CN107001602B - Polyester resin particle, its manufacturing method and molded product therefrom - Google Patents
Polyester resin particle, its manufacturing method and molded product therefrom Download PDFInfo
- Publication number
- CN107001602B CN107001602B CN201580071071.3A CN201580071071A CN107001602B CN 107001602 B CN107001602 B CN 107001602B CN 201580071071 A CN201580071071 A CN 201580071071A CN 107001602 B CN107001602 B CN 107001602B
- Authority
- CN
- China
- Prior art keywords
- polyester
- unit
- aforementioned
- polyester resin
- particle
- 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.)
- Active
Links
- 239000002245 particle Substances 0.000 title claims abstract description 128
- 239000004645 polyester resin Substances 0.000 title claims abstract description 88
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 214
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 139
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 129
- 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 claims abstract description 91
- 239000000654 additive Substances 0.000 claims abstract description 50
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000007790 solid phase Substances 0.000 claims abstract description 46
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 42
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004615 ingredient Substances 0.000 claims abstract description 11
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 9
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 8
- 229940106691 bisphenol a Drugs 0.000 claims description 44
- 238000001125 extrusion Methods 0.000 claims description 28
- 150000002009 diols Chemical group 0.000 claims description 25
- 238000000071 blow moulding Methods 0.000 claims description 20
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 10
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 7
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 193
- 239000000047 product Substances 0.000 description 72
- 150000001875 compounds Chemical class 0.000 description 42
- 238000000034 method Methods 0.000 description 36
- 238000002425 crystallisation Methods 0.000 description 33
- 230000008025 crystallization Effects 0.000 description 33
- 150000002148 esters Chemical group 0.000 description 28
- 229920001634 Copolyester Polymers 0.000 description 22
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 19
- 239000003086 colorant Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical group OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 14
- 238000000465 moulding Methods 0.000 description 14
- 230000032050 esterification Effects 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000004927 fusion Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 9
- -1 3,5- di-tert-butyl-hydroxy phenyl Chemical group 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 7
- 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 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- SBUXRMKDJWEXRL-ZWKOTPCHSA-N trans-body Chemical compound O=C([C@@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ZWKOTPCHSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229940011182 cobalt acetate Drugs 0.000 description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002530 phenolic antioxidant Substances 0.000 description 5
- 150000003077 polyols Chemical group 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- SBUXRMKDJWEXRL-ROUUACIJSA-N cis-body Chemical compound O=C([C@H]1N(C2=O)[C@H](C3=C(C4=CC=CC=C4N3)C1)CC)N2C1=CC=C(F)C=C1 SBUXRMKDJWEXRL-ROUUACIJSA-N 0.000 description 4
- 229940117927 ethylene oxide Drugs 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229940119177 germanium dioxide Drugs 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 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
- 230000002452 interceptive effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 239000012071 phase Substances 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
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 1
- WIXDSJRJFDWTNY-UHFFFAOYSA-N 1,3-ditert-butyl-5-methylbenzene Chemical class CC1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 WIXDSJRJFDWTNY-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- JATAKEDDMQNPOQ-UHFFFAOYSA-N 2,4,6-trimethoxybenzoic acid Chemical compound COC1=CC(OC)=C(C(O)=O)C(OC)=C1 JATAKEDDMQNPOQ-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical group OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 150000001991 dicarboxylic acids Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical group OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- OLLMEZGFCPWTGD-UHFFFAOYSA-N hexane;methanol Chemical compound OC.OC.CCCCCC OLLMEZGFCPWTGD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical group CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical group OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
Abstract
The present invention provides a kind of polyester resin particle, the polyester resin particle is by making it carry out polycondensation terephthalic acid (TPA), ethylene glycol, cyclohexanedimethanol or bisphenol A epoxy ethane additive product and polyester melting mixing, then carrying out polyester resin particle made of solid phase, aforementioned polyester is the carboxylate of the polyalcohol of ternary or more, the carboxylic acid has hindered phenol group, the content of the ingredient from aforementioned polyester in aforementioned polyester resin is 0.005~0.04 mass %, also, the inherent viscosity of aforementioned polyester is 0.9~1.5dl/g.The resistance to drawdown of such polyester resin particle is excellent, and the impact resistance of the molded product obtained using the polyester resin particle and tone are good.
Description
Technical field
The present invention relates to the polyester resin particle for the raw material for being suitable for extrusion and blow molding, its manufacturing method and by it
Obtained molded product.
Background technique
The spies such as the transparency, mechanical characteristic, gas barrier property, the every flavour property of the polyester resin such as pet resin
Property is excellent.In addition, for polyester resin, wholesomeness few to the worry of residual monomer, harmful additive when forming molded product
It is also excellent with safety.Therefore, for polyester resin, their characteristic is efficiently used, was used always in the past as replacement
Vinyl chloride resin resin, be widely used as in recent years for holding fruit juice, cold drink, seasoning, oil, cosmetics, washing
The hollow container of agent etc. uses.
As the forming method for manufacturing the hollow molded article formed by polyester resin, it is known that following extrusion-blown modling at
Type method: it is squeezed out by die hole through the resin of melting plasticising as cylindric parison, is in the soft state phase in the parison
Between, it is clamped with mold, is internally blown into the fluids such as air and is formed.This method is compared with injection-blow molding forming method, work
Sequence is simple, and the production and molding of mold do not need the technology of height, therefore, cost of equipment, mold manufacturing cost etc. just
Preferably, it is produced on a small quantity suitable for multi items.Moreover, with thin object, deep object, big object, the complicated shape with handle etc. can also be manufactured
Molded product the advantage that.
On the other hand, the usual melt viscosity of general polyester resin is low, thus to carry out extrusion and blow molding, then it squeezes out
Drawdown obviously occurs for parison afterwards, it is difficult to carry out figuration.Therefore, for typically for extrusion-blown modling bottle laminac,
Assign resistance to drawdown using method for adding micro crosslinking agent etc., even if can form, the molded product that obtains sometimes it is resistance to
Impact is also insufficient.In addition, for typically for polyester resin, when carrying out melt molding or whens when solid phase etc.,
If be heated for a long time, it is easy to happen oxidation, yellow coloring occurs, molecular weight and molecular weight, generates the heat deteriorations such as gel-like constituent.
In order to solve these problems, in the past, it proposes about the polyester resin for being suitable for extrusion and blow molding, thermoforming etc.
Various motions.As one of such conventional art, it is known that the technology of addition hindered phenolic antioxidant is (referring to patent document 1
~3).
In patent document 1, a kind of copolyester is described, the copolyester is with terephthalic acid units, ethylene glycol list
Member and 1,4-CHDM unit are principal component, and the content of hindered phenolic antioxidant is 0.2~1.0 mass %, Germanium
Meet defined condition with the content of antimony element (catalyst).It is described in patent document 1 by using with defined composition
Catalyst and hindered phenolic antioxidant, can inhibit decomposition reaction when polymerization, polymerize and quickly carry out, tone, the transparency are not
Deteriorate, the polyester of high polymerization degree can be obtained, and may also suppress thermal decomposition when molding, therefore, after also not causing molding
Tone deteriorate.A kind of polyester and resin composition is described in patent document 2, in the polyester and resin composition, in 100 weight
In part polyester resin, be combined with 0.05~1 parts by weight hindered phenolic antioxidant, the polyester resin contain dicarboxylic acid units and
Diol units, 1~60 mole of % in diol units are the diol units with cyclic acetal skeleton.Moreover, in patent document 2
It describes by adding aforementioned antioxidant, can inhibit the generation of yellow coloring, gel component.However, by patent document 1 and 2
The impact resistance that the polyester resin of middle record carries out molded product obtained from extrusion and blow molding is insufficient.
Describe a kind of manufacturing method of particle formed by polyester and resin composition in patent document 3, in the method,
By carrying out melt polymerization, to respectively obtain of the polyester (A) based on terephthalic acid units and ethylene glycol unit
The particle of grain and the polyester (B) based on terephthalic acid units, ethylene glycol unit and cyclohexanedimethanol unit, then,
By the particle of polyester (A), the particle of polyester (B) and hindered phenolic antioxidant melting mixing, solid phase is then carried out.So
And this method is since process number is more, therefore, it is difficult to which productivity manufactures particle well.In addition, the molding obtained using the particle
The transparency of product is sometimes insufficient.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2002-338674 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2007-326890 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2011-252087 bulletin.
Summary of the invention
Problems to be solved by the invention
The present invention is completed to solve the above problems, and it is an object of the present invention to provide can be obtained that resistance to drawdown is excellent, resistance to punching
Hitting property and the good molded product of tone, the manufacture suitable for heavy wall molded product, the raw material as extrusion and blow molding polyester
Resin particle and its manufacturing method.
