JP2005089516A - Polyester resin - Google Patents
Polyester resin Download PDFInfo
- Publication number
- JP2005089516A JP2005089516A JP2003321312A JP2003321312A JP2005089516A JP 2005089516 A JP2005089516 A JP 2005089516A JP 2003321312 A JP2003321312 A JP 2003321312A JP 2003321312 A JP2003321312 A JP 2003321312A JP 2005089516 A JP2005089516 A JP 2005089516A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- amount
- polyester resin
- mol
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 64
- 239000004645 polyester resin Substances 0.000 title claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- -1 phosphorus compound Chemical class 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 125000004429 atom Chemical group 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- 230000000737 periodic effect Effects 0.000 claims abstract description 19
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 67
- 238000005886 esterification reaction Methods 0.000 claims description 45
- 238000006068 polycondensation reaction Methods 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- 150000002009 diols Chemical class 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 150000002681 magnesium compounds Chemical class 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 13
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 238000005809 transesterification reaction Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 7
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- FIPPFBHCBUDBRR-UHFFFAOYSA-N henicosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCO FIPPFBHCBUDBRR-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- CNNRPFQICPFDPO-UHFFFAOYSA-N octacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCO CNNRPFQICPFDPO-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 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 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 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
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction 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
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ARWQHTZTOWMAEQ-UHFFFAOYSA-N (2-carboxyoxyphenyl) hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1OC(O)=O ARWQHTZTOWMAEQ-UHFFFAOYSA-N 0.000 description 1
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 229960002666 1-octacosanol Drugs 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-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
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- UDCSURCKPULYEL-UHFFFAOYSA-N 4,6-dibromobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(Br)C=C1Br UDCSURCKPULYEL-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
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-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
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ZMKAVICCBWPNSR-UHFFFAOYSA-G aluminum;tetrachlorotitanium;trichloride Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ti+4] ZMKAVICCBWPNSR-UHFFFAOYSA-G 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000001463 antimony compounds Chemical class 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- FJTUUPVRIANHEX-UHFFFAOYSA-N butan-1-ol;phosphoric acid Chemical compound CCCCO.OP(O)(O)=O FJTUUPVRIANHEX-UHFFFAOYSA-N 0.000 description 1
- LEAWWEHOHYFEPH-UHFFFAOYSA-N butan-1-olate;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Ti+4].[Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] LEAWWEHOHYFEPH-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
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 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
- PYFRLDVYGBCYLI-UHFFFAOYSA-N decyl dihydrogen phosphite Chemical compound CCCCCCCCCCOP(O)O PYFRLDVYGBCYLI-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- VVTXSHLLIKXMPY-UHFFFAOYSA-L disodium;2-sulfobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(C([O-])=O)C=CC=C1C([O-])=O VVTXSHLLIKXMPY-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 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
- 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
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 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
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- HZJQZHXRILHFBL-UHFFFAOYSA-L sodium oxalate titanium(4+) Chemical compound C(C(=O)[O-])(=O)[O-].[Na+].[Ti+4] HZJQZHXRILHFBL-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003504 terephthalic acids Chemical class 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-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
- BONLISHREBVIRW-UHFFFAOYSA-N tris[2-[2-(2-hydroxyethoxy)ethoxy]ethyl] phosphate Chemical compound OCCOCCOCCOP(=O)(OCCOCCOCCO)OCCOCCOCCO BONLISHREBVIRW-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明はポリエステル樹脂、特にフィルム成形に適したポリエステル樹脂に関する。 The present invention relates to a polyester resin, particularly a polyester resin suitable for film forming.
従来より、ポリエステル樹脂、例えばポリエチレンテレフタレート樹脂は、機械的強度、化学的安定性、ガスバリア性、保香性、衛生性等に優れ、又、比較的安価で軽量であるために、フィルムや繊維、及びボトル等として広く用いられている。一方、近年、高速成形化に伴い、例えば、フィルムの破断による生産性の低下が問題となっている。この問題の解決のためフィルム用としては体積固有抵抗値の低いポリエチレンテレフタレート樹脂が要求されている。 Conventionally, polyester resins such as polyethylene terephthalate resins are excellent in mechanical strength, chemical stability, gas barrier properties, fragrance retention, hygiene, etc., and are relatively inexpensive and lightweight. And widely used as bottles and the like. On the other hand, with the recent high-speed molding, for example, a reduction in productivity due to film breakage has become a problem. In order to solve this problem, a polyethylene terephthalate resin having a low volume resistivity is required for films.
これまで、アンチモンを重合触媒とするポリエチレンテレフタレート樹脂では種々の検討があるが、アンチモンそのものが異物となりフィルム表面の性状を荒らすという問題がある。
特許文献１ではアンチモン等の異物の問題解消のためにアンチモンの代わりにチタンを重合触媒とし、さらに体積固有抵抗値を改善するためにカルシウムとマグネシウムを合計６５ｐｐｍ以上添加する方法が開示されている。ところが我々の検討では重合速度に問題があることが判明した。
Up to now, various studies have been made on polyethylene terephthalate resins using antimony as a polymerization catalyst, but there is a problem that antimony itself becomes a foreign substance and roughens the properties of the film surface.
Patent Document 1 discloses a method in which titanium is used as a polymerization catalyst in place of antimony to solve the problem of foreign matters such as antimony, and calcium and magnesium are added in a total amount of 65 ppm or more in order to improve the volume resistivity value. However, our investigation revealed that there was a problem with the polymerization rate.
一方、ポリエステル樹脂の製法として特許文献２に色調、重合性、環状３量体の低減を目的としてリン化合物、マグネシウム等、チタン化合物の順序で添加するポリエステル樹脂の製法の開示がある。
しかしながら、我々の検討の結果、溶融重合性について改善の余地があること及びこの方法で得られるポリエステル樹脂は、フィルムの製造を考慮した場合、体積固有抵抗値の点で更に改善が望まれるものである。
On the other hand, as a method for producing a polyester resin, Patent Document 2 discloses a method for producing a polyester resin that is added in the order of a phosphorus compound, magnesium, and the like in order to reduce color tone, polymerizability, and cyclic trimer.
However, as a result of our investigation, there is room for improvement in melt polymerizability, and the polyester resin obtained by this method is desired to be further improved in terms of volume resistivity when considering the production of a film. is there.
また、特許文献３ではポリエステルの熱安定性の改善および色調の改良を目的として特定量のリン化合物、アルカリ金属またはアルカリ土類金属化合物およびチタン化合物を含有するポリエステル樹脂が開示され、又、特許文献４および特許文献５でもチタン化合物、マグネシウム化合物およびリン化合物を含有するポリエステルが開示されているが、我々の検討では体積固有抵抗の点で問題があることが判明した。
本発明は、前述の従来技術に鑑みてなされたもので、フィルムを生産性良く成形することが出来るポリエステル樹脂を提供することを目的とする。 The present invention has been made in view of the above-described prior art, and an object thereof is to provide a polyester resin capable of forming a film with high productivity.
本発明者等は、前記課題を解決すべく鋭意検討した結果、リン化合物、２価の金属化合物から選ばれた少なくとも１種の化合物、周期表第４Ａ族のチタン族元素から選ばれる少なくとも１種の元素の化合物の添加量を特定の範囲に選択することで、得られるポリエチレンテレフタレート樹脂の体積固有抵抗値を改善しかつ重合速度および色調を改善出来る
ことを見出した。
As a result of intensive studies to solve the above problems, the present inventors have found that at least one compound selected from a phosphorus compound and a divalent metal compound, and at least one selected from a titanium group element of Group 4A of the periodic table. It was found that by selecting the addition amount of the compound of the element in a specific range, the volume specific resistance value of the obtained polyethylene terephthalate resin can be improved and the polymerization rate and color tone can be improved.
即ち、本発明は、周期表第４Ａ族のチタン族元素から選ばれる少なくとも１種の元素の化合物（１）を周期表第４Ａ族のチタン族金属原子換算で３ｐｐｍ以上１０ｐｐｍ以下、少なくとも１種の２価の金属化合物（２）を金属原子換算で合計で１０ｐｐｍ以上３５ｐｐｍ以下、リン化合物（３）を式１を満たす量、かつ化合物（１）、化合物（２）、化合物（３）をそれぞれ式２を満す量含有し、２８５℃での体積固有抵抗値が２０×１０７Ω・ｃｍ以下であることを特徴とするポリエステル樹脂、を要旨とする。
式１：０．２≦Ｐ／Ｍ≦０．５
Ｐ:リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
式２： ２≦Ｍ（１−Ｐ／Ｍ)／Ａ≦６
Ｐ：リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
Ａ：周期表第４Ａ族のチタン族金属原子の量（ｍｏｌ）
を要旨とする。
式１：０．２≦Ｐ／Ｍ≦０．５
Ｐ:リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
式２： ２≦Ｍ（１−Ｐ／Ｍ)／Ａ≦６
Ｐ：リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
Ａ：周期表第４Ａ族のチタン族金属原子の量（ｍｏｌ）
That is, in the present invention, the compound (1) of at least one element selected from the Group 4A titanium group elements of the periodic table is 3 ppm or more and 10 ppm or less in terms of titanium group metal atoms of the Group 4A of the periodic table, and at least one kind of compound. The total amount of divalent metal compound (2) in terms of metal atoms is 10 ppm or more and 35 ppm or less, phosphorus compound (3) is an amount satisfying formula 1, and compound (1), compound (2), and compound (3) are each represented by formula And a polyester resin characterized in that the volume resistivity value at 285 ° C. is 20 × 10 7 Ω · cm or less.
Formula 1: 0.2 ≦ P / M ≦ 0.5
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
Formula 2: 2 ≦ M (1-P / M) / A ≦ 6
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
A: Amount of titanium group metal atom of Group 4A of the periodic table (mol)
Is the gist.
