, the temperature at the time of adding these solution A, solution B, and solution C in a reaction system does not have limitation in particular, However, It is preferable to add at the temperature of 260 degrees C or less.
本発明のポリエステルは、ポリエステル繊維、フィルム、ボトル等に好ましく成形することが出来るが、これら成形品を製造する場合、特別な製造方法は必要とせず、従来公知の溶融成形方法を好ましく選択することが出来る。 The polyester of the present invention can be preferably molded into polyester fibers, films, bottles and the like, but when manufacturing these molded products, a special manufacturing method is not required, and a conventionally known melt molding method is preferably selected. I can do it.
本発明をさらに下記実施例により具体的に説明するが、本発明の範囲はこれら実施例により限定されるものではない。尚、固有粘度、色相、チタン含有量及び紡糸口金に発生する付着物の層等については、下記記載の方法により測定した。
（ア）有機系整色剤の吸収波長測定、溶液Ｂの最大吸収波長測定：
有機系整色剤の吸収波長測定は、整色剤を室温で濃度２０ｍｇ／Ｌのクロロホルム溶液とし、光路長１ｃｍの石英セルに充填し、対照セルにはクロロホルムのみを充填して、日立分光光度計Ｕ−３０１０型を用いて、３８０〜７８０ｎｍの可視光領域での可視光吸収スペクトルを測定した。整色剤２種を混合する場合は合計で濃度２０ｍｇ／Ｌとなるようにした。最大吸収波長とその波長における吸光度に対する、４００、５００、６００、７００ｎｍの各波長での吸光度の割合を測定した。溶液Ｂの最大吸収波長測定は後述の通り調整した溶液の不溶部分を濾過して除去した後、３８０〜７８０ｎｍの可視光領域での可視光吸収スペクトルを測定した。
（イ）整色剤の質量減少開始温度：
理学電機工業株式会社製ＴＡＳ−２００熱天秤を用いてＪＩＳ Ｋ７１２０に従い、窒素雰囲気下中昇温速度１０℃／分で測定した。
（ウ）チタン、リン元素含有量：
溶液Ａ、溶液Ｃの場合、蛍光Ｘ線分析用の溶液サンプルホルダーを用い、ポリエステルサンプルの場合、サンプルをスチール板上で加熱溶融した後、圧縮プレス機で平坦面を有する試験成形体を作成し、蛍光Ｘ線装置（理学電機工業株式会社製 ＺＳＸ１００ｅ型）を用いて求めた。ポリエステル中のポリエステルに可溶性のチタン元素量については、ポリエステルサンプルをオルトクロロフェノールに溶解した後、０．５規定塩酸で抽出操作を行った。この抽出液について日立製作所製Ｚ−８１００型原子吸光光度計を用いて定量を行った。ここで０．５規定塩酸抽出後の抽出液中に酸化チタンの分散が確認された場合は遠心分離機で酸化チタン粒子を沈降させた。次に傾斜法により上澄み液のみを回収して、同様の操作を行った。これらの操作によりポリエステル中に酸化チタンを含有していてもポリエステルに可溶性のチタン元素の定量が可能となる。
（エ）ポリエステル中の真比重５．０以上の金属成分定性分析：
ポリエステルサンプルを硫酸アンモニウム、硫酸、硝酸、過塩素酸とともに混合して約３００℃で９時間湿式分解後、蒸留水で希釈し、理学電機工業株式会社製ＩＣＰ発光分析装置（ＪＹ１７０ ＵＬＴＲＡＣＥ）を用いて定性分析し、真比重５．０以上の金属元素の有無を確認した。１質量ｐｐｍ以上の存在が確認された金属元素について、その元素含有量を示した。アンチモン元素についてはこの操作により定性・定量分析を行った。
（オ）ポリエステルの固有粘度：
ポリエステルチップを１００℃、６０分間でオルトクロロフェノールに溶解した希薄溶液を、３５℃でウベローデ粘度計を用いて測定した値から求めた。
（カ）ポリエステルの色相（Ｌ＊値、ａ＊値、ｂ＊値）：
ポリエステルチップを２８５℃、真空下で１０分間溶融し、これをアルミニウム板上で厚さ３．０±１．０ｍｍのプレートに成形後ただちに氷水中で急冷し、該プレートを１４０℃、２時間乾燥結晶化処理を行った。その後、色差計調整用の白色標準プレート上に置き、プレート表面のハンターＬ＊及びｂ＊を、ミノルタ株式会社製ハンター型色差計（ＣＲ−２００型）を用いて測定した。Ｌ＊は明度を示し、その数値が大きいほど明度が高いことを示し、ｂ＊はその値が大きいほど黄着色の度合いが大きいことを示す。また他の詳細な操作はＪＩＳ Ｚ−８７２９に準じて行った。
（キ）紡糸口金に発生する付着物の層（口金異物堆積高さ）：
ポリエステルチップを２９０℃で溶融し、孔径０．１５ｍｍφ、孔数１２個の紡糸口金から吐出し、６００ｍ／分で２日間紡糸し、口金の吐出口外縁に発生する付着物の層の高さを測定した。この付着物層の高さが大きいほど吐出されたポリエステルの溶融物のフィラメント状流にベンディングが発生しやすく、このポリエステルの成形性は低くなる。すなわち、紡糸口金に発生する付着物層の高さは、当該ポリエステルの成形性の指標である。
The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. The intrinsic viscosity, hue, titanium content, and the layer of deposits generated on the spinneret were measured by the methods described below.
(A) Measurement of absorption wavelength of organic color adjusting agent, measurement of maximum absorption wavelength of solution B:
The absorption wavelength measurement of the organic color adjusting agent was carried out by using a color adjusting agent as a chloroform solution having a concentration of 20 mg / L at room temperature, filling a quartz cell with an optical path length of 1 cm, and filling a control cell with only chloroform. A visible light absorption spectrum in a visible light region of 380 to 780 nm was measured using a total U-3010 type. When mixing two color adjusting agents, the total concentration was 20 mg / L. The ratio of the absorbance at each wavelength of 400, 500, 600, and 700 nm to the maximum absorption wavelength and the absorbance at that wavelength was measured. The maximum absorption wavelength of solution B was measured by removing the insoluble portion of the solution prepared as described below, and then measuring the visible light absorption spectrum in the visible light region of 380 to 780 nm.
(I) Mass reduction start temperature of color adjusting agent:
Using a TAS-200 thermobalance manufactured by Rigaku Denki Kogyo Co., Ltd., the temperature was measured in a nitrogen atmosphere at a heating rate of 10 ° C./min according to JIS K7120.
(C) Titanium and phosphorus element content:
In the case of Solution A and Solution C, a solution sample holder for fluorescent X-ray analysis is used. In the case of a polyester sample, the sample is heated and melted on a steel plate, and then a test molded body having a flat surface is prepared with a compression press. It was determined using a fluorescent X-ray apparatus (ZSX100e type, manufactured by Rigaku Corporation). Regarding the amount of titanium element soluble in the polyester, the polyester sample was dissolved in orthochlorophenol and then extracted with 0.5 N hydrochloric acid. The extract was quantified using a Hitachi Z-8100 atomic absorption spectrophotometer. Here, when dispersion of titanium oxide was confirmed in the extract after extraction with 0.5 N hydrochloric acid, titanium oxide particles were precipitated using a centrifuge. Next, only the supernatant was recovered by the gradient method, and the same operation was performed. By these operations, even if titanium oxide is contained in the polyester, it is possible to determine the titanium element soluble in the polyester.
(D) Qualitative analysis of metal component having a true specific gravity of 5.0 or more in polyester:
A polyester sample is mixed with ammonium sulfate, sulfuric acid, nitric acid, and perchloric acid, wet-decomposed at about 300 ° C. for 9 hours, diluted with distilled water, and qualitatively analyzed using an ICP emission analyzer (JY170 ULTRACE) manufactured by Rigaku Corporation. Analysis was performed to confirm the presence or absence of a metal element having a true specific gravity of 5.0 or more. About the metal element by which presence of 1 mass ppm or more was confirmed, the element content was shown. Qualitative and quantitative analysis of antimony element was performed by this operation.