Means for solving the problems
The above subject can be solved by providing following polyester resin particles, and the polyester resin particle is by will be to benzene
Dioctyl phthalate, ethylene glycol, cyclohexanedimethanol or bisphenol A epoxy ethane additive product and polyester melting mixing make its carry out polycondensation,
Then polyester resin particle made of solid phase is carried out, aforementioned polyester is the carboxylate of the polyalcohol of ternary or more, the carboxylic
Acid has hindered phenol group, and the dicarboxylic acid units in aforementioned polyester are mainly formed by terephthalic acid units, in aforementioned polyester
Diol units are mainly by ethylene glycol unit and cyclohexanedimethanol unit or the unit shape from bisphenol A epoxy ethane additive product
At relative to the total amount of the diol units, the content of ethylene glycol unit is 75~98 moles of %, cyclohexanedimethanol unit and is come
Content from the unit of bisphenol A epoxy ethane additive product is 2~25 moles of %, comes from aforementioned polyester in aforementioned polyester resin
Ingredient content be 0.005~0.04 mass %, also, the inherent viscosity of aforementioned polyester be 0.9~1.5dl/g.
Carrying out molded product made of extrusion and blow molding using aforementioned particles is the preferred embodiment of the present invention.
The above subject can also be solved by providing the manufacturing method of aforementioned polyester resin particle, in the method, be passed through
Terephthalic acid (TPA), ethylene glycol, cyclohexanedimethanol or bisphenol A epoxy ethane additive product and aforementioned polyester melting mixing are made
It after it carries out polycondensation, is cut and obtains intermediate particle, the intermediate particle is then made to carry out solid phase.
The effect of invention
Resistance to drawdown when the available not only extrusion and blow molding of polyester resin particle of the invention is excellent but also impact resistance
Property and the good molded product of tone.Manufacturing method through the invention can easily manufacture such polyester resin particle.
Detailed description of the invention
[Fig. 1] is the figure for indicating the method for solving of half hitch crystallization time.
Specific embodiment
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.
Polyester resin particle of the invention is by by terephthalic acid (TPA), ethylene glycol, cyclohexanedimethanol or bisphenol-A epoxy
Ethane additive product and polyester melting mixing are to make it carry out polycondensation, then carry out polyester resin made of solid phase
Grain, aforementioned polyester are the carboxylates of the polyalcohol of ternary or more, which has hindered phenol group, the dicarboxyl in aforementioned polyester
Acid unit is mainly formed by terephthalic acid units, and the diol units in aforementioned polyester are mainly by ethylene glycol unit and hexamethylene
Dimethanol unit or unit from bisphenol A epoxy ethane additive product are formed, relative to the total amount of the diol units, ethylene glycol list
The content of member is 75~98 moles of %, and the content of cyclohexanedimethanol unit and the unit from bisphenol A epoxy ethane additive product is
2~25 moles of %, the content of the ingredient from aforementioned polyester in aforementioned polyester resin are 0.005~0.04 mass %, also,
The inherent viscosity of aforementioned polyester is 0.9~1.5dl/g.In the present invention, the polyester resin particle is known as the first particle sometimes.
Polyester of the invention mainly by based on terephthalic acid units dicarboxylic acid units, with ethylene glycol unit and
Diol units based on cyclohexanedimethanol unit or unit from bisphenol A epoxy ethane additive product and from aforementioned
The unit of polyester is formed.
For the content of the terephthalic acid units in polyester of the invention, relative to the dicarboxylic acids in aforementioned polyester
The total amount of unit, usually 80 moles of % or more, preferably 90 moles of % or more, more preferably 95 moles of % or more, further preferably
Dicarboxylic acid units in aforementioned polyester are essentially only terephthalic acid units.
Polyester of the invention contains cyclohexanedimethanol unit or the unit from bisphenol A epoxy ethane additive product as second
Diol units other than diol units.Herein, aforementioned polyester contains cyclohexanedimethanol unit and adds from bisphenol-A epoxy ethane
At at least one party in the unit of object as the diol units other than ethylene glycol unit.By containing cyclohexanedimethanol list
Member or the unit from bisphenol A epoxy ethane additive product can reduce the molten of polyester as the diol units other than ethylene glycol unit
Therefore point can reduce the forming temperature in direct blow molding.From the viewpoint of impact resistance under from low temperature, aforementioned polyester
Cyclohexanedimethanol unit is preferably comprised as the diol units other than ethylene glycol unit.On the other hand, from relative to high concentration
Alcohol chemical resistance from the viewpoint of, aforementioned polyester preferably comprise the unit from bisphenol A epoxy ethane additive product work
For the diol units other than ethylene glycol unit.
As long as the cyclohexanedimethanol unit in aforementioned polyester is selected from 1,2- cyclohexanedimethanol unit, 1,3- hexamethylene
The unit of at least one kind of divalent in dimethanol unit and 1,4 cyclohexane dimethanol unit.Wherein, from the easiness obtained,
It in terms of being easy to make aforementioned polyester to become crystalline polyester, in solid phase is not susceptible to intergranular deadlocked aspect, obtains
From the aspect of the impact resistance of molded product further increases, cyclohexanedimethanol unit is preferably 1,4-CHDM list
Member.
There are cis- bodies and trans- body in cyclohexanedimethanol unit, but in the cyclohexanedimethanol unit in aforementioned polyester
Cis- body and the ratio of trans- body be not particularly limited.Wherein, in terms of being easy to make aforementioned polyester to become crystalline polyester,
Intergranular deadlocked aspect is not susceptible to when solid phase, from the aspect of the impact resistance of obtained molded product further increases,
In the cyclohexanedimethanol unit in aforementioned polyester, cis- body: the ratio of trans- body is preferably the range of 0:100~50:50.
The unit from bisphenol A epoxy ethane additive product in aforementioned polyester is the addition at least 1 on each hydroxyl of bisphenol-A
Obtained from a ethylene oxide.In general, the addition amount of ethylene oxide is 2.0~4.0 moles relative to 1 mole of bisphenol-A.
Relative to the total amount of the diol units in aforementioned polyester, cyclohexanedimethanol unit in polyester of the invention and come
Total content from the unit of bisphenol A epoxy ethane additive product is 2~25 moles of %.Aforementioned cyclohexanedimethanol unit and from double
When the total content of the unit of phenol A ethylene oxide adduct is less than 2 moles of %, under the impact resistance and the transparency of obtained molded product
Drop.Aforementioned content is preferably 4 moles of % or more, more preferably 8 moles of % or more.On the other hand, aforementioned content is more than 25 moles of %
When, it is difficult to improve solid phase polymerization temperature, productivity decline, moreover, the tone of obtained molded product deteriorates.Aforementioned content is preferably
18 moles of % or less.
Relative to the total amount of the diol units in aforementioned polyester, the content of the ethylene glycol unit in polyester of the invention is 75
~98 moles of %.When the content of aforementioned ethylene glycol unit is less than 75 moles of %, it is difficult to solid phase polymerization temperature is improved, productivity declines,
Moreover, the tone of obtained molded product deteriorates.The content of aforementioned ethylene glycol unit is preferably 82 moles of % or more.On the other hand, preceding
When stating the content of ethylene glycol unit and being more than 98 moles of %, the impact resistance and transparency decline of obtained molded product.Aforementioned ethylene glycol
The content of unit is preferably 96 moles of % hereinafter, more preferably 92 moles of % or less.
Ethylene glycol unit, hexamethylene two relative to the total amount of the diol units in aforementioned polyester, in polyester of the invention
The total content of methanol unit and the unit from bisphenol A epoxy ethane additive product is usually 80 moles of % or more, and preferably 90 rub
You are % or more, more preferably 95 moles of % or more.In general, polyester of the invention contains relative to the diol units in aforementioned polyester
It is the diethylene glycol (DEG) unit as the by-product in polycondensation reaction of 1~5 mole of % for total amount.
The unit from polyester in aforementioned polyester is by by polyester and terephthalic acid (TPA), ethylene glycol and hexamethylene
Alkane dimethanol or bisphenol A epoxy ethane additive product together melting mixing and so that it is carried out polycondensation and containing in aforementioned polyester
Unit, the polyester are the carboxylates of the polyalcohol of ternary or more, which has hindered phenol group.It is aforementioned in the polycondensation
The polyol unit of polyester, the carboxylic acid with hindered phenol group are contained in aforementioned polyester by ester exchange reaction.
Foregoing polyols unit contains the main chain, branch or end in aforementioned polyester.Moreover, a part of foregoing polyols unit at
For crosslinking points, play a role as crosslinking agent.On the other hand, a part of the carboxylic acid with hindered phenol group contains preceding
The end of polyester is stated, a part is contained together with the polyol unit with the state being bonded with foregoing polyols unit aforementioned poly-
In ester.As noted above it is believed that by making not only to improve of the invention gather containing the unit from aforementioned polyester in aforementioned polyester
The resistance to drawdown of ester resin particle, and the tone of the molded product made becomes good.Aforementioned polyester is preferably 3 yuan or more
The carboxylate of 5 yuan of polyalcohols below.As aforementioned polyester, [ 3- (3, the 5- di-t-butyl -4- hydroxyls of pentaerythrite four can be enumerated
Base phenyl) propionic ester ] and 1,3,5- tri- [2- [3- (3,5- di-tert-butyl-hydroxy phenyl) propiono oxygroup] ethyl] hexahydro-
1,3,5- triazine -2,4,6- triketone etc..