Formula 1: 0.2 ≦ P / M ≦ 0.5
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
Formula 2: 2 ≦ M (1-P / M) / A ≦ 6
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
A: Amount of titanium group metal atom of Group 4A of the periodic table (mol)
本発明のポリエステル樹脂は、重合性良く製造されたものであり、特に、表面性状の好ましいフィルムの高速成型を可能とする。 The polyester resin of the present invention is produced with good polymerizability, and particularly enables high-speed molding of a film having a preferable surface property.
以下に本発明を詳細に説明する。
本発明のポリエステル樹脂は、芳香族ジカルボン酸を主成分とするジカルボン酸成分またはジカルボン酸のエステル誘導体と、ジオール成分とをエステル化又はエステル交換および重縮合することにより実施される。
原料として使用されるジカルボン酸成分の主成分である芳香族ジカルボン酸としては具体的にはテレフタル酸、フタル酸、イソフタル酸、ジブロモイソフタル酸、スルホイソフタル酸ナトリウム、フェニレンジオキシジカルボン酸、４，４’−ジフェニルジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸、４，４’−ジフェニルケトンジカルボン酸、４，４’−ジフェノキシエタンジカルボン酸、４，４’−ジフェニルスルホンジカルボン酸、２，６−ナフタレンジカルボン酸等の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脂環式ジカルボン酸、及び、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカジカルボン酸、ドデカジカルボン酸等の脂肪族ジカルボン酸等、エステル誘導体としては炭素数１〜６のアルキルエステルが挙げられる。
The present invention is described in detail below.
The polyester resin of the present invention is carried out by esterification or transesterification and polycondensation of a dicarboxylic acid component or a dicarboxylic acid ester derivative containing an aromatic dicarboxylic acid as a main component and a diol component.
Specific examples of the aromatic dicarboxylic acid that is the main component of the dicarboxylic acid component used as a raw material include terephthalic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4 '-Diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 4,4'-diphenylketone dicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,6- Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, and succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Fats such as undecadicarboxylic acid and dodecadicarboxylic acid Like family dicarboxylic acid, the ester derivatives include alkyl esters having 1 to 6 carbon atoms.
ジオール成分としては、主成分であるエチレングリコールや反応系内で副生するジエチレングリコールが挙げられ、その他のジオール成分としては、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、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、デカメチレングリコール、ネオペンチルグリコール、２−エチル−２−ブチル−１，３−プロパンジオール、ポリエチレングリコール、ポリテトラメチレンエーテルグリコール等の脂肪族ジオール、１，２−シクロヘキサンジオール
、１，４−シクロヘキサンジオール、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、２，５−ノルボルナンジメチロール等の脂環式ジオール、及び、キシリレングリコール、４，４’−ジヒドロキシビフェニル、２，２−ビス（４’−ヒドロキシフェニル）プロパン、２，２−ビス（４’−β−ヒドロキシエトキシ
フェニル）プロパン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−β−ヒドロキシエトキシフェニル）スルホン酸等の芳香族ジオール、並びに、２，２−ビス（４’−ヒドロキシフェニル）プロパンのエチレンオキサイド付加物又はプロピレンオキサイド付加物、等が挙げられる。
Examples of the diol component include ethylene glycol as a main component and diethylene glycol by-produced in the reaction system, and examples of other diol components include trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and octane glycol. Methylene glycol, decamethylene glycol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, aliphatic diol such as polyethylene glycol, polytetramethylene ether glycol, 1,2-cyclohexanediol, 1,4 Cycloaliphatic diols such as cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, 2,5-norbornane dimethylol, and xylylene glycol, 4 4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4- Examples include aromatic diols such as β-hydroxyethoxyphenyl) sulfonic acid, ethylene oxide adducts or propylene oxide adducts of 2,2-bis (4′-hydroxyphenyl) propane, and the like.
更に、前記ジオール成分及びジカルボン酸成分以外の共重合成分として、例えば、グリコール酸、ｐ−ヒドロキシ安息香酸、ｐ−β−ヒドロキシエトキシ安息香酸等のヒドロキシカルボン酸やアルコキシカルボン酸、及び、ステアリルアルコール、ヘネイコサノール、オクタコサノール、ベンジルアルコール、ステアリン酸、ベヘン酸、安息香酸、ｔ−ブチル安息香酸、ベンゾイル安息香酸等の単官能成分、トリカルバリル酸、トリメリット酸、トリメシン酸、ピロメリット酸、ナフタレンテトラカルボン酸、没食子酸、トリメチロールエタン、トリメチロールプロパン、グリセロール、ペンタエリスリトール、シュガーエステル等の三官能以上の多官能成分、等の一種又は二種以上が用いられていてもよい。 Furthermore, as a copolymer component other than the diol component and the dicarboxylic acid component, for example, glycolic acid, p-hydroxybenzoic acid, hydroxycarboxylic acid such as p-β-hydroxyethoxybenzoic acid, alkoxycarboxylic acid, and stearyl alcohol, Monofunctional components such as heneicosanol, octacosanol, benzyl alcohol, stearic acid, behenic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetetracarboxylic acid , Gallic acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, trifunctional or higher polyfunctional components such as sugar ester, etc., may be used alone or in combination.
中でも本発明のポリエステル樹脂は、テレフタル酸および／又は２，６−ナフタレンジカルボン酸を主成分とするジカルボン酸成分と、エチレングリコールを主成分とするジオール成分から製造されるポリエステル樹脂が好ましく、さらに好ましくはテレフタル酸を主成分とするカルボン酸成分から製造するポリエステル樹脂である。
本発明のポリエステル樹脂は、テレフタル酸がジカルボン酸成分の９５モル％以上を占めるのが好ましく、９８．５モル％以上を占めるのが更に好ましく、１００モル％を占めるのが特に好ましい。又、エチレングリコールが、ジオール成分の９５モル％以上を占めるのが好ましく、９７モル％以上を占めるのが更に好ましく、９８モル％以上を占めるのが特に好ましい。テレフタル酸及びエチレングリコールの占める割合が前記範囲未満では、ポリエステル樹脂としての機械的強度、耐熱性等が劣る傾向となる。
Among them, the polyester resin of the present invention is preferably a polyester resin produced from a dicarboxylic acid component mainly composed of terephthalic acid and / or 2,6-naphthalenedicarboxylic acid and a diol component mainly composed of ethylene glycol, more preferably. Is a polyester resin produced from a carboxylic acid component mainly composed of terephthalic acid.
In the polyester resin of the present invention, terephthalic acid preferably accounts for 95 mol% or more of the dicarboxylic acid component, more preferably 98.5 mol% or more, and particularly preferably 100 mol%. Further, ethylene glycol preferably accounts for 95 mol% or more of the diol component, more preferably 97 mol% or more, and particularly preferably 98 mol% or more. When the proportion of terephthalic acid and ethylene glycol is less than the above range, the mechanical strength, heat resistance, etc. of the polyester resin tend to be inferior.
本発明のポリエステル樹脂を製造する時の、ジカルボン酸に対するジオールの割合（モル比）は、通常１．０２〜２．０、好ましくは１．０３〜１．７の範囲である。
そして、本発明のポリエステル樹脂は、触媒成分として周期表第４Ａ族のチタン族元素からなる少なくとも１種の元素の化合物（１）を周期表第４Ａ族のチタン族金属原子換算で３ｐｐｍ以上１０ｐｐｍ以下、少なくとも１種の２価の金属化合物（２）を金属原子換算で合計で１０ｐｐｍ以上３５ｐｐｍ以下、リン化合物（３）を式１を満たす量、かつ化合物（１）、化合物（２）、化合物（３）をそれぞれ式２を満たす量含有する。
式１：０．２≦Ｐ／Ｍ≦０．５
Ｐ:リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
式２： ２≦Ｍ（１−Ｐ／Ｍ)／Ａ≦６
Ｐ：リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
Ａ：周期表第４Ａ族のチタン族金属原子の量（ｍｏｌ）
ここで、（１）周期表第４Ａ族のチタン族元素、即ち、チタン、ジルコニウム、ハフニウム、の化合物としては、これら元素の酸化物、水酸化物、アルコキシド、酢酸塩、炭酸塩、蓚酸塩、及びハロゲン化物等が挙げられる。これら元素の化合物の中で、チタン化合物が好ましく、そのチタン化合物としては、具体的には、例えば、テトラ−ｎ−プロピルチタネート、テトラ−ｉ−プロピルチタネート、テトラ−ｎ−ブチルチタネート、テトラ−ｎ−ブチルチタネートテトラマー、テトラ−ｔ−ブチルチタネート、テトラシクロヘキシルチタネート、テトラフェニルチタネート、テトラベンジルチタネート等のチタンアル
コキシド、チタンアルコキシドの加水分解により得られるチタン酸化物、チタンアルコキシドと珪素アルコキシド若しくはジルコニウムアルコキシドとの混合物の加水分解により得られるチタン−珪素若しくはジルコニウム複合酸化物、酢酸チタン、蓚酸チタン、蓚酸チタンカリウム、蓚酸チタンナトリウム、チタン酸カリウム、チタン酸ナトリウム、チタン酸−水酸化アルミニウム混合物、塩化チタン、塩化チタン−塩化アルミニウム混合物、臭化チタン、フッ化チタン、六フッ化チタン酸カリウム、六フッ化チタン酸コバルト、六フッ化チタン酸マンガン、六フッ化チタン酸アンモニウム、チタンアセチルアセトナート等が挙げられ、中で、テトラ−ｎ−プロピルチタネート、テトラ−ｉ−プロピルチタネート、テトラ−ｎ−ブチルチタネート等のチタンアルコキシド、蓚酸チタン、蓚酸チタンカリウムが好ましく、テトラ−ｎ−ブチルチタネートが特に好ましい。
When the polyester resin of the present invention is produced, the ratio (molar ratio) of diol to dicarboxylic acid is usually in the range of 1.02 to 2.0, preferably 1.03 to 1.7.
In the polyester resin of the present invention, the compound (1) of at least one element composed of a titanium group element of Group 4A of the periodic table as a catalyst component is 3 ppm or more and 10 ppm or less in terms of a titanium group metal atom of Group 4A of the periodic table. , At least one divalent metal compound (2) in a total amount of 10 ppm to 35 ppm in terms of metal atoms, phosphorus compound (3) in an amount satisfying formula 1, and compound (1), compound (2), compound ( 3) is contained in an amount satisfying the formula 2.
Formula 1: 0.2 ≦ P / M ≦ 0.5
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
Formula 2: 2 ≦ M (1-P / M) / A ≦ 6
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
A: Amount of titanium group metal atom of Group 4A of the periodic table (mol)
Here, (1) as a compound of the Group 4A titanium group elements of the periodic table, that is, titanium, zirconium, hafnium, oxides, hydroxides, alkoxides, acetates, carbonates, oxalates of these elements, And halides. Of these elemental compounds, titanium compounds are preferable, and specific examples of the titanium compounds include tetra-n-propyl titanate, tetra-i-propyl titanate, tetra-n-butyl titanate, and tetra-n. -Titanium alkoxides such as butyl titanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate, titanium oxide obtained by hydrolysis of titanium alkoxide, titanium alkoxide and silicon alkoxide or zirconium alkoxide Titanium-silicon or zirconium composite oxide obtained by hydrolysis of the mixture, titanium acetate, titanium oxalate, potassium titanium oxalate, sodium titanium oxalate, potassium titanate, sodium titanate , Titanium titanate-aluminum hydroxide mixture, titanium chloride, titanium chloride-aluminum chloride mixture, titanium bromide, titanium fluoride, potassium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, six Examples thereof include ammonium fluorinated titanate and titanium acetylacetonate. Among them, titanium alkoxides such as tetra-n-propyl titanate, tetra-i-propyl titanate, and tetra-n-butyl titanate, titanium oxalate, and potassium potassium oxalate are included. Tetra-n-butyl titanate is preferred and particularly preferred.
２価の金属化合物としてはマンガン、マグネシウムおよびカルシウム化合物が好ましく、これらの金属の酸化物、水酸化物、アルコキシド、酢酸塩、炭酸塩、蓚酸塩、及びハロゲン化物等、具体的には、例えば、酸化マグネシウム、水酸化マグネシウム、マグネシウムアルコキシド、酢酸マグネシウム、炭酸マグネシウム、酸化カルシウム、水酸化カルシウム、酢酸カルシウム、炭酸カルシウム、酸化マンガン、水酸化マンガン、酢酸マンガン等が挙げられる。中で、マグネシウム化合物、マンガン化合物が好ましく、マグネシウム化合物が特に好ましく、従って２価の金属化合物が実質的にマグネシウム化合物のみからなるのが好ましい。又、マグネシウム化合物の中でも、酢酸マグネシウムが好ましい。 As the divalent metal compound, manganese, magnesium and calcium compounds are preferable, and oxides, hydroxides, alkoxides, acetates, carbonates, oxalates and halides of these metals, specifically, for example, Examples thereof include magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, magnesium carbonate, calcium oxide, calcium hydroxide, calcium acetate, calcium carbonate, manganese oxide, manganese hydroxide, and manganese acetate. Among these, a magnesium compound and a manganese compound are preferable, and a magnesium compound is particularly preferable. Therefore, it is preferable that the divalent metal compound is substantially composed of only the magnesium compound. Of the magnesium compounds, magnesium acetate is preferred.
リン化合物としては、具体的には、例えば、正リン酸、ポリリン酸、及び、トリメチルホスフェート、トリエチルホスフェート、トリ−ｎ−ブチルホスフェート、トリオクチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリス（トリエチレングリコール）ホスフェート、メチルアシッドホスフェート、エチルアシッドホスフェート、イソプロピルアシッドホスフェート、ブチルアシッドホスフェート、モノブチルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、トリエチレングリコールアシッドホスフェート等のリン酸エステル等の５価のリン化合物、並びに、亜リン酸、次亜リン酸、及び、トリメチルホスファイト、ジエチルホスファイト、トリエチルホスファイト、トリスドデシルホスファイト、トリスノニルデシルホスファイト、エチルジエチルホスホノアセテート、トリフェニルホスファイト等の亜リン酸エステル、リチウム、ナトリウム、カリウム等の金属塩等の３価のリン化合物等が挙げられ、中で、５価のリン化合物のリン酸エステルが好ましく、トリメチルホスフェート、エチルアシッドホスフェートが特に好ましい。 Specific examples of the phosphorus compound include orthophosphoric acid, polyphosphoric acid, and trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (tri Ethylene glycol) phosphate, methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, monobutyl phosphate, dibutyl phosphate, dioctyl phosphate, pentavalent phosphorus compounds such as phosphate esters such as triethylene glycol acid phosphate, and Phosphorous acid, hypophosphorous acid, trimethyl phosphite, diethyl phosphite, triethyl phosphite, trisdodecyl phosphite And trisphosphorous compounds such as trisnonyl decyl phosphite, ethyl diethyl phosphonoacetate, triphenyl phosphite and the like, and trivalent phosphorus compounds such as metal salts such as lithium, sodium and potassium. Phosphoric acid ester of a monovalent phosphorus compound is preferable, and trimethyl phosphate and ethyl acid phosphate are particularly preferable.
本発明においては、前記（１）周期表第４Ａ族のチタン族元素からなる群より選ばれた少なくとも１種の元素の化合物を、それらの原子換算で３ｐｐｍ以上１０ｐｐｍ以下ポリエステル中に存在させることを必須とし、４ｐｐｍ以上存在させることが好ましく、上限は、好ましくは８ｐｐｍ、特に好ましくは６ｐｐｍである。
この量が前記の範囲未満では重合性が著しく悪化し生産性良く目的のポリエステル樹脂を生産することが出来ず、また前記の範囲を超過するとポリエステルの色調が極端に悪化しフィルムの生産に適さないものとなる。
In the present invention, (1) a compound of at least one element selected from the group consisting of titanium group elements of Group 4A of the periodic table is present in the polyester in an amount of 3 ppm to 10 ppm in terms of their atoms. It is essential to be present at 4 ppm or more, and the upper limit is preferably 8 ppm, particularly preferably 6 ppm.
If this amount is less than the above range, the polymerizability is significantly deteriorated and the desired polyester resin cannot be produced with good productivity, and if it exceeds the above range, the color tone of the polyester is extremely deteriorated and is not suitable for film production. It will be a thing.
また、前記（２）の少なくとも１種の２価の金属化合物を金属原子換算でポリエステル樹脂中に１０ｐｐｍ以上３５ｐｐｍ以下存在させることを必須とし、１５ｐｐｍ以上存在させることが好ましく、上限は好ましくは３０ｐｐｍ、特に好ましくは２２ｐｐｍである。
この量が前記範囲未満では体積固有抵抗値が高くなり、結果的にフィルムの生産性を悪化させ、前記範囲を超過すると得られるポリエステル樹脂の色調が悪化する。
Further, it is essential that at least one divalent metal compound of (2) is present in the polyester resin in terms of metal atoms in the range of 10 ppm to 35 ppm, preferably 15 ppm or more, and the upper limit is preferably 30 ppm, Particularly preferred is 22 ppm.
If this amount is less than the above range, the volume specific resistance value becomes high. As a result, the productivity of the film is deteriorated, and if it exceeds the above range, the color tone of the resulting polyester resin is deteriorated.
更に、前記（３）のリン化合物を以下の式１を満たす量含有することを必須とする。
式１：０．２≦Ｐ／Ｍ≦０．５
Ｐ:リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
前記範囲未満では、得られたポリエステル樹脂の安定性が悪くなり、色調が悪化する。一方、前記範囲を超過すると重合性が悪くなりかつ得られたポリエステル樹脂の体積固有抵抗値が高くなりフィルムの生産に適さないものとなる。
Furthermore, it is essential to contain the phosphorus compound of the above (3) in an amount satisfying the following formula 1.
Formula 1: 0.2 ≦ P / M ≦ 0.5
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
If it is less than the said range, stability of the obtained polyester resin will worsen and color tone will deteriorate. On the other hand, if the above range is exceeded, the polymerizability becomes poor and the volume resistivity of the obtained polyester resin becomes high, which makes it unsuitable for film production.
本発明のポリエステル樹脂は、上記化合物（１）、（２）および（３）以外の成分を含みうるが、特にチタン族元素の化合物を重縮合反応時に存在させることにより得られるものであり、従って公知のアンチモン化合物やゲルマニウム化合物を含有する必要性はなく、よって、アンチモンやゲルマニウムを実質的に含有しないのが好ましい。
本発明のポリエステル樹脂の製造方法は、前記テレフタル酸またはそのエステル誘導体を主成分とするジカルボン酸成分と、エチレングリコールを主成分とするジオール成分とを、エステル化反応或いはエステル交換反応を経て、前記（１）周期表第４Ａ族のチタン族元素からなる群より選ばれた少なくとも１種の元素の化合物、（２）少なくとも１種の２価の金属化合物、（３）リン化合物の存在下に重縮合させるものであるが、基本的にはポリエステル樹脂の慣用の製造方法による。即ち、前記テレフタル酸又はそのエステル
形成性誘導体を主成分とするジカルボン酸成分とエチレングリコールを主成分とするジオール成分とを、スラリー調製槽に投入して攪拌下に混合して原料スラリーとなし、エステル化反応槽で常圧〜加圧下、加熱下で、エステル化反応させ、或いは、エステル交換触媒の存在下にエステル交換反応させた後、得られたエステル化反応生成物或いはエステル交換反応生成物としてのポリエステル低分子量体を重縮合槽に移送し、前記化合物の存在下に、常圧から漸次減圧としての減圧下、加熱下で、溶融重縮合させる。
The polyester resin of the present invention may contain components other than the above compounds (1), (2) and (3), and is particularly obtained by allowing a titanium group element compound to be present during the polycondensation reaction. It is not necessary to contain a known antimony compound or germanium compound, and therefore it is preferable that the antimony or germanium is not substantially contained.
The method for producing a polyester resin according to the present invention includes a dicarboxylic acid component containing terephthalic acid or an ester derivative thereof as a main component and a diol component containing ethylene glycol as a main component via an esterification reaction or a transesterification reaction. (1) a compound of at least one element selected from the group consisting of titanium group elements of Group 4A of the periodic table, (2) at least one divalent metal compound, (3) heavy in the presence of a phosphorus compound Although it is what is condensed, it is based on the conventional manufacturing method of a polyester resin fundamentally. That is, a dicarboxylic acid component mainly composed of the terephthalic acid or its ester-forming derivative and a diol component mainly composed of ethylene glycol are charged into a slurry preparation tank and mixed under stirring to form a raw slurry. The esterification reaction product or transesterification reaction product obtained after the esterification reaction in the esterification reaction tank under normal pressure to under pressure, under heating, or the ester exchange reaction in the presence of a transesterification catalyst. The polyester low molecular weight product is transferred to a polycondensation tank, and in the presence of the compound, melt polycondensation is carried out under heating from normal pressure to gradually reduced pressure.
尚、ジカルボン酸成分としてテレフタル酸のエステル形成性誘導体を用いてエステル交換反応を行う場合は、通常、チタン化合物、マグネシウム化合物、カルシウム化合物、マンガン化合物、亜鉛化合物等のエステル交換触媒を用いる必要があり、そのエステル交換触媒を比較的多量に用いる必要があることから、本発明においては、ジカルボン酸成分としてテレフタル酸を用いてエステル化反応を経て製造する方法が好ましい。 In the case of performing an ester exchange reaction using an ester-forming derivative of terephthalic acid as a dicarboxylic acid component, it is usually necessary to use an ester exchange catalyst such as a titanium compound, a magnesium compound, a calcium compound, a manganese compound, or a zinc compound. Since the transesterification catalyst needs to be used in a relatively large amount, in the present invention, a method in which terephthalic acid is used as the dicarboxylic acid component to produce the ester exchange catalyst is preferable.
エステル化反応は、単一のエステル化反応槽、又は、複数のエステル化反応槽を直列に接続した多段反応装置を用いて、エチレングリコールの還流下、且つ、反応で生成する水と余剰のエチレングリコールを系外に除去しながら、エステル化率（原料ジカルボン酸成分の全カルボキシル基のうちジオール成分と反応してエステル化したものの割合）が、通常９０％以上、好ましくは９３％以上に達するまで行われる。又、得られるエステル化反応生成物としてのポリエステル低分子量体の数平均分子量は５００〜５，０００であるのが好ましい。 The esterification reaction is carried out by using a multistage reaction apparatus in which a single esterification reaction tank or a plurality of esterification reaction tanks are connected in series, under reflux of ethylene glycol, and water generated in the reaction and excess ethylene. While the glycol is removed from the system, the esterification rate (the ratio of the esterified by reacting with the diol component out of all the carboxyl groups of the raw dicarboxylic acid component) is usually 90% or more, preferably 93% or more Done. Moreover, it is preferable that the number average molecular weight of the polyester low molecular weight body as an esterification reaction product obtained is 500-5,000.
エステル化反応における反応条件としては、単一のエステル化反応槽の場合、通常２４０〜２８０℃程度の温度、大気圧に対する相対圧力を、通常０〜４００ｋＰａ（０〜４ｋｇ／ｃｍ2 Ｇ）程度とし、攪拌下に１〜１０時間程度の反応時間とする。又、複数のエステル化反応槽の場合は、第１段目のエステル化反応槽における反応温度を、通常２４０〜２７０℃、好ましくは２４５〜２６５℃、大気圧に対する相対圧力を、通常５〜３００ｋＰａ（０．０５〜３ｋｇ／ｃｍ2 Ｇ）、好ましくは１０〜２００ｋＰａ（０．１〜２ｋｇ／ｃｍ2 Ｇ）とし、最終段における反応温度を、通常２５０〜２８０℃、好ましくは２５５〜２７５℃、大気圧に対する相対圧力を、通常０〜１５０ｋＰａ（０〜１．５ｋｇ／ｃｍ2 Ｇ）、好ましくは０〜１３０ｋＰａ（０〜１．３ｋｇ／ｃｍ2 Ｇ）とする。尚、各段におけるエステル化率は、その増加量が等しくなるようにするのが好ましい。 As reaction conditions in the esterification reaction, in the case of a single esterification reaction tank, the temperature is usually about 240 to 280 ° C., and the relative pressure to the atmospheric pressure is usually about 0 to 400 kPa (0 to 4 kg / cm 2 G). The reaction time is about 1 to 10 hours under stirring. In the case of a plurality of esterification reaction tanks, the reaction temperature in the first stage esterification reaction tank is usually 240 to 270 ° C., preferably 245 to 265 ° C., and the relative pressure to atmospheric pressure is usually 5 to 300 kPa. (0.05 to 3 kg / cm 2 G), preferably 10 to 200 kPa (0.1 to 2 kg / cm 2 G), and the reaction temperature in the final stage is usually 250 to 280 ° C., preferably 255 to 275 ° C., The relative pressure with respect to atmospheric pressure is usually 0 to 150 kPa (0 to 1.5 kg / cm 2 G), preferably 0 to 130 kPa (0 to 1.3 kg / cm 2 G). In addition, it is preferable to make the increase amount equal in the esterification rate in each stage.
尚、エステル化反応において、例えば、トリエチルアミン、トリ−ｎ−ブチルアミン、
ベンジルジメチルアミン等の第三級アミン、水酸化テトラエチルアンモニウム、水酸化テトラ−ｎ−ブチルアンモニウム、水酸化トリメチルベンジルアンモニウム等の水酸化第四級アンモニウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、酢酸ナトリウム等の塩基性化合物等を少量添加しておくことにより、エチレングリコールからのジエチレングリコールの副生を抑制することができる。
In the esterification reaction, for example, triethylamine, tri-n-butylamine,
Tertiary amines such as benzyldimethylamine, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, quaternary ammonium hydroxides such as trimethylbenzylammonium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium acetate, etc. By adding a small amount of the basic compound or the like, by-production of diethylene glycol from ethylene glycol can be suppressed.
又、溶融重縮合は、単一の溶融重縮合槽、又は、複数の溶融重縮合槽を直列に接続した、例えば、第１段目が攪拌翼を備えた完全混合型の反応器、第２段及び第３段目が攪拌翼を備えた横型プラグフロー型の反応器からなる多段反応装置を用いて、減圧下に、生成するエチレングリコールを系外に留出させながら行われる。
溶融重縮合における反応条件としては、単一の重縮合槽の場合、通常２５０〜２９０℃程度の温度、常圧から漸次減圧として、最終的に、絶対圧力を、通常１．３〜０．０１３ｋＰａ（１０〜０．１Ｔｏｒｒ）程度とし、攪拌下に１〜２０時間程度の反応時間とする。又、複数の重縮合槽の場合は、第１段目の重縮合槽における反応温度を、通常２５０〜２９０℃、好ましくは２６０〜２８０℃、絶対圧力を、通常６５〜１．３ｋＰａ（５００〜１０Ｔｏｒｒ）、好ましくは２６〜２ｋＰａ（２００〜１５Ｔｏｒｒ）とし、最終段における反応温度を、通常２６５〜３００℃、好ましくは２７０〜２９５℃、絶対圧力を、通常１．３〜０．０１３ｋＰａ（１０〜０．１Ｔｏｒｒ）、好ましくは０．６５〜０．０６５ｋＰａ（５〜０．５Ｔｏｒｒ）とする。中間段における反応条件としては、それらの中間の条件が選択され、例えば、３段反応装置においては、第２段における反応温度を、通常２６５〜２９５℃、好ましくは２７０〜２８５℃、絶対圧力を、通常６．５〜０．１３ｋＰａ（５０〜１Ｔｏｒｒ）、好ましくは４〜０．２６ｋＰａ（３０〜２Ｔｏｒｒ）とする。
The melt polycondensation is performed by connecting a single melt polycondensation tank or a plurality of melt polycondensation tanks in series, for example, a fully mixed reactor in which the first stage is equipped with a stirring blade, The stage and the third stage are carried out by distilling the produced ethylene glycol out of the system under reduced pressure by using a multistage reactor comprising a horizontal plug flow reactor equipped with a stirring blade.
As reaction conditions in the melt polycondensation, in the case of a single polycondensation tank, the temperature is usually about 250 to 290 ° C. The pressure is gradually reduced from normal pressure, and finally the absolute pressure is usually 1.3 to 0.013 kPa. (10 to 0.1 Torr) and a reaction time of about 1 to 20 hours with stirring. In the case of a plurality of polycondensation tanks, the reaction temperature in the first stage polycondensation tank is usually 250 to 290 ° C., preferably 260 to 280 ° C., and the absolute pressure is usually 65 to 1.3 kPa (500 to 10 Torr), preferably 26 to 2 kPa (200 to 15 Torr), the reaction temperature in the final stage is usually 265 to 300 ° C., preferably 270 to 295 ° C., and the absolute pressure is usually 1.3 to 0.013 kPa (10 to 10 Torr). 0.1 Torr), preferably 0.65 to 0.065 kPa (5 to 0.5 Torr). As reaction conditions in the intermediate stage, those intermediate conditions are selected. For example, in a three-stage reactor, the reaction temperature in the second stage is usually 265 to 295 ° C., preferably 270 to 285 ° C., and the absolute pressure is Usually, it is 6.5 to 0.13 kPa (50 to 1 Torr), preferably 4 to 0.26 kPa (30 to 2 Torr).
又、重縮合時における、前記（１）周期表第１Ａ族のチタン族元素からなる群よ
り選択された少なくとも１種の元素の化合物、（２）少なくとも１種の２価の金属元素の化合物、及び、（３）リン化合物、の反応系への添加時期は、スラリー調製工程、エステル化反応或いはエステル交換反応工程の任意の段階、又は、溶融重縮合工程の初期の段階のいずれであってもよいが、（１）及び（２）の化合物は、エステル化反応或いはエステル交換反応工程、又は、溶融重縮合工程への移送段階に添加するのが好ましく、又、エステル化反応或いはエステル交換反応生成物のエステル化率が９０％以上となった段階で添加するのが好ましく、又、（１）の化合物を（２）の化合物より後に添加するのが好ましい。
Further, at the time of polycondensation, (1) a compound of at least one element selected from the group consisting of titanium group elements of Group 1A of the periodic table, (2) a compound of at least one divalent metal element, And (3) the phosphorus compound may be added to the reaction system at any stage of the slurry preparation process, esterification reaction or transesterification process, or at the initial stage of the melt polycondensation process. The compounds (1) and (2) are preferably added to the esterification reaction or transesterification reaction step, or the transfer step to the melt polycondensation step, and the esterification reaction or transesterification reaction is generated. It is preferably added when the esterification rate of the product becomes 90% or more, and the compound (1) is preferably added after the compound (2).
各化合物の具体的添加工程としては、例えば、（１）および（２）の化合物は、多段反応装置における最終段のエステル化反応槽、又は、溶融重縮合工程への移送段階のエステル化反応或いはエステル交換反応生成物に添加するのが好ましい。
又、重縮合時における、前記（１）、（２）、及び、（３）の各化合物の反応系への添加は、エチレングリコール等のアルコールや水等の溶液として行うのが好ましく、前記（１）の化合物としてチタン化合物を用いる場合のエチレングリコール溶液としては、チタン原子の濃度を０．０１〜０．３重量％とし、且つ水分濃度を０．１〜１重量％とするのが、反応系へのチタン化合物の分散性、及びそれによる溶融重縮合性の改良の面から好ましい。
As a specific addition process of each compound, for example, the compounds of (1) and (2) are used in the esterification reaction tank in the final stage in the multistage reaction apparatus or the esterification reaction in the transfer stage to the melt polycondensation process or Addition to the transesterification product is preferred.
The addition of the compounds (1), (2) and (3) to the reaction system during polycondensation is preferably performed as a solution of alcohol such as ethylene glycol or water. As the ethylene glycol solution in the case of using a titanium compound as the compound of 1), the reaction is to have a titanium atom concentration of 0.01 to 0.3% by weight and a water concentration of 0.1 to 1% by weight. From the viewpoint of improving the dispersibility of the titanium compound in the system and the resulting melt polycondensation.
このようにして溶融重合で得られたポリエステル樹脂は、通常ストランド状に溶融押し出しして反応器より抜き出したのち、チップカット工程でカットされチップ化される。
本発明の製造方法においてはフィルム用ポリエステル樹脂として好適な樹脂を得るために任意の時期に、平均粒子径０．０５〜５．０μｍの不活性粒子を添加することが出来る。
The polyester resin thus obtained by melt polymerization is usually melt-extruded into a strand shape, extracted from the reactor, and then cut and formed into chips.
In the production method of the present invention, inactive particles having an average particle diameter of 0.05 to 5.0 μm can be added at any time in order to obtain a resin suitable as a polyester resin for a film.
また、ポリエステル樹脂の色調を更に改善するために色剤を添加することも可能である。
本発明のポリエステル樹脂の固有粘度（〔η〕）は、フェノール／テトラクロロエタン（重量比１／１）の混合溶媒の溶液で３０℃で測定した値として、０．６０〜０．８０ｄｌ／ｇであるのが好ましく、０．６０〜０．７４ｄｌ／ｇであるのが更に好ましい。固有粘度（〔η〕）が前記範囲未満では、フィルムや繊維等の成形体としての機械的強度、及び透明性等が不足する傾向となり、一方、前記範囲超過では溶融成形性が劣る傾向となる。
It is also possible to add a colorant to further improve the color tone of the polyester resin.
The intrinsic viscosity ([η]) of the polyester resin of the present invention is 0.60 to 0.80 dl / g as a value measured at 30 ° C. with a mixed solvent solution of phenol / tetrachloroethane (weight ratio 1/1). It is preferable that it is 0.60 to 0.74 dl / g. If the intrinsic viscosity ([η]) is less than the above range, mechanical strength and transparency as a molded article such as film and fiber tend to be insufficient, whereas if it exceeds the range, melt moldability tends to be inferior. .
又、本発明のポリエステル樹脂は、２８５℃における体積固有抵抗が２０×１０７Ω・ｃｍ以下であることが必須であり、１×１０６〜１０×１０７Ω・ｃｍであるのが更に好ましく、１×１０７〜１０×１０７Ω・ｃｍであるのが特に好ましい。体積固有抵抗が前記範囲外では、フィルム等の高速成形性が低下する傾向となる。尚、かかる体積固有抵抗値は前記化合物（１）、（２）及び（３）を前述の使用割合にコントロールすることで得ることができる傾向にある。 The polyester resin of the present invention must have a volume resistivity at 285 ° C. of 20 × 10 7 Ω · cm or less, and more preferably 1 × 10 6 to 10 × 10 7 Ω · cm. It is particularly preferably 1 × 10 7 to 10 × 10 7 Ω · cm. When the volume resistivity is out of the above range, the high-speed moldability of the film or the like tends to decrease. Such volume resistivity value tends to be obtained by controlling the compounds (1), (2) and (3) to the above-mentioned use ratio.
これにより得られた本発明のポリエステル樹脂は、フィルム用ポリエチレンテレフタレート樹脂として好ましい体積固有抵抗、溶融粘度および色調を有する。
又、本発明のポリエステル樹脂は、色調として、ＪＩＳ Ｚ８７３０の参考１に記載されるＬａｂ表色系におけるハンターの色差式の色座標ｂ値が９以下であるのが好ましく、７以下であるのが更に好ましい。ｂ値が前記範囲超過では、成形体としての色調が黄味がかる傾向となる。
The polyester resin of this invention obtained by this has volume specific resistance, melt viscosity, and color tone preferable as a polyethylene terephthalate resin for films.
The polyester resin of the present invention preferably has a color coordinate b value of Hunter's color difference formula in the Lab color system described in Reference 1 of JIS Z8730 as a color tone of 9 or less, preferably 7 or less. Further preferred. If the b value exceeds the above range, the color tone of the molded product tends to be yellowish.
又、上記ポリエステル樹脂は必要に応じて、更に高重合度化を目的として、この溶融重縮合後の粒状体
を、例えば、窒素、二酸化炭素、アルゴン等の不活性ガス雰囲気下、大気圧に対する相対圧力として、通常１００ｋＰａ（１ｋｇ／ｃｍ2Ｇ）以下、好ましくは２０ｋＰａ０．２
ｋｇ／ｃｍ2Ｇ）以下の加圧下で通常５〜３０時間程度、或いは、絶対圧力として、通常
６．５〜０．０１３ｋＰａ（５０〜０．１Ｔｏｒｒ）、好ましくは１．３〜０．０６５ｋＰａ（１０ ０．５Ｔｏｒｒ）の減圧下で通常１〜２０時間程度、通常１９０〜３０℃、好ましくは１９５〜２２５℃の温度で加熱することにより、固相重縮合させてもよい。
If necessary, the polyester resin may be obtained by subjecting the granules after melt polycondensation to a relative pressure to atmospheric pressure in an inert gas atmosphere such as nitrogen, carbon dioxide, and argon for the purpose of further increasing the degree of polymerization. The pressure is usually 100 kPa (1 kg / cm 2 G) or less, preferably 20 kPa 0.2.
kg / cm 2 G) or less, usually for about 5 to 30 hours, or as absolute pressure, usually 6.5 to 0.013 kPa (50 to 0.1 Torr), preferably 1.3 to 0.065 kPa ( The solid phase polycondensation may be performed by heating at a temperature of usually about 190 to 30 ° C., preferably 195 to 225 ° C. under a reduced pressure of 10 0.5 Torr).
その際、固相重縮合に先立って、不活性ガス雰囲気下、又は、水蒸気雰囲気下或いは水蒸気含有不活性ガス雰囲気下で、通常１２０〜２００℃、好ましくは１３０〜１９０℃で、１分〜４時間程度加熱することにより、樹脂粒状体表面を結晶化させることが好ましい。
本発明の製造方法により得られるポリエステル樹脂は、例えば、押出成形によってシートに成形した後、熱成形することによってトレイや容器等に成形し、或いは、該シートを二軸延伸してフィルム等とし、包装資材等として有用なものとなる。
At that time, prior to solid phase polycondensation, it is usually 120 to 200 ° C., preferably 130 to 190 ° C. for 1 minute to 4 in an inert gas atmosphere, or in a water vapor atmosphere or a water vapor-containing inert gas atmosphere. It is preferable to crystallize the resin granule surface by heating for about an hour.
The polyester resin obtained by the production method of the present invention is, for example, formed into a sheet by extrusion molding, and then formed into a tray or a container by thermoforming, or the sheet is biaxially stretched to form a film, It is useful as a packaging material.
本発明のポリエステル樹脂の前記成形体への成形は、必要に応じて、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、滑剤、ブロッキング防止剤、防曇剤、核剤、可塑剤、着色剤等の、ポリエステル樹脂に通常用いられる添加剤を添加し、常法に従ってなされる。
特に、本発明のポリエステル樹脂は、フィルム、特に、二軸延伸フィルムとして好適であり、その成形法としては、ポリエステル樹脂をフィルム若しくはシート状に溶融押出しし、冷却ドラムにより急冷して未延伸フィルム若しくはシートとなし、次いで、該未延伸フィルム若しくはシートを予熱後、縦方向に延伸し、引き続いて横方向に延伸する逐次二軸延伸法、或いは、縦横方向に同時に二軸延伸する同時二軸延伸法等、従来公知の方法が採られる。その際の延伸倍率は、縦方向及び横方向共、通常２〜６倍の範囲とされ、又、
必要に応じて、二軸延伸後、熱固定及び／又は熱弛緩される。尚、二軸延伸フィルムとしての厚みは、通常１〜３００μｍ程度とされる。
Molding of the polyester resin of the present invention into the molded body may be carried out as necessary by using an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a lubricant, an antiblocking agent, an antifogging agent, a nucleating agent, and a plasticizer. Additives usually used for polyester resins, such as colorants, are added in accordance with conventional methods.
In particular, the polyester resin of the present invention is suitable as a film, in particular, a biaxially stretched film. As a molding method thereof, the polyester resin is melt-extruded into a film or a sheet and rapidly cooled by a cooling drum, or an unstretched film or Sequential biaxial stretching method in which the unstretched film or sheet is preheated and then stretched in the longitudinal direction and then stretched in the transverse direction, or simultaneously biaxially stretched in the longitudinal and transverse directions simultaneously. A conventionally well-known method is taken. The draw ratio at that time is usually in the range of 2 to 6 times in both the vertical and horizontal directions,
If necessary, after biaxial stretching, it is heat-set and / or heat-relaxed. In addition, the thickness as a biaxially stretched film shall be about 1-300 micrometers normally.
尚、前記二軸延伸フィルム等のフィルムにおいては、表面のブロッキング防止のために無機質又は有機質粒子からなる滑剤が添加されるのが好ましく、その無機質粒子としては、例えば、炭酸カルシウム、硫酸バリウム、アルミナ、シリカ、タルク、チタニア、カオリン、マイカ、ゼオライト等、及びそれらのシランカップリング剤、又はチタネートカップリング剤等による表面処理物が、又、有機質粒子としては、例えば、アクリル系樹脂、スチレン系樹脂、架橋樹脂等が、それぞれ挙げられ、。又、これら滑剤の粒子径は、平均粒子径が０．０５〜５．０μｍの範囲にあるのが好ましい。又、それら滑剤の添加量は、通常０．００１〜２．０重量％、好ましくは０．０５〜１．０重量％、更に好ましくは０．０５〜０．５重量％程度である。 In addition, in the film such as the biaxially stretched film, it is preferable to add a lubricant composed of inorganic or organic particles to prevent surface blocking. Examples of the inorganic particles include calcium carbonate, barium sulfate, and alumina. , Silica, talc, titania, kaolin, mica, zeolite, etc., and surface treated products thereof such as silane coupling agents or titanate coupling agents, and organic particles include, for example, acrylic resins, styrene resins , And cross-linked resins, respectively. The particle diameter of these lubricants is preferably in the range of 0.05 to 5.0 μm in average particle diameter. Moreover, the addition amount of these lubricants is 0.001-2.0 weight% normally, Preferably it is 0.05-1.0 weight%, More preferably, it is about 0.05-0.5 weight%.
以下、実施例により本発明を更に詳細に説明するが、本発明はその要旨を越えない限り以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
スラリー調製槽、及びそれに直列に接続された２段のエステル化反応槽、及び２段目のエステル化反応槽に直列に接続された３段の溶融重縮合槽からなる連続式重合装置を用い、スラリー調製槽に、テレフタル酸とエチレングリコールを重量比で８６５：４８５の割合で連続的に供給すると共に、エチルアシッドホスフェートのエチレングリコール溶液を、生成ポリエステル樹脂に対してリン原子としての含有量が８ｐｐｍとなる量で連続的に添加して、攪拌、混合することによりスラリーを調製し、このスラリーを、窒素雰囲気下で２６０℃、相対圧力５０ｋＰａ（０．５ｋｇ／ｃｍ２Ｇ）、平均滞留時間４．５時間に設定され、反応生成物が存在する第１段目のエステル化反応槽に供給し、次いで、第１段目のエステル化反応生成物を、窒素雰囲気下で２６０℃、相対圧力５ｋＰａ（０．０５ｋｇ／ｃｍ２Ｇ）、平均滞留時間１．２時間に設定された第２段目のエステル化反応槽に連続的に移送して、更にエステル化反応させた。その際、第２段目のエステル化反応槽に設けた上部配管を通じて、酢酸マグネシウム４水和物のエチレングリコール溶液を、生成ポリエステル樹脂に対してマグネシウム原子としての含有量が１５ｐｐｍとなる量で連続的に添加した。 Using a continuous polymerization apparatus comprising a slurry preparation tank, a two-stage esterification reaction tank connected in series to the slurry preparation tank, and a three-stage melt polycondensation tank connected in series to the second-stage esterification reaction tank, To the slurry preparation tank, terephthalic acid and ethylene glycol are continuously fed at a ratio of 865: 485 by weight, and an ethylene glycol solution of ethyl acid phosphate has a content of 8 ppm as a phosphorus atom with respect to the produced polyester resin. The slurry is prepared by continuously adding, stirring, and mixing in an amount to become 260 ° C., a relative pressure of 50 kPa (0.5 kg / cm 2 G), and an average residence time of 4 in a nitrogen atmosphere. Set to 5 hours and fed to the first stage esterification reactor where the reaction product is present, then the first stage esterification reaction product is fed to 260 ° C. under a nitrogen atmosphere, relative pressure 5kPa (0.05kg / cm 2 G) , and continuously transferred to the second stage esterification reaction tank set for an average retention time 1.2 hours, further ester It was made to react. At that time, the ethylene glycol solution of magnesium acetate tetrahydrate was continuously fed through the upper pipe provided in the second stage esterification reaction tank in such an amount that the content as magnesium atoms was 15 ppm with respect to the produced polyester resin. Was added.
引き続いて、前記で得られたエステル化反応生成物を溶融重縮合槽に移送する際、その移送配管中のエステル化反応生成物に、テトラブチルチタネートのエチレングリコール溶液を、生成ポリエステル樹脂に対してチタン原子としての含有量が４ｐｐｍとなる量で、連続的に添加しつつ、２７０℃、絶対圧力２．６ｋＰａ（２０Ｔｏｒｒ）に設定された第１段目の溶融重縮合槽、次いで、２７８℃、絶対圧力０．５ｋＰａ（４Ｔｏｒｒ）に設定された第２段目の溶融重縮合槽、次いで、２８０℃、絶対圧力０．３ｋＰａ（２Ｔｏｒｒ）に設定された第３段目の溶融重縮合槽に連続的に移送して、各重縮合槽における滞留時間を以下の通りとし、第１段目 ７０分、第２段目 ７０分、第３段目 ８０分、滞留時間が合計で２２０分となるようにして溶融重縮合させ、重縮合槽の底部に設けられた抜き出し口からストランド状に抜き出して、水冷後、カッターで切断してチップ状粒状体としたポリエステル樹脂を製造した。 Subsequently, when the esterification reaction product obtained above is transferred to a melt polycondensation tank, an ethylene glycol solution of tetrabutyl titanate is added to the polyester resin to the esterification reaction product in the transfer pipe. The first stage melt polycondensation tank set at 270 ° C. and an absolute pressure of 2.6 kPa (20 Torr) while continuously adding in an amount of 4 ppm as titanium atoms, then 278 ° C., Continuous to the second stage melt polycondensation tank set to an absolute pressure of 0.5 kPa (4 Torr), then to the third stage melt polycondensation tank set to 280 ° C. and an absolute pressure of 0.3 kPa (2 Torr) The residence time in each polycondensation tank is as follows, and the first stage is 70 minutes, the second stage is 70 minutes, the third stage is 80 minutes, and the residence time is 220 minutes in total. In Melt polycondensation Te, withdrawn from the discharge outlet provided at the bottom of the polycondensation tank in a strand form, to produce a water-cooled post, and cut with a cutter polyester resin was chip-shaped granules.
得られたポリエステル樹脂について、金属原子含有量、固有粘度、体積固有抵抗、色調及び静電密着性を、以下に示す方法により測定し、結果を表−１に示した。
＜金属原子含有量＞
樹脂試料２．５ｇを、硫酸存在下に過酸化水素で常法により灰化、完全分解後、蒸留水にて５０ｍｌに定容したものについて、プラズマ発光分光分析装置（ＪＯＢＩＮ ＹＶＯＮ社製ＩＣＰ−ＡＥＳ「ＪＹ４６Ｐ型」）を用いて定量し、ポリエステル樹脂中のｐｐｍ
量に換算した。尚、樹脂中に滑剤が含有されている場合には、予め樹脂を溶媒に溶解し、未溶解の滑剤を遠心分離した後、上澄み液の溶媒を蒸発、乾固させたものについて定量した。
About the obtained polyester resin, metal atom content, intrinsic viscosity, volume resistivity, color tone, and electrostatic adhesiveness were measured by the method shown below, and the result was shown in Table-1.
<Metal atom content>
A resin sample of 2.5 g was ashed with hydrogen peroxide in the presence of sulfuric acid in a conventional manner, completely decomposed, and then made up to a constant volume of 50 ml with distilled water. A plasma emission spectrometer (ICP-AES manufactured by JOBIN YVON) Quantitatively using “JY46P type”), ppm in polyester resin
Converted to quantity. When the resin contained a lubricant, the resin was dissolved in a solvent in advance, the undissolved lubricant was centrifuged, and then the supernatant was evaporated and dried.
＜固有粘度＞
粉砕した樹脂試料０．２５ｇを、フェノール／テトラクロロエタン（重量比１／１）の混合溶媒に、濃度（ｃ）を１．０ｇ／ｄｌとして、１１０℃で３０分間で溶解させた後、ウベローデ型毛細粘度管を用いて、３０℃で、原液との相対粘度（ηｒｅｌ ）を測定し、この相対粘度（ηｒｅｌ ）-１から求めた比粘度（ηｓｐ）と濃度（ｃ）との比（η
ｓｐ／ｃ）を求め、同じく濃度（ｃ）を０．５ｇ／ｄｌ、０．２ｇ／ｄｌ、０．１ｇ／ｄｌとしたときについてもそれぞれの比（ηｓｐ／ｃ）を求め、これらの値より、濃度（ｃ）を０に外挿したときの比（ηｓｐ／ｃ）を固有粘度〔η〕（ｄｌ／ｇ）として求めた。
<Intrinsic viscosity>
After 0.25 g of the pulverized resin sample was dissolved in a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1) at a concentration (c) of 1.0 g / dl at 110 ° C. for 30 minutes, an Ubbelohde type Using a capillary viscosity tube, the relative viscosity (ηrel) with the stock solution was measured at 30 ° C., and the ratio (ηsp) of the specific viscosity (ηsp) determined from the relative viscosity (ηrel) -1 to the concentration (c) (η
sp / c), and when the concentration (c) is 0.5 g / dl, 0.2 g / dl, and 0.1 g / dl, the respective ratios (ηsp / c) are also obtained. The ratio (ηsp / c) when the concentration (c) was extrapolated to 0 was determined as the intrinsic viscosity [η] (dl / g).
＜体積固有抵抗＞
樹脂試料１５ｇを、内径２０ｍｍ、長さ１８０ｍｍの枝付き試験管に入れ、管内を十分に窒素置換した後、１６０℃のオイルバス中に浸漬し、管内を真空ポンプで１Ｔｏｒｒ以下として４時間真空乾燥し、次いで、オイルバス温度を２８５℃に昇温して樹脂試料を溶融させた後、窒素復圧と減圧を繰り返して混在する気泡を取り除いた。この溶融体の中に、面積１ｃｍ2のステンレス製電極２枚を５ｍｍの間隔で並行に（相対しない裏面を絶縁
体で被覆）挿入し、温度が安定した後に、抵抗計（ヒューレット・パッカード社製「ＭＯＤＥＬ ＨＰ４３２９Ａ」）で直流電圧１００Ｖを印加し、そのときに抵抗値を体積固有抵抗（Ω・ｃｍ）とした。
<Volume specific resistance>
15 g of resin sample is put into a test tube with a branch having an inner diameter of 20 mm and a length of 180 mm, and the inside of the tube is sufficiently purged with nitrogen. Then, the tube is immersed in an oil bath at 160 ° C. Then, the temperature of the oil bath was raised to 285 ° C. to melt the resin sample, and then the mixed air bubbles were removed by repeating nitrogen re-pressure and pressure reduction. Two stainless steel electrodes with an area of 1 cm 2 were inserted in parallel in this melt at intervals of 5 mm (non-opposite back surface covered with an insulator), and after the temperature was stabilized, a resistance meter (manufactured by Hewlett-Packard Company) A DC voltage of 100 V was applied by “MODEL HP4329A”), and the resistance value at that time was defined as a volume specific resistance (Ω · cm).
＜色調＞
樹脂試料を、内径３６ｍｍ、深さ１５ｍｍの円柱状の粉体測色用セルに充填し、測色色差計（日本電色工業社製「ＮＤ−３００Ａ」）を用いて、ＪＩＳ Ｚ８７３０の参考１に記載されるＬａｂ表色系におけるハンターの色差式の色座標ｂ値を、反射法により測定セルを９０度ずつ回転させて４箇所測定した値の単純平均値として求めた。
<Color tone>
A resin sample was filled in a cylindrical powder colorimetric cell having an inner diameter of 36 mm and a depth of 15 mm, and using a colorimetric color difference meter (“ND-300A” manufactured by Nippon Denshoku Industries Co., Ltd.), Reference 1 of JIS Z8730 The color coordinate b value of the Hunter's color difference formula in the Lab color system described in the above was obtained as a simple average value of values measured at four locations by rotating the measurement cell by 90 degrees by the reflection method.
＜静電密着性＞
樹脂試料ポリマーを１８０℃で乾燥した後、２９０℃で溶融押し出し、表面温度４０℃に保持した回転冷却ドラム上で急冷固化させて未延伸フィルムを巻き取る際、静電ピンニング法にてフィルム厚み斑が小さく、安定して巻き取れる速度より、以下のように静電密着性を評価した。
<Electrostatic adhesion>
When the resin sample polymer is dried at 180 ° C., melt-extruded at 290 ° C., and rapidly cooled and solidified on a rotating cooling drum maintained at a surface temperature of 40 ° C. The electrostatic adhesion was evaluated as follows from the speed at which the film was small and could be wound up stably.
［４段階評価］
◎ 巻取り速度 ４０ｍ／ｍｉｎ以上
○ 巻取り速度 ３５ｍ以上４０ｍ／ｍｉｎ未満
△ 巻取り速度 ３０ｍ以上３５ｍ／ｍｉｎ未満
× 巻取り速度 ３０ｍ／ｍｉｎ未満
[4-level evaluation]
◎ Winding speed 40m / min or more ○ Winding speed 35m or more and less than 40m / min △ Winding speed 30m or more but less than 35m / min x Winding speed less than 30m / min
エチルアシッドホスフェート、酢酸マグネシウム４水和物およびテトラブチルチタネート、及び三酸化アンチモンの添加量を表−１に示すように変え、表中にあるように変えた外は、実施例１におけると同様にしてポリエステル樹脂チップを製造し、同様に評価し、結果を表−１に示した。 The addition amounts of ethyl acid phosphate, magnesium acetate tetrahydrate and tetrabutyl titanate, and antimony trioxide were changed as shown in Table 1, except that the amounts were changed as shown in the table. A polyester resin chip was manufactured and evaluated in the same manner, and the results are shown in Table-1.
エチルアシッドホスフェート、酢酸マグネシウム４水和物およびテトラブチルチタネート、及び三酸化アンチモンの添加量を表−１に示すように変え、表中にあるように変えた
外は、実施例１におけると同様にしてポリエステル樹脂チップを製造し、同様に評価し、結果を表１−１に示した。
The addition amounts of ethyl acid phosphate, magnesium acetate tetrahydrate and tetrabutyl titanate, and antimony trioxide were changed as shown in Table 1, except that the amounts were changed as shown in the table. A polyester resin chip was manufactured and evaluated in the same manner, and the results are shown in Table 1-1.
エチルアシッドホスフェート、酢酸マグネシウム４水和物およびテトラブチルチタネート、及び三酸化アンチモンの添加量を表−１に示すように変え、表中にあるように変えた外は、実施例１におけると同様にしてポリエステル樹脂チップを製造し、同様に評価し、結果を表−１に示した。 The addition amounts of ethyl acid phosphate, magnesium acetate tetrahydrate and tetrabutyl titanate, and antimony trioxide were changed as shown in Table 1, except that the amounts were changed as shown in the table. A polyester resin chip was manufactured and evaluated in the same manner, and the results are shown in Table-1.
実施例１に於いて、エチルアシッドホスフェートのエチレングリコール溶液を、生成ポリエステル樹脂に対してリン原子としての含有量を１１ｐｐｍとなる量に変更し、また酢酸マグネシウム４水和物のエチレングリコール溶液の添加を第２段目のエステル化反応槽に設けた上部配管に代えて、エステル化反応により得られたエステル化反応生成物を溶融重縮合槽に移送する際、その移送配管中のエステル化反応生成物にマグネシウム原子として２３ｐｐｍとなる量で添加し、引き続いて、その移送配管中のエステル化反応生成物に、テトラブチルチタネートのエチレングリコール溶液を、生成ポリエステル樹脂に対してチタン原子としての含有量が７ｐｐｍとなる量で、連続的に添加し実施例１におけると同様にポリエステル樹脂を製造し、同様に評価し、結果を表−１に示した。 In Example 1, the ethylene acid solution of ethyl acid phosphate was changed to an amount of 11 ppm as a phosphorus atom with respect to the produced polyester resin, and addition of an ethylene glycol solution of magnesium acetate tetrahydrate When the esterification reaction product obtained by the esterification reaction is transferred to the melt polycondensation tank instead of the upper pipe provided in the second stage esterification reaction tank, the esterification reaction product in the transfer pipe Is added to the product in an amount of 23 ppm as magnesium atoms, and subsequently, an ethylene glycol solution of tetrabutyl titanate is added to the esterification reaction product in the transfer pipe, and the content of titanium atoms in the resulting polyester resin is A polyester resin is produced in the same manner as in Example 1 by continuously adding in an amount of 7 ppm. Similarly evaluated and the results are shown in Table 1.
（比較例１〜４）
エチルアシッドホスフェート、酢酸マグネシウム４水和物、テトラブチルチタネートの添加量を表−１に示すように変えた外は、実施例１におけると同様にしてポリエステル樹脂チップを製造し、同様に評価し、結果を表−１に示した。
（比較例５）
スラリー調製槽、及びそれに直列に接続された２段のエステル化反応槽、内２段目のエステル化槽は４部屋に区分されており、及び２段目のエステル化反応槽に直列に接続された３段の溶融重縮合槽からなる連続式重合装置を用い、スラリー調製槽に、テレフタル酸とエチレングリコールを重量比で８６５：４８５の割合で連続的に供給すると共に、エチルアシッドホスフェートのエチレングリコール溶液を、生成ポリエステル樹脂に対して燐原子としての含有量が２５ｐｐｍとなる量で連続的に添加して、攪拌、混合することによりスラリーを調製し、このスラリーを、窒素雰囲気下で２６０℃、相対圧力５０ｋＰａ（０．５ｋｇ／ｃｍ2Ｇ）、平均滞留時間４．０時間に設定され、反応生成物が存在する第
１段目のエステル化反応槽に供給し、次いで、第１段目のエステル化反応生成物を、窒素雰囲気下で２６０℃、相対圧力５ｋＰａ（０．０５ｋｇ／ｃｍ2Ｇ）、平均滞留時間１．
５時間に設定された第２段目のエステル化反応槽に連続的に移送して、更にエステル化反応させた。その際、第２段目のエステル化槽の途中に設けた上部配管を通じて、酢酸マグネシウム４水和物および酢酸カルシウム１水和物のエチレングリコール溶液を、生成ポリエステル樹脂に対してマグネシウム原子としての含有量が５０ｐｐｍとなる量でかつカルシウム原子としての含有量が５０ｐｐｍとなる量で連続的に添加した。
(Comparative Examples 1-4)
A polyester resin chip was produced in the same manner as in Example 1 except that the amounts of ethyl acid phosphate, magnesium acetate tetrahydrate and tetrabutyl titanate were changed as shown in Table 1, and evaluated in the same manner. The results are shown in Table-1.
(Comparative Example 5)
The slurry preparation tank and the two-stage esterification reaction tank connected in series therewith, the second-stage esterification tank is divided into four rooms, and is connected in series to the second-stage esterification reaction tank. In addition, terephthalic acid and ethylene glycol were continuously fed to the slurry preparation tank at a ratio of 865: 485 by weight and ethylene glycol of ethyl acid phosphate. The solution is continuously added in an amount such that the content as a phosphorus atom is 25 ppm with respect to the produced polyester resin, and a slurry is prepared by stirring and mixing. The slurry is heated at 260 ° C. under a nitrogen atmosphere. relative pressure 50kPa (0.5kg / cm 2 G) , is set to the average residence time 4.0 hours, subjected to esterification reaction tank for the first stage reaction product is present And, then, the first stage esterification reaction product, 260 ° C. under a nitrogen atmosphere, relative pressure 5kPa (0.05kg / cm 2 G) , the average residence time 1.
It was continuously transferred to the second stage esterification reaction tank set for 5 hours, and further esterified. At that time, an ethylene glycol solution of magnesium acetate tetrahydrate and calcium acetate monohydrate was contained as magnesium atoms in the produced polyester resin through an upper pipe provided in the middle of the second stage esterification tank. The amount was continuously added so that the amount was 50 ppm and the content as calcium atoms was 50 ppm.
得られたエステル化反応生成物を用いて実施例１におけると同様にしてポリエステル樹脂チップを製造し、同様に評価した。結果を表１に示した。
（比較例６、７）
リン化合物をエステル化反応後に添加し、表１の通り条件を変更したことを除けば、実施例１におけると同様に製造し、同様に評価し、結果を表１に示した。
A polyester resin chip was produced in the same manner as in Example 1 using the obtained esterification reaction product, and evaluated in the same manner. The results are shown in Table 1.
(Comparative Examples 6 and 7)
A phosphorus compound was added after the esterification reaction, and the production was performed in the same manner as in Example 1 except that the conditions were changed as shown in Table 1. The results were shown in Table 1.
Claims (6)
式１：０．２≦Ｐ／Ｍ≦０．５
Ｐ:リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
式２： ２≦Ｍ（１−Ｐ／Ｍ)／Ａ≦６
Ｐ：リン原子の量（ｍｏｌ）
Ｍ：２価の金属原子の量（ｍｏｌ）
Ａ：周期表第４Ａ族のチタン族金属原子の量（ｍｏｌ） The compound (1) of at least one element selected from the Group 4A titanium group elements of the periodic table is 3 ppm to 10 ppm in terms of titanium group metal atoms of the Group 4A periodic table, and at least one divalent metal compound ( 2) in total 10 ppm to 35 ppm in terms of metal atoms, phosphorus compound (3) in an amount satisfying formula 1, and compound (1), compound (2) and compound (3) in an amount satisfying formula 2 And a volume resistivity value at 285 ° C. of 20 × 10 7 Ω · cm or less.
Formula 1: 0.2 ≦ P / M ≦ 0.5
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
Formula 2: 2 ≦ M (1-P / M) / A ≦ 6
P: Amount of phosphorus atom (mol)
M: amount of divalent metal atom (mol)
A: Amount of titanium group metal atom of Group 4A of the periodic table (mol)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003321312A JP4196795B2 (en) | 2003-09-12 | 2003-09-12 | Polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003321312A JP4196795B2 (en) | 2003-09-12 | 2003-09-12 | Polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005089516A true JP2005089516A (en) | 2005-04-07 |
| JP4196795B2 JP4196795B2 (en) | 2008-12-17 |
Family
ID=34453036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003321312A Expired - Lifetime JP4196795B2 (en) | 2003-09-12 | 2003-09-12 | Polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4196795B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007026650A1 (en) * | 2005-08-29 | 2007-03-08 | Mitsubishi Chemical Corporation | Polybutylene terephthalate and process for production thereof |
| JP2007070462A (en) * | 2005-09-07 | 2007-03-22 | Mitsubishi Chemicals Corp | Polyester resin for film and method for producing the same |
| JP2007077219A (en) * | 2005-09-13 | 2007-03-29 | Mitsubishi Polyester Film Copp | Polyester film for optical use |
| JP2007238703A (en) * | 2006-03-07 | 2007-09-20 | Teijin Fibers Ltd | Polyester composition excellent in fiber-forming property, and fiber consisting of the same |
| JP2010163613A (en) * | 2008-12-19 | 2010-07-29 | Mitsubishi Chemicals Corp | Polyester resin |
| EP2345684A1 (en) | 2010-01-18 | 2011-07-20 | Fujifilm Corporation | Polymerization method for polyester resin, polyester resin composition, and polyester film |
| JP2020075998A (en) * | 2018-11-07 | 2020-05-21 | 三菱ケミカル株式会社 | Polyester resin |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5575680B2 (en) | 2010-03-09 | 2014-08-20 | 富士フイルム株式会社 | Polyester resin composition and method for producing the same, polyester film, and solar cell power generation module |
-
2003
- 2003-09-12 JP JP2003321312A patent/JP4196795B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007026650A1 (en) * | 2005-08-29 | 2007-03-08 | Mitsubishi Chemical Corporation | Polybutylene terephthalate and process for production thereof |
| JP2007070462A (en) * | 2005-09-07 | 2007-03-22 | Mitsubishi Chemicals Corp | Polyester resin for film and method for producing the same |
| JP2007077219A (en) * | 2005-09-13 | 2007-03-29 | Mitsubishi Polyester Film Copp | Polyester film for optical use |
| JP2007238703A (en) * | 2006-03-07 | 2007-09-20 | Teijin Fibers Ltd | Polyester composition excellent in fiber-forming property, and fiber consisting of the same |
| JP2010163613A (en) * | 2008-12-19 | 2010-07-29 | Mitsubishi Chemicals Corp | Polyester resin |
| EP2345684A1 (en) | 2010-01-18 | 2011-07-20 | Fujifilm Corporation | Polymerization method for polyester resin, polyester resin composition, and polyester film |
| JP2020075998A (en) * | 2018-11-07 | 2020-05-21 | 三菱ケミカル株式会社 | Polyester resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4196795B2 (en) | 2008-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5533898B2 (en) | Polyester resin composition and molded product | |
| JP4196795B2 (en) | Polyester resin | |
| JP5668284B2 (en) | Polyester resin | |
| JP6314452B2 (en) | Polyester resin and production method | |
| KR101808136B1 (en) | Polyester composition for solar battery and method for producing same | |
| JP4951903B2 (en) | Polyester resin for film and method for producing the same | |
| JP2000256452A (en) | Production of polyester resin | |
| JP5566184B2 (en) | Biaxially oriented polyester film for solar cell backside sealing | |
| JP4951951B2 (en) | Method for producing polyester resin composition | |
| JP2023106155A (en) | Polyester resin and method for producing the same | |
| JP7243151B2 (en) | Method for producing polyester film | |
| JP2016188351A (en) | Polyester film | |
| WO2016056604A1 (en) | Polyester resin and method for producing same | |
| JP6601048B2 (en) | Polyester resin for film and method for producing the same | |
| JP4067331B2 (en) | Production method of polyester resin | |
| JP2005023312A (en) | Producing method of polyester resin | |
| JP4609427B2 (en) | Polyester resin and film comprising the same | |
| JP2016188352A (en) | Polyester resin and polyester resin composition | |
| JP5589533B2 (en) | Production method of polyester film | |
| JP4251827B2 (en) | Polyester resin | |
| JP4715876B2 (en) | Polyester resin | |
| JP2014080609A (en) | Biaxially stretched polyester film for solar cell back surface protection and method for producing polyester resin | |
| JP2005272509A (en) | Manufacturing method of polyester | |
| JP2006199973A (en) | Method for producing polyester resin | |
| JP2006265324A (en) | Polyester film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060417 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080603 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080610 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080725 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20080909 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20080922 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111010 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4196795 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111010 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111010 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121010 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121010 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131010 Year of fee payment: 5 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |