JP2018159005A - Polyester resin composition - Google Patents
Polyester resin composition Download PDFInfo
- Publication number
- JP2018159005A JP2018159005A JP2017057399A JP2017057399A JP2018159005A JP 2018159005 A JP2018159005 A JP 2018159005A JP 2017057399 A JP2017057399 A JP 2017057399A JP 2017057399 A JP2017057399 A JP 2017057399A JP 2018159005 A JP2018159005 A JP 2018159005A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- resin composition
- acid
- heat
- rare earth
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 85
- 239000004645 polyester resin Substances 0.000 title claims abstract description 85
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 43
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 36
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 27
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 40
- 150000002009 diols Chemical class 0.000 description 28
- 238000006864 oxidative decomposition reaction Methods 0.000 description 27
- 238000005886 esterification reaction Methods 0.000 description 26
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 25
- 238000000034 method Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 230000001590 oxidative effect Effects 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005809 transesterification reaction Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 4
- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical compound O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 2
- TYFJTEPDESMEHE-UHFFFAOYSA-N 6,8-dihydroxy-3-[2-(4-methoxyphenyl)ethyl]-3,4-dihydroisochromen-1-one Chemical compound C1=CC(OC)=CC=C1CCC1OC(=O)C2=C(O)C=C(O)C=C2C1 TYFJTEPDESMEHE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AFEBURQVBVFCHW-UHFFFAOYSA-N CC(C)P(O)=O Chemical compound CC(C)P(O)=O AFEBURQVBVFCHW-UHFFFAOYSA-N 0.000 description 2
- MTWVYGIIHVUGNL-UHFFFAOYSA-N CCCCP(O)=O Chemical compound CCCCP(O)=O MTWVYGIIHVUGNL-UHFFFAOYSA-N 0.000 description 2
- DGLXNOJGOHKWTN-UHFFFAOYSA-N CCCP(O)=O Chemical compound CCCP(O)=O DGLXNOJGOHKWTN-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 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
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- UHHOEOSKGDFVPB-UHFFFAOYSA-N di(propan-2-yl)phosphinic acid Chemical compound CC(C)P(O)(=O)C(C)C UHHOEOSKGDFVPB-UHFFFAOYSA-N 0.000 description 2
- KSHDLNQYVGBYHZ-UHFFFAOYSA-N dibutylphosphinic acid Chemical compound CCCCP(O)(=O)CCCC KSHDLNQYVGBYHZ-UHFFFAOYSA-N 0.000 description 2
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 2
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 description 2
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 2
- WMDPJKZHARKRQI-UHFFFAOYSA-N dipropylphosphinic acid Chemical compound CCCP(O)(=O)CCC WMDPJKZHARKRQI-UHFFFAOYSA-N 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052730 francium Inorganic materials 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
- 238000004898 kneading Methods 0.000 description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 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
- 230000000704 physical effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-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
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- MQYFWRJEFAZXHE-UHFFFAOYSA-N (2-phenylphenyl)phosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1C1=CC=CC=C1 MQYFWRJEFAZXHE-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 1
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 description 1
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- ZSSWXNPRLJLCDU-UHFFFAOYSA-N 1-diethylphosphorylethane Chemical compound CCP(=O)(CC)CC ZSSWXNPRLJLCDU-UHFFFAOYSA-N 0.000 description 1
- YHQMSHVVGOSZEW-UHFFFAOYSA-N 1-dimethoxyphosphorylethane Chemical compound CCP(=O)(OC)OC YHQMSHVVGOSZEW-UHFFFAOYSA-N 0.000 description 1
- SNZSAFILJOCMFM-UHFFFAOYSA-N 1-dipropylphosphorylpropane Chemical compound CCCP(=O)(CCC)CCC SNZSAFILJOCMFM-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KDRBAEZRIDZKRP-UHFFFAOYSA-N 2,2-bis[3-(aziridin-1-yl)propanoyloxymethyl]butyl 3-(aziridin-1-yl)propanoate Chemical compound C1CN1CCC(=O)OCC(COC(=O)CCN1CC1)(CC)COC(=O)CCN1CC1 KDRBAEZRIDZKRP-UHFFFAOYSA-N 0.000 description 1
- WFUUAJVRMXKBBI-UHFFFAOYSA-N 2-[1-(2-hydroxyethyl)cyclohexyl]ethanol Chemical compound OCCC1(CCO)CCCCC1 WFUUAJVRMXKBBI-UHFFFAOYSA-N 0.000 description 1
- MUHNBZQOTATUGE-UHFFFAOYSA-N 2-[4-[2-[4-(2-hydroxyethoxy)cyclohexyl]propan-2-yl]cyclohexyl]oxyethanol Chemical compound C1CC(OCCO)CCC1C(C)(C)C1CCC(OCCO)CC1 MUHNBZQOTATUGE-UHFFFAOYSA-N 0.000 description 1
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 1
- GEZGQQFKEOIGJS-UHFFFAOYSA-N 2-di(propan-2-yl)phosphorylpropane Chemical compound CC(C)P(=O)(C(C)C)C(C)C GEZGQQFKEOIGJS-UHFFFAOYSA-N 0.000 description 1
- HWUGMDUGNYFQTA-UHFFFAOYSA-N 2-methyl-2-(2,4,8,10-tetraoxaspiro[5.5]undecan-5-yl)propan-1-ol Chemical compound OCC(C)(C)C1OCOCC11COCOC1 HWUGMDUGNYFQTA-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- DQULYJXGTXMNTM-UHFFFAOYSA-N 2-phosphonobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1P(O)(O)=O DQULYJXGTXMNTM-UHFFFAOYSA-N 0.000 description 1
- ZKKXCRILZNBJJM-UHFFFAOYSA-N 3-phosphonobenzoic acid Chemical compound OC(=O)C1=CC=CC(P(O)(O)=O)=C1 ZKKXCRILZNBJJM-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
- 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
- QDSFNOHWQKVVEB-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)morpholine Chemical compound CCOP(=O)(OCC)CN1CCOCC1 QDSFNOHWQKVVEB-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IEQICHVXWFGDAN-UHFFFAOYSA-N 4-phosphonobenzoic acid Chemical compound OC(=O)C1=CC=C(P(O)(O)=O)C=C1 IEQICHVXWFGDAN-UHFFFAOYSA-N 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- ATLPLEZDTSBZQG-UHFFFAOYSA-N propan-2-ylphosphonic acid Chemical compound CC(C)P(O)(O)=O ATLPLEZDTSBZQG-UHFFFAOYSA-N 0.000 description 1
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-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
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- XUHUMYVYHLHMCD-UHFFFAOYSA-N tris(2-cyclohexylphenyl) phosphite Chemical compound C1CCCCC1C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C1CCCCC1)OC1=CC=CC=C1C1CCCCC1 XUHUMYVYHLHMCD-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- HBYRZSMDBQVSHO-UHFFFAOYSA-N tris(2-tert-butyl-4-methylphenyl) phosphite Chemical compound CC(C)(C)C1=CC(C)=CC=C1OP(OC=1C(=CC(C)=CC=1)C(C)(C)C)OC1=CC=C(C)C=C1C(C)(C)C HBYRZSMDBQVSHO-UHFFFAOYSA-N 0.000 description 1
- WRSPWQHUHVRNFV-UHFFFAOYSA-N tris[3,5-di(nonyl)phenyl] phosphite Chemical compound CCCCCCCCCC1=CC(CCCCCCCCC)=CC(OP(OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)=C1 WRSPWQHUHVRNFV-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、耐熱酸化分解性および透明性に優れたポリエステル樹脂組成物に関するものである。 The present invention relates to a polyester resin composition excellent in heat-resistant oxidative degradation and transparency.
ポリエステルは機械特性、熱特性、耐薬品性、電気特性、成形性に優れ、様々な用途に用いられている。 Polyester is excellent in mechanical properties, thermal properties, chemical resistance, electrical properties, and moldability, and is used in various applications.
しかし、ポリエステルは熱分解や酸化分解により機械物性が低下するため、長期にわたって使用する場合、これら分解を抑制すべく様々な検討がなされてきた。特に、電気絶縁用フィルムは高温条件下にさらされることから高い耐熱性と耐酸化分解性が要求されてきた。近年、上記のようなフィルムの要求特性はさらに向上してきており、耐熱酸化分解性に優れたフィルムが求められてきている。この課題に対して、以下の文献に示されるような検討がされてきている。 However, since the mechanical properties of polyester deteriorate due to thermal decomposition or oxidative decomposition, various studies have been made to suppress such decomposition when used over a long period of time. In particular, since the film for electrical insulation is exposed to high temperature conditions, high heat resistance and oxidative decomposition resistance have been required. In recent years, the required properties of the above film have been further improved, and a film excellent in heat-resistant oxidative degradation has been demanded. In order to solve this problem, studies as shown in the following documents have been made.
例えば、特許文献１にはポリエステル樹脂組成物に銅元素とアルカリ金属元素およびリン元素を含有させ、耐熱性と耐酸化分解性を向上させる技術が開示されている。 For example, Patent Document 1 discloses a technique for improving the heat resistance and oxidative decomposition resistance by adding a copper element, an alkali metal element, and a phosphorus element to a polyester resin composition.
また、特許文献２にはポリエステル樹脂組成物に特定の銅化合物を特定範囲内で配合し透明性の向上を図る技術が開示されている。 Patent Document 2 discloses a technique for improving transparency by blending a polyester resin composition with a specific copper compound within a specific range.
しかしながら、これら従来技術では、銅元素による着色や透明性の低下が見られ、透明性を維持するために添加量を減らすと、耐熱酸化分解性が低下する課題があった。 However, in these conventional techniques, coloring due to copper element and a decrease in transparency were observed, and there was a problem that the heat-resistant oxidative degradation was reduced when the addition amount was reduced in order to maintain transparency.
本発明の目的は、良好な耐熱酸化分解性および透明性を両立したポリエステル樹脂組成物を提供することにある。 An object of the present invention is to provide a polyester resin composition having both good heat-resistant oxidative degradation and transparency.
上記課題を解決すべく検討を行った結果、本発明により、良好な耐熱酸化分解性および透明性を両立するポリエステル樹脂組成物を見出した。 As a result of investigations to solve the above problems, the present invention has found a polyester resin composition having both good heat-resistant oxidative degradation and transparency.
すなわち、本発明の目的は以下の手段によって達成される。
希土類元素、アルカリ金属元素、およびリン元素を含有したポリエステル樹脂組成物であって、式（Ｉ）を満たすことを特徴とするポリエステル樹脂組成物。
That is, the object of the present invention is achieved by the following means.
A polyester resin composition containing a rare earth element, an alkali metal element, and a phosphorus element, wherein the polyester resin composition satisfies the formula (I).
Ｍ／Ａ≧０．１ （Ｉ）
(Ｍは希土類元素の総和モル量、Ａはアルカリ金属元素の総和モル量を示す。)
M / A ≧ 0.1 (I)
(M represents the total molar amount of rare earth elements, and A represents the total molar amount of alkali metal elements.)
本発明によれば、良好な耐熱酸化分解性および透明性を有するポリエステル樹脂組成物を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the polyester resin composition which has favorable heat-resistant oxidative decomposition property and transparency can be provided.
以下に本発明を詳細に説明する。
本発明におけるポリエステル樹脂とは、ジカルボン酸成分とジオール成分を主原料として重縮合して得られるポリエステル樹脂を指す。ポリエステル中の主たる成分は、ジカルボン酸成分およびジオール成分である構成単位が、合計で８０モル％以上であることが得られた製品の物理特性、および本発明の目的効果から好ましい。より好ましくは９０モル％以上、さらに好ましくは９５モル％以上である。
The present invention is described in detail below.
The polyester resin in the present invention refers to a polyester resin obtained by polycondensation using a dicarboxylic acid component and a diol component as main raw materials. The main components in the polyester are preferred from the physical properties of the product obtained and the object and effects of the present invention in which the constituent units of the dicarboxylic acid component and the diol component are 80 mol% or more in total. More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more.
本発明におけるジカルボン酸成分としては、マロン酸、コハク酸、グルタル酸、アジピン酸等の脂肪族ジカルボン酸類、アダマンタンジカルボン酸、ノルボルネンジカルボン酸、シクロヘキサンジカルボン酸等の脂環族ジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、１，８−ナフタレンジカルボン酸、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、５−ナトリウムスルホイソフタル酸等の芳香族ジカルボン酸、もしくはそのエステル誘導体が挙げられる。これらの中でも、ポリエステル樹脂組成物の耐熱酸化分解性や、組成物をフィルムにした際の機械強度の観点から、芳香族ジカルボン酸が好ましい。その中でもテレフタル酸、ナフタレンジカルボン酸がより好ましく、フィルムを得る際の製膜性の観点からテレフタル酸がさらに好ましい。 Examples of the dicarboxylic acid component in the present invention include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and adipic acid, alicyclic dicarboxylic acids such as adamantane dicarboxylic acid, norbornene dicarboxylic acid, and cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid. Acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4 ′ -Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid and 5-sodium sulfoisophthalic acid, or ester derivatives thereof. Among these, aromatic dicarboxylic acids are preferable from the viewpoint of the heat-resistant oxidative decomposition property of the polyester resin composition and the mechanical strength when the composition is formed into a film. Among these, terephthalic acid and naphthalenedicarboxylic acid are more preferable, and terephthalic acid is more preferable from the viewpoint of film forming properties when a film is obtained.
本発明におけるジオール成分としては、各種ジオールを採用できる。例えば、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，４−ブタンジオール、２−メチル−１，３−プロパンジオール、ヘキサンジオール、ネオペンチルグリコールなどの脂肪族ジオール、脂環式ジオールとしてはシクロヘキサンジメタノール、シクロヘキサンジエタノール、デカヒドロナフタレンジメタノール、デカヒドロナフタレンジエタノール、ノルボルナンジメタノール、ノルボルナンジエタノール、トリシクロデカンジメタノール、トリシクロデカンジエタノール、テトラシクロドデカンジメタノール、テトラシクロドデカンジエタノール、デカリンジメタノール、デカリンジエタノールなどの飽和脂環式１級ジオール、２，６−ジヒドロキシ−９−オキサビシクロ［３，３，１］ノナン、３，９−ビス（２−ヒドロキシ−１，１−ジメチルエチル）−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン（スピログリコール）、５−メチロール−５−エチル−２−（１，１−ジメチル−２−ヒドロキシエチル）−１，３−ジオキサン、イソソルビドなどの環状エーテルを含む飽和ヘテロ環１級ジオール、その他シクロヘキサンジオール、ビシクロヘキシル−４，４’−ジオール、２，２−ビス（４−ヒドロキシシクロヘキシルプロパン）、２，２−ビス（４−（２−ヒドロキシエトキシ）シクロヘキシル）プロパン、シクロペンタンジオール、３−メチル−１，２−シクロペンタジオール、４−シクロペンテン−１，３−ジオール、アダマンジオールなどの各種脂環式ジオールや、パラキシレングリコール、ビスフェノールＡ、ビスフェノールＳ，スチレングリコール、９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレン、９，９’−ビス（４−ヒドロキシフェニル）フルオレンなどの芳香環式ジオールが例示できる。またゲル化しない範囲で、ジオール以外にもトリメチロールプロパン、ペンタエリスリトールなどの多官能アルコールも採用できる。 Various diols can be employed as the diol component in the present invention. For example, aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentyl glycol, and fat Cyclic diols include cyclohexanedimethanol, cyclohexanediethanol, decahydronaphthalene diethanol, decahydronaphthalene diethanol, norbornane dimethanol, norbornane diethanol, tricyclodecane dimethanol, tricyclodecane diethanol, tetracyclododecane dimethanol, tetracyclododecane Saturated alicyclic primary diols such as diethanol, decalin dimethanol, decalin diethanol, 2,6-dihydroxy-9-oxabicyclo [3,3,1] nonane, 3 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (spiroglycol), 5-methylol-5-ethyl-2- (1) , 1-dimethyl-2-hydroxyethyl) -1,3-dioxane, saturated heterocyclic primary diols including cyclic ethers such as isosorbide, other cyclohexanediols, bicyclohexyl-4,4′-diols, 2,2-bis (4-hydroxycyclohexylpropane), 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiol, 4-cyclopentene-1,3- Various alicyclic diols such as diol and adamant diol, para-xylene glycol, bisphenol A, bisphenol S, styrene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9'-bis (4-hydroxyphenyl) aromatic diols such as fluorene can be exemplified. In addition to the diol, polyfunctional alcohols such as trimethylolpropane and pentaerythritol can be employed as long as they do not gel.
この中で、沸点２３０℃以下のジオールであることが好ましく、脂肪族ジオールが好ましい。その中でも、例えば、組成物をフィルムにした際の伸度および柔軟性といった機械的特性の観点からエチレングリコールが特に好ましい。
なお、本発明の効果の範囲を損なわない程度に、他のジカルボン酸やヒドロキシカルボン酸誘導体、ジオールが共重合されていてもよい。
Among these, a diol having a boiling point of 230 ° C. or lower is preferable, and an aliphatic diol is preferable. Among them, for example, ethylene glycol is particularly preferable from the viewpoint of mechanical properties such as elongation and flexibility when the composition is formed into a film.
In addition, other dicarboxylic acids, hydroxycarboxylic acid derivatives, and diols may be copolymerized to such an extent that the scope of the effect of the present invention is not impaired.
本発明のポリエステル樹脂組成物は、優れた耐熱酸化分解性および透明性を得るために、希土類元素を含有することが必要である。希土類元素として具体的には、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕが挙げられる。希土類元素として耐熱酸化分解性および色調、入手のしやすさの観点から、この中でもＬａ、Ｃｅのいずれかが好ましく、より好ましくはＣｅである。希土類元素は２種類以上含有していてもかまわない。 The polyester resin composition of the present invention needs to contain a rare earth element in order to obtain excellent heat-resistant oxidative degradation and transparency. Specific examples of the rare earth element include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Of these, La or Ce is preferable, and Ce is more preferable, from the viewpoint of heat-resistant oxidative decomposition property, color tone, and availability as the rare earth element. Two or more rare earth elements may be contained.
希土類元素の含有量としては、十分な耐熱酸化分解性を得るためには０．１モル／トン以上であることが好ましく、より好ましくは１．０モル／トン以上、さらに好ましくは１．５モル／トン以上である。また、上限としては、１０．０モル／トン以下であることが好ましく、より好ましくは６．０モル／トン以下、さらに好ましくは５．０モル／トン以下である。希土類元素が前記上限以下であると、ポリエステル樹脂との相溶性が良好で、成形加工時の粗大異物の発生が少ない。 The content of the rare earth element is preferably 0.1 mol / ton or more, more preferably 1.0 mol / ton or more, and further preferably 1.5 mol or more in order to obtain sufficient heat-resistant oxidative decomposition property. / T or more. Moreover, as an upper limit, it is preferable that it is 10.0 mol / ton or less, More preferably, it is 6.0 mol / ton or less, More preferably, it is 5.0 mol / ton or less. When the rare earth element is not more than the above upper limit, the compatibility with the polyester resin is good, and the generation of coarse foreign matters during molding is small.
本発明のポリエステル樹脂組成物においては、優れた耐熱酸化分解性および透明性を付与するために、アルカリ金属元素が含まれることが必要である。アルカリ金属元素として具体的には、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｆｒが挙げられるが、耐熱酸化分解性の観点から、Ｌｉ、Ｎａ、Ｋのいずれかであることが好ましく、より好ましくは、Ｎａ、Ｋのいずれかである。アルカリ金属元素は２種類以上含有していてもかまわない。 In the polyester resin composition of this invention, in order to provide the outstanding heat-resistant oxidative decomposition property and transparency, it is necessary to contain an alkali metal element. Specific examples of the alkali metal element include Li, Na, K, Rb, Cs, and Fr. From the viewpoint of heat-resistant oxidative decomposability, any of Li, Na, and K is preferable, and more preferable. , Na, or K. Two or more kinds of alkali metal elements may be contained.
アルカリ金属元素の含有量は、０．１モル／トン以上が好ましく、より好ましくは１．０モル／トン以上である。アルカリ金属元素が０．１モル／トン以上であれば、希土類元素の耐熱酸化分解性効果がさらに向上する。また、アルカリ金属元素の含有量の上限は、１０．０モル／トン以下であることが好ましく、より好ましくは４．０モル／トン以下、さらに好ましくは３．０モル／トン以下である。アルカリ金属元素が１０．０モル／トン以下であれば、成形時にポリエステルの低分子量体と不溶性の異物を形成することがなく、透明性が良好である。 The content of the alkali metal element is preferably 0.1 mol / ton or more, more preferably 1.0 mol / ton or more. When the alkali metal element is 0.1 mol / ton or more, the heat-resistant oxidative decomposition effect of the rare earth element is further improved. Moreover, it is preferable that the upper limit of content of an alkali metal element is 10.0 mol / ton or less, More preferably, it is 4.0 mol / ton or less, More preferably, it is 3.0 mol / ton or less. When the alkali metal element is 10.0 mol / ton or less, the low molecular weight body of polyester and insoluble foreign matter are not formed during molding, and transparency is good.
本発明のポリエステル樹脂組成物において、優れた耐熱酸化分解性を得るために、希土類元素の総和モル量（Ｍ）とアルカリ金属元素の総和モル量（Ａ）の比（Ｍ／Ａ）が０．１以上であることが必要である。Ｍ／Ａとして好ましくは０．５以上、より好ましくは０．８以上である。また、上限は特に設けないが、耐熱酸化分解性および透明性の観点から５．０以下が好ましく、より好ましくは３．０以下、さらに好ましくは１．５以下である。 In the polyester resin composition of the present invention, the ratio (M / A) of the total molar amount (M) of rare earth elements to the total molar amount (A) of alkali metal elements is 0. It must be one or more. M / A is preferably 0.5 or more, more preferably 0.8 or more. Moreover, although an upper limit is not particularly provided, it is preferably 5.0 or less, more preferably 3.0 or less, and still more preferably 1.5 or less, from the viewpoints of heat-resistant oxidative degradation and transparency.
優れた耐熱酸化分解性および透明性を得るためにリン元素を含むことが必要である。リン元素の含有量としては、十分な耐熱酸化分解性を得るために下限として０．３モル／トン以上であることが好ましく、より好ましくは１．０モル／トン以上、さらに好ましくは１．５モル／トン以上である。また、上限としては、６．０モル／トン以下であることが好ましく、より好ましくは４．０モル／トン以下である。リン元素が６．０モル／トン以下であると、組成物中の酸性度が高くなり過ぎないので、耐熱酸化分解性が良好である。 In order to obtain excellent heat-resistant oxidative decomposition and transparency, it is necessary to contain a phosphorus element. The phosphorus element content is preferably 0.3 mol / ton or more, more preferably 1.0 mol / ton or more, and still more preferably 1.5 mol or less as a lower limit in order to obtain sufficient heat-resistant oxidative decomposability. More than mol / ton. Moreover, as an upper limit, it is preferable that it is 6.0 mol / tons or less, More preferably, it is 4.0 mol / tons or less. When the phosphorus element is 6.0 mol / ton or less, since the acidity in the composition does not become too high, the heat-resistant oxidative decomposition property is good.
本発明のポリエステル樹脂組成物において、耐熱酸化分解性および透明性の観点から、希土類元素とアルカリ金属元素の総和モル量（ＭＡ）とリン元素の総和モル量（Ｐ）の比（ＭＡ／Ｐ）は、０．５以上６．０以下であることが好ましい。ＭＡ／Ｐが０．５以上であると組成物中の酸性度が高くなり過ぎないので、耐熱酸化分解性が良好である。ＭＡ／Ｐが６．０以下であると、副反応が抑制されて透明性が良好となる。ＭＡ／Ｐはより好ましくは１．０以上、さらに好ましくは１．３以上である。また、ＭＡ／Ｐはより好ましくは５．０以下、さらに好ましくは３．５以下である。 In the polyester resin composition of the present invention, the ratio of the total molar amount (MA) of the rare earth element and the alkali metal element to the total molar amount (P) of the phosphorus element (MA / P) from the viewpoint of heat-resistant oxidative decomposition and transparency. Is preferably 0.5 or more and 6.0 or less. When the MA / P is 0.5 or more, the acidity in the composition does not become too high, and the heat-resistant oxidative decomposition property is good. When MA / P is 6.0 or less, side reactions are suppressed and transparency is improved. MA / P is more preferably 1.0 or more, and still more preferably 1.3 or more. Further, MA / P is more preferably 5.0 or less, and further preferably 3.5 or less.
一般的に希土類元素は、複数のイオン価数状態となることができる。ポリエステルの熱分解や酸化分解の起点となるラジカルに対して、希土類元素が電子の授受によりイオン価数を変えて消費し、ラジカルを不活性化することができるため、熱分解や酸化分解を抑制する効果を付与できる。本発明では、耐熱酸化分解性を付与する目的で希土類元素を使用している。しかし、原理の詳細は明らかではないが、ポリエステル樹脂に希土類元素単独で含有させた場合は期待されるラジカル不活性化効果は得られず、かえってポリエステル樹脂の分解を促進することがわかった。そこで、鋭意検討した結果、アルカリ金属元素を希土類元素に対して特定以上の割合で併用し、かつリン元素を併用することで、希土類元素がより効果的に熱酸化分解を抑制できることを見出した。 In general, rare earth elements can be in multiple ionic valence states. Suppresses thermal decomposition and oxidative degradation because rare earth elements can be consumed by changing the ionic valence of electrons by giving and receiving electrons to radicals that are the starting point of thermal decomposition and oxidative decomposition of polyester. Effect can be added. In the present invention, rare earth elements are used for the purpose of imparting heat-resistant oxidative decomposability. However, although the details of the principle are not clear, it has been found that when the rare earth element alone is contained in the polyester resin, the expected radical inactivating effect cannot be obtained, and the decomposition of the polyester resin is promoted. Thus, as a result of intensive studies, it was found that the rare earth element can more effectively suppress thermal oxidative decomposition by using an alkali metal element in combination with the rare earth element at a specific ratio and a phosphorus element.
本発明のポリエステル樹脂組成物の色調は、実施例の（５）として記載した測定方法により求められるＬ値で評価する。Ｌ値は、５０以上が好ましく、より好ましくは５５以上、さらに好ましくは５８以上である。この範囲とすることで、フィルムや繊維などの色調が良好なポリエステル樹脂組成物成形体を提供することが可能となる。 The color tone of the polyester resin composition of the present invention is evaluated by the L value obtained by the measurement method described as (5) in the examples. The L value is preferably 50 or more, more preferably 55 or more, and still more preferably 58 or more. By setting it as this range, it becomes possible to provide the polyester resin composition molded object with favorable color tone, such as a film and a fiber.
本発明のポリエステル樹脂組成物の溶液ヘイズは、実施例の（６）として記載した測定方法により求められる。溶液ヘイズとしては、１０％以下が好ましく、より好ましくは８％以下、さらに好ましくは５％以下である。この範囲とすることで、得られる樹脂組成物からなる成形体は異物が少なく、透明性に優れたものとなる。 The solution haze of the polyester resin composition of this invention is calculated | required by the measuring method described as (6) of an Example. The solution haze is preferably 10% or less, more preferably 8% or less, and still more preferably 5% or less. By setting it as this range, the molded object which consists of a resin composition obtained has few foreign materials, and becomes the thing excellent in transparency.
本発明のポリエステル樹脂組成物の耐熱酸化分解性は、実施例の（８）として記載した測定方法により求められるΔＣＯＯＨで評価する。ΔＣＯＯＨとして好ましくは１００ｅｑ／トン以下、より好ましくは５０ｅｑ／トン以下、特に好ましくは４０ｅｑ／トン以下である。上記範囲を満たすことで、長期使用において高耐熱酸化分解性が必要とされる電絶フィルム用途などに好適なポリエステル樹脂組成物を提供することが可能となる。 The heat-resistant oxidative decomposability of the polyester resin composition of the present invention is evaluated by ΔCOOH determined by the measurement method described as (8) in the examples. ΔCOOH is preferably 100 eq / ton or less, more preferably 50 eq / ton or less, and particularly preferably 40 eq / ton or less. By satisfy | filling the said range, it becomes possible to provide the polyester resin composition suitable for the ionization film use etc. for which high heat-resistant oxidative decomposition property is required in long-term use.
ここで、耐熱酸化分解性試験では、試験精度の観点から、試験するポリエステル樹脂組成物の形態を統一することが重要である。当該耐熱酸化分解性試験では実施例の（７）として記載した方法で作製したプレスシート状形態で試験する。 Here, in the heat-resistant oxidative degradation test, it is important to unify the form of the polyester resin composition to be tested from the viewpoint of test accuracy. In the heat-resistant oxidative degradation test, the test is performed in the form of a press sheet produced by the method described as (7) in the examples.
本発明のポリエステル樹脂組成物の透明性は、実施例の（９）として記載した測定方法により求められる全光線透過率で評価する。全光線透過率として好ましくは７５％以上、より好ましくは８０％以上、特に好ましくは８５％以上である。上記範囲を満たすことで、透明性に優れた成型体を得ることが可能となる。 The transparency of the polyester resin composition of the present invention is evaluated by the total light transmittance determined by the measuring method described as (9) in the examples. The total light transmittance is preferably 75% or more, more preferably 80% or more, and particularly preferably 85% or more. By satisfy | filling the said range, it becomes possible to obtain the molded object excellent in transparency.
次に、本発明におけるポリエステル樹脂組成物の製造方法について、説明する。
本発明のポリエステル樹脂組成物は、希土類元素、アルカリ金属元素、およびリン元素を含有したポリエステル樹脂組成物であって、希土類元素の総和モル量とアルカリ金属元素の総和モル量の比を０．１以上とすることで、得ることができる。
Next, the manufacturing method of the polyester resin composition in this invention is demonstrated.
The polyester resin composition of the present invention is a polyester resin composition containing a rare earth element, an alkali metal element, and a phosphorus element, and the ratio of the total molar amount of rare earth elements to the total molar amount of alkali metal elements is 0.1. It can obtain by setting it as the above.
本発明において希土類元素、アルカリ金属元素およびリン元素をポリエステルに導入する方法としては、例えば、ポリエステル重縮合反応が完結するまでにそれぞれの元素を含む化合物を添加する方法、ポリエステル溶融ポリマー中へそれぞれの元素を含む化合物を添加し、混錬する方法、それぞれの元素を含む複数のポリエステルを溶融し、混錬する方法などが挙げられる。 In the present invention, the method of introducing the rare earth element, alkali metal element and phosphorus element into the polyester includes, for example, a method of adding a compound containing each element until the polyester polycondensation reaction is completed, Examples thereof include a method of adding a compound containing an element and kneading, and a method of melting and kneading a plurality of polyesters containing each element.
ポリエステル樹脂組成物の製造方法として、ポリエステル重合反応が完結するまでに希土類元素、アルカリ金属元素およびリン元素を含む化合物を添加する方法について詳細に説明する。 As a method for producing a polyester resin composition, a method for adding a compound containing a rare earth element, an alkali metal element and a phosphorus element until the polyester polymerization reaction is completed will be described in detail.
ポリエステル樹脂組成物の製造方法は、ジカルボン酸またはジカルボン酸エステルおよびジオールをエステル化反応（Ａ）またはエステル交換反応（Ｂ）させる、１段階目の反応と、それに続く重縮合反応（Ｃ）からなる。 The method for producing a polyester resin composition comprises a first-stage reaction in which a dicarboxylic acid or dicarboxylic acid ester and a diol are esterified (A) or transesterified (B), followed by a polycondensation reaction (C). .
１段階目の工程のうち、エステル化反応（Ａ）の工程は、ジカルボン酸成分とジオール成分を所定の温度でエステル化させ、所定量の水が留出するまで反応を行い、低重合体を得る工程である。また、エステル交換反応（Ｂ）の工程は、ジカルボン酸アルキルエステル成分とジオール成分を所定の温度でエステル交換反応させ、所定量のアルコールが留出するまで反応を行い、低重合体を得る工程である。 Of the first step, the esterification reaction (A) step comprises esterifying the dicarboxylic acid component and the diol component at a predetermined temperature, and reacting until a predetermined amount of water is distilled off. It is a process to obtain. The step of transesterification (B) is a step in which a dicarboxylic acid alkyl ester component and a diol component are transesterified at a predetermined temperature, and a reaction is performed until a predetermined amount of alcohol is distilled to obtain a low polymer. is there.
一般的に、ジカルボン酸成分とジオール成分を原料としてエステル化反応（Ａ）を行う場合、予めエステル化反応物を貯留しておき、ジカルボン酸成分とジオール成分のスラリーを添加してエステル化反応を開始する手法が、ジオール成分に難溶なジカルボン酸成分のハンドリング性向上、反応時間の短縮の点から選択されている。エステル化反応物を貯留しない場合でも、エステル化反応は進行するが、加圧設備や触媒が必要となる場合がある。本発明においてもエステル化反応物を予め貯留してエステル化反応を実施することが望ましい。 Generally, when the esterification reaction (A) is performed using a dicarboxylic acid component and a diol component as raw materials, an esterification reaction product is stored in advance, and a slurry of the dicarboxylic acid component and the diol component is added to perform the esterification reaction. The starting method is selected from the viewpoint of improving the handling property of the dicarboxylic acid component that is hardly soluble in the diol component and shortening the reaction time. Even if the esterification reaction product is not stored, the esterification reaction proceeds, but a pressurization facility or a catalyst may be required. Also in the present invention, it is desirable to carry out the esterification reaction by storing the esterification reaction product in advance.
本発明におけるポリエステル樹脂組成物の製造方法において、ジカルボン酸成分とジオール成分からエステル化反応物を得る際、エステル化反応性、耐熱酸化分解性および色調の観点から、エステル化反応開始前のジカルボン酸成分とジオール成分のモル比（ジオール成分／ジカルボン酸成分）は、１．０５以上１．４０以下の範囲であることが好ましい。モル比を１．０５以上１．４０以下にすることによって、エステル化反応を効率的に進行させることができ、ジオール成分の２量体の副生を抑えることができる。その結果として、得られるポリエステル樹脂組成物の耐熱酸化分解性および色調を良好にすることができる。モル比が１．０５未満であると、エステル化反応が効率的に進まないため、タイムサイクルが長くなる場合がある。また、モル比が１．４０を超えると、副生するジオール成分の２量体によって耐熱酸化分解性が低下する場合がある。 In the method for producing a polyester resin composition in the present invention, when an esterification reaction product is obtained from a dicarboxylic acid component and a diol component, the dicarboxylic acid before the start of the esterification reaction from the viewpoint of esterification reactivity, heat-resistant oxidative degradation, and color tone The molar ratio of the component to the diol component (diol component / dicarboxylic acid component) is preferably in the range of 1.05 to 1.40. By setting the molar ratio to 1.05 or more and 1.40 or less, the esterification reaction can proceed efficiently, and the by-production of the dimer of the diol component can be suppressed. As a result, the heat-resistant oxidative decomposition property and color tone of the obtained polyester resin composition can be improved. If the molar ratio is less than 1.05, since the esterification reaction does not proceed efficiently, the time cycle may be long. On the other hand, when the molar ratio exceeds 1.40, the heat-resistant oxidative decomposition property may be lowered by the dimer of the diol component by-produced.
なお、本発明におけるエステル化反応において、触媒としてアルカリ金属塩、チタン化合物、アンモニウム塩などを用いても構わないが、重縮合反応段階での熱分解や異物の発生などの観点から、エステル化反応は無触媒で実施することが好ましい。ここで、エステル化反応は無触媒においてもカルボキシル基末端による自己触媒作用によって、反応は十分に進行する。 In the esterification reaction in the present invention, an alkali metal salt, a titanium compound, an ammonium salt, or the like may be used as a catalyst. From the viewpoint of thermal decomposition or generation of foreign matters in the polycondensation reaction stage, the esterification reaction Is preferably carried out without a catalyst. Here, the esterification reaction proceeds sufficiently even in the absence of a catalyst by autocatalysis by the carboxyl group terminal.
また、本発明におけるポリエステル樹脂組成物の製造方法において、ジカルボン酸アルキルエステル成分とジオール成分からエステル交換反応（Ｂ）を経てエステル化物を得る際、エステル交換反応性、耐酸化分解性の観点から、エステル交換反応開始前のジカルボン酸アルキルエステル成分とジオール成分のモル比（ジオール成分／ジカルボン酸アルキルエステル成分）は１．７以上２．３以下の範囲であることが好ましい。上記範囲とすることで、エステル交換反応を効率的に進行させることができ、またジオール成分の２量体の副生を抑えることができる。その結果として、得られるポリエステル樹脂組成物の耐熱酸化分解性および色調を良好にすることができる。モル比が１．７を下回る場合は、エステル化反応が効率的に進行しないため、タイムサイクルが長くなり色調が悪化する場合がある。一方、モル比が２．３を超えると、副生するジオール成分の２量体によって耐熱酸化分解性が低下する場合がある。 Further, in the method for producing a polyester resin composition in the present invention, when obtaining an esterified product from a dicarboxylic acid alkyl ester component and a diol component through a transesterification reaction (B), from the viewpoint of transesterification reactivity and oxidation-degradation resistance, The molar ratio of the dicarboxylic acid alkyl ester component to the diol component (diol component / dicarboxylic acid alkyl ester component) before the start of the transesterification reaction is preferably in the range of 1.7 to 2.3. By setting it as the said range, transesterification can be advanced efficiently and the byproduct of the dimer of a diol component can be suppressed. As a result, the heat-resistant oxidative decomposition property and color tone of the obtained polyester resin composition can be improved. When the molar ratio is less than 1.7, since the esterification reaction does not proceed efficiently, the time cycle becomes long and the color tone may deteriorate. On the other hand, when the molar ratio exceeds 2.3, the heat-resistant oxidative decomposition property may be lowered by the dimer of the diol component by-produced.
本発明におけるポリエステル樹脂組成物の製造方法において、エステル交換反応に用いられる触媒は、公知のエステル交換触媒を用いることができる。エステル交換触媒及び助触媒としては、有機マンガン化合物、有機マグネシウム化合物、有機カルシウム化合物、有機コバルト化合物などが好ましく使用される。具体的には、炭酸塩、酢酸塩、安息香酸塩、酸化物、水酸化物などがあるが、これに限定されるものではない。 In the method for producing a polyester resin composition in the present invention, a known transesterification catalyst can be used as the catalyst used in the transesterification reaction. As the transesterification catalyst and the cocatalyst, an organic manganese compound, an organic magnesium compound, an organic calcium compound, an organic cobalt compound, or the like is preferably used. Specific examples include carbonates, acetates, benzoates, oxides and hydroxides, but are not limited thereto.
２段階目の工程である重縮合反応（Ｃ）は、エステル化反応（Ａ）またはエステル交換反応（Ｂ）で得られた低重合体を移送した反応器内を減圧にすることにより、重縮合反応を開始し、反応器内の温度、圧力および攪拌速度を調節し重合反応を行い、攪拌トルクが所定の値に到達した時、すなわちポリエステル樹脂組成物が所望の粘度に到達した時まで重縮合反応を行うことにより、高分子量ポリエステル樹脂を得る工程である。 The polycondensation reaction (C), which is the second step, is performed by reducing the pressure in the reactor to which the low polymer obtained in the esterification reaction (A) or transesterification reaction (B) has been transferred. Start the reaction, adjust the temperature, pressure and stirring speed in the reactor to carry out the polymerization reaction, and polycondensate until the stirring torque reaches the specified value, that is, until the polyester resin composition reaches the desired viscosity This is a step of obtaining a high molecular weight polyester resin by carrying out the reaction.
本発明におけるポリエステル樹脂組成物の製造に用いられる重縮合触媒は、公知の重縮合触媒を用いることができる。例えば、アンチモン化合物、ゲルマニウム化合物、チタン化合物、アルミニウム化合物、スズ化合物などが挙げられる。 A known polycondensation catalyst can be used as the polycondensation catalyst used in the production of the polyester resin composition in the present invention. For example, an antimony compound, a germanium compound, a titanium compound, an aluminum compound, a tin compound, and the like can be given.
希土類元素、アルカリ金属元素およびリン元素は、（Ａ）または（Ｂ）工程、それに続く（Ｃ）工程のいずれの段階で添加しても良いが、耐熱酸化分解性および色調に優れたポリエステル樹脂組成物を効率的に製造することができる点で、（Ａ）または（Ｂ）工程終了から（Ｃ）工程完了までの間で添加することが好ましい。この時、（Ａ）または（Ｂ）工程は、反応率が９５％に到達した段階を反応終了とする。希土類元素、アルカリ金属元素およびリン元素はそれぞれジオール成分と混合した状態で添加することが好ましい。 The rare earth element, alkali metal element and phosphorus element may be added at any stage of the process (A) or (B) and the subsequent process (C), but the polyester resin composition is excellent in heat-resistant oxidative degradation and color tone. It is preferable to add from the end of the step (A) or (B) to the completion of the step (C) in that the product can be efficiently produced. At this time, in the step (A) or (B), the reaction is completed when the reaction rate reaches 95%. The rare earth element, alkali metal element and phosphorus element are preferably added in a state of being mixed with the diol component.
添加する希土類元素としては具体的には、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕが挙げられ、希土類元素として耐酸化分解性や入手のしやすさの観点から、この中でもＬａ、Ｃｅが好ましく、より好ましくはＣｅである。 Specific examples of rare earth elements to be added include Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Among these, La and Ce are preferable, and Ce is more preferable from the viewpoint of oxidation resistance and availability.
希土類元素を含む化合物としては、有機酸塩、ハロゲン化塩、水酸化物、アルコキシド、酸化物、有機アルキル化合物などの各種の金属化合物を用いることができる。具体的には、トリス(アセチルアセトナト)ランタン(ＩＩＩ)、塩化ランタン(ＩＩＩ)、酢酸ランタン(ＩＩＩ)、ステアリン酸ランタン(ＩＩＩ)、リン酸ランタン(ＩＩＩ)、酸化セリウム（ＩＩＩ）、酸化セリウム（ＩＶ）、塩化セリウム（ＩＩＩ）、フッ化セリウム（ＩＩＩ）、硫酸セリウム（ＩＩＩ）、硫酸セリウム（ＩＶ）、硝酸セリウム（ＩＩＩ）アンモニウム、ペンタニトラトセリウム（ＩＩＩ）酸アンモニウム、硝酸セリウム（ＩＶ）アンモニウム、ヘキサニトラトセリウム（ＩＶ）酸アンモニウム、硝酸セリウム（ＩＩＩ）、水酸化セリウム（ＩＶ）、炭酸セリウム（ＩＩＩ）、シュウ酸セリウム（ＩＩＩ）、酢酸セリウム（ＩＩＩ）、酢酸セリウム（ＩＶ）などの化合物が挙げられる。その中でも、耐熱酸化分解性の観点から、有機酸塩が好ましく、その中でも酢酸塩などのカルボン酸塩が特に好ましい。なお、これらの化合物は単独で用いてもよいし、２種類以上組み合わせて使用してもよい。 As the compound containing a rare earth element, various metal compounds such as organic acid salts, halide salts, hydroxides, alkoxides, oxides, and organic alkyl compounds can be used. Specifically, tris (acetylacetonato) lanthanum (III), lanthanum chloride (III), lanthanum acetate (III), lanthanum stearate (III), lanthanum phosphate (III), cerium oxide (III), cerium oxide (IV), cerium (III) chloride, cerium fluoride (III), cerium sulfate (III), cerium sulfate (IV), cerium (III) ammonium nitrate, ammonium pentanitratocerium (III), cerium nitrate (IV ) Ammonium, ammonium hexanitratocerium (IV), cerium nitrate (III), cerium hydroxide (IV), cerium carbonate (III), cerium oxalate (III), cerium acetate (III), cerium acetate (IV) And the like. Of these, organic acid salts are preferable from the viewpoint of heat-resistant oxidative degradation, and carboxylates such as acetate are particularly preferable. In addition, these compounds may be used independently and may be used in combination of 2 or more types.
十分な耐熱酸化分解性を得るために、希土類元素を含む化合物を希土類元素として０．１モル／トン以上添加することが好ましく、より好ましくは１．０モル／トン以上、さらに好ましくは１．５モル／トン以上である。また、上限としては、希土類元素として１０．０モル／トン以下であることが好ましく、より好ましくは６．０モル／トン以下、さらに好ましくは５．０モル／トン以下である。希土類元素が上限以下であると、ポリエステル樹脂との相溶性が良好であるので、粗大異物の発生が少なく目的とするポリエステル組成物を得ることができる。 In order to obtain sufficient heat-resistant oxidative decomposability, it is preferable to add a compound containing a rare earth element as a rare earth element in an amount of 0.1 mol / ton or more, more preferably 1.0 mol / ton or more, and still more preferably 1.5 mol / ton. More than mol / ton. Moreover, as an upper limit, it is preferable that it is 10.0 mol / tons or less as a rare earth element, More preferably, it is 6.0 mol / tons or less, More preferably, it is 5.0 mol / tons or less. If the rare earth element is less than or equal to the upper limit, the compatibility with the polyester resin is good, so that the desired polyester composition can be obtained with less generation of coarse foreign matter.
添加するアルカリ金属元素としては、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｆｒが挙げられるが、耐熱酸化分解性および耐加水分解性の観点から、Ｌｉ、Ｎａ、Ｋのいずれかであることが好ましく、より好ましくは、Ｎａ、Ｋのいずれかである。 Examples of the alkali metal element to be added include Li, Na, K, Rb, Cs, and Fr. From the viewpoints of heat-resistant oxidative degradation and hydrolysis resistance, any of Li, Na, and K is preferable. More preferably, it is either Na or K.
アルカリ金属元素を含む化合物としては、有機酸塩、水酸化物、アルコキシド、酸化物、有機アルキル化合物など各種のアルカリ金属化合物を用いることができる。具体的には、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、安息香酸リチウム、安息香酸ナトリウム、安息香酸カリウム、リン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸三ナトリウム、リン酸二水素カリウム、リン酸水素二カリウム、リン酸三カリウム、リン酸二水素リチウム、リン酸水素二リチウム、リン酸三リチウム、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、カリウムメトキシド、ｎ−ブチルリチウムなどの化合物が挙げられる。なお、これらの化合物は単独で用いてもよいし、２種類以上組み合わせて使用しても構わない。 As the compound containing an alkali metal element, various alkali metal compounds such as organic acid salts, hydroxides, alkoxides, oxides, and organic alkyl compounds can be used. Specifically, lithium acetate, sodium acetate, potassium acetate, lithium benzoate, sodium benzoate, potassium benzoate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, phosphorus Dipotassium hydrogen phosphate, tripotassium phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, n-butyl A compound such as lithium may be used. In addition, these compounds may be used independently and may be used in combination of 2 or more types.
アルカリ金属元素を含む化合物の添加量としては、０．１モル／トン以上添加することが好ましく、より好ましくは１．０モル／トン以上である。希土類元素とアルカリ金属元素が含有されることで、希土類元素の耐熱酸化分解性がさらに向上する。また、上限として、１０．０モル／トン以下であることが好ましく、より好ましくは４．０モル／トン以下、さらに好ましくは３．０モル／トン以下である。アルカリ金属元素が１０．０モル／トン以下であると、ポリエステルの低分子量体と不溶性の異物を形成することがなく、透明性が良好である。 The addition amount of the compound containing an alkali metal element is preferably 0.1 mol / ton or more, more preferably 1.0 mol / ton or more. By containing the rare earth element and the alkali metal element, the heat-resistant oxidative decomposition property of the rare earth element is further improved. Moreover, as an upper limit, it is preferable that it is 10.0 mol / ton or less, More preferably, it is 4.0 mol / ton or less, More preferably, it is 3.0 mol / ton or less. When the alkali metal element is 10.0 mol / ton or less, the low molecular weight material of polyester and insoluble foreign matter are not formed, and the transparency is good.
本発明におけるポリエステル樹脂組成物の製造方法において、優れた耐熱酸化分解性を得るために、希土類元素の総和モル量（Ｍ）とアルカリ金属元素の総和モル量（Ａ）の比（Ｍ／Ａ）が０．１以上となるように、希土類元素やアルカリ金属元素を含む化合物を添加することが必要である。Ｍ／Ａとして好ましくは０．５以上、より好ましくは０．８以上である。また、上限は特に設けないが、耐熱酸化分解性および透明性の観点から５．０以下が好ましく、より好ましくは３．０以下、さらに好ましくは１．５以下である。 In the method for producing a polyester resin composition according to the present invention, in order to obtain excellent heat-resistant oxidative decomposability, the ratio of the total molar amount of rare earth elements (M) to the total molar amount of alkali metal elements (A) (M / A) Therefore, it is necessary to add a compound containing a rare earth element or an alkali metal element so that the ratio becomes 0.1 or more. M / A is preferably 0.5 or more, more preferably 0.8 or more. Moreover, although an upper limit is not particularly provided, it is preferably 5.0 or less, more preferably 3.0 or less, and still more preferably 1.5 or less, from the viewpoints of heat-resistant oxidative degradation and transparency.
優れた耐熱酸化分解性および色調を得るためにリン元素を含む化合物を添加することが必要である。なお、添加したリン化合物はポリエステル重合中に反応系外に揮発することがあり、ポリエステル樹脂組成物への残存量は添加量よりも少ないことが一般的である。そこで、十分な耐熱酸化分解性を得るために下限として０．４モル／トン以上のリン元素を含む化合物を添加することが好ましく、より好ましくは１．２モル／トン以上、さらに好ましくは１．８モル／トン以上である。また、上限としては、７.５モル／トン以下であることが好ましく、より好ましくは５．０モル／トン以下である。リン元素が７.５モル／トン以下であると、組成物中の酸性度が高くなり過ぎず、成型体の耐熱酸化分解性が良好である。 In order to obtain excellent heat-resistant oxidative degradation and color tone, it is necessary to add a compound containing phosphorus element. In addition, the added phosphorus compound may volatilize out of the reaction system during polyester polymerization, and the residual amount in the polyester resin composition is generally smaller than the added amount. Therefore, in order to obtain sufficient heat-resistant oxidative decomposability, it is preferable to add a compound containing 0.4 mol / ton or more of phosphorus element as a lower limit, more preferably 1.2 mol / ton or more, and still more preferably 1. 8 mol / ton or more. Moreover, as an upper limit, it is preferable that it is 7.5 mol / tons or less, More preferably, it is 5.0 mol / tons or less. When the phosphorus element is 7.5 mol / ton or less, the acidity in the composition does not become too high, and the heat-resistant oxidative decomposition property of the molded article is good.
添加するリン化合物は特に限定しないが、ホスファイト系化合物、ホスフェイト系化合物、ホスホン酸系化合物、ホスフィン酸系化合物、ホスフィンオキサイド系化合物、亜ホスホン酸系化合物、亜ホスフィン酸系化合物、ホスフィン系化合物等が挙げられる。 The phosphorus compound to be added is not particularly limited, but phosphite compounds, phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, phosphine compounds, etc. Is mentioned.
ホスファイト系化合物としては、具体的には、トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（ジノニルフェニル）ホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、トリス（２−ｔ−ブチル−４−メチルフェニル）ホスファイト、トリス（シクロヘキシルフェニル）ホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト等が挙げられる。 Specific examples of the phosphite compound include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4 -Di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butyl) Phenyl) octyl phosphite and the like.
ホスフェイト系化合物としては、リン酸、リン酸トリメチル、リン酸トリエチル、リン酸トリフェニル、リン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸三ナトリウム、リン酸二水素カリウム、リン酸水素二カリウム、リン酸三カリウム、リン酸二水素リチウム、リン酸水素二リチウム、リン酸三リチウム、リン酸カルシウム、リン酸マグネシウム等が挙げられる。 Phosphate compounds include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate , Tripotassium phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, calcium phosphate, magnesium phosphate and the like.
ホスホン酸系化合物としては、メチルホスホン酸、エチルホスホン酸、プロピルホスホン酸、イソプロピルホスホン酸、ブチルホスホン酸、フェニルホスホン酸、ベンジルホスホン酸、トリルホスホン酸、キシリルホスホン酸、ビフェニルホスホン酸、ナフチルホスホン酸、アントリルホスホン酸、２−カルボキシフェニルホスホン酸、３−カルボキシフェニルホスホン酸、４−カルボキシフェニルホスホン酸、メチルホスホン酸ジメチルエステル、メチルホスホン酸ジエチルエステル、エチルホスホン酸ジメチルエステル、エチルホスホン酸ジエチルエステル、フェニルホスホン酸ジメチルエステル、フェニルホスホン酸ジエチルエステル、フェニルホスホン酸ジフェニルエステル、ベンジルホスホン酸ジメチルエステル、リチウム（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、ナトリウム（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、マグネシウムビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、カルシウムビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、ジエチルホスホノ酢酸、ジエチルホスホノ酢酸メチル、ジエチルホスホノ酢酸エチル等が挙げられる。 Phosphonic acid compounds include methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid Anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, methylphosphonic acid dimethylester, methylphosphonic acid diethylester, ethylphosphonic acid dimethylester, ethylphosphonic acid diethylester, phenyl Phosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, benzylphosphonic acid dimethyl ester, lithium (3, -Ethyl di-tert-butyl-4-hydroxybenzylphosphonate), sodium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), magnesium bis (3,5-di-tert-butyl- Ethyl 4-hydroxybenzylphosphonate), calcium bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl), diethylphosphonoacetic acid, diethylphosphonoacetic acid methyl, diethylphosphonoacetic acid ethyl and the like. It is done.
ホスフィン酸系化合物としては、次亜リン酸、次亜リン酸ナトリウム、メチルホスフィン酸、エチルホスフィン酸、プロピルホスフィン酸、イソプロピルホスフィン酸、ブチルホスフィン酸、フェニルホスフィン酸、トリルホスフィン酸、キシリルホスフィン酸、ビフェニリルホスフィン酸、ジフェニルホスフィン酸、ジメチルホスフィン酸、ジエチルホスフィン酸、ジプロピルホスフィン酸、ジイソプロピルホスフィン酸、ジブチルホスフィン酸、ジトリルホスフィン酸等が挙げられる。 Phosphinic acid compounds include hypophosphorous acid, sodium hypophosphite, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, xylylphosphinic acid Biphenylylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, ditolylphosphinic acid and the like.
ホスフィンオキサイド系化合物としては、トリメチルホスフィンオキサイド、トリエチルホスフィンオキサイド、トリプロピルホスフィンオキサイド、トリイソプロピルホスフィンオキサイド、トリブチルホスフィンオキサイド、トリフェニルホスフィンオキサイド等が挙げられる。 Examples of the phosphine oxide compound include trimethylphosphine oxide, triethylphosphine oxide, tripropylphosphine oxide, triisopropylphosphine oxide, tributylphosphine oxide, triphenylphosphine oxide, and the like.
亜ホスホン酸系化合物としては、メチル亜ホスホン酸、エチル亜ホスホン酸、プロピル亜ホスホン酸、イソプロピル亜ホスホン酸、ブチル亜ホスホン酸、フェニル亜ホスホン酸等が挙げられる。 Examples of the phosphonous acid compound include methylphosphonous acid, ethylphosphonous acid, propylphosphonous acid, isopropylphosphonous acid, butylphosphonous acid, and phenylphosphonous acid.
亜ホスフィン酸系化合物としては、メチル亜ホスフィン酸、エチル亜ホスフィン酸、プロピル亜ホスフィン酸、イソプロピル亜ホスフィン酸、ブチル亜ホスフィン酸、フェニル亜ホスフィン酸、ジメチル亜ホスフィン酸、ジエチル亜ホスフィン酸、ジプロピル亜ホスフィン酸、ジイソプロピル亜ホスフィン酸、ジブチル亜ホスフィン酸、ジフェニル亜ホスフィン酸等が挙げられる。 Phosphinic acid compounds include methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid. Examples include phosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid, and the like.
ホスフィン系化合物としては、メチルホスフィン、ジメチルホスフィン、トリメチルホスフィン、メエルホスフィン、ジエチルホスフィン、トリエチルホスフィン、フェニルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン等が挙げられる。
なお、これらのリン化合物は単独で用いてもよいし、２種類以上組み合わせて使用しても構わない。
Examples of the phosphine compound include methylphosphine, dimethylphosphine, trimethylphosphine, melephosphine, diethylphosphine, triethylphosphine, phenylphosphine, diphenylphosphine, and triphenylphosphine.
In addition, these phosphorus compounds may be used independently and may be used in combination of 2 or more types.
本発明のポリエステル樹脂組成物の製造方法において、耐熱酸化分解性および透明性の観点から、希土類元素とアルカリ金属元素の総和モル量（ＭＡ）とリン元素の総和モル量（Ｐ）の比（ＭＡ／Ｐ）は、０．５以上６．０以下となるように、希土類元素やアルカリ金属元素、リン元素を含む化合物を添加することが好ましい。ＭＡ／Ｐを０．５以上とすると組成物中の酸性度が高くなり過ぎず、耐熱酸化分解性が良好である。一方、ＭＡ／Ｐが６．０以下であると副反応により色調の劣化を抑制できる。ＭＡ／Ｐの下限はより好ましくは１．０以上、さらに好ましくは１．３以上である。ＭＡ／Ｐの上限はより好ましくは５．０以下、さらに好ましくは３．５以下である。 In the method for producing a polyester resin composition of the present invention, the ratio of the total molar amount (MA) of the rare earth element and the alkali metal element to the total molar amount (P) of the phosphorus element (MA) from the viewpoint of heat-resistant oxidative decomposition and transparency. It is preferable to add a compound containing a rare earth element, an alkali metal element, or a phosphorus element so that / P) is 0.5 or more and 6.0 or less. When MA / P is 0.5 or more, the acidity in the composition does not become too high, and the heat-resistant oxidative decomposition property is good. On the other hand, when MA / P is 6.0 or less, the deterioration of the color tone can be suppressed by a side reaction. The lower limit of MA / P is more preferably 1.0 or more, and still more preferably 1.3 or more. The upper limit of MA / P is more preferably 5.0 or less, still more preferably 3.5 or less.
本発明のポリエステル樹脂組成物においては、必要に応じて、色調調整剤、酸化防止剤、紫外線吸収剤、難燃剤、蛍光増白剤、艶消剤、可塑剤もしくは消泡剤又はその他の添加剤等を添加しても構わない。 In the polyester resin composition of the present invention, a color tone adjusting agent, an antioxidant, an ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, a plasticizer or an antifoaming agent, or other additives as necessary. Etc. may be added.
また、本発明においては、さらに高分子量のポリエステル樹脂組成物を得るために、固相重合をおこなってもよい。固相重合の装置・方法は特に限定されないが、例えば、減圧下でポリエステル樹脂組成物の融点以下の温度で加熱処理されることで実施される。 In the present invention, solid phase polymerization may be performed in order to obtain a higher molecular weight polyester resin composition. The apparatus and method for solid-phase polymerization are not particularly limited. For example, the solid-state polymerization is carried out by heat treatment at a temperature below the melting point of the polyester resin composition under reduced pressure.
本発明のポリエステル樹脂組成物は、耐熱酸化分解性および透明性がいずれも良好であり、繊維、フィルムなどの成形品に広く利用することができる。その中でも特に、近年長期耐久性の要求が高まっている電気絶縁用フィルムや太陽電池用バックシートフィルムなどに好適に用いることができる。 The polyester resin composition of the present invention is good in both heat-resistant oxidative degradation and transparency, and can be widely used for molded articles such as fibers and films. Among them, in particular, it can be suitably used for an electrical insulation film, a back sheet film for solar cells, and the like, which have recently been demanded for long-term durability.
以下実施例を挙げて、本発明をさらに詳細に説明する。なお、実施例中の物性値は以下の方法で測定した。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured with the following method.
（１）樹脂組成物中のリン元素量の定量
理学電機（株）製蛍光Ｘ線分析装置（型番：３２７０）を用いて測定した。
(1) Quantification of amount of phosphorus element in resin composition It was measured using a fluorescent X-ray analyzer (model number: 3270) manufactured by Rigaku Corporation.
（２）樹脂組成物中の希土類元素量及びアルカリ金属元素量の定量
原子吸光法（日立製作所製：偏光ゼーマン原子吸光光度計１８０−８０。フレーム：アセチレン−空気）にて定量を行った。
(2) Quantification of amount of rare earth element and amount of alkali metal element in resin composition Quantification was performed by atomic absorption method (manufactured by Hitachi, Ltd .: polarization Zeeman atomic absorption photometer 180-80, frame: acetylene-air).
（３）樹脂組成物の固有粘度（ＩＶ）
ｏ−クロロフェノール溶媒を用い、２５℃で測定した。
(3) Intrinsic viscosity of resin composition (IV)
It measured at 25 degreeC using the o-chlorophenol solvent.
（４）組成物のカルボキシル基末端量（ＣＯＯＨ）
Ｍａｕｌｉｃｅの方法によって測定した。（文献 Ｍ．Ｊ．Ｍａｕｌｉｃｅ，Ｆ．Ｈｕｉｚｉｎｇａ，Ａｎａｌ．Ｃｈｅｍ．Ａｃｔａ，２２ ３６３ （１９６０）） 。
(4) Carboxyl group terminal amount of composition (COOH)
Measured by the method of Malice. (Reference M. J. Malice, F. Huizinga, Anal. Chem. Acta, 22 363 (1960)).
（５）樹脂組成物の色調（Ｌ値）
ポリエステル樹脂組成物のチップを１０ｇサンプリングし、色調（Ｌ値）について、スガ試験機（株）製のＳＣ３Ｐカラーマシンを使用して測定した。Ｌ値は、白−黒系の色相を表し、ポリマーの色調としてはＬ値が高いほど、色調が良好である。
(5) Color tone of resin composition (L value)
10 g of a chip of the polyester resin composition was sampled, and the color tone (L value) was measured using an SC3P color machine manufactured by Suga Test Instruments Co., Ltd. The L value represents a white-black hue, and as the color tone of the polymer, the higher the L value, the better the color tone.
（６）樹脂組成物の溶液ヘイズ
ポリエステル樹脂組成物２ｇを２０ｍＬのオルトクロロフェノール／１，１，２，２−テトラクロロエタンの３／２（容積比）混合溶液に溶解し、光路長２０ｍｍのセルを用い、ヘイズメーター（スガ試験機社製 ＨＺ−１）を用いて、積分球式光電光度法にて測定した。溶液ヘイズが低いほど、透明性が良好である。
(6) Solution haze of resin composition 2 g of polyester resin composition was dissolved in 20 mL of a 3/2 (volume ratio) mixed solution of orthochlorophenol / 1,1,2,2-tetrachloroethane, and a cell having an optical path length of 20 mm. , And a haze meter (HZ-1 manufactured by Suga Test Instruments Co., Ltd.) was used to measure by an integrating sphere photoelectric photometry method. The lower the solution haze, the better the transparency.
（７）プレスシートの作製
１５０℃１２時間真空乾燥したポリエステル樹脂組成物７ｇを、平滑なプレート間にはさみ２８０℃で１分間溶融し、その後２８０℃１．５ＭＰａで１分間プレスし、水槽に沈めて冷却することで縦１２０ｍｍ×横１２０ｍｍ×厚み０．４ｍｍのプレスシートを作製した。
(7) Preparation of press sheet 7 g of polyester resin composition vacuum-dried at 150 ° C. for 12 hours was melted at 280 ° C. for 1 minute between flat plates, then pressed at 280 ° C. and 1.5 MPa for 1 minute, and submerged in a water tank. Then, a press sheet having a length of 120 mm, a width of 120 mm, and a thickness of 0.4 mm was produced.
（８）組成物の耐熱酸化分解性（ΔＣＯＯＨ）
上記（７）にて作製したプレスシートを、縦１０ｍｍ×横１００ｍｍ×厚み０．４ｍｍの短冊状に切り出し、内径１５ｍｍのガラス試験管に入れ、１５０℃１２時間真空乾燥した後、ガラス試験管をオイルバスに挿入して２００℃、酸素濃度２０％の空気雰囲気下で２４時間熱処理した。該熱処理前後のポリエステル樹脂組成物のカルボキシル基末端量を測定し、該熱処理後から該熱処理前を減したカルボキシル基末端増加量（ΔＣＯＯＨ）により耐熱酸化分解性評価を実施した。ΔＣＯＯＨとしては１００ｅｑ／トン以下であるとき、耐熱酸化分解性が良好であると判断した。
(8) Thermal oxidative decomposability (ΔCOOH) of the composition
The press sheet produced in the above (7) is cut into a strip shape having a length of 10 mm, a width of 100 mm, and a thickness of 0.4 mm, put in a glass test tube having an inner diameter of 15 mm, and vacuum-dried at 150 ° C. for 12 hours. It was inserted into an oil bath and heat-treated in an air atmosphere at 200 ° C. and an oxygen concentration of 20% for 24 hours. The amount of carboxyl group ends of the polyester resin composition before and after the heat treatment was measured, and the heat oxidation and decomposition resistance evaluation was performed by the amount of increase in carboxyl group ends (ΔCOOH) obtained by reducing the amount before and after the heat treatment. When ΔCOOH was 100 eq / ton or less, the heat-resistant oxidative degradation was judged to be good.
（９）組成物の透明性（全光線透過率）
ＪＩＳ−Ｋ−７３６１−１に基づき、上記（７）にて作成したプレスシートの全光線透過率を、シングルビーム式ヘイズメーターを使用して測定した。全光線透過率としては７５％以上であるとき、透明性が良好であると判断した。
(9) Transparency of the composition (total light transmittance)
Based on JIS-K-7361-1, the total light transmittance of the press sheet prepared in the above (7) was measured using a single beam haze meter. When the total light transmittance was 75% or more, it was judged that the transparency was good.
（実施例１）
２５５℃にて溶解したビスヒドロキシエチルテレフタレート１０５重量部が仕込まれたエステル化反応器に、テレフタル酸８６重量部とエチレングリコール３７重量部（テレフタル酸に対し１．１５倍モル）からなるスラリーを徐々に添加し、エステル化反応を進行させた。反応系内の温度は２４５〜２５５℃になるようにコントロールし、反応率が９５％に到達した段階でエステル化反応を終了とした。
Example 1
In an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C., a slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times moles relative to terephthalic acid) was gradually added. The esterification reaction was allowed to proceed. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was terminated when the reaction rate reached 95%.
こうして得られた２５５℃のエステル化反応物１０５重量部（ポリエチレンテレフタレート（以降ＰＥＴとする）１００重量部相当）を重合装置に移送し、三酸化二アンチモン０．０３重量部（１．０モル／トン相当）／エチレングリコール０．６０重量部の混合溶液、酢酸セリウム（ＩＩＩ）１水和物０．１０重量部（３．０モル／トン相当）／エチレングリコール２．００重量部の混合溶液、および酢酸ナトリウム０．０２重量部（２．０モル／トン相当）／エチレングリコール０．４０重量部の混合溶液を添加し、５分攪拌した。その後、リン酸（８５％水溶液）０．０３重量部（２．５モル／トン相当）／エチレングリコール０．４０重量部の混合溶液を添加した。 105 parts by weight of the thus obtained esterification reaction product at 255 ° C. (equivalent to 100 parts by weight of polyethylene terephthalate (hereinafter referred to as PET)) was transferred to a polymerization apparatus, and 0.03 part by weight of antimony trioxide (1.0 mol / mol) was transferred. A mixed solution of 0.60 parts by weight of ethylene glycol, 0.10 parts by weight of cerium acetate (III) monohydrate (equivalent to 3.0 mol / tons) /2.00 parts by weight of ethylene glycol, Then, a mixed solution of 0.02 part by weight of sodium acetate (equivalent to 2.0 mol / ton) /0.40 part by weight of ethylene glycol was added and stirred for 5 minutes. Thereafter, a mixed solution of phosphoric acid (85% aqueous solution) 0.03 part by weight (equivalent to 2.5 mol / ton) / ethylene glycol 0.40 part by weight was added.
次いで、重合装置内温度を徐々に２９０℃まで昇温しながら、重合装置内圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させた。固有粘度０．７０相当の溶融粘度に到達した時点で、反応を終了とし、反応系内を窒素ガスにて常圧にし、重合装置下部より冷水中にストランド状に吐出、カッティングし、ペレット状のポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表１に示す。
実施例１で得られたポリエステル樹脂組成物は、耐熱酸化分解性および透明性のいずれも良好であった。
Subsequently, while the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure in the polymerization apparatus was gradually reduced from normal pressure to 133 Pa or less to distill ethylene glycol. When the melt viscosity corresponding to an intrinsic viscosity of 0.70 is reached, the reaction is terminated, the inside of the reaction system is brought to atmospheric pressure with nitrogen gas, discharged into cold water from the lower part of the polymerization apparatus, cut into a strand, cut into pellets A polyester resin composition was obtained. The properties of the obtained polyester resin composition are shown in Table 1.
The polyester resin composition obtained in Example 1 was good in both heat-resistant oxidative decomposability and transparency.
（実施例２、３、比較例１）
酢酸セリウム（ＩＩＩ）１水和物の添加量を表１に記載の量に変更した以外は、実施例１に示した方法と同様に実施した。得られたポリエステル樹脂組成物の特性を表１に示す。
(Examples 2 and 3, Comparative Example 1)
The same procedure as described in Example 1 was performed except that the addition amount of cerium (III) acetate monohydrate was changed to the amount shown in Table 1. The properties of the obtained polyester resin composition are shown in Table 1.
実施例２、３で得られたポリエステル樹脂組成物は、耐熱酸化分解性および透明性のいずれも良好であった。 The polyester resin compositions obtained in Examples 2 and 3 were good in both heat-resistant oxidative degradation and transparency.
比較例１で得られたポリエステル樹脂組成物は、希土類元素を含有しないため耐熱酸化分解性が不十分であった。 Since the polyester resin composition obtained in Comparative Example 1 did not contain a rare earth element, the heat-resistant oxidative decomposition property was insufficient.
（実施例４、比較例２、３）
酢酸セリウム（ＩＩＩ）１水和物を表１に記載の化合物に変更した以外は、実施例１に示した方法と同様に実施した。得られたポリエステル樹脂組成物の特性を表１に示す。
(Example 4, Comparative Examples 2 and 3)
The same procedure as described in Example 1 was performed except that cerium (III) acetate monohydrate was changed to the compounds shown in Table 1. The properties of the obtained polyester resin composition are shown in Table 1.
実施例４で得られたポリエステル樹脂組成物は、耐熱酸化分解性および透明性いずれも良好であった。 The polyester resin composition obtained in Example 4 was good in both heat-resistant oxidative decomposability and transparency.
比較例２で得られたポリエステル樹脂組成物は、耐熱酸化分解性が不十分であり、銅元素による着色が強く、透明性が不十分であり、耐熱酸化分解性および透明性のいずれも不良であった。 The polyester resin composition obtained in Comparative Example 2 has insufficient heat-resistant oxidative decomposability, is strongly colored by copper elements, has insufficient transparency, and has poor heat-resistant oxidative decomposability and transparency. there were.
比較例３で得られたポリエステル樹脂組成物は、希土類元素を含有しないため耐熱酸化分解性が不十分であった。 Since the polyester resin composition obtained in Comparative Example 3 did not contain a rare earth element, the heat-resistant oxidative decomposition property was insufficient.
（実施例５）
酢酸ナトリウムを水酸化カリウムに変更した以外は、実施例１に示した方法と同様に実施した。得られたポリエステル樹脂組成物の特性を表１に示す。
(Example 5)
The same procedure as described in Example 1 was performed except that sodium acetate was changed to potassium hydroxide. The properties of the obtained polyester resin composition are shown in Table 1.
実施例５で得られたポリエステル樹脂組成物は、耐熱酸化分解性および透明性いずれも良好であった。 The polyester resin composition obtained in Example 5 was good in both heat-resistant oxidative degradation and transparency.
（実施例６）
２５５℃にて溶解したビスヒドロキシエチルテレフタレート１０５重量部が仕込まれたエステル化反応器に、テレフタル酸８６重量部とエチレングリコール３７重量部（テレフタル酸に対し１．１５倍モル）からなるスラリーを徐々に添加し、エステル化反応を進行させた。反応系内の温度は２４５〜２５５℃になるようにコントロールし、反応率が９５％に到達した段階でエステル化反応を終了とした。
(Example 6)
In an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C., a slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times moles relative to terephthalic acid) was gradually added. The esterification reaction was allowed to proceed. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was terminated when the reaction rate reached 95%.
こうして得られた２５５℃のエステル化反応物１０５重量部（ＰＥＴ１００重量部相当）を重合装置に移送し、三酸化二アンチモン０．０３重量部（１．０モル／トン相当）／エチレングリコール０．６０重量部の混合溶液、および酢酸セリウム（ＩＩＩ）１水和物０．１０重量部（３．０モル／トン相当）／エチレングリコール２．００重量部の混合溶液を添加し、５分攪拌した。その後、リン酸二水素ナトリウム２水和物０．０３重量部（２．０モル／トン相当）／エチレングリコール０．６０重量部の混合溶液を添加した。 105 parts by weight of the thus obtained esterification reaction product at 255 ° C. (corresponding to 100 parts by weight of PET) was transferred to a polymerization apparatus, 0.03 part by weight of antimony trioxide (corresponding to 1.0 mol / ton) / ethylene glycol A mixed solution of 60 parts by weight and a mixed solution of 0.10 parts by weight of cerium (III) acetate monohydrate (equivalent to 3.0 mol / ton) /2.00 parts by weight of ethylene glycol was added and stirred for 5 minutes. . Thereafter, a mixed solution of 0.03 part by weight of sodium dihydrogen phosphate dihydrate (corresponding to 2.0 mol / ton) /0.60 part by weight of ethylene glycol was added.
次いで、重合装置内温度を徐々に２９０℃まで昇温しながら、重合装置内圧力を常圧から１３３Ｐａ以下まで徐々に減圧してエチレングリコールを留出させた。固有粘度０．７０相当の溶融粘度に到達した時点で、反応を終了とし、反応系内を窒素ガスにて常圧にし、重合装置下部より冷水中にストランド状に吐出、カッティングし、ペレット状のポリエステル樹脂組成物を得た。得られたポリエステル樹脂組成物の特性を表１に示す。 Subsequently, while the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure in the polymerization apparatus was gradually reduced from normal pressure to 133 Pa or less to distill ethylene glycol. When the melt viscosity corresponding to an intrinsic viscosity of 0.70 is reached, the reaction is terminated, the inside of the reaction system is brought to atmospheric pressure with nitrogen gas, discharged into cold water from the lower part of the polymerization apparatus, cut into a strand, cut into pellets A polyester resin composition was obtained. The properties of the obtained polyester resin composition are shown in Table 1.
実施例６で得られたポリエステル樹脂組成物は、耐酸化分解性および透明性のいずれも良好であった。 The polyester resin composition obtained in Example 6 was good in both oxidative degradation resistance and transparency.
（実施例７、８、比較例４）
酢酸ナトリウムの添加量を表２に記載の量に変更した以外は、実施例１に示した方法と同様に実施した。得られたポリエステル樹脂組成物の特性を表２に示す。
(Examples 7 and 8, Comparative Example 4)
The same procedure as described in Example 1 was performed except that the amount of sodium acetate added was changed to the amount shown in Table 2. Table 2 shows the characteristics of the obtained polyester resin composition.
実施例７、８で得られたポリエステル樹脂組成物は、耐熱酸化分解性および透明性のいずれも良好であった。 The polyester resin compositions obtained in Examples 7 and 8 were good in both heat-resistant oxidative degradation and transparency.
比較例４で得られたポリエステル樹脂組成物は、アルカリ金属元素を含有しないため耐熱酸化分解性が不十分であった。 Since the polyester resin composition obtained in Comparative Example 4 did not contain an alkali metal element, the heat-resistant oxidative degradation was insufficient.
（実施例９、１０、比較例５）
リン酸の添加量を表２に記載の量に変更した以外は、実施例１に示した方法と同様に実施した。得られたポリエステル樹脂組成物の特性を表２に示す。
(Examples 9, 10 and Comparative Example 5)
The same procedure as described in Example 1 was performed except that the addition amount of phosphoric acid was changed to the amount shown in Table 2. Table 2 shows the characteristics of the obtained polyester resin composition.
実施例９、１０で得られたポリエステル樹脂組成物は、耐熱酸化分解性および透明性のいずれも良好であった。 The polyester resin compositions obtained in Examples 9 and 10 were good in both heat-resistant oxidative degradation and transparency.
比較例５で得られたポリエステル樹脂組成物は、リン元素を含有しないため耐熱酸化分解性および透明性ともに不十分であった。 Since the polyester resin composition obtained in Comparative Example 5 did not contain a phosphorus element, both the heat oxidative decomposition property and the transparency were insufficient.
（実施例１１〜１３）
酢酸セリウム１水和物、酢酸ナトリウム、およびリン酸の添加量を表２に記載の量に変更した以外は、実施例１に示した方法と同様に実施した。得られたポリエステル樹脂組成物の特性を表２に示す。
(Examples 11 to 13)
The same procedure as described in Example 1 was performed except that the addition amounts of cerium acetate monohydrate, sodium acetate, and phosphoric acid were changed to the amounts shown in Table 2. Table 2 shows the characteristics of the obtained polyester resin composition.
実施例１１〜１３で得られたポリエステル樹脂組成物は、耐熱酸化分解性および透明性のいずれも良好であった。 The polyester resin compositions obtained in Examples 11 to 13 were good in both heat-resistant oxidative degradation and transparency.
Claims (4)
Ｍ／Ａ≧０．１ （Ｉ）
(Ｍは希土類元素の総和モル量、Ａはアルカリ金属元素の総和モル量を示す。) A polyester resin composition containing a rare earth element, an alkali metal element, and a phosphorus element, wherein the polyester resin composition satisfies the formula (I).
M / A ≧ 0.1 (I)
(M represents the total molar amount of rare earth elements, and A represents the total molar amount of alkali metal elements.)
ΔＣＯＯＨ≦１００ｅｑ／トン （ＩＩ）
(ΔＣＯＯＨは２００℃、空気雰囲気下で２４時間処理したときのカルボキシル基末端の増加量を示す。) The polyester resin composition according to claim 1, wherein Formula (II) is satisfied.
ΔCOOH ≦ 100 eq / ton (II)
(ΔCOOH indicates the amount of increase of carboxyl group terminals when treated at 200 ° C. in an air atmosphere for 24 hours.)
ＨＺ≦１０％ （ＩＩＩ）
(ＨＺはポリエステル樹脂組成物２ｇを、オルトクロロフェノール／１，１，２，２，テトラクロロエタンの３／２（容積比）の溶液２０ｍＬに溶解したときの、ヘイズメーターで測定した溶液ヘイズを示す。) The polyester resin composition according to claim 1, wherein the polyester resin composition satisfies the formula (III).
HZ ≦ 10% (III)
(HZ represents the solution haze measured with a haze meter when 2 g of the polyester resin composition was dissolved in 20 mL of a 3/2 (volume ratio) of orthochlorophenol / 1,1,2,2, tetrachloroethane. .)
０．５≦ＭＡ／Ｐ≦６．０ （ＩＶ）
(ＭＡは希土類元素およびアルカリ金属元素の総和モル量、Ｐはリン元素の総和モル量を示す。) The polyester resin composition according to claim 1, wherein the polyester resin composition satisfies Formula (IV).
0.5 ≦ MA / P ≦ 6.0 (IV)
(MA represents the total molar amount of rare earth elements and alkali metal elements, and P represents the total molar amount of phosphorus elements.)
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| JP2005120126A (en) * | 2003-10-14 | 2005-05-12 | Toray Ind Inc | Biaxially oriented polyester film |
| JP2005314660A (en) * | 2004-03-30 | 2005-11-10 | Toray Ind Inc | Polyester composition and polyester film |
| JP2016180090A (en) * | 2015-03-24 | 2016-10-13 | 東レ株式会社 | Polyester resin composition and method for producing the same |
| JP2017008286A (en) * | 2014-10-31 | 2017-01-12 | 東レ株式会社 | Polyester resin composition and manufacturing method therefor |
| JPWO2015118966A1 (en) * | 2014-02-07 | 2017-03-23 | 東レ株式会社 | Polyester resin composition and method for producing the same |
| JP2017178997A (en) * | 2016-03-28 | 2017-10-05 | 東レ株式会社 | Polyester resin composition |
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| JP2005120126A (en) * | 2003-10-14 | 2005-05-12 | Toray Ind Inc | Biaxially oriented polyester film |
| JP2005314660A (en) * | 2004-03-30 | 2005-11-10 | Toray Ind Inc | Polyester composition and polyester film |
| JPWO2015118966A1 (en) * | 2014-02-07 | 2017-03-23 | 東レ株式会社 | Polyester resin composition and method for producing the same |
| JP2017008286A (en) * | 2014-10-31 | 2017-01-12 | 東レ株式会社 | Polyester resin composition and manufacturing method therefor |
| JP2016180090A (en) * | 2015-03-24 | 2016-10-13 | 東レ株式会社 | Polyester resin composition and method for producing the same |
| JP2017178997A (en) * | 2016-03-28 | 2017-10-05 | 東レ株式会社 | Polyester resin composition |
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