(E) Intrinsic viscosity of polyester:
A dilute solution obtained by dissolving a polyester chip in orthochlorophenol at 100 ° C. for 60 minutes was determined from a value measured at 35 ° C. using an Ubbelohde viscometer.
(F) Hue of polyester (L * value, a * value, b * value):
The polyester chip was melted at 285 ° C. under vacuum for 10 minutes, molded into an aluminum plate with a thickness of 3.0 ± 1.0 mm, immediately quenched in ice water, and the plate was dried at 140 ° C. for 2 hours. Crystallization was performed. Then, it placed on the white standard plate for color difference adjustment, and measured Hunter L * and b * of the plate surface using Minolta Co., Ltd. Hunter type color difference meter (CR-200 type). L * indicates lightness, and the larger the value, the higher the lightness, and b * the greater the value, the greater the degree of yellowing. Other detailed operations were performed according to JIS Z-8729.
(G) Deposited layer generated on the spinneret (the height of foreign matter deposit):
Polyester chips are melted at 290 ° C., discharged from a spinneret with a hole diameter of 0.15 mmφ and 12 holes, spun at 600 m / min for 2 days, and the height of the deposit layer generated at the outer edge of the discharge port of the base is set. It was measured. As the height of the adhered layer increases, bending tends to occur in the filament-like flow of the discharged polyester melt, and the moldability of the polyester decreases. That is, the height of the deposit layer generated in the spinneret is an index of the moldability of the polyester.
（Ａ）溶液Ａの調製
［実施例１］
テトラ−ｎ−ブトキシチタン７．７質量部を室温でエチレングリコール１００質量部に溶解させてチタン触媒溶液を調製した。この溶液中のチタン元素含有量は１．０質量％であった。
(A) Preparation of Solution A [Example 1]
A titanium catalyst solution was prepared by dissolving 7.7 parts by mass of tetra-n-butoxytitanium in 100 parts by mass of ethylene glycol at room temperature. The titanium element content in this solution was 1.0% by mass.
［実施例２］
無水トリメリット酸９．４質量部をエチレングリコールに添加し、徐々に昇温しながら、テトラ−ｎ−ブトキシチタン８．４質量部を添加し、８０℃で６０分間保持し、徐々に冷却させてチタン触媒溶液を調整した。この溶液中のチタン元素含有量は１．０質量％であった。
[Example 2]
Add 9.4 parts by mass of trimellitic anhydride to ethylene glycol, add 8.4 parts by mass of tetra-n-butoxytitanium while gradually raising the temperature, hold at 80 ° C. for 60 minutes, and gradually cool. To prepare a titanium catalyst solution. The titanium element content in this solution was 1.0% by mass.
［実施例３−４］
溶媒を表１に示すグリコールに変更したこと以外は実施例１と同様に実施した。
[Example 3-4]
The same procedure as in Example 1 was performed except that the solvent was changed to the glycol shown in Table 1.
［比較例１］
三酸化アンチモン１．３２質量部を１５０℃のエチレングリコール１００質量部に溶解させてアンチモン触媒溶液を調製した。この溶液中のアンチモン元素含有量は０．５４質量％であった。
[Comparative Example 1]
An antimony catalyst solution was prepared by dissolving 1.32 parts by mass of antimony trioxide in 100 parts by mass of ethylene glycol at 150 ° C. The antimony element content in this solution was 0.54% by mass.
（Ｂ）溶液Ｂの調製
［実施例５−８、比較例２］
表２に示す種類、比率の整色剤０．１質量部を１００℃の表１に示すグリコール１００質量部に溶解させて整色剤溶液を調製した。これら溶液の吸収スペクトルを表２に示す。
(B) Preparation of Solution B [Example 5-8, Comparative Example 2]
A color adjusting agent solution was prepared by dissolving 0.1 part by mass of the color adjusting agent of the type and ratio shown in Table 2 in 100 parts by mass of glycol shown in Table 1 at 100 ° C. Table 2 shows the absorption spectra of these solutions.
（Ｃ）溶液Ｃの調整
［実施例９］
トリエチルホスホノアセテート２５質量部を室温でエチレングリコール１００質量部に溶解させてリン安定剤溶液を調製した。この溶液中のリン元素含有量は２．８質量％であった。
(C) Preparation of solution C [Example 9]
A phosphorus stabilizer solution was prepared by dissolving 25 parts by mass of triethylphosphonoacetate in 100 parts by mass of ethylene glycol at room temperature. The phosphorus element content in this solution was 2.8% by mass.
［実施例１０］
リン酸トリメチル３３質量部を室温でエチレングリコール１００質量部に溶解し、徐々に昇温して１４０℃で６時間、発生するメタノールを留去させながら反応させた後、室温まで冷却してリン安定剤溶液を調整した。この溶液のリン元素含有量は５．５質量％であった。
[Example 10]
After dissolving 33 parts by mass of trimethyl phosphate in 100 parts by mass of ethylene glycol at room temperature, gradually raising the temperature and reacting at 140 ° C. for 6 hours while distilling off the generated methanol, cooling to room temperature and phosphorus stabilization The agent solution was prepared. The phosphorus element content of this solution was 5.5% by mass.
（Ｄ）ポリエステルの製造
［実施例１１−１４、比較例３−５］
予め２２５質量部のオリゴマーが滞留する反応器内に、撹拌下、窒素雰囲気で２５５℃、常圧下に維持された条件下に、１７９質量部の高純度テレフタル酸（ＴＡ）と９５質量部のエチレングリコール（ＥＧ）とを混合して調製されたスラリーを一定速度で供給した。反応で発生する水とエチレングリコールを系外に留去しながら、エステル化反応を４時間し反応を完結させた。このエステル化反応の完結２０分前に、エステル化反応で得られるオリゴマー２２５質量部に対して表３に示す種類、量のチタン触媒の溶液Ａを添加した。この時のエステル化率は９８％以上で、生成されたオリゴマーの重合度は、約５〜７であった。
(D) Production of polyester [Examples 11-14, Comparative Example 3-5]
In a reactor in which 225 parts by mass of oligomers are retained in advance, 179 parts by mass of high-purity terephthalic acid (TA) and 95 parts by mass of ethylene are maintained under stirring and under a nitrogen atmosphere at 255 ° C. and normal pressure. A slurry prepared by mixing with glycol (EG) was fed at a constant rate. While distilling off water and ethylene glycol generated by the reaction, the esterification reaction was completed for 4 hours to complete the reaction. Twenty minutes before the completion of the esterification reaction, the titanium catalyst solution A of the type and amount shown in Table 3 was added to 225 parts by mass of the oligomer obtained by the esterification reaction. The esterification rate at this time was 98% or more, and the degree of polymerization of the produced oligomer was about 5 to 7.
２６０℃で１０分間保持後、表３に示す種類、量の溶液Ｂ、溶液Ｃを添加して重縮合反応槽に移した。引き続き重縮合反応槽内の反応温度を２６０から２８９℃に、また反応圧力を大気圧から３０Ｐａにそれぞれ段階的に上昇及び減圧し、反応で発生する水、エチレングリコールを系外に除去しながら重縮合反応を行った。 After holding at 260 ° C. for 10 minutes, the types and amounts of solutions B and C shown in Table 3 were added and transferred to a polycondensation reaction tank. Subsequently, the reaction temperature in the polycondensation reaction vessel is gradually increased and reduced from 260 to 289 ° C. and the reaction pressure is increased from atmospheric pressure to 30 Pa, respectively, and water and ethylene glycol generated in the reaction are removed from the system while removing water. A condensation reaction was performed.
重縮合反応の進行度合いを、系内の撹拌翼への負荷をモニターしなから確認し、所望の重合度に達した時点で、反応を終了した。その後、系内の反応物を吐出部からストランド状に連続的に押し出し、冷却、カッティングして、約３ｍｍ程度の粒状ペレットを得た。得られたポリエチレンテレフタレートの品質を表４に示した。 The progress of the polycondensation reaction was confirmed without monitoring the load on the stirring blades in the system, and the reaction was terminated when the desired degree of polymerization was reached. Thereafter, the reactant in the system was continuously extruded in a strand form from the discharge part, cooled and cut to obtain a granular pellet of about 3 mm. The quality of the obtained polyethylene terephthalate is shown in Table 4.
［実施例１５−２０、比較例６−８］
表３に示す芳香族ジカルボン酸ジメチルエステルとグリコールと触媒の溶液Ａを反応容器に添加して、０．０７ＭＰａの加圧を行い１４０℃から２４０℃に昇温しながらエステル交換反応させた。その後、表３に示す溶液Ｂ、溶液Ｃを常温で予め混合した後で添加し、エステル交換反応を終了させた。
[Examples 15-20, Comparative Example 6-8]
A solution A of aromatic dicarboxylic acid dimethyl ester, glycol and catalyst shown in Table 3 was added to the reaction vessel, and 0.07 MPa was applied to carry out a transesterification reaction while raising the temperature from 140 ° C to 240 ° C. Thereafter, the solution B and the solution C shown in Table 3 were added after mixing at room temperature in advance, and the transesterification reaction was terminated.
その後反応生成物を重合容器に移し、２８９℃まで昇温し、３０Ｐａまで減圧して重縮合反応を行った。重縮合反応の進行度合いを、系内の撹拌翼への負荷をモニターしなから確認し、所望の重合度に達した時点で、反応を終了した。その後、系内の反応物を吐出部からストランド状に連続的に押し出し、冷却、カッティングして、約３ｍｍ程度の粒状ペレットを得た。得られたポリエチレンテレフタレートの品質を表４に示した。 Thereafter, the reaction product was transferred to a polymerization vessel, heated to 289 ° C., and the pressure was reduced to 30 Pa to carry out a polycondensation reaction. The progress of the polycondensation reaction was confirmed without monitoring the load on the stirring blades in the system, and the reaction was terminated when the desired degree of polymerization was reached. Thereafter, the reactant in the system was continuously extruded in a strand form from the discharge part, cooled and cut to obtain a granular pellet of about 3 mm. The quality of the obtained polyethylene terephthalate is shown in Table 4.
本発明によればポリエステルの優れた特性を保持しながら、ＳｂやＧｅ触媒を使用しないポリエステルの欠点であった色相の悪化を解消することができる。また、口金への付着物の発生量が非常に少なく、優れた成形性を有するポリエステルを提供することが出来る。 According to the present invention, it is possible to eliminate the deterioration of hue, which is a drawback of polyesters that do not use Sb or Ge catalyst, while maintaining the excellent properties of polyesters. Further, it is possible to provide a polyester having a very small amount of deposits on the die and having excellent moldability.
Claims (16)
０．００≦Ａ４００／Ａｍａｘ≦０．２０ （１）
０．１０≦Ａ５００／Ａｍａｘ≦０．７０ （２）
０．５５≦Ａ６００／Ａｍａｘ≦１．００ （３）
０．００≦Ａ７００／Ａｍａｘ≦０．０５ （４）
［上記数式中、Ａ４００、Ａ５００、Ａ６００及びＡ７００はそれぞれ波長４００ｎｍ、５００ｎｍ、６００ｎｍ及び７００ｎｍでの可視光吸収スペクトルにおける吸光度を、Ａｍａｘは最大吸収波長での可視光吸収スペクトルにおける吸光度を表す。］ Absorbance at the maximum absorption wavelength in a wavelength range of 380 to 780 nm measured with a visible / ultraviolet spectrophotometer in a chloroform solution having a concentration of 20 mg / L of an organic colorant dissolved or dispersed in solution B and an optical path length of 1 cm. The polyester polymerization catalyst according to any one of claims 1 to 5, wherein the ratio of the absorbance at each wavelength to the above satisfies all of the following formulas (1) to (4).
0.00 ≦ A 400 / A max ≦ 0.20 (1)
0.10 ≦ A 500 / A max ≦ 0.70 (2)
0.55 ≦ A 600 / A max ≦ 1.00 (3)
0.00 ≦ A 700 / A max ≦ 0.05 (4)
[In the above formula, A 400 , A 500 , A 600 and A 700 are the absorbance in the visible light absorption spectrum at wavelengths of 400 nm, 500 nm, 600 nm and 700 nm, respectively, and A max is the absorbance in the visible light absorption spectrum at the maximum absorption wavelength. Represents. ]
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