JP6043377B2 - Polyester resin composition and blow molded article comprising the same - Google Patents
Polyester resin composition and blow molded article comprising the same Download PDFInfo
- Publication number
- JP6043377B2 JP6043377B2 JP2015026559A JP2015026559A JP6043377B2 JP 6043377 B2 JP6043377 B2 JP 6043377B2 JP 2015026559 A JP2015026559 A JP 2015026559A JP 2015026559 A JP2015026559 A JP 2015026559A JP 6043377 B2 JP6043377 B2 JP 6043377B2
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- JP
- Japan
- Prior art keywords
- polyester resin
- resin composition
- viscosity
- molded product
- blow molding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004645 polyester resin Substances 0.000 title claims description 116
- 229920001225 polyester resin Polymers 0.000 title claims description 115
- 239000000203 mixture Substances 0.000 title claims description 98
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 16
- 238000007334 copolymerization reaction Methods 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 13
- 238000005259 measurement Methods 0.000 claims description 7
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- 238000000071 blow moulding Methods 0.000 description 76
- 239000000047 product Substances 0.000 description 74
- 238000006116 polymerization reaction Methods 0.000 description 56
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 41
- 238000000465 moulding Methods 0.000 description 33
- 239000007790 solid phase Substances 0.000 description 27
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- -1 Polyethylene terephthalate Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 14
- 230000008025 crystallization Effects 0.000 description 14
- 238000005886 esterification reaction Methods 0.000 description 14
- 239000000155 melt Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 238000005979 thermal decomposition reaction Methods 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920001634 Copolyester Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000013638 trimer Substances 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical class FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 2
- IQXDUKXUDQPOBC-UHFFFAOYSA-N [3-octadecanoyloxy-2-[[3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propoxy]methyl]-2-(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC IQXDUKXUDQPOBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids 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
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 150000001463 antimony compounds Chemical class 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 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
- 238000000691 measurement method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 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
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- KMEHEQFDWWYZIO-UHFFFAOYSA-N triacontyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC KMEHEQFDWWYZIO-UHFFFAOYSA-N 0.000 description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-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
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- CZGWDPMDAIPURF-UHFFFAOYSA-N (4,6-dihydrazinyl-1,3,5-triazin-2-yl)hydrazine Chemical compound NNC1=NC(NN)=NC(NN)=N1 CZGWDPMDAIPURF-UHFFFAOYSA-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
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- BLJHFERYMGMXSC-UHFFFAOYSA-N 3-[3-(hydrazinesulfonyl)phenyl]sulfonylbenzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=C(C=CC=2)S(=O)(=O)NN)=C1 BLJHFERYMGMXSC-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
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- PBWGCNFJKNQDGV-UHFFFAOYSA-N 6-phenylimidazo[2,1-b][1,3]thiazol-5-amine Chemical compound N1=C2SC=CN2C(N)=C1C1=CC=CC=C1 PBWGCNFJKNQDGV-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- XGIAHMUOCFHQTI-UHFFFAOYSA-N Cl.Cl.Cl.Cl.CC Chemical compound Cl.Cl.Cl.Cl.CC XGIAHMUOCFHQTI-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CGBXSWXZXBQCMR-UHFFFAOYSA-N Glycerol 1-hexadecanoate Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCC(O)=O CGBXSWXZXBQCMR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- FSEJJKIPRNUIFL-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-octadecanoyloxypropyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)COC(=O)CCCCCCCCCCCCCCCCC FSEJJKIPRNUIFL-UHFFFAOYSA-N 0.000 description 1
- FWCDLNRNBHJDQB-UHFFFAOYSA-N [2-(hydroxymethyl)-3-octadecanoyloxy-2-(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC FWCDLNRNBHJDQB-UHFFFAOYSA-N 0.000 description 1
- VURIDHCIBBJUDI-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO VURIDHCIBBJUDI-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940090958 behenyl behenate Drugs 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical class [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 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
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical compound C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- UQDVHJGNIFVBLG-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O UQDVHJGNIFVBLG-UHFFFAOYSA-N 0.000 description 1
- GAQPWOABOQGPKA-UHFFFAOYSA-N octadecyl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCCCCCCCC GAQPWOABOQGPKA-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000003746 surface roughness Effects 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
- 229920006230 thermoplastic polyester resin Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- NDLIRBZKZSDGSO-UHFFFAOYSA-N tosyl azide Chemical compound CC1=CC=C(S(=O)(=O)[N-][N+]#N)C=C1 NDLIRBZKZSDGSO-UHFFFAOYSA-N 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 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
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、透明性に優れたブロー成形品を生産性よく得ることができる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 capable of obtaining a blow molded product excellent in transparency with high productivity.
ポリエチレンテレフタレート（ＰＥＴ）は、機械的特性、化学的安定性、透明性等に優れ、かつ、安価であり、各種のシート、フィルム、容器等として幅広く用いられており、特に昨今では、炭酸飲料、果汁飲料、液体調味料、食用油、酒、ワイン用等の中空容器（ボトル）用途の伸びが著しい。しかも、塩化ビニル樹脂製中空成形品におけるような残留モノマーや有害添加剤の心配が少なく、衛生性及び安全性が高い点から、従来の塩化ビニル樹脂などからなるボトルからの置き換えも進んでいる。 Polyethylene terephthalate (PET) is excellent in mechanical properties, chemical stability, transparency and the like, is inexpensive, and is widely used as various sheets, films, containers and the like. The growth in the use of hollow containers (bottles) for fruit juice drinks, liquid seasonings, edible oils, liquors, wines, etc. is remarkable. Moreover, since there is little concern about residual monomers and harmful additives in hollow molded articles made of vinyl chloride resin, and hygiene and safety are high, replacement from conventional bottles made of vinyl chloride resin and the like is also progressing.
一般に、プラスチック製のボトルなどを製造するにあたっては、成形の容易性、高生産性、成形機械や金型などの設備費が比較的安くてすむなどの点から、溶融可塑化した樹脂をダイオリフィスを通して押出して円筒状のパリソンを形成し、これを金型に挟んで内部に空気を吹き込むいわゆるダイレクトブロー成形法が採用されている。そして、このダイレクトブロー成形による場合は、成形を円滑に行うために、溶融状態で押出されたパリソンが吹き込み成形時にドローダウンするのを回避する必要があり、そのため、使用樹脂に高い溶融粘度が要求される。したがって、高い溶融粘度を有する樹脂として、塩化ビニル樹脂やポリオレフィン樹脂などがダイレクトブロー成形においては広く用いられている。 In general, when plastic bottles are manufactured, melt-plasticized resin is used as die orifices in terms of ease of molding, high productivity, and relatively low equipment costs such as molding machines and molds. A so-called direct blow molding method is employed in which a cylindrical parison is formed through extrusion, and air is blown into the mold by sandwiching the parison between the molds. In the case of this direct blow molding, it is necessary to avoid that the parison extruded in the molten state is drawn down during the blow molding in order to perform the molding smoothly. Therefore, a high melt viscosity is required for the resin used. Is done. Accordingly, vinyl chloride resins, polyolefin resins, and the like are widely used in direct blow molding as resins having a high melt viscosity.
ダイレクトブロー成形品においても塩化ビニル樹脂からポリエステル樹脂への置き換えが検討されているが、ポリエステル樹脂は、一般にダイレクトブロー成形に適する高い溶融粘度を有していない。このため、押出されたパリソンが吹き込み成形時にドローダウンし、吹き込み成形が行えないという問題があり、また、ブロー時に結晶化が起こりやすいため、成形が可能であっても白化が生じ、透明性が不十分になるという問題があった。 In direct blow molded products, replacement of vinyl chloride resin with polyester resin has been studied, but polyester resins generally do not have a high melt viscosity suitable for direct blow molding. For this reason, there is a problem that the extruded parison draws down during blow molding, and blow molding cannot be performed, and crystallization is likely to occur during blow, so whitening occurs even if molding is possible, and transparency is increased. There was a problem of becoming insufficient.
透明性を向上させるために、ポリエチレンテレフタレートに他のモノマー成分を共重合したポリエステル樹脂が提案されている。これにより結晶化は抑制できるが、それだけでは溶融粘度を上昇させることができない。そこで、３官能以上の多価カルボン酸／多価アルコールによる架橋の手段により高粘度化させ、ドローダウンの問題を解決する方法が提案されてきた（例えば特許文献１参照）。しかしながら、このような架橋の手段により高粘度化させると、成形性は向上するものの、多価カルボン酸や多価アルコールの量が多い場合は、ゲル化しやすく、熱安定性に劣り、得られる成形品は色調や透明性に劣るという問題があった。 In order to improve transparency, a polyester resin obtained by copolymerizing polyethylene terephthalate with other monomer components has been proposed. This can suppress crystallization, but it cannot increase the melt viscosity by itself. Therefore, a method has been proposed in which the viscosity is increased by means of crosslinking with a trifunctional or higher polyvalent carboxylic acid / polyhydric alcohol to solve the drawdown problem (see, for example, Patent Document 1). However, when the viscosity is increased by such a cross-linking means, the moldability is improved, but when the amount of polyvalent carboxylic acid or polyhydric alcohol is large, the gel is easily gelled, the heat stability is poor, and the obtained molding The product had a problem that it was inferior in color tone and transparency.
また、ダイレクトブロー成形では押出機よりダイスを介して押出した円筒状のパリソンを、垂直に二分割された割金型により型締めして挟み込み、この割金型のキャビティーの底辺に配設した刃部であるピンチオフ部で溶融樹脂の下部を切断すると共に熱溶着シールし、上部ではパリソンカッターで筒状の溶融樹脂の上部を切断することで有底筒体のパリソンを形成し、次いで割金型の頂部より挿入のエアノズルによってブローエアをパリソンに吹き込みブロー成形を行うため、切断された樹脂の端材が発生する。この端材については乾燥、結晶化を行った後、再生材として原料樹脂チップにドライブレンドし再びダイレクトブロー成形に使用するリサイクルを行い、コストダウンを図っている。しかしながら、一旦成形品を形成した樹脂組成物は、成形時の熱履歴によって極限粘度が低下しているため、成形工程を経た端材を多量にドライブレンドしてリサイクルすると、成形時にドローダウンが生じ、成形出来ないという問題があった。 In direct blow molding, a cylindrical parison extruded through a die from an extruder is clamped and clamped by a vertically split split mold and placed at the bottom of this split mold cavity. The lower part of the molten resin is cut at the pinch-off part, which is the blade part, and heat-sealed and sealed, and the upper part of the cylindrical molten resin is cut with a parison cutter at the upper part to form a bottomed cylindrical parison, then split Since blow air is blown into the parison by an air nozzle inserted from the top of the mold and blow molding is performed, a cut resin end material is generated. This milled material is dried and crystallized, and then recycled as a recycled material to a raw material resin chip and recycled for direct blow molding again to reduce costs. However, the resin composition once formed into a molded product has a lower intrinsic viscosity due to the heat history at the time of molding, so if you dry-blend a large amount of milled material that has undergone the molding process, it will draw down during molding. There was a problem that it could not be molded.
本発明は、上記の問題点を解決し、ブロー成形時にドローダウンや結晶化による白化の問題が生じることなく、熱安定性にも優れており、透明性に優れたブロー成形品を生産性よく得ることができるポリエステル樹脂組成物を提供しようとするものである。また、一旦成形工程を経て端材となったものを、再度ブロー成形に用いても良好に成形が可能となる、リサイクル性にも優れたポリエステル樹脂組成物を提供しようとするものである。さらに、本発明のポリエステル樹脂組成物を用いて形成されてなるブロー成形品を提供しようとするものである。 The present invention solves the above-mentioned problems, does not cause problems of whitening due to drawdown or crystallization at the time of blow molding, has excellent thermal stability, and has excellent productivity for blow molded products with excellent transparency. An object of the present invention is to provide a polyester resin composition that can be obtained. Another object of the present invention is to provide a polyester resin composition having excellent recyclability, which can be molded well even if it is once again subjected to blow molding after being subjected to a molding process. Furthermore, the present invention intends to provide a blow molded product formed using the polyester resin composition of the present invention.
本発明者等は、上記の課題を解決するために、鋭意検討した結果、本発明に到達した。
すなわち、本発明は、次の（１）、（２）を要旨とするものである。
（１）エチレンテレフタレートを主たる繰り返し単位とし、１，４−シクロヘキサンジ
メタノールを共重合成分として２〜２０モル％含有するポリエステル樹脂を主成分とし、ヒンダードフェノール系抗酸化剤を０．０１〜１．０質量％含有する樹脂組成物であって、極限粘度が０．７〜１．４であり、３００℃での伸長粘度測定で得られる伸長粘度−せん断速度曲線において、せん断速度５００ｓ−1における伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）が４〜１０であり、かつカルボキシル末端基濃度が２０当量／t以下であることを特徴とするポリエステル樹脂組成物。
（２）（１）記載のポリエステル樹脂組成物を用いて形成されてなるブロー成形品。
The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve the above problems.
That is, the gist of the present invention is the following (1) and (2).
(1) The main repeating unit is ethylene terephthalate, the main component is a polyester resin containing 2 to 20 mol% of 1,4-cyclohexanedimethanol as a copolymerization component, and a hindered phenol-based antioxidant is 0.01 to 1.0 mass% resin composition having an intrinsic viscosity of 0.7 to 1.4, and an elongation viscosity-shear rate curve obtained by measuring an extension viscosity at 300 ° C., a shear rate of 500 s −1 A polyester resin composition having a ratio (ηe / η) of elongation viscosity (ηe) to shear viscosity (η) of 4 to 10 and a carboxyl end group concentration of 20 equivalent / t or less.
(2) A blow molded product formed using the polyester resin composition according to (1).
本発明のポリエステル樹脂組成物は、特定の組成からなるポリエステル樹脂を用い、粘度の特性値〔極限粘度及び、伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）〕を適正範囲のものとすることによって、特にダイレクトブロー成形に好適な粘度特性を有している。そして、耐衝撃性にも優れるものである。さらに、カルボキシル末端基濃度が２０当量／ｔ以下と低いものであることにより、ブロー成形時の熱処理による熱分解が生じにくく、熱安定性に優れている。
このため、本発明のポリエステル樹脂組成物は、ブロー成形時にドローダウンや結晶化による白化の問題が生じることなく、透明性に優れたブロー成形品を生産性よく得ることができる。さらに、本発明のポリエステル樹脂組成物は、一旦成形工程を経て端材となったものを、再度ブロー成形に用いても、端材を構成する樹脂組成物はブロー成形時に熱分解が生じていないため、リサイクル成形時にドローダウンが生じることなく、透明性に優れたブロー成形品を生産性よく得ることができる（リサイクル性にも優れている）。
そして、本発明のブロー成形品は、本発明のポリエステル樹脂組成物を用いて形成されたものであるため、生産性よく得ることができ、透明性に優れており、種々の用途に用いることができる。
The polyester resin composition of the present invention uses a polyester resin having a specific composition, and the viscosity characteristic value [the intrinsic viscosity and the ratio of the extensional viscosity (ηe) to the shear viscosity (η) (ηe / η)] is in an appropriate range. By having the above, it has a viscosity characteristic particularly suitable for direct blow molding. And it is excellent also in impact resistance. Furthermore, since the carboxyl end group concentration is as low as 20 equivalent / t or less, thermal decomposition due to heat treatment during blow molding hardly occurs, and the thermal stability is excellent.
For this reason, the polyester resin composition of this invention can obtain the blow molded product excellent in transparency with high productivity, without the problem of whitening by drawdown or crystallization at the time of blow molding. Furthermore, even if the polyester resin composition of the present invention is once subjected to a molding process and then used as blow material again, the resin composition constituting the mill material does not undergo thermal decomposition during blow molding. Therefore, a blow-molded product having excellent transparency can be obtained with good productivity without causing drawdown during recycling molding (excellent recyclability).
And since the blow molded article of the present invention is formed using the polyester resin composition of the present invention, it can be obtained with good productivity, is excellent in transparency, and can be used for various applications. it can.
以下、本発明を詳細に説明する。
本発明のポリエステル樹脂組成物はブロー成形用に好適なものであり、ブロー成形としては、溶融可塑化した樹脂をダイオリフィスを通して押出して円筒状のパリソンを形成し、これを金型に挟んで内部に空気を吹き込むダイレクトブロー成形法、もしくは射出成形でパリソンを形成し、これを延伸ブロー成形する延伸ブロー成形法が挙げられるが、中でもダイレクトブロー成形法に好適なものである。
Hereinafter, the present invention will be described in detail.
The polyester resin composition of the present invention is suitable for blow molding. In blow molding, a melt-plasticized resin is extruded through a die orifice to form a cylindrical parison, which is sandwiched between molds and placed inside. Examples thereof include a direct blow molding method in which air is blown into the film, or a stretch blow molding method in which a parison is formed by injection molding and then stretch blow molded. Among these, the direct blow molding method is preferred.
本発明のポリエステル樹脂組成物は、エチレンテレフタレートを主たる繰り返し単位とし、１，４−シクロヘキサンジメタノールを共重合成分として２〜２０モル％含有するポリエステル樹脂を主成分とするものである。
本発明におけるポリエステル樹脂は、１，４−シクロヘキサンジメタノールの共重合量が２〜２０モル％であり、中でも２〜１８モル％であることが好ましく、さらには３〜１５モル％であることが好ましい。１，４−シクロヘキサンジメタノールを共重合することにより、ポリエステル樹脂の結晶化速度をブロー成形に適したものに調整することができ、ブロー成形時の結晶化による白化を防ぐことができる。
The polyester resin composition of the present invention is mainly composed of a polyester resin containing ethylene terephthalate as a main repeating unit and 2 to 20 mol% of 1,4-cyclohexanedimethanol as a copolymerization component.
In the polyester resin of the present invention, the copolymerization amount of 1,4-cyclohexanedimethanol is 2 to 20 mol%, preferably 2 to 18 mol%, more preferably 3 to 15 mol%. preferable. By copolymerizing 1,4-cyclohexanedimethanol, the crystallization speed of the polyester resin can be adjusted to be suitable for blow molding, and whitening due to crystallization during blow molding can be prevented.
１，４−シクロヘキサンジメタノールの共重合量が２モル％よりも少ない場合は、樹脂の結晶化速度が速いものとなるため、ブロー成形した際に、得られる成形品が結晶化して白化し、透明性に劣るものとなる。一方、１，４−シクロヘキサンジメタノールの共重合量が２０モル％を超えると、樹脂が非晶性のものとなるため、高温での乾燥や固相重合が困難となる。あるいは、高温乾燥時や固相重合工程においてブロッキングが起こりやすくなるため好ましくない。 When the copolymerization amount of 1,4-cyclohexanedimethanol is less than 2 mol%, since the resin crystallization speed becomes fast, when blow molding, the resulting molded product crystallizes and whitens, It becomes inferior to transparency. On the other hand, when the copolymerization amount of 1,4-cyclohexanedimethanol exceeds 20 mol%, the resin becomes amorphous, and thus drying at high temperature and solid phase polymerization become difficult. Alternatively, blocking is likely to occur during high temperature drying or in a solid phase polymerization process, which is not preferable.
ポリエステル樹脂中のグリコール成分は、６０モル％以上がエチレングリコールであることが好ましく、中でも７０モル％以上がエチレングリコールであることが好ましく、さらには８０モル％以上がエチレングリコールであることが好ましい。エチレングリコールの含有量が６０モル％未満であると、得られるポリエステル樹脂の結晶性や耐熱性が劣るものとなる。一方、９８モル％を超えると、１，４−シクロヘキサンジメタノールの割合が少なくなるため、１，４−シクロヘキサンジメタノールを含有することによる前記の効果に乏しいものとなる。
なお、エチレングリコールと１，４−シクロヘキサンジメタノールの合計量は、全グリコール成分の７０モル％以上であることが好ましく、中でも８０モル％以上であることが好ましい。
The glycol component in the polyester resin is preferably 60 mol% or more of ethylene glycol, more preferably 70 mol% or more of ethylene glycol, and even more preferably 80 mol% or more of ethylene glycol. When the content of ethylene glycol is less than 60 mol%, the resulting polyester resin has poor crystallinity and heat resistance. On the other hand, when it exceeds 98 mol%, since the ratio of 1,4-cyclohexanedimethanol decreases, the above-mentioned effect due to containing 1,4-cyclohexanedimethanol becomes poor.
The total amount of ethylene glycol and 1,4-cyclohexanedimethanol is preferably 70 mol% or more of all glycol components, and more preferably 80 mol% or more.
また、エチレングリコールと１，４−シクロヘキサンジメタノール以外のグリコール成分としては、例えば、ネオペンチルグリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサメチレンジオール、ジエチレングリコール、ダイマージオール、ビスフェノールＡ又はビスフェノールＳのエチレンオキシド付加体等を用いることができる。 Examples of glycol components other than ethylene glycol and 1,4-cyclohexanedimethanol include neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexamethylenediol, diethylene glycol, and dimer. Ethylene oxide adducts of diol, bisphenol A or bisphenol S can be used.
一方、酸成分は、６０モル％以上がテレフタル酸であることが好ましく、中でもテレフタル酸の割合は７０モル％以上、さらには８０モル％以上であることが好ましい。テレフタル酸の割合が６０モル％未満であると、樹脂の結晶性が低下し、非晶性のものとなりやすい。 On the other hand, 60 mol% or more of the acid component is preferably terephthalic acid, and among them, the ratio of terephthalic acid is preferably 70 mol% or more, and more preferably 80 mol% or more. When the proportion of terephthalic acid is less than 60 mol%, the crystallinity of the resin is lowered and the resin tends to be amorphous.
テレフタル酸以外のジカルボン酸成分としては、フタル酸、無水フタル酸、イソフタル酸、ナフタレンジカルボン酸、アジピン酸、１,４−シクロヘキサンジカルボン酸、セバシン酸、ダイマー酸等が挙げられ、これらを２種類以上併用してもよく、これらの酸のエステル形成性誘導体を使用してもよい。 Examples of dicarboxylic acid components other than terephthalic acid include phthalic acid, phthalic anhydride, isophthalic acid, naphthalenedicarboxylic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, dimer acid, and the like. These acids may be used in combination, or ester-forming derivatives of these acids may be used.
本発明のポリエステル樹脂組成物は、上記したポリエステル樹脂を主成分とするものであり、後述するような各種添加剤を必要に応じて含有するものであるが、ポリエステル樹脂組成物中のポリエステル樹脂の含有量は、９０質量％以上であることが好ましく、中でも９５質量％以上であることが好ましい。 The polyester resin composition of the present invention contains the above-described polyester resin as a main component and contains various additives as described below as necessary. The polyester resin composition in the polyester resin composition The content is preferably 90% by mass or more, and more preferably 95% by mass or more.
そして、本発明のポリエステル樹脂組成物は、以下に詳述するような各種粘度とカルボキシル末端基濃度の特性値を同時に満足するものである。これらの特性値を満足するものを得るためには、後述するような添加剤を重合時に添加することが好ましく、さらには適切な条件で溶融重合と固相重合を行うことが重要となる。 And the polyester resin composition of this invention satisfies the various viscosity and the characteristic value of a carboxyl terminal group density | concentration which are explained in full detail below simultaneously. In order to obtain those satisfying these characteristic values, it is preferable to add additives as described later during polymerization, and it is important to perform melt polymerization and solid phase polymerization under appropriate conditions.
まず、本発明のポリエステル樹脂組成物は、極限粘度（ＩＶ）が、０．７〜１．４であることが必要であり、中でもダイレクトブロー成形用途に用いる際には、０．９〜１．４であることが好ましい。
なお、極限粘度（ＩＶ）は、フェノールと四塩化エタンとの等質量混合物を溶媒として、温度２０℃で測定するものである。
極限粘度はポリマーの分子量に関与する値であり、後述するような固相重合を行うことにより本発明の範囲のものを得ることができる。
First, the intrinsic viscosity (IV) of the polyester resin composition of the present invention is required to be 0.7 to 1.4, and when used for direct blow molding, 0.9 to 1. 4 is preferred.
The intrinsic viscosity (IV) is measured at a temperature of 20 ° C. using a mixture of equal mass of phenol and ethane tetrachloride as a solvent.
The intrinsic viscosity is a value related to the molecular weight of the polymer, and those within the scope of the present invention can be obtained by performing solid phase polymerization as described later.
極限粘度が０．７未満の場合は、ブロー成形時にパリソンのドローダウンが大きくなり、成形自体が困難となる。中でもダイレクトブロー成形時にはパリソンのドローダウンが顕著となる。一方、極限粘度が１．４を超える場合は、成形温度を上げる必要があり、得られる成形品の色調や透明性が悪くなる。また、成形温度を高くすることによって、樹脂の熱分解が促進され、成形時に極限粘度の低下が生じるため、パリソンのドローダウンが大きくなり、成形が困難になったり、得られる成形品は厚みムラが生じたものとなる。さらに、このような成形品を得る際に生じた端材を再生材として再びブロー成形に供すると、ドローダウンが生じやすく、安定的な生産が困難となり、得られる成形品は厚みムラが生じたものとなる。 When the intrinsic viscosity is less than 0.7, the parison drawdown becomes large during blow molding, and molding itself becomes difficult. Above all, the parison drawdown becomes remarkable during direct blow molding. On the other hand, when the intrinsic viscosity exceeds 1.4, it is necessary to raise the molding temperature, and the color tone and transparency of the obtained molded product are deteriorated. In addition, by increasing the molding temperature, the thermal decomposition of the resin is promoted and the intrinsic viscosity is lowered during molding, so the drawdown of the parison increases, making molding difficult, and the resulting molded product has uneven thickness. Will occur. Furthermore, when the end material generated when obtaining such a molded product is subjected to blow molding again as a recycled material, drawdown is likely to occur, stable production becomes difficult, and the resulting molded product has uneven thickness. It will be a thing.
そして、本発明のポリエステル樹脂組成物は、伸長粘度（ηe）とせん断粘度（ｂ）の比（ηe／η）が４〜１０であることとが必要であり、中でも４．５〜９であることが好ましい。なお、伸長粘度は、伸長変形、例えば棒状の試料を中心軸方向に引っ張るような変形を与えた時に発生する応力を伸長速度で割ることにより得られるものである。せん断粘度は、せん断変形を与えた時に生じるせん断応力をその時のせん断速度で割ったものである。 The polyester resin composition of the present invention requires that the ratio (ηe / η) of the extensional viscosity (ηe) to the shear viscosity (b) is 4 to 10, and is 4.5 to 9 among them. It is preferable. The elongational viscosity is obtained by dividing the stress generated when an elongation deformation, for example, a deformation that pulls a rod-shaped sample in the direction of the central axis, by the elongation rate. The shear viscosity is obtained by dividing the shear stress generated when shear deformation is given by the shear rate at that time.
本発明においては、上記したような極限粘度を特定の範囲のものとするだけではブロー成形に適した特性を有する樹脂組成物とすることはできず、伸長粘度（ηe）とせん断粘度（ｂ）の比（ηe／η）を適切な範囲のものとすることで、特にダイレクトブローのようなドローダウンを生じやすい成形方法においても、ドローダウンが生じることなく、透明性に優れ、厚みムラのない品位の高い成形品を生産性よく得ることが可能となることを見出した。かつ、後述するようなカルボキシル末端基量を満足する場合には、熱安定性が顕著に向上し、再生材として使用した際にもドローダウン性に優れ、リサイクル性が良好となることを見出した。 In the present invention, it is not possible to obtain a resin composition having characteristics suitable for blow molding only by limiting the intrinsic viscosity as described above to a specific range, and it is possible to obtain an extensional viscosity (ηe) and a shear viscosity (b). By making the ratio (ηe / η) within an appropriate range, even in a molding method that tends to cause drawdown, such as direct blow, there is no drawdown, excellent transparency, and no thickness unevenness. It has been found that high-quality molded products can be obtained with high productivity. And when satisfying the carboxyl end group amount as will be described later, it has been found that the thermal stability is remarkably improved, the drawdown property is excellent even when used as a recycled material, and the recyclability is good. .
伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）が４〜１０であると、ポリエステル樹脂における分子鎖の絡み合いや、架橋密度が好適なものになると思われ、このため、ポリエステル樹脂組成物が自重により落下する際の速度や粘性が特にダイレクトブロー成形に適したものとすることが可能となる。 When the ratio (ηe / η) of the extensional viscosity (ηe) to the shear viscosity (η) is 4 to 10, it is considered that the entanglement of molecular chains in the polyester resin and the crosslink density are suitable. The speed and viscosity when the resin composition falls due to its own weight can be particularly suitable for direct blow molding.
伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）が４未満であると、ブロー成形時にパリソンのドローダウンが大きくなり、成形が困難になったり、得られる成形品は厚みムラが生じたものとなる。一方、伸長粘度（ηe）とせん断粘度（ｂ）の比（ηe／η）が１０を超えると、ブロー成形時にポリエステル樹脂組成物が自重により落下する速度が遅くなり、成形温度を上げる必要があり、成形時の熱処理により樹脂組成物の熱分解が生じる。このため、得られる成形品の色調や透明性が悪化したり、パリソンのドローダウンが大きくなり、得られる成形品は厚みムラが生じたものとなる。また、リサイクル性にも劣るものとなる。 When the ratio (ηe / η) of the extensional viscosity (ηe) to the shear viscosity (η) is less than 4, the drawdown of the parison increases during blow molding, making molding difficult, and the resulting molded product has uneven thickness. Will occur. On the other hand, if the ratio (ηe / η) between the extensional viscosity (ηe) and the shear viscosity (b) exceeds 10, the rate at which the polyester resin composition drops due to its own weight during blow molding becomes slow, and it is necessary to raise the molding temperature. The heat treatment during molding causes thermal decomposition of the resin composition. For this reason, the color tone and transparency of the obtained molded product are deteriorated, the drawdown of the parison is increased, and the obtained molded product has uneven thickness. In addition, the recyclability is poor.
なお、本発明における伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）は以下のようにして測定するものである。
ポリエステル樹脂組成物を、フローテスター（島津製作所社製 ＣＦＴ−５００）を用いて、２種類のノズル（ノズルの直径×長さが、０．５×１ｍｍ、０．５×１０ｍｍのもの）でせん断粘度（η）を測定する。このとき、せん断速度１００〜１００００ｓ−1、測定温度３００℃で測定を行う。そして、せん断速度５００ｓ−1で測定されるせん断粘度（η）の値を用い、Cogswellによって提唱されている以下の式（１）により、伸長粘度（ηe）を算出する(Cogswell法)。
The ratio (ηe / η) of the extensional viscosity (ηe) and the shear viscosity (η) in the present invention is measured as follows.
Using a flow tester (CFT-500 manufactured by Shimadzu Corporation), the polyester resin composition is sheared with two types of nozzles (nozzle diameter × length is 0.5 × 1 mm, 0.5 × 10 mm). Viscosity (η) is measured. At this time, measurement is performed at a shear rate of 100 to 10,000 s −1 and a measurement temperature of 300 ° C. Then, using the value of the shear viscosity (η) measured at a shear rate of 500 s −1 , the elongational viscosity (ηe) is calculated by the following equation (1) proposed by Cogswell (Cogswell method).
これらは、Baglay補正により求めることができる。
Cogswell法は、Cogswell,F.N.:Polym.Eng.Sci.12,64(1972)を参照のこと。
Baglay補正は、Baglay,E.B.:J Appl.Phys,28,624(1957)を参照のこと。
このようにして測定、算出した伸長粘度（ηe）とせん断粘度（η）の値を用い、両者の比（ηe／η）を算出するものである。
These can be obtained by Baglay correction.
For the Cogswell method, see Cogswell, FN: Polym. Eng. Sci. 12, 64 (1972).
For Baglay correction, see Baglay, EB: J Appl. Phys, 28, 624 (1957).
The ratio (ηe / η) between the two is calculated using the values of the elongation viscosity (ηe) and the shear viscosity (η) thus measured and calculated.
伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）を上記範囲のものとするには、後述するような添加剤をポリエステル樹脂の重合時に適量添加することが好ましく、さらには適切な条件で溶融重合と固相重合を行うことが必要である。つまり、ポリエステル樹脂中に分子鎖の絡み合いを生じさせ、適度な架橋構造を有する樹脂組成物とすることにより、上記の粘度特性を有するものとすることが可能となる。 In order to make the ratio (ηe / η) of the extensional viscosity (ηe) to the shear viscosity (η) within the above range, it is preferable to add an appropriate amount of an additive as described later at the time of polymerization of the polyester resin. It is necessary to perform melt polymerization and solid phase polymerization under such conditions. That is, it becomes possible to make the polyester resin have the above-mentioned viscosity characteristics by causing entanglement of molecular chains in the polyester resin to obtain a resin composition having an appropriate cross-linked structure.
さらに、本発明のポリエステル樹脂組成物は、カルボキシル末端基濃度が２０当量／ｔ以下であることが必要であり、中でも１９当量／ｔ以下であることが好ましく、さらには１８．５当量／ｔ以下であることが好ましい。ポリエステル樹脂組成物のカルボキシル末端基濃度を２０当量／ｔ以下とすることによって、ブロー成形時の熱処理により樹脂の熱分解が生じることを抑えることができ、安定した成形が可能となる。また、リサイクル性にも優れたものとなる。 Further, the polyester resin composition of the present invention needs to have a carboxyl end group concentration of 20 equivalent / t or less, preferably 19 equivalent / t or less, more preferably 18.5 equivalent / t or less. It is preferable that By setting the carboxyl end group concentration of the polyester resin composition to 20 equivalent / t or less, it is possible to suppress thermal decomposition of the resin due to heat treatment during blow molding, and stable molding becomes possible. In addition, the recyclability is excellent.
カルボキシル末端基濃度が２０当量／ｔを超える場合は、たとえ、樹脂組成物の極限粘度や、伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）が上記したような範囲のものであったとしても、ブロー成形時の熱処理によって、樹脂の熱分解が生じやすくなる。樹脂の熱分解が生じると、成形時に樹脂の粘度が低下し、パリソンのドローダウンが生じ、得られる成形品は厚みムラが生じたものとなる。また、得られる成形品や成形時に発生する端材も樹脂の熱分解が生じたものとなっているため、このような端材を再生材として再びブロー成形に供すると、ブロー成形時にドローダウンが生じ、安定的な生産が困難となる。このため、得られる成形品は透明性に劣るとともに、厚みムラも生じたものとなる。 When the carboxyl end group concentration exceeds 20 equivalents / t, the intrinsic viscosity of the resin composition and the ratio (ηe / η) of the extensional viscosity (ηe) to the shear viscosity (η) are in the above range Even if it is, it becomes easy to produce thermal decomposition of resin by the heat processing at the time of blow molding. When the thermal decomposition of the resin occurs, the viscosity of the resin decreases during molding, and a drawdown of the parison occurs, and the resulting molded product has uneven thickness. Also, since the molded product obtained and the end material generated at the time of molding are those that have undergone thermal decomposition of the resin, if such an end material is used as a recycled material and again subjected to blow molding, drawdown may occur during blow molding. And stable production becomes difficult. For this reason, the obtained molded product is inferior in transparency and has uneven thickness.
さらに、本発明のポリエステル樹脂組成物は、環状３量体の含有量が０．６質量％以下であることが好ましく、中でも０．５質量％以下であることが好ましい。環状３量体の含有量が０．６質量％以下であるポリエステル樹脂組成物を成形に供することで、金型等の汚染の改善が認められる。環状３量体の含有量が、０．６質量％を超えると成形時に金型やノズルなどの装置類に付着し、汚染する。これらの汚染は、成形品の表面荒れや白化などの原因となるため、金型やノズルを頻繁に清掃する必要がある。 Furthermore, the polyester resin composition of the present invention preferably has a cyclic trimer content of 0.6% by mass or less, and more preferably 0.5% by mass or less. By using a polyester resin composition having a cyclic trimer content of 0.6% by mass or less for molding, improvement of contamination of molds and the like is observed. If the content of the cyclic trimer exceeds 0.6% by mass, it adheres to and contaminates devices such as molds and nozzles during molding. Since these contaminations cause surface roughness and whitening of the molded product, it is necessary to frequently clean the mold and nozzle.
なお、ポリエステル樹脂組成物のカルボキシル末端基濃度を２０当量／ｔ以下としたり、環状３量体の含有量を０．６質量％以下とするには、ポリエステル樹脂を得るための溶融重合反応後に、後述するような特定の条件で固相重合反応を行うことにより可能となる。 In addition, in order to make the carboxyl end group concentration of the polyester resin composition 20 equivalent / t or less, or to make the content of the cyclic trimer 0.6 mass% or less, after the melt polymerization reaction for obtaining the polyester resin, This can be achieved by performing a solid phase polymerization reaction under specific conditions as described below.
そして、ポリエステル樹脂組成物の粘度特性を本発明で規定する上記範囲を満足するものとするためには、ポリエステル樹脂組成物中に、脂肪酸エステルやヒンダードフェノール系抗酸化剤が添加されていることが好ましい。樹脂組成物中のこれらの含有量は、０．０１〜１．０質量％であることが好ましく、中でも０．０５〜１．０質量％であることが好ましい。 And in order to satisfy the said range which prescribes | regulates the viscosity characteristic of a polyester resin composition by this invention, fatty acid ester and a hindered phenolic antioxidant should be added in the polyester resin composition. Is preferred. The content of these in the resin composition is preferably 0.01 to 1.0% by mass, and more preferably 0.05 to 1.0% by mass.
脂肪酸エステルの具体例としては、蜜ロウ（ミリシルパルミテートを主成分とする混合物）、ステアリン酸ステアリル、ベヘン酸ベヘニル、ベヘン酸ステアリル、グリセリンモノパルミテート、グリセリンモノステアレート、グリセリンジステアレート、グリセリントリステアレート、ペンタエリスリトールモノパルミテート、ペンタエリスリトールモノステアレート、ペンタエリスリトールジステアレート、ペンタエリスリトールトリステアレート、ペンタエリスリトールテトラステアレート、ジペンタエリスリトールヘキサステアレート等が挙げられる。中でも、グリセリンモノステアレート、ペンタエリスリトールテトラステアレート、ジペンタエリスリトールヘキサステアレートが好ましい。 Specific examples of fatty acid esters include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, Examples thereof include glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, dipentaerythritol hexastearate and the like. Among these, glycerin monostearate, pentaerythritol tetrastearate, and dipentaerythritol hexastearate are preferable.
また、ヒンダードフェノール系抗酸化剤としては、２，６−ジ−ｔ−ブチル−４−メチルフェノール、ｎ−オクタデシル−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート、テトラキス〔メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕メタン、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、４，４’−ブチリデンビス−（３−メチル−６−ｔ−ブチルフェノール）、トリエチレングリコール−ビス〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート〕、３，９−ビス｛２−〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ〕−１，１’−ジメチルエチル｝−２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン等が用いられるが、効果とコストの点で、テトラキス〔メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕メタンが好ましい。 Examples of hindered phenol antioxidants include 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxy. Phenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9- Bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1'-dimethylethyl} -2, , 8,10-tetraoxaspiro [5,5] undecane, etc. are used, but tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate in terms of effect and cost. Methane is preferred.
脂肪酸エステルやヒンダードフェノール系抗酸化剤は、ポリエステル樹脂の重合反応工程中に添加することで、該化合物の一部がポリエステル樹脂中に共重合され、ポリエステルの分子鎖中に組み込まれることで、分子鎖の絡み合いや、架橋構造が生じ、ポリエステル樹脂組成物の粘性を高くすることができる。さらに後述するような重合反応工程を経ることによって、伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）を４〜１０とすることが可能となる。 Fatty acid esters and hindered phenol antioxidants are added during the polyester resin polymerization reaction step, so that part of the compound is copolymerized in the polyester resin and incorporated into the molecular chain of the polyester. Entanglement of molecular chains and a crosslinked structure occur, and the viscosity of the polyester resin composition can be increased. Further, by passing through a polymerization reaction step as described later, the ratio (ηe / η) of the extensional viscosity (ηe) to the shear viscosity (η) can be set to 4-10.
ポリエステル樹脂組成物中の脂肪酸エステルやヒンダードフェノール系抗酸化剤の含有量が０．０１質量％未満では、ポリエステル樹脂組成物の粘性を向上させる効果に乏しいものとなり、特に伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）を４以上のものとすることが困難となる。一方、１．０質量％を超えると、粘性が高くなり、伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）が１０を超える場合が多くなる。 When the content of the fatty acid ester or the hindered phenol antioxidant in the polyester resin composition is less than 0.01% by mass, the polyester resin composition has a poor effect of improving the viscosity of the polyester resin composition. It becomes difficult to set the shear viscosity (η) ratio (ηe / η) to 4 or more. On the other hand, if it exceeds 1.0% by mass, the viscosity increases, and the ratio (ηe / η) of the extensional viscosity (ηe) to the shear viscosity (η) often exceeds 10.
本発明のポリエステル樹脂組成物は、上記のような特定の組成からなるポリエステル樹脂を用い、特定の粘度の特性値を満足するものであるため、耐衝撃性にも優れるものである。耐衝撃性に優れることを示す指標としては、シャルピー衝撃強度を３．８ｋＪ／ｍ２以上のものとすることができる。
なお、シャルピー衝撃強度は、次のようにして測定するものである。ポリエステル樹脂組成物を日精樹脂社製ＮＥＸ１１０型射出成形機に投入し、シリンダー温度２７０℃、金型表面温度１５℃で、一般物性測定用試験片（ＩＳＯ型）を作製する。そして、一般物性測定用試験片（ＩＳＯ型）にＶ字型切込みを入れたものを試験サンプルとして用い、ＩＳＯ １７９−１に従って測定する。
Since the polyester resin composition of the present invention uses a polyester resin having a specific composition as described above and satisfies a specific viscosity characteristic value, the polyester resin composition also has excellent impact resistance. As an index indicating excellent impact resistance, Charpy impact strength can be 3.8 kJ / m 2 or more.
The Charpy impact strength is measured as follows. The polyester resin composition is put into a NEX110 type injection molding machine manufactured by Nissei Plastic Co., Ltd., and a test piece for general physical property measurement (ISO type) is produced at a cylinder temperature of 270 ° C. and a mold surface temperature of 15 ° C. Then, a test piece for general physical property measurement (ISO type) with a V-shaped cut is used as a test sample, and measurement is performed according to ISO 179-1.
本発明のポリエステル樹脂組成物中には、上記のような添加剤の他、着色防止剤として、例えば、亜リン酸、リン酸、トリメチルフォスファイト、トリフェニルフォスファイト、トリデシルフォスファイト、トリメチルフォスフェート、トリデシルフォスフェート、トリフェニルフォスフォート等のリン化合物を用いることができ、これらのリン化合物は単独で使用しても２種以上使用してもよい。
また、ポリエステル樹脂の熱分解による着色を抑制するために酢酸コバルト等のコバルト化合物、酢酸マンガン等のマンガン化合物、アントラキノン系染料化合物、銅フタロシアニン系化合物等の添加剤が含有されていてもよい。
In the polyester resin composition of the present invention, in addition to the additives as described above, examples of the coloring inhibitor include phosphorous acid, phosphoric acid, trimethyl phosphite, triphenyl phosphite, tridecyl phosphite, trimethyl phosphite. Phosphorus compounds such as phosphate, tridecyl phosphate, and triphenyl phosphate can be used. These phosphorus compounds may be used alone or in combination of two or more.
In addition, additives such as cobalt compounds such as cobalt acetate, manganese compounds such as manganese acetate, anthraquinone dye compounds, and copper phthalocyanine compounds may be contained in order to suppress coloring due to thermal decomposition of the polyester resin.
また、本発明のポリエステル樹脂組成物中には、下記に示すような発泡剤が含有されていてもよく、発泡ブロー成形により、本発明のブロー成形品を発泡ブロー成形品としてもよい。
発泡剤としては、熱分解型の、例えば、アゾ、Ｎ−ニトロソ、複素環式窒素含有及びスルホニルヒドラジド基のような分解しうる基を含有する有機化合物、炭酸アンモニウムや炭酸水素ナトリウムなどの無機化合物を挙げることができる。その具体例としては、アゾジカルボンアミド、アゾビスイソブチロニトリル、アゾシクロヘキシルニトリル、ジアゾアミノベンゼン、ジニトロソペンタメチレンテトラミン、Ｎ，Ｎ’−ジメチル−Ｎ，Ｎ’−ジニトロソテレフタルアミド、ベンゼンスルホニルヒドラジド、４，４’−オキシ−ビス（ベンゼンスルホニル）ヒドラジド、ジフェニルスルホン−３，３’−ジスルホニルヒドラジド、４−トルエンスルホニルヒドラジド、４，４’−オキシ−ビス（ベンゼンスルホニル）セミカルバジド、４−トルエンスルホニルセミカルバジド、バリウムアゾジカルボキシレート、５−フェニルテトラゾール、トリヒドラジノトリアジン、４−トルエンスルフォニルアザイド、４，４’−ジフェニルジスルフォニルアザイドなどが挙げられる。
The polyester resin composition of the present invention may contain a foaming agent as shown below, and the blow molded product of the present invention may be made into a foam blow molded product by foam blow molding.
Examples of the foaming agent include pyrolysis-type organic compounds containing decomposable groups such as azo, N-nitroso, heterocyclic nitrogen and sulfonyl hydrazide groups, and inorganic compounds such as ammonium carbonate and sodium hydrogen carbonate. Can be mentioned. Specific examples thereof include azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, diazoaminobenzene, dinitrosopentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosotephthalamide, benzenesulfonyl Hydrazide, 4,4′-oxy-bis (benzenesulfonyl) hydrazide, diphenylsulfone-3,3′-disulfonylhydrazide, 4-toluenesulfonyl hydrazide, 4,4′-oxy-bis (benzenesulfonyl) semicarbazide, 4- Examples include toluenesulfonyl semicarbazide, barium azodicarboxylate, 5-phenyltetrazole, trihydrazinotriazine, 4-toluenesulfonyl azide, 4,4′-diphenyldisulfonyl azide, and the like.
発泡剤としては、ガス状フルオロカーボン、窒素、二酸化炭素、空気、ヘリウム、アルゴンなど常温で気体のものや、液状フルオロカーボン、ペンタンなどの常温で液体のものも使用できる。 As the foaming agent, gaseous agents such as gaseous fluorocarbon, nitrogen, carbon dioxide, air, helium, and argon, and those that are liquid at ordinary temperatures such as liquid fluorocarbon and pentane can be used.
本発明のポリエステル樹脂組成物は、他の熱可塑性樹脂や他の共重合成分を含有するポリエステル樹脂と混合（ブレンド）して用いることもできる。そして、このように本発明のポリエステル樹脂組成物と他の樹脂とを混合した樹脂組成物を用いて得られる成形体は、耐衝撃性を向上させることができる場合がある。 The polyester resin composition of the present invention can also be used by mixing (blending) with other thermoplastic resins and polyester resins containing other copolymerization components. And the molded object obtained by using the resin composition which mixed the polyester resin composition of this invention and other resin in this way may be able to improve impact resistance.
次に、本発明のポリエステル樹脂組成物の製造方法について説明する。本発明におけるポリエステル樹脂組成物は、エステル化反応、溶融重合反応及び固相重合反応工程を経て得られるものであることが好ましい。エステル化反応と溶融重合反応のみでは、ポリエステル樹脂組成物の極限粘度を高くすることが困難となる。得られたとしても、溶融重合反応の反応時間が長くなり、得られるポリエステル樹脂組成物は色調が悪いものとなる。固相重合反応における工程や条件を特定のものにすることによって、特有の粘性を有し、かつカルボキシル末端基濃度の低い本発明のポリエステル樹脂組成物を得ることができる。 Next, the manufacturing method of the polyester resin composition of this invention is demonstrated. The polyester resin composition in the present invention is preferably obtained through an esterification reaction, a melt polymerization reaction, and a solid phase polymerization reaction step. Only the esterification reaction and the melt polymerization reaction make it difficult to increase the intrinsic viscosity of the polyester resin composition. Even if it is obtained, the reaction time of the melt polymerization reaction becomes long, and the resulting polyester resin composition has a poor color tone. By making the steps and conditions in the solid phase polymerization reaction specific, the polyester resin composition of the present invention having a specific viscosity and a low carboxyl end group concentration can be obtained.
具体的には、例えば、次のような方法で製造することができる。
酸成分としてテレフタル酸あるいはそのエステル形成性誘導体、グリコール成分としてエチレングリコールを所定の割合でエステル化反応器に仕込み、加圧下、１６０〜２８０℃の温度でエステル化反応を行う。この後、反応生成物を重合反応器に移し、１，４−シクロヘキサンジメタノール、重縮合触媒、必要に応じて脂肪酸エステルやヒンダードフェノール系抗酸化剤、着色防止剤等の添加剤を添加し、通常１ｈＰａ以下の減圧下で２４０〜２９０℃、好ましくは２５０〜２８０℃の温度で溶融重合反応を行う。ここで得られる共重合ポリエステル（プレポリマー）の極限粘度は、０．５〜０．８の範囲であることが好ましい。
Specifically, for example, it can be produced by the following method.
Terephthalic acid or an ester-forming derivative thereof as an acid component and ethylene glycol as a glycol component are charged into an esterification reactor at a predetermined ratio, and an esterification reaction is performed at a temperature of 160 to 280 ° C. under pressure. Thereafter, the reaction product is transferred to a polymerization reactor, and 1,4-cyclohexanedimethanol, a polycondensation catalyst, and additives such as fatty acid esters, hindered phenol antioxidants, and coloring inhibitors are added as necessary. In general, the melt polymerization reaction is performed at a temperature of 240 to 290 ° C., preferably 250 to 280 ° C. under a reduced pressure of 1 hPa or less. The intrinsic viscosity of the copolymerized polyester (prepolymer) obtained here is preferably in the range of 0.5 to 0.8.
重縮合触媒としては、一般的にＰＥＴに用いられる公知の化合物、例えば、ゲルマニウム、アンチモン、チタンおよびコバルト化合物などの１種以上を用いることができるが、好ましくはゲルマニウムまたはアンチモンの化合物を使用する。さらに、得られるポリエステル樹脂の透明性を非常に重視する場合においては、ゲルマニウム化合物を使用することが好ましい。ゲルマニウムまたはアンチモンの化合物としては、それらの酸化物、無機酸塩、有機酸塩、ハロゲン化物、硫化物などが例示される。これらの重縮合触媒は、生成するポリエステル樹脂の酸成分１モルに対し５×１０−５モル〜３．０×１０−４モルの範囲内、中でも６×１０−５モル〜２．０×１０−４モルの範囲内となるような量で用いることが好ましい。 As the polycondensation catalyst, one or more known compounds generally used for PET, for example, germanium, antimony, titanium, and cobalt compounds can be used, but germanium or antimony compounds are preferably used. Further, when the transparency of the resulting polyester resin is very important, it is preferable to use a germanium compound. Examples of germanium or antimony compounds include oxides, inorganic acid salts, organic acid salts, halides, and sulfides thereof. These polycondensation catalysts are used in the range of 5 × 10 −5 mol to 3.0 × 10 −4 mol, particularly 6 × 10 −5 mol to 2.0 × 10, with respect to 1 mol of the acid component of the polyester resin to be produced. It is preferably used in such an amount that it is within the range of -4 mol.
続いて、上記した溶融重合反応により得られたプレポリマーをダイス状、円柱状などの任意の形状のチップとし、該ポリエステルチップを結晶化装置に連続的に供給し、１５０〜１８０℃の温度で１〜３時間熱処理を行い、結晶化を行う。この後、乾燥機に供給し、１８０℃以下の温度で４〜１０時間乾燥後、予備加熱機に送り、２〜５時間の範囲で下記固相重合温度まで加熱した後、固相重合機へ連続的に供給する。固相重合反応は、窒素ガスなどの不活性ガス下で行うのが好ましく、１７０〜２３０℃の範囲内の温度で行うのが好ましく、１８０〜２２０℃の範囲内の温度で行うのがより好ましい。また、重合時間は４０時間〜７０時間の範囲で、固相重合機内にて反応させることにより、目標の粘度特性とカルボキシル末端基量を有するポリエステル樹脂組成物を得ることができる。 Subsequently, the prepolymer obtained by the above-described melt polymerization reaction is used as a chip having an arbitrary shape such as a die or a cylinder, and the polyester chip is continuously supplied to a crystallization apparatus at a temperature of 150 to 180 ° C. Heat treatment is performed for 1 to 3 hours for crystallization. Then, after supplying to a dryer, drying at a temperature of 180 ° C. or less for 4 to 10 hours, sending to a preheater and heating to the following solid phase polymerization temperature in the range of 2 to 5 hours, Supply continuously. The solid phase polymerization reaction is preferably performed under an inert gas such as nitrogen gas, preferably at a temperature in the range of 170 to 230 ° C, and more preferably at a temperature in the range of 180 to 220 ° C. . The polymerization time is in the range of 40 hours to 70 hours, and a polyester resin composition having a target viscosity characteristic and a carboxyl end group amount can be obtained by reacting in a solid phase polymerization machine.
本発明のポリエステル樹脂組成物は、上記したように、ブロー成形に適したものであるが、射出成形や延伸法を採用しても、色調、透明性に優れた成形品（射出成形体、シート、フィルム等）を得ることができる。 As described above, the polyester resin composition of the present invention is suitable for blow molding, but even if an injection molding or stretching method is adopted, a molded product (injection molded body, sheet) having excellent color tone and transparency. , Film, etc.) can be obtained.
次に、本発明のブロー成形品は、本発明のポリエステル樹脂組成物を用いて形成されたものである。本発明のブロー成形品は、汎用のダイレクトブロー成形機や延伸ブロー成形機を用いて製造することが可能であり、成形機のシリンダー各部及びノズルの温度は、２３０〜２８０℃の範囲とするのが好ましい。 Next, the blow molded product of the present invention is formed using the polyester resin composition of the present invention. The blow molded product of the present invention can be manufactured using a general-purpose direct blow molding machine or stretch blow molding machine, and the temperature of each part of the cylinder and the nozzle of the molding machine is in the range of 230 to 280 ° C. Is preferred.
そして、本発明のブロー成形品は、本発明の樹脂組成物のみを用いて形成された単層構造のブロー成形品であってもよいし、本発明の樹脂組成物を少なくとも一部に用いた多層構造のブロー成形品であってもよい。 The blow molded article of the present invention may be a single-layer blow molded article formed using only the resin composition of the present invention, or at least a part of the resin composition of the present invention is used. It may be a blow molded article having a multilayer structure.
次に、実施例を用いて本発明を具体的に説明する。なお、実施例中の各種の特性値等の測定、評価方法は次の通りである。
（ａ）極限粘度
前記と同様の方法で測定した。
なお、リサイクル性の評価において、得られたダイレクトブロー成形品及び延伸ブロー成形品の極限粘度は、成形品より切片を切り出してサンプルとし、前記と同様の方法で測定した。
（ｂ）ポリエステル樹脂の組成
得られたポリエステル樹脂組成物を、重水素化ヘキサフルオロイソプロパノールと重水素化クロロホルムとの容量比が１／２０の混合溶媒に溶解させ、日本電子社製ＬＡ−４００型ＮＭＲ装置にて１Ｈ−ＮＭＲを測定し、得られたチャートの各成分のプロトンのピークの積分強度から、共重合成分の種類と含有量を求めた。
（ｃ）伸長粘度（ηe）とせん断粘度（η）の比
前記と同様の方法で測定した。
Next, the present invention will be specifically described using examples. The measurement and evaluation methods for various characteristic values in the examples are as follows.
(A) Intrinsic viscosity It was measured by the same method as described above.
In the evaluation of recyclability, the intrinsic viscosity of the obtained direct blow-molded product and stretch blow-molded product was measured by the same method as described above by cutting a section from the molded product as a sample.
(B) Composition of polyester resin The obtained polyester resin composition was dissolved in a mixed solvent having a volume ratio of deuterated hexafluoroisopropanol and deuterated chloroform of 1/20, and LA-400 type manufactured by JEOL Ltd. 1H-NMR was measured with an NMR apparatus, and the type and content of the copolymerization component were determined from the integrated intensity of the proton peak of each component of the obtained chart.
(C) Ratio of elongational viscosity (ηe) to shear viscosity (η) Measured by the same method as described above.
（ｄ）カルボキシル末端基濃度
得られたポリエステル樹脂組成物０．１ｇをベンジルアルコール１０ｍｌに溶解し、この溶液にクロロホルム１０ｍｌを加えた後、１／１０規定の水酸化カリウムベンジルアルコール溶液で滴定して求めた。
（ｅ）環状３量体含有量
得られたポリエステル樹脂組成物１００ｍｇをヘキサフルオロイソプロパノールとクロロホルムとの容量比が１／２０の混合溶媒に溶解させ、アセトニトリルを加え、抽出したのち、液体クロマトグラフィーを用いて以下の条件にて測定し、環状３量体の量を算出した。
カラム：ＷＡＴＥＲＳ マイクロボンダスフィア
充填剤：Ｓｉ−Ｃ１８ ５μ １００Ａ
検出器：ＷＡＴＥＲＳ ２９９６型 ＰＤＡ検出器（光源波長 ２５４ｎｍ）
測定時流速：１ｍｌ／分
移動相溶媒：アセトニトリル／水=７／３及びアセトニトリル
(D) Carboxyl end group concentration 0.1 g of the obtained polyester resin composition was dissolved in 10 ml of benzyl alcohol, 10 ml of chloroform was added to this solution, and then titrated with 1/10 N potassium hydroxide benzyl alcohol solution. Asked.
(E) Cyclic trimer content 100 mg of the obtained polyester resin composition was dissolved in a mixed solvent having a volume ratio of hexafluoroisopropanol and chloroform of 1/20, and acetonitrile was added for extraction, followed by liquid chromatography. It was measured under the following conditions, and the amount of cyclic trimer was calculated.
Column: WATERS Micro Bonder Sphere
Filler: Si-C18 5μ 100A
Detector: WATERS 2996 type PDA detector (light source wavelength 254 nm)
Measurement flow rate: 1 ml / min Mobile phase solvent: acetonitrile / water = 7/3 and acetonitrile
（ｆ）ダイレクトブロー成形性
得られたダイレクトブロー成形品（サンプル数１００本）の胴部の厚さを測定し、最厚部と最薄部の厚さの差が０．３０ｍｍまでのものを合格とし、合格のサンプル数を示した。合格のサンプル数が９０本以上であるものを○、９０本未満であるものを×とした。
（ｇ）ダイレクトブロー成形のリサイクル性
得られたダイレクトブロー成形品を粉砕機で粉砕した粉砕品５０質量部、各例にて得られたポリエステル樹脂組成物５０質量部をブレンドし、除湿乾燥機に投入し乾燥した後、実施例１と同様にしてダイレクトブロー成形を行い、成形品を得た。得られた成形品（サンプル数１００本）につき、（ｆ）と同様にして成形性を評価した。
(F) Direct blow moldability The thickness of the body of the obtained direct blow molded product (100 samples) was measured, and the difference between the thickness of the thickest part and the thinnest part was up to 0.30 mm. The sample was accepted and the number of samples accepted was shown. A sample having 90 or more acceptable samples was evaluated as “◯”, and a sample having less than 90 samples as “×”.
(G) Recyclability of direct blow molding 50 parts by mass of the pulverized product obtained by pulverizing the obtained direct blow molded product with a pulverizer and 50 parts by mass of the polyester resin composition obtained in each example were blended into a dehumidifying dryer. After charging and drying, direct blow molding was performed in the same manner as in Example 1 to obtain a molded product. About the obtained molded product (100 samples), the moldability was evaluated in the same manner as (f).
（ｈ）ダイレクトブロー成形品のヘーズ
得られたダイレクトブロー成形品及び（ｇ）で得られたダイレクトブロー成形品のそれぞれにおいて、サイズ：厚さ２ｍｍ×長さ５ｃｍ×幅５ｃｍの試験片（１００個）を切り出して試験片の濁度を日本電色工業社製の濁度計ＭＯＤＥＬ １００１ＤＰで測定し（空気：ヘーズ０％）、ｎ数１００の平均値とした。この値が小さいほど透明性が良好であり、３％以下であれば透明性に優れていると判定した。なお、このとき、（ｆ）の成形性の評価において合格となった成形品のみを用いた。
(H) Haze of direct blow-molded product In each of the obtained direct blow-molded product and the direct blow-molded product obtained in (g), a test piece of size: 2 mm thick × 5 cm long × 5 cm wide (100 pieces) ) Was cut out, and the turbidity of the test piece was measured with a turbidimeter MODEL 1001DP manufactured by Nippon Denshoku Industries Co., Ltd. (air: haze 0%) to obtain an average value of n number 100. The smaller this value, the better the transparency, and if it was 3% or less, it was judged that the transparency was excellent. At this time, only the molded product that passed the evaluation of the moldability of (f) was used.
（ｉ）延伸ブロー成形性
得られた延伸ブロー成形品（サンプル数１００本）の胴部の厚さを測定し、最厚部と最薄部の厚さの差が３０μｍまでのものを合格とし、合格のサンプル数を示した。合格のサンプル数が９０本以上であるものを○、９０本未満であるものを×とした。
（ｊ）延伸ブロー成形のリサイクル性
得られた延伸ブロー成形品を粉砕機で粉砕した粉砕品５０質量部、各例にて得られたポリエステル樹脂組成物５０質量部をブレンドし、除湿乾燥機に投入し乾燥した後、実施例１と同様にして延伸ブロー成形を行い、成形品を得た。得られた成形品（サンプル数１００本）につき、（ｉ）と同様にして成形性を評価した。
(I) Stretch blow moldability The thickness of the body of the obtained stretch blow molded article (100 samples) is measured, and the difference between the thickness of the thickest part and the thinnest part is up to 30 μm. , Showed the number of samples passed. A sample having 90 or more acceptable samples was evaluated as “◯”, and a sample having less than 90 samples as “×”.
(J) Recyclability of stretch blow molding 50 parts by mass of a pulverized product obtained by pulverizing the obtained stretch blow molded product with a pulverizer, and 50 parts by mass of the polyester resin composition obtained in each example were blended into a dehumidifying dryer. After charging and drying, stretch blow molding was performed in the same manner as in Example 1 to obtain a molded product. About the obtained molded article (100 samples), the moldability was evaluated in the same manner as (i).
（ｋ）延伸ブロー成形品のヘーズ
得られた延伸ブロー成形品及び（ｊ）で得られた延伸ブロー成形品のそれぞれにおいて、サイズ：厚さ３００μｍ×長さ５ｃｍ×幅５ｃｍの試験片（１００個）を切り出して試験片の濁度を日本電色工業社製の濁度計ＭＯＤＥＬ １００１ＤＰで測定し（空気：ヘーズ０％）、ｎ数１００の平均値とした。この値が小さいほど透明性が良好であり、３％以下であれば透明性に優れていると判定した。なお、このとき、（ｉ）の成形性の評価において合格となった成形品のみを用いた。
(K) Haze of stretch blow-molded product In each of the obtained stretch blow-molded product and the stretch blow-molded product obtained in (j), a test piece (100 pieces of size: thickness 300 μm × length 5 cm × width 5 cm) ) Was cut out, and the turbidity of the test piece was measured with a turbidimeter MODEL 1001DP manufactured by Nippon Denshoku Industries Co., Ltd. (air: haze 0%) to obtain an average value of n number 100. The smaller this value, the better the transparency, and if it was 3% or less, it was judged that the transparency was excellent. At this time, only the molded product that passed the evaluation of the moldability of (i) was used.
実施例１
エステル化反応器に、テレフタル酸（ＴＰＡ）とエチレングリコール（ＥＧ）のスラリー（ＴＰＡ／ＥＧモル比＝１／１．６）を供給し、温度２５０℃、圧力５０ｈＰａの条件で反応させ、エステル化反応率９５％の反応生成物（数平均重合度：５）を得た。
ＴＰＡとＥＧの反応生成物５９．４質量部を重合反応器に仕込み、続いて、１，４―シクロヘキサンジメタノール３．８質量部、重合触媒として二酸化ゲルマニウム０．００８質量部、酢酸コバルト０．００４質量部、ヒンダードフェノール系抗酸化剤（ＡＤＥＫＡ社製：アデカスタブＡＯ−６０）０．１２質量部を、それぞれ加え、反応器を減圧にして６０分後に最終圧力０．９ｈＰａ、温度２８０℃で４時間、溶融重合反応を行い、共重合ポリエステルのプレポリマーを得た。このプレポリマーの極限粘度は、０．６６であった。
続いて、該プレポリマーを結晶化装置に連続的に供給し１５０℃で結晶化をさせた後、乾燥機に供給し１６０℃で８時間乾燥後、予備加熱機に送り１９０℃まで加熱した後、固相重合機へ供給し、窒素ガス下にて固相重合反応を１９０℃で５０時間行い、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シャルピー衝撃強度（前述の測定方法に従って測定した）は、４．０ｋＪ／ｍ２であった。
Example 1
The esterification reactor is fed with a slurry of terephthalic acid (TPA) and ethylene glycol (EG) (TPA / EG molar ratio = 1 / 1.6) and reacted under the conditions of a temperature of 250 ° C. and a pressure of 50 hPa for esterification. A reaction product (number average degree of polymerization: 5) having a reaction rate of 95% was obtained.
59.4 parts by mass of a reaction product of TPA and EG were charged into a polymerization reactor, followed by 3.8 parts by mass of 1,4-cyclohexanedimethanol, 0.008 parts by mass of germanium dioxide as a polymerization catalyst, and 0. 004 parts by mass, 0.12 parts by mass of a hindered phenolic antioxidant (manufactured by ADEKA: Adeka Stub AO-60) were added, respectively, and the reactor was evacuated and after 60 minutes, the final pressure was 0.9 hPa and the temperature was 280 ° C. A melt polymerization reaction was performed for 4 hours to obtain a prepolymer of a copolyester. The intrinsic viscosity of this prepolymer was 0.66.
Subsequently, the prepolymer was continuously supplied to a crystallization apparatus and crystallized at 150 ° C., then supplied to a dryer, dried at 160 ° C. for 8 hours, then sent to a preheater and heated to 190 ° C. The polyester resin composition was obtained by supplying it to a solid phase polymerization machine and carrying out a solid phase polymerization reaction at 190 ° C. for 50 hours under nitrogen gas. The resulting polyester resin composition had a Charpy impact strength (measured according to the measurement method described above) of 4.0 kJ / m 2 .
（１）得られたポリエステル樹脂組成物をチップ化し、乾燥させた後、ダイレクトブロー成形機(タハラ社製)を用い、押出温度２６０℃で樹脂を押出して円筒形パリソンを形成し、パリソンが軟化状態にあるうちに金型で挟み、底部形成を行い、これをブローしてボトルを成形した。このとき、パリソン径２ｃｍで長さが２５ｃｍとなったところで底部形成を行い、ブロー成形して５００ｃｃの中空容器（ダイレクトブロー成形品）を得た。
（２）また、得られたポリエステル樹脂組成物をチップ化し、乾燥させた後、シリンダー各部およびノズル温度（押出温度）を２６０℃、スクリュー回転数１００ｒｐｍ、射出時間１０秒、冷却時間１０秒、金型温度１５℃に設定した射出成型機（日精エーエスビー社製、ＡＳＢ−５０ＴＨ型）を用いてプリフォームを成形した。次いで、このプリフォームを１００℃雰囲気下、ブロー圧力２ＭＰａで延伸ブロー成形し、胴部の平均肉厚３００μｍ、内径３．５ｃｍ、高さ１５ｃｍの円筒状のボトル（内容積１５０ｃｃの中空容器；延伸ブロー成形品）を得た。
(1) After the obtained polyester resin composition is chipped and dried, a direct blow molding machine (manufactured by Tahara) is used to extrude the resin at an extrusion temperature of 260 ° C. to form a cylindrical parison, and the parison is softened While it was in the state, it was sandwiched between molds, the bottom was formed, and this was blown to form a bottle. At this time, when the parison diameter was 2 cm and the length was 25 cm, the bottom was formed and blow-molded to obtain a 500 cc hollow container (direct blow-molded product).
(2) Further, after the obtained polyester resin composition was chipped and dried, each part of the cylinder and nozzle temperature (extrusion temperature) were 260 ° C., screw rotation speed 100 rpm, injection time 10 seconds, cooling time 10 seconds, gold A preform was molded by using an injection molding machine (manufactured by Nissei ASB Co., Ltd., ASB-50TH type) set at a mold temperature of 15 ° C. Next, this preform was stretch blow molded at a blow pressure of 2 MPa in an atmosphere of 100 ° C., and a cylindrical bottle (a hollow container having an internal volume of 150 cc; stretched; an average thickness of 300 μm, an inner diameter of 3.5 cm, and a height of 15 cm) A blow molded product) was obtained.
実施例２〜４、９、比較例１、５〜６
１，４―シクロヘキサンジメタノールの共重合量や、ヒンダードフェノール系抗酸化剤の含有量が表１の値となるように組成を変更した以外は、実施例１と同様にして、共重合ポリエステルのプレポリマーを得た。そして得られたプレポリマーを用い、実施例１と同様にして固相重合反応を行い、ポリエステル樹脂組成物を得た。
さらに、得られたポリエステル樹脂組成物を用い、実施例１と同様にしてダイレクトブロー成形品、及び延伸ブロー成形品を得た。
なお、比較例６においては、ダイレクトブロー成形機及び延伸ブロー成形機における押出温度を２９０℃として行った。
Examples 2 to 4, 9 and Comparative Examples 1, 5 to 6
A copolymerized polyester was prepared in the same manner as in Example 1 except that the composition was changed so that the copolymerization amount of 1,4-cyclohexanedimethanol and the content of the hindered phenol antioxidant became the values shown in Table 1. Of a prepolymer was obtained. And using the obtained prepolymer, the solid-state polymerization reaction was performed like Example 1, and the polyester resin composition was obtained.
Furthermore, using the obtained polyester resin composition, a direct blow molded product and a stretch blow molded product were obtained in the same manner as in Example 1.
In Comparative Example 6, the extrusion temperature in the direct blow molding machine and the stretch blow molding machine was 290 ° C.
実施例５
１，４―シクロヘキサンジメタノールの共重合量が表１の値となるように変更した以外は、実施例１と同様にしてエステル化反応、溶融重合反応を行い、共重合ポリエステルのプレポリマーを得た。そして得られたプレポリマーを用い、乾燥機の乾燥条件を１３０℃、１０時間、予備加熱機による加熱温度を１８０℃とした以外は実施例１と同様にして固相重合反応を行い、ポリエステル樹脂組成物を得た。
さらに、得られたポリエステル樹脂組成物を用い、実施例１と同様にしてダイレクトブロー成形品及び延伸ブロー成形品を得た。
Example 5
Except that the copolymerization amount of 1,4-cyclohexanedimethanol was changed to the value shown in Table 1, esterification reaction and melt polymerization reaction were carried out in the same manner as in Example 1 to obtain a copolymerized polyester prepolymer. It was. Then, using the obtained prepolymer, a solid-state polymerization reaction was performed in the same manner as in Example 1 except that the drying conditions of the dryer were 130 ° C., 10 hours, and the heating temperature of the preheater was 180 ° C. A composition was obtained.
Further, using the obtained polyester resin composition, a direct blow molded product and a stretch blow molded product were obtained in the same manner as in Example 1.
実施例６
１，４―シクロヘキサンジメタノールの共重合量が表１の値となるように変更した以外は、実施例１と同様にしてエステル化反応、溶融重合反応を行い、共重合ポリエステルのプレポリマーを得た。そして得られたプレポリマーを用い、乾燥機の乾燥条件を１２０℃、１８時間、予備加熱機による加熱温度を１７５℃とした以外は実施例１と同様にして固相重合反応を行い、ポリエステル樹脂組成物を得た。
さらに、得られたポリエステル樹脂組成物を用い、実施例１と同様にしてダイレクトブロー成形品及び延伸ブロー成形品を得た。
Example 6
Except that the copolymerization amount of 1,4-cyclohexanedimethanol was changed to the value shown in Table 1, esterification reaction and melt polymerization reaction were carried out in the same manner as in Example 1 to obtain a copolymerized polyester prepolymer. It was. Then, using the obtained prepolymer, a solid state polymerization reaction was performed in the same manner as in Example 1 except that the drying conditions of the dryer were 120 ° C. for 18 hours, and the heating temperature by the preheater was 175 ° C. A composition was obtained.
Further, using the obtained polyester resin composition, a direct blow molded product and a stretch blow molded product were obtained in the same manner as in Example 1.
実施例７
実施例１と同様にしてエステル化反応、溶融重合反応を行い、共重合ポリエステルのプレポリマーを得た。そして得られたプレポリマーを用い、固相重合反応時間を４０時間とした以外は実施例１と同様にして固相重合反応を行い、ポリエステル樹脂組成物を得た。
さらに、得られたポリエステル樹脂組成物を用い、実施例１と同様にしてダイレクトブロー成形品及び延伸ブロー成形品を得た。
Example 7
An esterification reaction and a melt polymerization reaction were carried out in the same manner as in Example 1 to obtain a copolymerized polyester prepolymer. Then, using the obtained prepolymer, a solid phase polymerization reaction was performed in the same manner as in Example 1 except that the solid phase polymerization reaction time was 40 hours to obtain a polyester resin composition.
Further, using the obtained polyester resin composition, a direct blow molded product and a stretch blow molded product were obtained in the same manner as in Example 1.
実施例８
ヒンダードフェノール系抗酸化剤の含有量が表１の値となるように組成を変更した以外は、実施例１と同様にしてエステル化反応、溶融重合反応を行い、共重合ポリエステルのプレポリマーを得た。そして得られたプレポリマーを用い、固相重合反応時間を６０時間とした以外は実施例１と同様にして固相重合反応を行い、ポリエステル樹脂組成物を得た。
さらに、得られたポリエステル樹脂組成物を用い、実施例１と同様にしてダイレクトブロー成形品及び延伸ブロー成形品を得た。
Example 8
Except that the composition was changed so that the content of the hindered phenol antioxidant was the value shown in Table 1, the esterification reaction and the melt polymerization reaction were carried out in the same manner as in Example 1, and the prepolymer of the copolyester was obtained. Obtained. Then, using the obtained prepolymer, a solid phase polymerization reaction was performed in the same manner as in Example 1 except that the solid phase polymerization reaction time was changed to 60 hours to obtain a polyester resin composition.
Further, using the obtained polyester resin composition, a direct blow molded product and a stretch blow molded product were obtained in the same manner as in Example 1.
実施例１０
実施例１と同様にしてエステル化反応、溶融重合反応を行い、共重合ポリエステルのプレポリマーを得た。そして得られたプレポリマーを用い、固相重合反応時間を１５時間とした以外は実施例１と同様にして固相重合反応を行い、ポリエステル樹脂組成物を得た。
さらに、得られたポリエステル樹脂組成物を、実施例１と同様にしてダイレクトブロー成形及び延伸ブロー成形に供した。
Example 10
An esterification reaction and a melt polymerization reaction were carried out in the same manner as in Example 1 to obtain a copolymerized polyester prepolymer. Then, using the obtained prepolymer, a solid phase polymerization reaction was performed in the same manner as in Example 1 except that the solid phase polymerization reaction time was set to 15 hours to obtain a polyester resin composition.
Furthermore, the obtained polyester resin composition was subjected to direct blow molding and stretch blow molding in the same manner as in Example 1.
比較例２
１，４―シクロヘキサンジメタノールの共重合量が表１の値となるように組成を変更した以外は、実施例１と同様にして、共重合ポリエステルのプレポリマーを得た。得られたプレポリマーを実施例１と同様、結晶化装置に連続的に供給したが、固着したため結晶化を行うことができなかった。
そこでエステル化反応、溶融重合反応を行って得た共重合ポリエステルのプレポリマーに、固相重合を行わなかった以外は、実施例１と同様にしてポリエステル樹脂組成物を得た。
そして、得られたポリエステル樹脂組成物を、実施例１と同様にしてダイレクトブロー成形及び延伸ブロー成形に供した。
Comparative Example 2
A copolyester prepolymer was obtained in the same manner as in Example 1 except that the composition was changed so that the copolymerization amount of 1,4-cyclohexanedimethanol was the value shown in Table 1. The obtained prepolymer was continuously supplied to the crystallization apparatus in the same manner as in Example 1. However, crystallization could not be performed because of fixing.
Thus, a polyester resin composition was obtained in the same manner as in Example 1 except that the prepolymer of the copolyester obtained by the esterification reaction and the melt polymerization reaction was not subjected to solid phase polymerization.
The obtained polyester resin composition was subjected to direct blow molding and stretch blow molding in the same manner as in Example 1.
比較例３
実施例１で得られた共重合ポリエステルのプレポリマーに固相重合反応を行わなかった以外は、実施例１と同様にしてポリエステル樹脂組成物を得た。
そして、得られたポリエステル樹脂組成物を、実施例１と同様にしてダイレクトブロー成形及び延伸ブロー成形に供した。
Comparative Example 3
A polyester resin composition was obtained in the same manner as in Example 1 except that the prepolymer of the copolyester obtained in Example 1 was not subjected to a solid phase polymerization reaction.
The obtained polyester resin composition was subjected to direct blow molding and stretch blow molding in the same manner as in Example 1.
比較例４
実施例１と同様にしてエステル化反応、溶融重合反応を行い、得られた共重合ポリエステルのプレポリマーを得た。そして得られたプレポリマーを用い、固相重合反応時間を８０時間とした以外は実施例１と同様にして固相重合反応を行い、ポリエステル樹脂組成物を得た。
さらに、得られたポリエステル樹脂組成物を用い、ダイレクトブロー成形機、及び延伸ブロー成形における押出温度を２９０℃とした以外は、実施例１と同様にしてダイレクトブロー成形品及び延伸ブロー成形品を得た。
Comparative Example 4
An esterification reaction and a melt polymerization reaction were performed in the same manner as in Example 1 to obtain a prepolymer of the obtained copolymer polyester. Then, using the obtained prepolymer, a solid phase polymerization reaction was carried out in the same manner as in Example 1 except that the solid phase polymerization reaction time was 80 hours to obtain a polyester resin composition.
Further, using the obtained polyester resin composition, a direct blow molded product and a stretch blow molded product were obtained in the same manner as in Example 1 except that the extrusion temperature in the direct blow molding machine and stretch blow molding was 290 ° C. It was.
比較例７
溶融重合反応時間を８時間とした以外は、実施例１と同様にしてエステル化反応、溶融重合反応を行い、得られた共重合ポリエステルのプレポリマーをポリエステル樹脂組成物とした（固相重合反応を行わなかった）。
そして、得られたポリエステル樹脂組成物を用い、実施例１と同様にしてダイレクトブロー成形品及び延伸ブロー成形品を得た。
Comparative Example 7
Except that the melt polymerization reaction time was 8 hours, an esterification reaction and a melt polymerization reaction were carried out in the same manner as in Example 1, and the resulting prepolymer of the copolyester was used as a polyester resin composition (solid phase polymerization reaction). Did not do).
And using the obtained polyester resin composition, it carried out similarly to Example 1, and obtained the direct blow molded product and the stretch blow molded product.
実施例１〜１０、比較例１〜７で得られたポリエステル樹脂組成物及び成形品の特性値、評価結果を表１に示す。 Table 1 shows the characteristic values and evaluation results of the polyester resin compositions and molded articles obtained in Examples 1 to 10 and Comparative Examples 1 to 7.
表１から明らかなように、実施例１〜１０で得られたポリエステル樹脂組成物は、１，４−シクロヘキサンジメタノール成分、極限粘度、伸長粘度（ηe）とせん断粘度（η）の比（ηe／η）、カルボキシル末端基量が本発明で規定する範囲内のものであったため、熱安定性に優れており、結晶化による白化の問題やドローダウンが生じることなく、操業性よくダイレクトブロー成形及び延伸ブロー成形を行うことができた。そして、得られたブロー成形品（容器）は厚みムラがなく、透明性に優れたものであった。さらには、リサイクル性にも優れ、一旦成形工程を経て端材となったものを用いても、操業性よくブロー成形を行うことができ、かつ得られたブロー成形品（容器）は厚みムラがなく、透明性に優れたものであった。
また、実施例１０で得られたポリエステル樹脂組成物は、極限粘度が低かったため、ダイレクトブロー成形の際のドローダウンが大きくなり、ダイレクトブロー成形品を得ることができなかった。しかしながら、延伸ブロー成形は他の実施例と同様、操業性よく行うことができ、得られた成形品については厚みムラがなく、透明性に優れたものであった。また、リサイクル性にも優れていた。
As is apparent from Table 1, the polyester resin compositions obtained in Examples 1 to 10 were 1,4-cyclohexanedimethanol component, intrinsic viscosity, ratio of elongational viscosity (ηe) to shear viscosity (η) (ηe / Η), because the carboxyl end group amount is within the range specified in the present invention, it is excellent in thermal stability and direct blow molding with good operability without causing whitening problems and drawdown due to crystallization. And stretch blow molding could be performed. And the obtained blow molded product (container) had no thickness unevenness and was excellent in transparency. Furthermore, it is also excellent in recyclability, and even if it has been used as an end material after a molding process, blow molding can be performed with good operability, and the resulting blow molded product (container) has uneven thickness. It was excellent in transparency.
In addition, since the polyester resin composition obtained in Example 10 had a low intrinsic viscosity, the drawdown during direct blow molding was increased, and a direct blow molded product could not be obtained. However, stretch blow molding can be performed with good operability as in the other examples, and the obtained molded product has no thickness unevenness and is excellent in transparency. It was also excellent in recyclability.
一方、比較例１で得られたポリエステル樹脂組成物は１，４―シクロヘキサンジメタノールの共重合量が少なかったため、ダイレクトブロー成形及び延伸ブロー成形した際に、成形品が結晶化して白化し、透明性に劣るものとなった。また、ポリエステル樹脂の結晶化速度が速くなりすぎたため、ダイレクトブロー成形性も悪化し、厚みムラの生じた成形品が多くなった。
比較例２では、１，４―シクロヘキサンジメタノールの共重合量が多かったため、固相重合時に融着が起こり、固相重合反応を行うことができなかった。そのため得られたポリエステル樹脂組成物は極限粘度の低いものとなり、また、伸長粘度（ηe）とせん断粘度（η）の比が大きいものとなり、ダイレクトブロー成形を行うことができなかった。また、カルボキシル末端基量が本発明で規定する範囲外となったため、延伸ブロー成形においてはポリマーの熱分解が生じ、成形性、特にリサイクル性に劣るものであった。
On the other hand, since the polyester resin composition obtained in Comparative Example 1 had a small amount of 1,4-cyclohexanedimethanol copolymerization, when the direct blow molding and stretch blow molding were performed, the molded product was crystallized and whitened to become transparent. It became inferior. Moreover, since the crystallization speed of the polyester resin became too fast, the direct blow moldability was also deteriorated, and the number of molded products with uneven thickness increased.
In Comparative Example 2, since the copolymerization amount of 1,4-cyclohexanedimethanol was large, fusion occurred during the solid phase polymerization, and the solid phase polymerization reaction could not be performed. Therefore, the obtained polyester resin composition has a low intrinsic viscosity, and has a large ratio of elongational viscosity (ηe) to shear viscosity (η), and direct blow molding cannot be performed. In addition, since the carboxyl end group amount was outside the range defined in the present invention, the polymer was thermally decomposed in stretch blow molding, and the moldability, particularly the recyclability, was poor.
比較例３で得られたポリエステル樹脂組成物は、固相重合反応を行わなかったため、極限粘度の低いものとなり、ダイレクトブロー成形を行うことができなかった。また、カルボキシル末端基量が本発明で規定する範囲外となったため、ポリマーの熱分解が生じ、成形性、特にリサイクル性に劣るものであった。
比較例４で得られたポリエステル樹脂組成物は、極限粘度が高すぎたため、成形温度を上げて(ダイレクトブロー成形、延伸ブロー成形ともに２９０℃とした)成形を行った。このため、成形時にポリエステル樹脂の熱分解が生じたため、得られた成形品のヘーズが悪く、成形性も悪化し、厚みムラの生じた成形品が多くなった。また、端材を再生材として再び成形に供した際にも、樹脂の熱分解が生じたため、得られた成形品は厚みムラが生じ、リサイクル性も低かった。延伸ブロー成形については、極限粘度が高すぎたため、延伸ブロー成形品を得ることができなかった。
Since the polyester resin composition obtained in Comparative Example 3 did not undergo a solid phase polymerization reaction, it had a low intrinsic viscosity, and direct blow molding could not be performed. Moreover, since the carboxyl end group amount was outside the range defined in the present invention, the polymer was thermally decomposed, and the moldability, particularly the recyclability, was poor.
Since the polyester resin composition obtained in Comparative Example 4 had an intrinsic viscosity that was too high, the molding was performed at a higher molding temperature (both direct blow molding and stretch blow molding were performed at 290 ° C.). For this reason, since thermal decomposition of the polyester resin occurred during molding, the haze of the obtained molded product was poor, the moldability was also deteriorated, and the number of molded products with uneven thickness increased. In addition, when the milled material was used again as a recycled material, the resin was thermally decomposed, resulting in uneven thickness and low recyclability. About stretch blow molding, since the intrinsic viscosity was too high, a stretch blow molded product could not be obtained.
比較例５で得られたポリエステル樹脂組成物は、ヒンダードフェノール系抗酸化剤の含有量が少なかったため、伸長粘度（ηe）とせん断粘度（η）の比が４未満となった。このため、ダイレクトブロー成形時のパリソンのドローダウンが大きくなり、成形品は厚みムラの生じたものとなった。また、ヒンダードフェノール系抗酸化剤の含有量が少ないため、ポリエステル樹脂の熱安定性が悪く、ダイレクトブロー成形、延伸ブロー成形共にリサイクル性に劣るものとなった。
比較例６で得られたポリエステル樹脂組成物は、ヒンダードフェノール系抗酸化剤の含有量が多かったため、伸長粘度（ηe）とせん断粘度（η）の比が高すぎるものとなった。このため、成形温度を上げて(ダイレクトブロー成形、延伸ブロー成形ともに２９０℃とした)成形したため、成形時にポリエステル樹脂の熱分解が生じ、得られた成形品のヘーズが悪く、成形性も悪化し、厚みムラの生じた成形品が多くなった。また、端材を再生材として再びブロー成形に供した際にも、樹脂の熱分解が生じたため、得られた成形品は厚みムラが生じ、リサイクル性も劣るものであった。
Since the polyester resin composition obtained in Comparative Example 5 had a low content of hindered phenol antioxidant, the ratio of elongational viscosity (ηe) to shear viscosity (η) was less than 4. For this reason, the drawdown of the parison at the time of direct blow molding became large, and the molded product was uneven in thickness. Further, since the content of the hindered phenol-based antioxidant is small, the thermal stability of the polyester resin is poor, and both direct blow molding and stretch blow molding are inferior in recyclability.
Since the polyester resin composition obtained in Comparative Example 6 contained a large amount of hindered phenol antioxidant, the ratio of the extensional viscosity (ηe) to the shear viscosity (η) was too high. For this reason, since the molding temperature was raised (both direct blow molding and stretch blow molding were 290 ° C.), the polyester resin was thermally decomposed during molding, resulting in poor haze and poor moldability. The number of molded products with uneven thickness increased. Also, when the milled material was used again for blow molding as a recycled material, thermal decomposition of the resin occurred, resulting in uneven thickness and poor recyclability.
比較例７で得られたポリエステル樹脂組成物は、極限粘度の低いものとなり、ダイレクトブロー成形を行うことができなかった。また、カルボキシル末端基量が多すぎたため、延伸ブロー成形においては、ポリエステル樹脂組成物の熱安定性が悪く、成形時のパリソンのドローダウンが大きくなり、成形品は厚みムラの生じたものとなった。さらに、リサイクル性にも劣るものとなった。
The polyester resin composition obtained in Comparative Example 7 had a low intrinsic viscosity, and direct blow molding could not be performed. In addition, since the amount of carboxyl end groups is too large, in stretch blow molding, the thermal stability of the polyester resin composition is poor, the parison drawdown during molding becomes large, and the molded product has uneven thickness. It was. Furthermore, the recyclability was inferior.
Claims (2)
A blow molded article formed using the polyester resin composition according to claim 1.
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