The content of the unit from aforementioned polyester in polyester resin of the invention is 0.005~0.04 mass %.This
Locate, the content of the ingredient from aforementioned polyester in polyester resin is the list from aforementioned polyester being directed into polyester chain
The total amount of member and the ingredient not being fed in polyester chain.It should be noted that thinking to carry out when melting mixing before addition
Polyester is stated to mainly contain in polyester chain.When the content of unit from aforementioned polyester is less than 0.005 mass %, polyester tree
The resistance to drawdown of rouge particle may decline；In polymerization or when molding, when heating to polyester, which will be easy to send out
Raw yellow coloring, the tone of obtained molded product may decline.On the other hand, the content of the unit from aforementioned polyester is super
When crossing 0.04 mass %, excessively being carried out because being crosslinked caused by the unit of polyester, melt viscosity may be increased excessively,
The impact resistance of obtained molded product may decline.The content of unit from aforementioned polyester be preferably 0.03 mass % with
Under, more preferably 0.02 mass % or less.
Relative to the total amount of the entire infrastructure unit in aforementioned polyester, terephthalic acid units in polyester of the invention,
Ethylene glycol unit, cyclohexanedimethanol unit, the unit from bisphenol A epoxy ethane additive product and the unit from polyester
Total content is preferably 80 moles of % or more, more preferably 90 moles of % or more, further preferably 95 moles of % or more.Before manufacture
When stating polyester of the content less than 80 moles of %, when carrying out solid phase, be easy to happen it is deadlocked caused by the softening because of resin,
High polymerization degreeization may become difficult.
As needed, aforementioned polyester can have terephthalic acid units, ethylene glycol unit, cyclohexanedimethanol unit, come
2 functionality compounds' units from the unit of bisphenol A epoxy ethane additive product and other than the unit from aforementioned polyester.For
For the content (being its total amount in the case that there is two or more unit) of other 2 functionality compounds units, relative to composition
The total amount of the entire infrastructure unit of aforementioned polyester, preferably 20 moles of % hereinafter, more preferably 10 moles of % hereinafter, further preferably
For 5 moles of % or less.As other the 2 functionality compounds units that can contain in aforementioned polyester, as long as dicarboxylic acid units,
Diol units, hydroxycarboxylic acid unit can be 2 functionality chemical combination of aliphatic 2 functionality compounds unit, ester ring type
Any unit in object unit, aromatic 2 functionality compounds unit.For example, can enumerate by M-phthalic acid, O-phthalic
The aromatic dicarboxylic acids such as acid, 2,6- naphthalenedicarboxylic acid, 4,4'- biphenyl dicarboxylic acid and their ester formative derivative；Hexamethylene two
The aliphatic dicarboxylic acids such as formic acid, adipic acid, decanedioic acid, dimeric dibasic acid or their ester formative derivative；Neopentyl glycol, 1,4- fourth
The aliphatic diols such as glycol, 1,5- pentanediol, 1,6-HD, diethylene glycol (DEG), dimer diol；The ethyleneoxide addition of bisphenol S
The structural unit of divalent derived from object etc..
For aforementioned polyester, in the range for not interfering effect of the invention, in addition to terephthalic acid units, ethylene glycol
Unit, cyclohexanedimethanol unit, the unit from bisphenol A epoxy ethane additive product, the unit from aforementioned polyester and on
Other than 2 functionality compounds' units except stating, can also have other multi-functional compounds' units.Other multi-functional chemical combination
Object unit is more officials as derived from the multi-functional compounds with 3 or more carboxyls, hydroxyl and/or their ester formative base
It can property compound unit.The total amount of entire infrastructure unit relative to aforementioned polyester, other multi-functional compounds' units contain
Amount (have two or more unit in the case where, be its total amount) be preferably 0.04 mass % hereinafter, more preferably 0.02 mass % with
Under, further preferably contain substantially no.As other multi-functional compounds' units, can enumerate by trimellitic acid, equal benzene four
Multi-functional compounds' unit etc. derived from acid, trimesic acid, trimethylolpropane and glycerol.
In addition, as needed, aforementioned polyester can also have by the unitary carboxylic other than the aforementioned carboxylic acid with hindered phenol group
Other mono-functionalizations derived from least one kind of monofunctional compounds in acid, monohydric alcohol and their ester formative derivative
Compound units.Other monofunctional compounds' units are functioned as end-caps unit, carry out point in aforementioned polyester
The sealing end of subchain terminal groups and/or branch terminals base prevents the generation of the excessive crosslinking and gel in aforementioned polyester.It is aforementioned poly-
When ester has other such monofunctional compounds' units, the total amount of the entire infrastructure unit relative to aforementioned polyester, other
The content (being its total amount in the case where having two or more unit) of monofunctional compounds' unit is preferably 1 mole of % hereinafter, more
Preferably 0.5 mole of % or less.When the content of other monofunctional compounds' units in aforementioned polyester is more than 1 mole of %, manufacture
Polymerization speed when aforementioned polyester is slack-off, and productivity is easily reduced.As other monofunctional compounds' units, can enumerate by selecting
From derived from the monofunctional compounds in benzoic acid, 2,4,6- trimethoxybenzoic acid, 2- naphthoic acid, stearic acid and stearyl alcohol
Unit etc..
Polyester resin particle of the invention is by by terephthalic acid (TPA), ethylene glycol, cyclohexanedimethanol or bisphenol-A epoxy
Ethane additive product and aforementioned polyester melting mixing are to carry out polycondensation, then carry out product made of solid phase.
By by terephthalic acid (TPA), ethylene glycol, cyclohexanedimethanol or bisphenol A epoxy ethane additive product and aforementioned polynary
Method of the ester melting mixing to carry out polycondensation is not particularly limited, the following methods can be given: using terephthalic acid (TPA) or its ester
Formative derivative, ethylene glycol, cyclohexanedimethanol or bisphenol A epoxy ethane additive product, aforementioned polyester and as needed
2 functionality compounds, multi-functional compounds or monofunctional compounds except above-mentioned as raw material, carry out esterification or
Ester exchange reaction, the polyester oligomer then made carry out melt polycondensation.Specifically, the following methods can be given: using pair
Phthalic acid, ethylene glycol and cyclohexanedimethanol or bisphenol A epoxy ethane additive product carry out esterification or ester exchange reaction
Afterwards, the method added aforementioned polyester into obtained polyester oligomer and it is made to carry out melt polycondensation；Using terephthalic acid (TPA),
Ethylene glycol, cyclohexanedimethanol or bisphenol A epoxy ethane additive product and aforementioned polyester carry out esterification or ester exchange reaction
Afterwards, the method that the polyester oligomer made carries out melt polycondensation；Deng.Aforementioned polyester can carry out esterification or transesterification
It adds, can also be added after carrying out these reactions before reaction.In addition, about the raw material other than aforementioned polyester, also suitably
Ground can add before carrying out esterification or ester exchange reaction, can also add after carrying out these reactions.
As described above, one of the features of the present invention is by by aforementioned polyester and terephthalic acid (TPA), ethylene glycol and hexamethylene
Alkane dimethanol or bisphenol A epoxy ethane additive product together melting mixing to make its carry out polycondensation.Polyester resin particle as a result,
Resistance to drawdown improves.In addition, the heat deterioration of polyester resin when can inhibit subsequent polymerization process, molding, it is good to can be obtained tone
Good molded product.
For above-mentioned esterification or ester exchange reaction, by above-mentioned raw material, polymerization catalyst and as needed
The additives such as anti-coloring agent be encased in reactor, in the case where absolute pressure is about 0.5MPa pressurization below or under normal pressure, in
160~280 DEG C of temperature carries out while evaporating the water generated or alcohol.
It is preferably poly- to what is obtained as needed for the melt polycondensation reaction after esterification or ester exchange reaction
The additives such as above-mentioned raw material, polycondensation catalyst and anti-coloring agent are added in ester oligomer, under 1kPa decompression below, in
260~290 DEG C of temperature carries out, until obtaining the polyester of desired viscosity.The reaction temperature of melt polycondensation reaction is less than 260
DEG C when, the polymerization activity of polymerization catalyst is low, may cannot get the polyester of targeted degree of polymerization.On the other hand, melt polymerization
Reaction temperature when being more than 290 DEG C, decomposition reaction is easy to carry out, as a result, may cannot get the polyester of targeted degree of polymerization.Melting contracting
It is poly- to react the intermittent polycondensation device that such as groove profile can be used, the continous way polycondensation dress including the revolving horizontal type reactor of 2 axis
It sets etc. and to carry out.
As polymerization catalyst used in above-mentioned polycondensation, the compound of Germanium, antimony element, titanium elements is preferably comprised.
As the compound containing antimony element, antimony trioxide, antimony chloride, antimony acetate etc. can be used, as the compound containing Germanium,
Germanium dioxide, germanium tetrachloride, tetraethoxy germanium etc. can be used, as the compound containing titanium elements, four isopropyl of metatitanic acid can be used
Ester, butyl titanate etc..Wherein, from polymerization catalyst, obtained polyester physical property and cost from the aspect of, preferably three oxygen
Change antimony and germanium dioxide.When using polycondensation catalyst, additive amount be preferably based on the quality of dicarboxylic acid component 0.002~
Amount in the range of 0.8 mass %.
When using anti-coloring agent in above-mentioned polycondensation, for example, can be used using phosphorous acid as the phosphate cpd of representative or its ester,
It can be used alone, and can also be used in combination of two or more.As phosphate cpd, for example, can enumerate phosphorous acid, phosphite ester, phosphoric acid,
Trimethyl phosphate, triphenyl phosphate etc..The usage amount of anti-coloring agent is preferred relative to the total amount of dicarboxylic acid component and diester ingredient
In the range of 80~1000ppm.In addition, colouring caused by order to inhibit the thermal decomposition because of polyester, cobalt acetate is preferably added
Equal cobalt compounds, usage amount is relative to the total amount of dicarboxylic acid component and diester ingredient more preferably in the range of 100~1000ppm
It is interior.
In above-mentioned polycondensation, in order to form terephthalic acid units, terephthalate can be used.The terephthalate
Alcohol part is not particularly limited, and can enumerate the monohydric alcohols such as methanol, ethyl alcohol；Ethylene glycol, the ring of structural unit as aforementioned polyester
Polyalcohols such as hexane dimethanol, bisphenol A epoxy ethane additive product etc..
In above-mentioned polycondensation, in order to form ethylene glycol unit, the monoesters or diester of ethylene glycol can be used.The carboxylic acid of the carboxylate
Part is not particularly limited, and can enumerate the monocarboxylic acids such as formic acid, acetic acid, propionic acid.
Consider from treatability etc., the inherent viscosity of the polyester as obtained from melt polycondensation preferably 0.4~
In the range of 0.9dl/g.If the inherent viscosity of aforementioned polyester as obtained from melt polycondensation will gather less than 0.4dl/g
When ester takes out from reactor, melt viscosity is too low, it is difficult to the shapes such as strands shape or sheet extrusion, and, it is difficult to equably
Cut into graininess.In addition, will the polyester as obtained from melt polycondensation carry out solid phase when, molecular weight will need
Will for a long time, productivity may reduce.The inherent viscosity of aforementioned polyester is more preferably 0.5dl/g or more, further preferably
0.6dl/g or more.On the other hand, if the inherent viscosity of aforementioned polyester is higher than 0.9dl/g, melt viscosity is excessively high, accordingly, it is possible to
It is difficult to take out polyester from reactor, alternatively, coloring may be easy to produce due to heat deterioration.The inherent viscosity of aforementioned polyester is more
Preferably 0.85dl/g is hereinafter, further preferably 0.8dl/g or less.
After the polyester obtained in the manner described above to be extruded into the shapes such as strands shape, sheet and carries out cooling, line is utilized
Expect that pelleter (strand cutter), slicer (sheet cutter) etc. by its severing, manufacture cylindric, elliptic cylindrical shape, circle
The intermediate particle of the shapes such as plate, dice shape.Cooling after extrusion above-mentioned is for example using using the water cooling of sink, use
Method, the air-cooling etc. of cooling drum carry out.
In order to further increase the degree of polymerization of the intermediate particle obtained as described above, which is subjected to solid polycondensation
It closes.It is preferred that a part crystallization of polyester is heated and made in advance before carrying out solid phase.It operates, can prevent in this way
Only particle when solid phase is deadlocked.The temperature of crystallization is preferably 100~180 DEG C.It, can be true as the method for crystallization
It is crystallized in empty tumbler, can also be heated and be crystallized in air circulating type heating device.It is followed in air
When being heated in ring type heating device, internal temperature is preferably 100~160 DEG C.Using air circulating type heating device into
In the case where row heating, compared with the case where using vacuum tumbler to be crystallized, heat transfer is good, therefore can be shortened crystallization
Time required for changing, device are also cheap.Time required for crystallizing is not particularly limited, and usually 30 minutes~24 hours
Left and right.It by particle drying is also preferred in the temperature less than 100 DEG C before crystallization.
The temperature of solid phase is preferably 170~250 DEG C.When the temperature of solid phase is less than 170 DEG C, solid phase when
Between it is elongated, productivity may decline.The temperature of solid phase is more preferably 175 DEG C or more, further preferably 180 DEG C or more.
On the other hand, when the temperature of solid phase is more than 250 DEG C, particle may be deadlocked.The temperature of solid phase is more preferably 240 DEG C
Hereinafter, further preferably 230 DEG C or less.The time of solid phase is usually 5~70 hours or so.In addition, in solid phase
When the catalyst used in melt polymerization can also coexist.
In addition, solid phase preferably carries out under reduced pressure or in the non-active gas such as nitrogen.In addition, in order not to which particle occurs
Between it is deadlocked, preferably on one side making to carry out solid polycondensation while particle is mobile using the method appropriate such as rotation method, gas fluidized bed method
It closes.Pressure when carrying out solid phase under reduced pressure is preferably 1kPa or less.
For aforementioned polyester resin, in the range for not interfering effect of the invention, other additives, example can be contained
Such as, the stabilizers such as the colorants such as dyestuff, pigment, ultraviolet absorbing agent, antistatic agent, fire retardant, flame retardant, lubrication can be enumerated
Agent, plasticizer, inorganic filler etc..The content of these additives in aforementioned polyester resin is preferably 10 mass % hereinafter, more excellent
Select 5 mass % or less.
The inherent viscosity for carrying out polyester obtained from solid phase needs in the range of 0.9~1.5dl/g.Inherent viscosity
When less than 0.9dl/g, not only resistance to drawdown deteriorates, but also the intensity of obtained molded product, impact resistance and transparency decline.It is special
Property viscosity is preferably 1.0dl/g or more, more preferably 1.05dl/g or more.On the other hand, when inherent viscosity is more than 1.5dl/g,
Melt viscosity becomes excessively high, and melt-moldability may decline, and productivity also reduces.Inherent viscosity be preferably 1.4dl/g with
Under, more preferably 1.3dl/g or less.
From the viewpoint of further increasing from the transparency of obtained molded product, polyester tree obtained from solid phase is carried out
Half hitch crystallization time under the crystallization peak temperature of the polyester contained in rouge particle is preferably 30 minutes or more.When the half hitch crystallization
Between more preferably 30 minutes or more." crystallization peak temperature " so-called in the present invention, refers to using differential thermometric analysis meter (DSC),
With amorphous polyester resin particle is warming up to the temperature (280 DEG C) of fusing point or more from room temperature (20 DEG C) by 10 DEG C/min and is measured
Along with the temperature of the exothermal peak of crystallization.In addition, " half hitch crystallization time under crystallization peak temperature " refers to, differential is being used
Polyester resin particle is warming up to the temperature (280 DEG C) of fusing point or more and makes its melting, then with -50 by thermometric analysis meter (DSC)
DEG C/min quenching to crystallization peak temperature, then under the crystallization peak temperature keep carry out isothermal crystalization when, from reach knot
Crystallization peak temperature starts, the time until the calorific value generated by isothermal crystalization becomes the 1/2 of total calorific value.
From prevent in solid phase tumbler internal particle occur it is deadlocked from the viewpoint of, aforementioned polyester resin particle
In the crystalline fusion enthalpy of polyester that contains be preferably 20J/g or more.As containing in carrying out particle obtained from solid phase
Therefore the polyester crystallized under long-time high temperature has crystalline fusion enthalpy big in this way.Crystalline fusion enthalpy is more preferably
23J/g or more.Crystalline fusion enthalpy is usually 60J/g or less.
By the way that obtained polyester resin particle is carried out melt molding, various molded products can be obtained.Forming method is without spy
It does not limit, the various melt molding methods such as extrusion molding, injection moulding can be used.In addition, can also be further to melt molding product
It carries out secondary operation and obtains molded product.Wherein, viscosity when polyester resin particle of the invention is due to melt molding is high, thus
Suitable for extrusion molding.It is preferred that the temperature of resin combination when by extrusion molding be set as (+10 DEG C of the fusing point of polyester resin)~
Temperature in the range of (+70 DEG C of the fusing point of polyester resin) is more preferably set as (+10 DEG C of the fusing point of polyester resin)~(poly-
+ 40 DEG C of the fusing point of ester resin) in the range of temperature.By relatively fusing point at a temperature of squeezed out, can inhibit vertical
It stretches.
Using polyester and resin composition of the invention, using such as extrusion moldings such as T die head method, inflation method manufacture sheet material,
When film, do not occur drawdown, reduced amplitude, film wave, non-fusant, can with high production rate manufacture high-quality sheet material or film.Moreover,
In the case where carrying out the secondary operation such as thermoforming using the sheet material or film obtained as described above, it is being molded into depth support pulling shaping
When product, large-scale molded product, drawdown is small, and the degree of crystallization is good, in the work for applying the external force such as vacuum attraction or compressed air
In sequence, it is not susceptible to uneven thickness, albefaction, target molded product can be obtained with good plastic property.
Moreover, being particularly suitable for using polyester resin particle of the invention being extrusion and blow molding in extrusion molding.It squeezes
The method of blow molding is not particularly limited out, can be carried out similarly with previously known extrusion and blow molding method.For example, can
It is carried out using following methods: polyester resin particle melting extrusion of the invention being formed to cylindric parison, at the parison
It during soft state, is clamped with blow molding with mold, is blown into the gases such as air, the rule for the shape for being expanded into parison along mold cavity
Fixed hollow shape.In the case where having used polyester resin particle of the invention, the drawdown of the parison of extrusion is good, can give birth to
Yield manufactures hollow molded article well.
The transparency of the molded product obtained as described above is excellent, and appearance, tone are good, mechanical strength especially impact resistance
Property it is high.Moreover, each characteristic such as gas barrier property, every flavour property, moisture-proof, resistance to chemical reagents is also excellent, therefore, it can be used for various uses.Separately
Outside, it can also be formed with the molded product with the stepped construction of other thermoplastic resins etc..
Polyester resin particle with following characteristics is also it is preferable that the dicarboxylic acid units in aforementioned polyester are mainly by benzene
Dioctyl phthalate unit is formed, and the diol units in aforementioned polyester mainly by ethylene glycol unit and cyclohexanedimethanol unit or come from
The unit of bisphenol A epoxy ethane additive product is formed, and relative to the total amount of the diol units, the content of ethylene glycol unit is 75~98
The content of mole %, cyclohexanedimethanol unit and the unit from bisphenol A epoxy ethane additive product is 2~25 moles of %, aforementioned
Polyester resin contains 0.005~0.04 ingredient of the mass % from polyester, which is the carboxylic acid of the polyalcohol of ternary or more
Ester, the carboxylic acid have a hindered phenol group, and the inherent viscosity of aforementioned polyester is 0.9~1.5dl/g, crystalline fusion enthalpy be 20J/g with
On, and half hitch crystallization time is 30 minutes or more.Had using the molded product that the polyester resin particle obtains especially excellent
The transparency.
Aforementioned polyester mainly by based on terephthalic acid units dicarboxylic acid units, with ethylene glycol unit, hexamethylene
Diol units based on dimethanol unit or unit from bisphenol A epoxy ethane additive product and the unit from polyester
It is formed.Dicarboxylic acid units, diol units and unit from polyester it is respective constitute it is same as the first particle.
The content of the unit from aforementioned polyester in aforementioned polyester resin is 0.005~0.04 mass %.From aforementioned
The content of the unit of polyester is preferably 0.03 mass % hereinafter, more preferably 0.02 mass % or less.
Terephthalic acid units, second two relative to the total amount of the entire infrastructure unit in aforementioned polyester, in aforementioned polyester
Alcohol unit, cyclohexanedimethanol unit, the unit from bisphenol A epoxy ethane additive product and the unit from aforementioned polyester
Total content is preferably 80 moles of % or more, more preferably 90 moles of % or more, further preferably 95 moles of % or more.
As needed, aforementioned polyester can also have terephthalic acid units, ethylene glycol unit, cyclohexanedimethanol unit,
2 functionality compounds' units other than unit from bisphenol A epoxy ethane additive product and the unit from polyester.Relative to
The total amount of the entire infrastructure unit of aforementioned polyester is constituted, the content of other 2 functionality compounds units (has two or more unit
In the case where, be its total amount) be preferably 20 moles of % hereinafter, more preferably 10 moles of % hereinafter, further preferably 5 moles of % with
Under.As other the 2 functionality compounds units that can contain in aforementioned polyester, can enumerate as can be poly- in the first particle
Other 2 functionality compounds units for containing in ester and those of be illustrated above.
For aforementioned polyester, in the range for not interfering effect of the invention, in addition to terephthalic acid units, ethylene glycol
Unit, cyclohexanedimethanol unit, the unit from bisphenol A epoxy ethane additive product, the unit from polyester and it is above-mentioned it
Other than 2 outer functionality compounds' units, can also have other multi-functional compounds' units.Whole relative to aforementioned polyester
The total amount of structural unit, the content (being its total amount in the case that there is two or more unit) of other multi-functional compounds' units
Preferably 0.04 mass % is hereinafter, more preferably 0.02 mass % is hereinafter, further preferably contain substantially no.As other more officials
Can property compound unit, can enumerate as other multi-functional compounds' units that can contain in the polyester in the first particle and
Those of be illustrated above.
As needed, aforementioned polyester can also have by other than the aforementioned carboxylic acid with hindered phenol group monocarboxylic acid, one
Member it is pure and mild they ester formative derivative at least one kind of monofunctional compounds derived from other monofunctional compounds it is single
Member.When aforementioned polyester has other such monofunctional compounds' units, entire infrastructure unit relative to aforementioned polyester
Total amount, the content (have two or more unit in the case where, be its total amount) of other monofunctional compounds' units are preferably 1 to rub
That % is hereinafter, more preferably 0.5 mole of % or less.As other monofunctional compounds' units, can enumerate as can be at first
Other monofunctional compounds' units for containing in polyester in grain and those of be illustrated above.
Half hitch crystallization time under the crystallization peak temperature of the polyester contained in aforementioned polyester resin particle needs to be 30 points
It is more than clock.When half hitch crystallization time was less than 30 minutes, the transparency decline of obtained molded product.More preferable half hitch crystallization time is
40 minutes or more.The definition of the half hitch crystallization time and preferred scope are identical as the first particle.
The crystalline fusion enthalpy of the polyester contained in aforementioned polyester resin particle needs for 20J/g or more.Crystalline fusion enthalpy is excellent
It is selected as 23J/g or more.On the other hand, crystalline fusion enthalpy is usually 60J/g or less.
The inherent viscosity of aforementioned polyester needs in the range of 0.9~1.5dl/g.The inherent viscosity of aforementioned polyester is preferably
1.0dl/g or more, more preferably 1.05dl/g or more.On the other hand, the inherent viscosity of aforementioned polyester be preferably 1.4dl/g with
Under, more preferably 1.3dl/g or less.
Aforementioned polyester resin can not interfere the range of effect of the invention to contain other additives, for example, dye can be enumerated
The stabilizers such as the colorants such as material, pigment, ultraviolet absorbing agent, antistatic agent, fire retardant, flame retardant, lubricant, plasticizer,
Inorganic filler etc..The content of these additives in aforementioned polyester resin is preferably 10 mass % hereinafter, more preferably 5 mass %
Below.
The manufacturing method of aforementioned polyester resin particle is not particularly limited, preferably as manufacture the first particle method and
Method described above, that is, by by terephthalic acid (TPA), ethylene glycol, cyclohexanedimethanol or bisphenol-A epoxy ethane addition
Then object and aforementioned polyester melting mixing are cut to make it carry out polycondensation and obtain intermediate particle, then made in this
Between particle carry out solid phase method.
In the case where using anti-coloring agent in above-mentioned polycondensation, for example, can be used using phosphorous acid as the phosphoric acid chemical combination of representative
Object or its ester, can be used alone, and can also be used in combination of two or more.As phosphate cpd, for example, phosphorous acid, phosphorous acid can be enumerated
Ester, phosphoric acid, trimethyl phosphate, triphenyl phosphate etc..The usage amount of anti-coloring agent is relative to dicarboxylic acid component and diester ingredient
Total amount is preferably in the range of 80~1000ppm.In addition, being coloured caused by order to inhibit the thermal decomposition because of polyester, preferably add
Add the cobalt compounds such as cobalt acetate, usage amount is relative to the total amount of dicarboxylic acid component and diester ingredient preferably in 100~1000ppm
In the range of.
Embodiment
Hereinafter, illustrating the present invention in further detail by embodiment, but the present invention is not by any limit of these embodiments
System.
(1) inherent viscosity
It is viscous in the characteristic of 30 DEG C of temperature measuring polyester using the equal mass mixings object of phenol and tetrachloroethanes as solvent
Degree.
(2) glass transition temperature (Tg), crystalline fusion enthalpy (Δ Hm) and half hitch crystallization time
Using differential scanning calorimetry (DSC) (TA イ Application ス Star Le メ Application ト TA Q2000 type), with 10 DEG C/min of heating
The glass transition temperature (Tg) and crystalline fusion enthalpy (Δ Hm) of velocity determination polyester (particle after solid phase).It needs to illustrate
, for glass transition temperature (Tg), with 10 DEG C/min of heating rate by polyester (particle after solid phase)
280 DEG C are warming up to from room temperature (20 DEG C), then amorphous particle is obtained, then again with 10 to 20 DEG C with -50 DEG C/min of quenchings
DEG C/min heating rate heat up, calculated using data at this time.
Using differential scanning calorimetry (DSC) (TA イ Application ス Star Le メ Application ト TA Q2000 type), with 10 DEG C/min of heating
Polyester (particle after solid phase) is warming up to 280 DEG C from room temperature (20 DEG C) by speed, then with -50 DEG C/min of quenchings to 20
DEG C, amorphous particle is obtained, is then warming up to the temperature (280 DEG C) of fusing point or more with 10 DEG C/min of heating rate again.Describe
Point of the heat at this time relative to temperature, obtains curve, and the temperature (crystallization of the exothermal peak of accompanying crystallization is found out by curve obtained
Change peak temperature).Then, the polyester melted at 280 DEG C is quenched to aforementioned peak temperature with -50 DEG C/min of cooling rate, then
It is kept under aforementioned crystalline peak temperature, carries out isothermal crystalization.Describe point of the accumulation heat relative to the time at this time, obtains
Since curve become total reaching crystallization peak temperature, to the calorific value generated by isothermal crystalization by curve obtained measurement
Thus time until the 1/2 of calorific value finds out half hitch crystallization time (second).Asking for half hitch crystallization time is illustrated that in Fig. 1
The figure of solution method.
(3) color of resin (b value)
According to ASTM-D2244(color scale system2), use Nippon Denshoku Industries Co., Ltd.'s colour examining color
Difference meter " ZE-2000 ", measures the color of resin (b value) of polyester resin particle.
(4) resin pressure
It is 290 in barrel maximum temperature using extrusion and blow molding device (Co., Ltd. タ Ha ラ system " MSE-40E type ")
DEG C, die head temperature be 250 DEG C, under conditions of molding cycle is 15 seconds, screw speed 22rpm, mold temperature are 20 DEG C, squeeze out
The transparent bottle container (27.5g ± 0.5g) that blow molding is 220mL at volume.The resin that die head is born when measurement bottle molding
Pressure.
(5) impact resistance
In the polyester in empty container be packed into water 220ml, covered with screw lid, be repeated fallen to from the height of 1.5m it is mixed
The operation in solidifying soil face, until the hollow container ruptures.Number evaluation impact resistance is fallen when rupturing according to hollow container.
Embodiment 1
[ melt polymerization ]
Production by 100.0 mass parts of terephthalic acid (TPA), 38.1 mass parts of ethylene glycol and hexamethylene-Isosorbide-5-Nitrae-dimethanol CHDM,
The mixing ratio (cis- body/trans- body) of cis- body and trans- body is 30/70 ] slurry that 13.0 mass parts are formed, is added thereto
0.043 mass parts of 0.012 mass parts of germanium dioxide, 0.012 mass parts of phosphorous acid and cobalt acetate.(absolute pressure under elevated pressure
The slurry 0.25MPa) is heated to 250 DEG C of temperature, carries out esterification, manufactures oligomer.Then, the oligomer that will be obtained
Polycondensation slot is moved to, relative to 100 mass parts of oligomer, adds [ 3-(3, the 5- bis- of pentaerythrite four as polyester thereto
Tert-butyl-hydroxy phenyl) propionic ester ] 0.024 mass parts and the bis- (2,6- di-t-butyl -4- first of 3,9- as anti-coloring agent
Phenoxyl) four oxa- -3,9- of -2,4,8,10- two phospha spiral shell [ 5,5 ] hendecane, 0.048 mass parts.Under the decompression of 1hPa,
In 280 DEG C of temperature, make oligomer melt polycondensation above-mentioned, formation characteristic viscosity is the polyester resin of 0.70dl/g.It will obtain
Polyester resin be extruded into strands shape from nozzle and be water-cooled, be then cut into that cylindric (diameter is about 2.5mm, and length is about
For 2.5mm), the intermediate particle of polyester resin is obtained.
[ crystallization of intermediate particle ]
The intermediate particle of polyester resin obtained from operating as described above is put into rotary type vacuum solid polycondensation and is attached together
It is 24 hours dry in 90 DEG C with 1hPa in setting, next carry out crystallizing for 10 hours in 160 DEG C.
[ solid phase ]
After above-mentioned crystallization, obtained in 200 DEG C of progress, 38 hours solid phases containing copolyester with 1hPa
Polyester resin particle (solid phase particle).Utilize the inherent viscosity of method above-mentioned measurement copolyester, result 1.15dl/
g.In addition, the b value of the solid phase particle measured using method above-mentioned, result is -1.10.Utilize 1H-NMR spectrum (dress
Set: Japan Electronics society system " JNM-GX-500 type ", solvent: deuterated trifluoroacetic acid) confirm the monomer component for constituting the copolyester
Ratio, result is terephthalic acid units: ethylene glycol unit: 1,4-CHDM unit: diethylene glycol (DEG)=100.0:
82.8:14.2:3.0(molar ratio), the content of the unit from polyester is 0.025 mass %.Method above-mentioned will be utilized, made
Tg, Δ Hm and the half hitch crystallization time of copolyester obtained from being measured with differential scanning calorimetry (DSC) to polyester resin particle
It is shown in table 1.
[ molding of extrusion-blown modling bottle ]
Using polyester resin particle obtained from operating as described above, the method system recorded in " (4) resin pressure " is utilized
Make cylindrical bottles.Resin pressure at this time is 21.2MPa.Observe by the naked eye to the oral area of obtained cylindrical bottles the transparency into
Row evaluation.In addition, being evaluated using the method recorded in " (5) impact resistance " the cylindrical bottles.Their result is shown
In table 1.
Embodiment 2
Additive amount relative to the polyester of 100 mass parts of oligomer is changed to 0.009 mass parts, by anti-coloring agent
Additive amount is changed to 0.019 mass parts, in addition to this, operates similarly with example 1, and manufactures polyester resin particle, uses this
Particle makes cylindrical bottles, and evaluates them.It the results are shown in table 1.Constitute the obtained monomer of copolyester at
The ratio divided is terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol unit: diethylene glycol (DEG)=100.0:82.6:
14.5:2.9(molar ratio), the content of the unit from polyester is 0.010 mass %.
Embodiment 3
Anti-coloring agent is not added into oligomer, in addition to this, is operated similarly with example 1, polyester resin is manufactured
Grain makes cylindrical bottles using the particle, and evaluates them.It the results are shown in table 1.Constitute obtained copolyester
Monomer component ratio be terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol unit: diethylene glycol (DEG)=
100.0:80.9:16.0:3.1(molar ratio), the content of the unit from polyester is 0.025 mass %.
Embodiment 4
Additive amount relative to the polyester of 100 mass parts of oligomer is changed to 0.005 mass parts, also, not to low
Anti-coloring agent is added in polymers, in addition to this, is operated similarly with example 1, and is manufactured polyester resin particle, is used the particle system
Make cylindrical bottles, and they are evaluated.It the results are shown in table 1.Constitute the ratio of the monomer component of obtained copolyester
Rate is terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol unit: diethylene glycol (DEG)=100.0:83.2:14.0:2.8
(molar ratio), the content of the unit from polyester are 0.005 mass %.
Embodiment 5
Using by 18.3 matter of 100.0 mass parts of terephthalic acid (TPA), 35.5 mass parts of ethylene glycol and hexamethylene -1,4- dimethanol
Measure part formed slurry, the additive amount relative to the polyester of 100 mass parts of oligomer is changed to 0.009 mass parts, not to
Anti-coloring agent is added in oligomer, in addition to this, is operated similarly with example 1, and is manufactured polyester resin particle, is used the particle
Cylindrical bottles are made, and they are evaluated.It the results are shown in table 1.Constitute the monomer component of obtained copolyester
Ratio is terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol unit: diethylene glycol (DEG)=100.0:77.1:20.0:
2.9(molar ratio), the content of the unit from polyester is 0.010 mass %.
Embodiment 6
It has used by 100.0 mass parts of terephthalic acid (TPA), 42.3 mass parts of ethylene glycol and hexamethylene -1,4- dimethanol 4.6
In addition to this slurry that mass parts are formed operates similarly to Example 5, manufacture polyester resin particle, made using the particle
Cylindrical bottles, and they are evaluated.It the results are shown in table 1.Constitute the ratio of the monomer component of obtained copolyester
For terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol unit: diethylene glycol (DEG)=100.0:92.0:5.0:3.0(rubs
That ratio), the content of the unit from polyester is 0.010 mass %.
Embodiment 7
It has used by 100.0 mass parts of terephthalic acid (TPA), 38.1 mass parts of ethylene glycol and hexamethylene -1,4- dimethanol 13.0
The slurry that mass parts are formed, be changed to 100 hours, in addition to this, is operated similarly to Example 5 the time of solid phase,
Polyester resin particle is manufactured, makes cylindrical bottles using the particle, and evaluate them.It the results are shown in table 1.It constitutes
The ratio of the monomer component of obtained copolyester is terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol list
Member: diethylene glycol (DEG)=100.0:83.1:14.0:2.9(molar ratio), the content of the unit from polyester is 0.010 mass %.
Embodiment 8
It has used by 100.0 mass parts of terephthalic acid (TPA), 38.1 mass parts of ethylene glycol and hexamethylene -1,4- dimethanol 13.0
The slurry that mass parts are formed, be changed to 18 hours, in addition to this, is operated similarly to Example 5 the time of solid phase, is made
Polyester resin particle is made, makes cylindrical bottles using the particle, and evaluate them.It the results are shown in table 1.It is configured
The ratio of the monomer component of the copolyester arrived is terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol unit:
Diethylene glycol (DEG)=100.0:83.1:14.0:2.9(molar ratio), the content of the unit from polyester is 0.010 mass %.
Embodiment 9
It has used by 100.0 mass parts of terephthalic acid (TPA), 42.6 mass parts of ethylene glycol and bisphenol-A epoxy ethane 2mol addition
In addition to this slurry that 11.4 mass parts of object are formed operates similarly with example 1, manufacture polyester resin particle, use this
Grain production cylindrical bottles, and they are evaluated.It the results are shown in table 1.Constitute the monomer component of obtained copolyester
Ratio be terephthalic acid units: ethylene glycol unit: bisphenol-A epoxy ethane 2mol addition product unit: diethylene glycol (DEG)=100.0:
92.1:5.0:2.9(molar ratio), the content of the unit from polyester is 0.010 mass %.
Embodiment 10
It has used by 100.0 mass parts of terephthalic acid (TPA), 43.5 mass parts of ethylene glycol and bisphenol-A epoxy ethane 2mol addition
In addition to this slurry that 6.85 mass parts of object are formed operates similarly with example 1, manufacture polyester resin particle, use this
Grain production cylindrical bottles, and they are evaluated.It the results are shown in table 1.Constitute the monomer component of obtained copolyester
Ratio be terephthalic acid units: ethylene glycol unit: bisphenol-A epoxy ethane 2mol addition product unit: diethylene glycol (DEG)=100.0:
94.1:3.0:2.9(molar ratio), the content of the unit from polyester is 0.010 mass %.
Comparative example 1
It operates similarly with example 1, obtains intermediate particle.The glass transition temperature of obtained intermediate particle and
The measurement of color of resin.In addition, carrying out extrusion molding using method similarly to Example 1 to aforementioned intermediate particle and being blow molded into
Type.These results are shown in table 1.The ratio for constituting the monomer component of aforementioned intermediate particle is terephthalic acid units: ethylene glycol
Unit: 1,4-CHDM unit: diethylene glycol (DEG)=100.0:82.9:14.2:2.9(molar ratio), the unit from polyester
Content be 0.025 mass %.It should be noted that carrying out extrusion molding blow molding to aforementioned intermediate particle, as a result, parison
Drawdown, thus container is not obtained.
Comparative example 2
Additive amount relative to the polyester of 100 mass parts of oligomer is changed to 0.048 mass parts, also, not to low
Anti-coloring agent is added in polymers, in addition to this, is operated similarly with example 1, and is manufactured polyester resin particle, is used the particle system
Make cylindrical bottles, and they are evaluated.It the results are shown in table 1.Constitute the ratio of the monomer component of obtained copolyester
Rate is terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol unit: diethylene glycol (DEG)=100.0:82.8:14.2:
3.0(molar ratio), the content of the unit from polyester is 0.050 mass %.
Comparative example 3
Polyester is added not into oligomer and in addition to this anti-coloring agent operates similarly with example 1, and manufacture is poly-
Ester resin particle makes cylindrical bottles using the particle, and evaluates them.It the results are shown in table 1.What composition obtained
The ratio of the monomer component of copolyester is terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol: diethylene glycol (DEG)=
100.0:82.2:15.0:2.8(molar ratio).It should be noted that being squeezed out to polyester resin particle (solid phase particle)
Blow molding is formed, as a result parison drawdown, thus does not obtain container.
Comparative example 4
It has used by 92.0 mass parts of terephthalic acid (TPA), 8.0 mass parts of M-phthalic acid (IPA) and 44.4 mass of ethylene glycol
The slurry that part is formed, also, the additive amount relative to the polyester of 100 mass parts of oligomer is changed to 0.009 mass parts, it removes
Except this, operate similarly with example 1, manufacture polyester resin particle, using the particle make cylindrical bottles, and to they into
Row evaluation.It the results are shown in table 1.The ratio for constituting the monomer component of obtained copolyester is terephthalic acid units:
Naphthalate units: ethylene glycol unit: diethylene glycol (DEG)=92.0:8.0:96.9:3.1(molar ratio), the unit from polyester contains
Amount is 0.010 mass %.
Comparative example 5
It has used by 8.32 matter of 100.0 mass parts of terephthalic acid (TPA), 38.1 mass parts of ethylene glycol and 1,4- butanediol (BD)
The slurry that part is formed is measured, also, the additive amount relative to the polyester of 100 mass parts of oligomer is changed to 0.009 mass parts,
In addition to this, it operates similarly with example 1, manufactures polyester resin particle, make cylindrical bottles using the particle, and to them
It is evaluated.It the results are shown in table 1.The ratio for constituting the monomer component of obtained copolyester is terephthalic acid units:
Ethylene glycol unit: 1,4-butanediol:: diethylene glycol (DEG)=100.0:83.0:14.0:3.0(molar ratio), the unit from polyester
Content is 0.010 mass %.
Comparative example 6
It is not added with polyester, in addition to this, is operated similarly with example 1, polyester resin particle is manufactured, uses the particle
Cylindrical bottles are made, and they are evaluated.It the results are shown in table 1.Constitute the monomer component of obtained copolyester
Ratio is terephthalic acid units: ethylene glycol unit: 1,4 cyclohexane dimethanol: diethylene glycol (DEG)=100.0:80.0:17.0:3.0
(molar ratio).It should be noted that carrying out extrusion molding blow molding to polyester resin particle (solid phase particle), as a result,
Parison drawdown, thus container is not obtained.
Comparative example 7
The slurry formed by 100.0 mass parts of terephthalic acid (TPA) and 44.8 mass parts of ethylene glycol is made, adds two thereto
0.010 mass parts of 0.010 mass parts of germanium oxide, 0.010 mass parts of phosphorous acid and cobalt acetate.(absolute pressure under elevated pressure
2.5kg/cm2) slurry is heated to 250 DEG C of temperature, esterification is carried out, until esterification yield becomes 95%, is manufactured oligomeric
Object.Then, obtained oligomer is moved into 5m3Capacity polycondensation slot in, under the decompression of 0.1Torr, in 270 DEG C of temperature
Degree, makes oligomer melt polycondensation above-mentioned, and composite character viscosity is the polyester of 0.70dl/g.Obtained polyester is squeezed out from nozzle
It at strands shape and is water-cooled, is then cut into cylindric (diameter is about 2.5mm, and length is about 2.5mm), obtains polyester (A)
Particle.
It makes (cis- by 100.0 mass parts of terephthalic acid (TPA), 17.8 mass parts of ethylene glycol and 1,4 cyclohexane dimethanol
Body: the mixing ratio 30:70 of trans- body) 62.5 mass parts formed slurry, thereto add 0.015 mass parts of germanium dioxide, Asia
0.010 mass parts of 0.010 mass parts of phosphoric acid and cobalt acetate.(absolute pressure 2.5kg/cm under elevated pressure2) be heated to the slurry
250 DEG C of temperature carries out esterification, until esterification yield becomes 95%, manufactures oligomer.Then, obtained oligomer is moved to
5m3Capacity polycondensation slot in, under the decompression of 0.1Torr, in 270 DEG C of temperature, make oligomer melt polycondensation above-mentioned, it is raw
The polyester for being 0.70dl/g at inherent viscosity.Obtained polyester is extruded into strands shape from nozzle and is water-cooled, is then cut
It is cut into cylindric (diameter is about 2.5mm, and length is about 2.5mm), obtains the particle of polyester (B).
Cooperate the particle of above-mentioned polyester (A) and polyester (B), in turn, phase in such a way that mass ratio (A/B) becomes 70/30
100 mass parts are added up to for polyester (A) and polyester (B), add [ the tertiary fourth of 3-(3,5- bis- of pentaerythrite four as polyester
Base -4- hydroxy phenyl) propionic ester ] 0.024 mass parts and the bis- (2,6- di-t-butyl -4- methylbenzenes of 3,9- as anti-coloring agent
Oxygroup) -2,4,8,10- tetra- oxa- -3,9- bis- phospha spiral shell [ 5,5 ] hendecane, 0.048 mass parts are simultaneously pre-mixed, and are then supplied
To biaxial extruder (Toshiba Machinery Co., Ltd.'s system " TEM-48SS ").The barrel temperature of extruder is set as 330 DEG C, by mould
Head temperature be set as 320 DEG C, purging vacuum pressure be 700mmHg(absolute pressure 60mmHg), the item that extrusion output is 150kg/hr
Melting mixing, extrusion line are carried out under part.It is exported in extruder die head, directly measures molten resin with thermometer, as a result, resin
Temperature is 332 DEG C.The strands of extrusion are water-cooled immediately, are next cut into that cylindric (diameter is about 2.5mm, and length is about
For 2.5mm), the intermediate particle of polyester and resin composition is obtained.
The intermediate particle of polyester and resin composition obtained from operating as described above puts into rotary type vacuum solid phase
It is 24 hours dry in 90 DEG C under the decompression of 0.01Torr in polyplant, next carry out crystallizing for 10 hours in 160 DEG C.
After above-mentioned crystallization, under the decompression of 0.01Torr, in 200 DEG C of progress, 38 hours solid phases, gathered
The solid phase particle of ester resin composition.Cylindrical bottles are made using obtained particle, and they are evaluated.By its
As a result shown in table 1.The ratio for constituting the monomer component of obtained copolyester is terephthalic acid units: ethylene glycol unit: 1,
4- cyclohexanedimethanol unit: diethylene glycol (DEG)=100.0:82.8:14.2:3.0(molar ratio), the content of the unit from polyester
For 0.025 mass %.
Comparative example 8
Using by 100.0 mass parts of terephthalic acid (TPA), 37.3 mass parts of ethylene glycol and bisphenol-A epoxy ethane 2mol addition product
The slurry that 31.8 mass parts are formed, production polyester (B) are in addition to this operated in the same way with comparative example 7, manufacture polyester resin
Grain makes cylindrical bottles using the particle, and evaluates them.It the results are shown in table 1.Constitute obtained copolyester
Monomer component ratio be terephthalic acid units: ethylene glycol unit: bisphenol-A epoxy ethane 2mol addition product unit: two is sweet
Alcohol=100.0:92.0:5.0:3.0(molar ratio), the content of the unit from polyester is 0.010 mass %.
[table 1]
Polyester resin particle of the invention has the melt viscosity of appropriateness, resin pressure when extrusion and blow molding for 18~
23MPa, resistance to drawdown are excellent.In addition, the impact resistance and tone of the molded product obtained using these particles are good.Another party
Face, when that will carry out intermediate particle obtained from melt polycondensation and carry out extrusion and blow molding (comparative example 1), parison drawdown, not
To container.When being not added with polyester (comparative example 3,6), not only parison drawdown, the tone for the resin for not obtaining container, and obtaining
It is bad.On the other hand, when the additive amount of polyester is excessive (comparative example 2), the impact resistance of obtained container is insufficient.It is copolymerized into
When being divided into M-phthalic acid (comparative example 4), 1,4-butanediol (comparative example 5), the impact resistance of obtained container is insufficient.It will lead to
It crosses oligomer melting mixing to make 2 kinds obtained from its polycondensation of particle melting mixing, then progress together with polyester
When solid phase (comparative example 7,8), the transparency of obtained molded product is insufficient.
As verified in above-described embodiment, by adding the polyester of specified amount in melt polycondensation, by polyester
Resistance to drawdown when resin particle forms improves, and obtains impact resistance and the good molded product of tone, and the polyester is
The carboxylate of polyalcohol more than ternary, the carboxylic acid have hindered phenol group.
Claims (3)
1. polyester resin particle is by adding terephthalic acid (TPA), ethylene glycol, cyclohexanedimethanol or bisphenol-A epoxy ethane
So that it is carried out polycondensation at object and polyester melting mixing, then carry out polyester resin particle made of solid phase, feature exists
In, aforementioned polyester is the carboxylate of the polyalcohol of ternary or more, which has hindered phenol group,
Dicarboxylic acid units in aforementioned polyester are mainly formed by terephthalic acid units,
Diol units in aforementioned polyester mainly by ethylene glycol unit and cyclohexanedimethanol unit or come from bisphenol-A epoxy second
The unit of alkane addition product is formed, and relative to the total amount of the diol units, the content of ethylene glycol unit is 75~98 moles of %, hexamethylene
The content of alkane dimethanol unit and the unit from bisphenol A epoxy ethane additive product is 2~25 moles of %,
The content of the ingredient from aforementioned polyester in aforementioned polyester resin is 0.005~0.04 mass %, also,
The inherent viscosity of aforementioned polyester is 0.9~1.5dl/g.
2. molded product is carried out made of extrusion and blow molding using particle described in claim 1.
3. the manufacturing method of polyester resin particle according to claim 1, by by terephthalic acid (TPA), ethylene glycol, hexamethylene
Alkane dimethanol or bisphenol A epoxy ethane additive product and aforementioned polyester melting mixing make its carry out polycondensation, then cut and
Intermediate particle is obtained, the intermediate particle is then made to carry out solid phase.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014266421 | 2014-12-26 | ||
| JP2014-266421 | 2014-12-26 | ||
| PCT/JP2015/086199 WO2016104689A1 (en) | 2014-12-26 | 2015-12-25 | Polyester resin pellets, process for producing same, and molded article obtained therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107001602A CN107001602A (en) | 2017-08-01 |
| CN107001602B true CN107001602B (en) | 2019-08-16 |
Family
ID=56150701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580071071.3A Active CN107001602B (en) | 2014-12-26 | 2015-12-25 | Polyester resin particle, its manufacturing method and molded product therefrom |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6757669B2 (en) |
| KR (1) | KR102428493B1 (en) |
| CN (1) | CN107001602B (en) |
| TW (1) | TWI691522B (en) |
| WO (1) | WO2016104689A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190084129A (en) * | 2016-11-30 | 2019-07-15 | 주식회사 쿠라레 | POLYESTER, METHOD FOR PRODUCING THE SAME, AND PRODUCTION THEREOF |
| CN115335430B (en) * | 2020-03-26 | 2023-07-28 | 东洋纺株式会社 | Polyester resin and method for producing blow-molded article made of polyester resin |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08165338A (en) * | 1994-12-15 | 1996-06-25 | Nippon Ester Co Ltd | Copolyester |
| JP3468628B2 (en) * | 1995-11-16 | 2003-11-17 | 株式会社クラレ | Copolyester and its molded product |
| CA2189286C (en) * | 1995-11-16 | 2000-05-30 | Shinji Tai | Copolyesters and molded articles comprising the same |
| JP3481804B2 (en) * | 1995-12-01 | 2003-12-22 | 株式会社クラレ | Copolyesters and molded articles made from them |
| JP3481814B2 (en) * | 1997-03-10 | 2003-12-22 | 株式会社クラレ | Copolyester pellets and molded articles made from them |
| JP2003238781A (en) * | 2002-02-14 | 2003-08-27 | Mitsubishi Engineering Plastics Corp | Polybutylene terephthalate resin composition and molded item |
| JP2002338674A (en) | 2001-05-15 | 2002-11-27 | Nippon Ester Co Ltd | Copolyester and molded article |
| JP2013007058A (en) * | 2003-02-18 | 2013-01-10 | Mitsubishi Chemicals Corp | Method for producing polybutylene terephthalate |
| JP2005082656A (en) * | 2003-09-05 | 2005-03-31 | Mitsubishi Rayon Co Ltd | Polyester pellet and method for producing the same |
| JP5309429B2 (en) | 2006-06-06 | 2013-10-09 | 三菱瓦斯化学株式会社 | Polyester resin composition |
| JP5606803B2 (en) | 2010-06-02 | 2014-10-15 | 株式会社クラレ | Method for producing solid phase polymerization pellets comprising polyester resin composition |
| JP2013136723A (en) * | 2011-11-29 | 2013-07-11 | Nippon Ester Co Ltd | Polyester resin composition and direct blow molded product thereof |
| WO2013153703A1 (en) * | 2012-04-11 | 2013-10-17 | 東洋紡株式会社 | Polyester blow-molded article, and method for modling polyester blow-molded article |
| WO2013153702A1 (en) * | 2012-04-11 | 2013-10-17 | 東洋紡株式会社 | Polyester blow-molded article, and method for modling polyester blow-molded article |
| JP6600131B2 (en) * | 2014-02-17 | 2019-10-30 | ユニチカ株式会社 | Polyester resin composition and blow molded article comprising the same |
| JP6212008B2 (en) * | 2014-02-18 | 2017-10-11 | ユニチカ株式会社 | Polyester resin composition and blow molded article comprising the same |
-
2015
- 2015-12-24 TW TW104143621A patent/TWI691522B/en active
- 2015-12-25 JP JP2016566500A patent/JP6757669B2/en active Active
- 2015-12-25 CN CN201580071071.3A patent/CN107001602B/en active Active
- 2015-12-25 WO PCT/JP2015/086199 patent/WO2016104689A1/en active Application Filing
- 2015-12-25 KR KR1020177020602A patent/KR102428493B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| CN107001602A (en) | 2017-08-01 |
| JPWO2016104689A1 (en) | 2017-10-05 |
| TWI691522B (en) | 2020-04-21 |
| TW201638143A (en) | 2016-11-01 |
| WO2016104689A1 (en) | 2016-06-30 |
| KR102428493B1 (en) | 2022-08-02 |
| JP6757669B2 (en) | 2020-09-23 |
| KR20170101267A (en) | 2017-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11859046B2 (en) | High-viscosity polyester with improved impact properties | |
| CN107148438B (en) | Process for producing polyesters containing at least one 1,4:3, 6-dianhydrohexitol unit with improved coloration | |
| CN1827686B (en) | Crystalline polyglycolic acid, polyglycolic acid composition and production process thereof | |
| CN109996829A (en) | Polyester, its manufacturing method and the molded product formed by it | |
| CN102971358A (en) | Ultra-high IV polyester for extrusion blow molding and method for its production | |
| CN101291974A (en) | PET polymer with improved properties | |
| US20180355101A1 (en) | Thermoplastic copolyesters comprising 1,4:3,6-dianhydrohexitol and various aromatic diacids | |
| CN107001602B (en) | Polyester resin particle, its manufacturing method and molded product therefrom | |
| TWI754709B (en) | Polyester, method for producing the same and shaped article of the same | |
| JP7161987B2 (en) | Use of thermoplastic polyesters for manufacturing injection parts | |
| JP6152989B2 (en) | Mixed pellet containing polyester pellet and resin composition | |
| JP7320499B2 (en) | Thermoplastic polyesters with high incorporation of 1,4:3,6-dianhydro-L-iditol units | |
| JP6985698B2 (en) | Polyester resin and blow molded products | |
| US20220002476A1 (en) | Method for preparing a polyester of the poly(1,4:3,6-dianhydrohexitol-cocyclohexylene terephthalate) type | |
| JP6659248B2 (en) | Laminated bottle and method for producing laminated bottle | |
| US20230013441A1 (en) | Method for manufacturing a polyester containing at least one 1,4:3,6-dianhydrohexitol unit with reduced colouring and improved rates of incorporation of the unit(s) | |
| JP5606803B2 (en) | Method for producing solid phase polymerization pellets comprising polyester resin composition | |
| JP3482641B2 (en) | Copolyester applied to extrusion | |
| TW202411290A (en) | Polyester and shaped article of the same | |
| JP2023532478A (en) | Thermoplastic polyester for manufacturing 3D printed objects | |
| JP2017178995A (en) | Polyester resin composition and direct blow molded article made from the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |