JP2015030808A - Polyester resin composition - Google Patents
Polyester resin composition Download PDFInfo
- Publication number
- JP2015030808A JP2015030808A JP2013162023A JP2013162023A JP2015030808A JP 2015030808 A JP2015030808 A JP 2015030808A JP 2013162023 A JP2013162023 A JP 2013162023A JP 2013162023 A JP2013162023 A JP 2013162023A JP 2015030808 A JP2015030808 A JP 2015030808A
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- unit derived
- resin composition
- diol
- acid
- 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.)
- Pending
Links
- 239000004645 polyester resin Substances 0.000 title claims abstract description 163
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 162
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 150000002009 diols Chemical class 0.000 claims abstract description 42
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 26
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 24
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 24
- -1 1,1-dimethyl-2-hydroxyethyl Chemical group 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 13
- 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 claims description 8
- 238000002834 transmittance Methods 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 125000002015 acyclic group Chemical group 0.000 claims description 4
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 4
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 claims description 4
- HXEWWQYSYQOUSD-UHFFFAOYSA-N 2-[5-ethyl-5-(hydroxymethyl)-1,3-dioxan-2-yl]-2-methylpropan-1-ol Chemical compound CCC1(CO)COC(C(C)(C)CO)OC1 HXEWWQYSYQOUSD-UHFFFAOYSA-N 0.000 claims description 3
- CHDRADPXNRULGA-UHFFFAOYSA-N naphthalene-1,3-dicarboxylic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC(C(O)=O)=C21 CHDRADPXNRULGA-UHFFFAOYSA-N 0.000 claims description 3
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 16
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 12
- 239000011112 polyethylene naphthalate Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 239000006096 absorbing agent Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000005809 transesterification reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction 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
- 239000012760 heat stabilizer Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 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
- 235000013361 beverage Nutrition 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000014171 carbonated beverage Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 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
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CVBWTNHDKVVFMI-LBPRGKRZSA-N (2s)-1-[4-[2-[6-amino-8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]purin-9-yl]ethyl]piperidin-1-yl]-2-hydroxypropan-1-one Chemical compound C1CN(C(=O)[C@@H](O)C)CCC1CCN1C2=NC=NC(N)=C2N=C1SC(C(=C1)Br)=CC2=C1OCO2 CVBWTNHDKVVFMI-LBPRGKRZSA-N 0.000 description 1
- QLMQETZMAZOZRM-UHFFFAOYSA-N (4-hydroxy-2,3-diphenylphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 QLMQETZMAZOZRM-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- WTKQQTGCQAFYOL-UHFFFAOYSA-N 3,4-dihydro-2h-naphthalene-1,1-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)(C(O)=O)CCCC2=C1 WTKQQTGCQAFYOL-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 240000002234 Allium sativum Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KKQNEOAHDGRPDJ-UHFFFAOYSA-N CO.CO.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1 Chemical compound CO.CO.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1 KKQNEOAHDGRPDJ-UHFFFAOYSA-N 0.000 description 1
- HDICIMRANLAWOM-UHFFFAOYSA-N CO.CO.C1CCc2ccccc2C1 Chemical compound CO.CO.C1CCc2ccccc2C1 HDICIMRANLAWOM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 244000294411 Mirabilis expansa Species 0.000 description 1
- 235000015429 Mirabilis expansa Nutrition 0.000 description 1
- JMMSLMMJRMCXPW-UHFFFAOYSA-N OC.OC.C1CC2CCC1C2 Chemical compound OC.OC.C1CC2CCC1C2 JMMSLMMJRMCXPW-UHFFFAOYSA-N 0.000 description 1
- YMVIYCFGOTYKGI-UHFFFAOYSA-N OC.OC.C1CCCCCCCCC1 Chemical compound OC.OC.C1CCCCCCCCC1 YMVIYCFGOTYKGI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 244000195452 Wasabia japonica Species 0.000 description 1
- 235000000760 Wasabia japonica Nutrition 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- XUGISPSHIFXEHZ-GPJXBBLFSA-N [(3r,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C1C=C2C[C@H](OC(C)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 XUGISPSHIFXEHZ-GPJXBBLFSA-N 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
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- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
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- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
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- 239000006224 matting agent Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000005487 naphthalate group Chemical group 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 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
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ジオール単位として環状アセタール骨格を有するジオールに由来する単位を含有し、ジカルボン酸単位としてナフタレン骨格を有するジカルボン酸に由来する単位を含有するポリエステル樹脂（Ａ）と、環状アセタール骨格を有しないポリエステル樹脂（Ｂ）とを含有し、透明性、ＵＶバリア性に優れるポリエステル樹脂組成物に関する。 The present invention includes a polyester resin (A) containing a unit derived from a diol having a cyclic acetal skeleton as a diol unit and a unit derived from a dicarboxylic acid having a naphthalene skeleton as a dicarboxylic acid unit, and a cyclic acetal skeleton. Polyester resin (B), and a polyester resin composition having excellent transparency and UV barrier properties.
ポリエチレンテレフタレート（以下「ＰＥＴ」ということがある）は透明性、機械的性能、耐溶剤性、保香性、耐候性、リサイクル性等にバランスのとれた樹脂であり、ボトルやフィルムなどの用途に用いられている。しかしながらＰＥＴには耐熱性に関して以下のような欠点が存在する。すなわち、ＰＥＴのガラス転移温度は８０℃程度であるため、殺菌、滅菌が必要とされる容器、耐熱透明飲料用カップ、再加熱を要する容器、赤道直下を越えるような輸出製品の包材等、高い耐熱性が要求される用途には利用できない。また、ＵＶバリア性に関しては、ＰＥＴは波長３５０ｎｍ程度の光を殆ど透過する為、樹脂自体にＵＶバリア性は殆どない。 Polyethylene terephthalate (hereinafter sometimes referred to as “PET”) is a resin that balances transparency, mechanical performance, solvent resistance, aroma retention, weather resistance, recyclability, etc., and is suitable for applications such as bottles and films. It is used. However, PET has the following drawbacks regarding heat resistance. That is, since the glass transition temperature of PET is about 80 ° C., containers that require sterilization and sterilization, cups for heat-resistant transparent beverages, containers that require reheating, packaging materials for export products that exceed the equator, etc. It cannot be used for applications that require high heat resistance. Regarding the UV barrier property, since PET almost transmits light having a wavelength of about 350 nm, the resin itself has almost no UV barrier property.
このため、従来、耐熱性の要求される分野に対しては、ポリエチレンナフタレート（以下「ＰＥＮ」ということがある）が用いられてきた。
また、ＵＶバリア性の要求される分野に対しては同様にＰＥＮの使用や、ＰＥＴに対しＵＶ吸収剤を添加する事等が検討されてきた。
For this reason, polyethylene naphthalate (hereinafter sometimes referred to as “PEN”) has been used for fields requiring heat resistance.
Similarly, for fields requiring UV barrier properties, the use of PEN and the addition of UV absorbers to PET have been studied.
しかし、ＰＥＮは高価な樹脂である事から使用できる用途は限られている。この対応としてＰＥＴとＰＥＮのブレンドが検討されてきたが、ＰＥＴとＰＥＮの屈折率（ｎｄ）が夫々１．５７５、１．６４６であり屈折率差が０．０７１と大きい為、ＰＥＴとＰＥＮから透明性に優れた組成物を得る事は困難であった。ＰＥＴとＰＥＮから透明な組成物を得る方法として種々検討されており、予めこれらの樹脂を特定の条件で溶融混練しておく方法や、非常に滞留時間が長く混練性の良い押出し機を使用する事が開示されている（特許文献１）。これらの方法はスクリューの形状や、温度、スクリュー回転数、生産性などに制約があり汎用性には劣るものであった。このように従来、耐熱性が要求される用途に適した安価なポリエステル樹脂や、耐熱性に優れ、容易に透明化する事ができるポリエステル樹脂組成物は知られていなかった。 However, since PEN is an expensive resin, the applications that can be used are limited. As a response to this, blends of PET and PEN have been studied. Since the refractive index (nd) of PET and PEN is 1.575 and 1.646, respectively, and the difference in refractive index is as large as 0.071. It was difficult to obtain a composition having excellent transparency. Various methods have been studied as a method for obtaining a transparent composition from PET and PEN, and a method in which these resins are previously melt-kneaded under specific conditions, or an extruder having a very long residence time and good kneadability is used. This is disclosed (Patent Document 1). These methods are inferior in versatility due to restrictions on the screw shape, temperature, screw rotation speed, productivity, and the like. Thus, an inexpensive polyester resin suitable for applications requiring heat resistance and a polyester resin composition that has excellent heat resistance and can be easily made transparent have not been known.
一方、ＵＶバリア性を付与するためにＰＥＴにＵＶ吸収剤を添加する手法は、ＵＶ吸収剤が一般に高価であるため、経済的な方法とは言えない。また、ＵＶ吸収剤を溶融混練する際には着色する場合が多く、外観良好な製品を得る事は難しかった。加えて、この手法はＵＶ吸収剤がブリードアウトして射出成型機の金型が汚れる事、押出し機のロールが汚れる事、成形時の樹脂の着色が著しくなる事等の問題点がある。このブリードアウトの対応として、シートやフィルムにおいてはＵＶ吸収剤を加える層の外側をＵＶ吸収剤を加えない層にする多層構成が開示されているが、設備投資が必要であり経済的な方法とは言えない（特許文献２）。 On the other hand, the method of adding a UV absorber to PET in order to impart UV barrier properties is not an economical method because UV absorbers are generally expensive. Moreover, when the UV absorber is melt-kneaded, it is often colored, and it has been difficult to obtain a product with a good appearance. In addition, this method has problems such as the UV absorber bleeds out and the mold of the injection molding machine gets dirty, the roll of the extruder gets dirty, and the resin becomes very colored during molding. As a countermeasure for this bleed-out, a multilayer structure is disclosed in which the outer side of the layer to which the UV absorber is added in the sheet or film is a layer to which no UV absorber is added. (Patent Document 2).
本発明の目的は前記の如き状況に鑑み、透明性、ＵＶバリア性に優れたポリエステル樹脂組成物を提供することにある。 An object of the present invention is to provide a polyester resin composition excellent in transparency and UV barrier properties in view of the above situation.
本発明者らは鋭意検討した結果、環状アセタール骨格を有するジオールに由来する単位とナフタレン骨格を有するジカルボン酸に由来する単位を含有するポリエステル樹脂と、環状アセタール骨格を有しないポリエステル樹脂とを含有するポリエステル樹脂組成物であって、当該ポリエステル樹脂組成物中の全ジオール構成単位中の環状アセタール骨格を有するジオール単位の割合が０．０５〜２０モル％、全ジカルボン酸単位中のナフタレン骨格を有するジカルボン酸に由来する単位の割合が０．１〜３０モル％であるであるポリエステル樹脂組成物が、透明性、ＵＶバリア性等に優れることを見出し、本発明を完成するに至った。 As a result of intensive studies, the inventors of the present invention contain a polyester resin containing a unit derived from a diol having a cyclic acetal skeleton, a unit derived from a dicarboxylic acid having a naphthalene skeleton, and a polyester resin not having a cyclic acetal skeleton. The ratio of the diol unit which has a cyclic acetal skeleton in all the diol structural units in the said polyester resin composition is 0.05-20 mol%, the dicarboxylic having a naphthalene skeleton in all the dicarboxylic acid units It has been found that a polyester resin composition in which the proportion of units derived from an acid is 0.1 to 30 mol% is excellent in transparency, UV barrier properties, etc., and has completed the present invention.
すなわち、本発明は以下の通りである。
［１］
ジオール単位として環状アセタール骨格を有するジオールに由来する単位を含有し、ジカルボン酸単位としてナフタレン骨格を有するジカルボン酸に由来する単位を含有するポリエステル樹脂（Ａ）と、環状アセタール骨格を有しないポリエステル樹脂（Ｂ）とを含有し、以下の（１）〜（４）の特徴を有するポリエステル樹脂組成物（Ｃ）。
（１）ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）のナトリウムＤ線を光源として測定した屈折率差が０．００５以下である。
（２）ポリエステル樹脂組成物（Ｃ）中の全ジオール構成単位中の環状アセタール骨格を有するジオールに由来する単位の割合が０．０５〜２０モル％である。
（３）ポリエステル樹脂組成物（Ｃ）中の全ジカルボン酸単位中のナフタレン骨格を有するジカルボン酸に由来する単位の割合が０．１〜３０モル％である。
（４）波長３５０ｎｍの光の透過率が３０％／２００μｍ以下である。
That is, the present invention is as follows.
[1]
A polyester resin (A) containing a unit derived from a diol having a cyclic acetal skeleton as a diol unit and a unit derived from a dicarboxylic acid having a naphthalene skeleton as a dicarboxylic acid unit; and a polyester resin having no cyclic acetal skeleton ( B) and a polyester resin composition (C) having the following characteristics (1) to (4).
(1) The refractive index difference measured using the sodium D line of the polyester resin (A) and the polyester resin (B) as a light source is 0.005 or less.
(2) The ratio of the unit derived from the diol which has a cyclic acetal skeleton in all the diol structural units in the polyester resin composition (C) is 0.05 to 20 mol%.
(3) The ratio of the unit derived from the dicarboxylic acid having a naphthalene skeleton in all the dicarboxylic acid units in the polyester resin composition (C) is 0.1 to 30 mol%.
(4) The transmittance of light having a wavelength of 350 nm is 30% / 200 μm or less.
［２］
ポリエステル樹脂（Ａ）中の環状アセタール骨格を有するジオールに由来する単位が、一般式（１）：
又は一般式（２）：
で表されるジオールに由来する単位である［１］に記載のポリエステル樹脂組成物（Ｃ）。
[2]
The unit derived from the diol having a cyclic acetal skeleton in the polyester resin (A) is represented by the general formula (1):
Or general formula (2):
The polyester resin composition (C) according to [1], which is a unit derived from a diol represented by:
［３］
ポリエステル樹脂（Ａ）中の環状アセタール骨格を有するジオールに由来する単位が、３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、又は５−メチロール−５−エチル−２−（１，１−ジメチル−２−ヒドロキシエチル）−１，３−ジオキサンに由来する単位である［１］に記載のポリエステル樹脂組成物（Ｃ）。
[3]
The unit derived from the diol having a cyclic acetal skeleton in the polyester resin (A) is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5. .5] The polyester resin composition according to [1], which is a unit derived from undecane or 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane. (C).
［４］
ポリエステル樹脂（Ａ）中のナフタレン骨格を有するジカルボン酸に由来する単位が、１，３−ナフタレンジカルボン酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸からなる群から選ばれる１種以上のジカルボン酸に由来する単位である［１］〜［３］のいずれか一項に記載のポリエステル樹脂組成物（Ｃ）。
[4]
The unit derived from the dicarboxylic acid having a naphthalene skeleton in the polyester resin (A) is 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. The polyester resin composition (C) according to any one of [1] to [3], which is a unit derived from one or more dicarboxylic acids selected from the group consisting of 2,7-naphthalenedicarboxylic acid.
［５］
ポリエステル樹脂（Ａ）中のナフタレン骨格を有するジカルボン酸に由来する単位が、２，６−ナフタレンジカルボン酸に由来する単位である［１］〜［３］のいずれか一項に記載のポリエステル樹脂組成物（Ｃ）。
[5]
The polyester resin composition according to any one of [1] to [3], wherein the unit derived from a dicarboxylic acid having a naphthalene skeleton in the polyester resin (A) is a unit derived from 2,6-naphthalenedicarboxylic acid. Product (C).
［６］
ポリエステル樹脂（Ｂ）がポリエチレンテレフタレートである［１］〜［５］のいずれか一項に記載のポリエステル樹脂組成物（Ｃ）。
[6]
The polyester resin composition (C) according to any one of [1] to [5], wherein the polyester resin (B) is polyethylene terephthalate.
本発明のポリエステル樹脂組成物は、透明性、ＵＶバリア性に優れており、射出成形体、シート、フィルム、シート成形体、中空容器等として用いることができ、本発明の工業的意義は大きい。 The polyester resin composition of the present invention is excellent in transparency and UV barrier properties, and can be used as an injection molded article, sheet, film, sheet molded article, hollow container, etc., and the industrial significance of the present invention is great.
以下、本発明を実施するための形態（以下、単に「本実施形態」という。）について詳細に説明する。以下の本実施形態は、本発明を説明するための例示であり、本発明を以下の内容に限定する趣旨ではない。本発明は、その要旨の範囲内で適宜に変形して実施できる。 Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.
まず、本実施形態のポリエステル樹脂組成物（Ｃ）を得るために使用するポリエステル樹脂（Ａ）について説明する。ポリエステル樹脂（Ａ）は、ジオール単位として一般式（１）：
一般式（１）及び（２）の化合物としては、３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、５−メチロール−５−エチル−２−（１，１−ジメチル−２−ヒドロキシエチル）−１，３−ジオキサン等が特に好ましい。 Examples of the compounds of the general formulas (1) and (2) include 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane and the like are particularly preferable.
ポリエステル樹脂（Ａ）中の環状アセタール骨格を有するジオールに由来する単位の割合は、好ましくはジオール単位中１〜８０モル％である。環状アセタール骨格を有するジオールに由来する単位を持つ事でポリエステル樹脂（Ａ）のガラス転移温度が上昇し、本発明のポリエステル樹脂組成物の耐熱性が向上する為好ましい。 The ratio of the unit derived from the diol having a cyclic acetal skeleton in the polyester resin (A) is preferably 1 to 80 mol% in the diol unit. Having a unit derived from a diol having a cyclic acetal skeleton is preferable because the glass transition temperature of the polyester resin (A) is increased and the heat resistance of the polyester resin composition of the present invention is improved.
本実施形態のポリエステル樹脂（Ａ）は、環状アセタール骨格を有しないジオールに由来する単位を有しても良い。環状アセタール骨格を有しないジオールに由来する単位の割合は好ましくは２０〜９９モル％である。環状アセタール骨格を有しないジオールに由来する単位としては、特に制限はされないが、エチレングリコール、トリメチレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、プロピレングリコール、ネオペンチルグリコール等の脂肪族ジオール類；１，３−シクロヘキサンジメタノール、１，４−シクロヘキサンジメタノール、１，２−デカヒドロナフタレンジメタノール、１，３−デカヒドロナフタレンジメタノール、１，４−デカヒドロナフタレンジメタノール、１，５−デカヒドロナフタレンジメタノール、１，６−デカヒドロナフタレンジメタノール、２，７−デカヒドロナフタレンジメタノール、テトラリンジメタノール、ノルボルナンジメタノール、トリシクロデカンジメタノール、ペンタシクロドデカンジメタノール等の脂環式ジオール類；ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等のポリエーテル化合物類；４，４’−（１−メチルエチリデン）ビスフェノール、メチレンビスフェノール（ビスフェノールＦ）、４，４’−シクロヘキシリデンビスフェノール（ビスフェノールＺ）、４，４’−スルホニルビスフェノール（ビスフェノールＳ）等のビスフェノール類；前記ビスフェノール類のアルキレンオキシド付加物；ヒドロキノン、レゾルシン、４，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルベンゾフェノン等の芳香族ジヒドロキシ化合物；及び前記芳香族ジヒドロキシ化合物のアルキレンオキシド付加物等のジオールに由来する単位が例示できる。ポリエステル樹脂（Ａ）の機械強度、耐熱性を考慮するとエチレングリコール、トリメチレングリコール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノール等に由来する単位が好ましく、エチレングリコールに由来する単位が特に好ましい。なお、ポリエステル樹脂（Ａ）は環状アセタール骨格を有しないジオールに由来する単位を上記したものの中から１種類含んでも、２種類以上含んでも良い。 The polyester resin (A) of this embodiment may have a unit derived from a diol that does not have a cyclic acetal skeleton. The proportion of units derived from a diol having no cyclic acetal skeleton is preferably 20 to 99 mol%. The unit derived from a diol having no cyclic acetal skeleton is not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, Aliphatic diols such as propylene glycol and neopentyl glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1 , 4-Decahydronaphthalene diethanol, 1,5-decahydronaphthalene diethanol, 1,6-decahydronaphthalene diethanol, 2,7-decahydronaphthalene diethanol, tetralin dimethanol, norbornane dimethanol, Cycloaliphatic diols such as cyclodecane dimethanol and pentacyclododecane dimethanol; polyether compounds such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 4,4 ′-(1-methylethylidene) bisphenol, methylenebisphenol ( Bisphenols such as bisphenol F), 4,4′-cyclohexylidenebisphenol (bisphenol Z), 4,4′-sulfonylbisphenol (bisphenol S); alkylene oxide adducts of the bisphenols; hydroquinone, resorcin, 4,4 Aromatic dihydroxy compounds such as' -dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylbenzophenone; and the aromatic dihydroxy Units derived from diols such as alkylene oxide adducts of compounds can be exemplified. In consideration of the mechanical strength and heat resistance of the polyester resin (A), units derived from ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, etc. are preferred, and units derived from ethylene glycol are preferred. Particularly preferred. In addition, the polyester resin (A) may contain one type or two or more types of units derived from a diol having no cyclic acetal skeleton.
本実施形態に用いるポリエステル樹脂（Ａ）は、ジカルボン酸単位としてナフタレン骨格を有するジカルボン酸に由来する単位を含有する。ナフタレン骨格を有するジカルボン酸単位としては特に制限はないが、例えば１，３−ナフタレンジカルボン酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸に由来する単位である事が好ましく、機械的性能の面から２，６−ナフタレンジカルボン酸に由来する単位である事が特に好ましい。ポリエステル樹脂（Ａ）はナフタレン骨格を有するジカルボン酸に由来する単位を１種類含んでも、２種類以上含んでも良い。 The polyester resin (A) used in the present embodiment contains units derived from dicarboxylic acid having a naphthalene skeleton as dicarboxylic acid units. The dicarboxylic acid unit having a naphthalene skeleton is not particularly limited. For example, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, It is preferably a unit derived from 7-naphthalenedicarboxylic acid, particularly preferably a unit derived from 2,6-naphthalenedicarboxylic acid from the viewpoint of mechanical performance. The polyester resin (A) may contain one type of unit derived from dicarboxylic acid having a naphthalene skeleton or two or more types.
ポリエステル樹脂（Ａ）のジカルボン酸単位中のナフタレン骨格を有するジカルボン酸に由来する単位の割合は、好ましくは１〜１００モル％である。ナフタレン骨格を有するジカルボン酸に由来する単位の割合が上記範囲である事で、ポリエステル樹脂（Ａ）のガラス転移温度が上昇し、本発明のポリエステル樹脂組成物の耐熱性が向上する為好ましい。 The ratio of the unit derived from the dicarboxylic acid having a naphthalene skeleton in the dicarboxylic acid unit of the polyester resin (A) is preferably 1 to 100 mol%. It is preferable for the ratio of the units derived from the dicarboxylic acid having a naphthalene skeleton to be in the above range because the glass transition temperature of the polyester resin (A) is increased and the heat resistance of the polyester resin composition of the present invention is improved.
本実施形態のポリエステル樹脂（Ａ）は、ナフタレン骨格を有しないジカルボン酸に由来する単位を有しても良い。ナフタレン骨格を有しないジカルボン酸に由来する単位は特に制限はされないが、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、シクロヘキサンジカルボン酸、デカンジカルボン酸、ノルボルナンジカルボン酸、トリシクロデカンジカルボン酸、ペンタシクロドデカンジカルボン酸等の脂肪族ジカルボン酸；テレフタル酸、イソフタル酸、フタル酸、２−メチルテレフタル酸、ビフェニルジカルボン酸、テトラリンジカルボン酸等の芳香族ジカルボン酸に由来する単位が例示できる。これらの中で、ポリエステル樹脂（Ａ）の熱物性、機械物性等の面から芳香族ジカルボン酸に由来する単位が好ましく、テレフタル酸、イソフタル酸に由来する単位が特に好ましい。ポリエステル樹脂（Ａ）はナフタレン骨格を有しないジカルボン酸に由来する単位を１種類含んでも、２種類以上含んでも良い。 The polyester resin (A) of this embodiment may have a unit derived from a dicarboxylic acid not having a naphthalene skeleton. The unit derived from dicarboxylic acid having no naphthalene skeleton is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid Aliphatic dicarboxylic acids such as norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecane dicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, biphenyldicarboxylic acid, tetralin dicarboxylic acid A unit derived from an acid can be exemplified. Among these, a unit derived from an aromatic dicarboxylic acid is preferable from the viewpoint of thermal properties and mechanical properties of the polyester resin (A), and a unit derived from terephthalic acid and isophthalic acid is particularly preferable. The polyester resin (A) may contain one type of unit derived from dicarboxylic acid not having a naphthalene skeleton, or may contain two or more types.
本実施形態に用いるポリエステル樹脂（Ａ）は、耐熱性を考慮すると環状アセタール骨格を有するジオールに由来する単位として３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカンに由来する単位を、ナフタレン骨格を有するジカルボン酸に由来する単位として２，６−ナフタレンジカルボン酸に由来する単位を含有する事が好ましく、経済性、機械的性能のバランスをも考慮すると環状アセタール骨格を有しないジオールに由来する単位としてエチレングリコールに由来する単位、ナフタレン骨格を有しないジカルボン酸に由来する単位としてテレフタル酸に由来する単位を含有する事が好ましい。 The polyester resin (A) used in this embodiment is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) 2,4,8 as a unit derived from a diol having a cyclic acetal skeleton in consideration of heat resistance. , 10-tetraoxaspiro [5.5] undecane is preferably a unit derived from 2,6-naphthalenedicarboxylic acid as a unit derived from dicarboxylic acid having a naphthalene skeleton, Considering the balance of mechanical performance, the unit derived from ethylene glycol as a unit derived from diol having no cyclic acetal skeleton, and the unit derived from terephthalic acid as a unit derived from dicarboxylic acid not having a naphthalene skeleton Is preferred.
また、ポリエステル樹脂（Ａ）には本発明の目的を損なわない範囲でブチルアルコール、ヘキシルアルコール、オクチルアルコール等のモノアルコール単位やトリメチロールプロパン、グリセリン、ペンタエリスリトール等の３価以上の多価アルコール単位、安息香酸、プロピオン酸、酪酸等のモノカルボン酸単位やトリメリット酸、トリメシン酸、ピロメリット酸等の３価以上の多価カルボン酸単位を導入することもできる。 In addition, the polyester resin (A) has a monoalcohol unit such as butyl alcohol, hexyl alcohol and octyl alcohol and a trihydric or higher polyhydric alcohol unit such as trimethylolpropane, glycerin and pentaerythritol as long as the object of the present invention is not impaired. It is also possible to introduce monocarboxylic acid units such as benzoic acid, propionic acid and butyric acid and trivalent or higher polyvalent carboxylic acid units such as trimellitic acid, trimesic acid and pyromellitic acid.
ポリエステル樹脂（Ａ）を製造する方法に特に制限はなく、従来公知の方法を適用できる。例えばエステル交換法、直接エステル化法等の溶融重合法又は溶液重合法、固相重合法を挙げることができる。エステル交換触媒、エステル化触媒、重縮合触媒、エーテル化防止剤、熱安定剤、光安定剤等の各種安定剤、重合調整剤等も従来既知のものを用いることが出来る。
エステル交換触媒、エステル化触媒、重縮合触媒としては特に限定は無いが、例えば、亜鉛、鉛、セリウム、カドミウム、マンガン、コバルト、リチウム、ナトリウム、カリウム、カルシウム、ニッケル、マグネシウム、バナジウム、アルミニウム、チタン、アンチモン、ゲルマニウム、スズ等の金属の化合物（例えば、脂肪酸塩、炭酸塩、リン酸塩、水酸化物、塩化物、酸化物、アルコキシド）や金属マグネシウム等が挙げられる。これらは単独で又は二種以上を組み合わせて使用することができる。触媒としては、上記した中でマンガン、コバルト、亜鉛、チタン、カルシウム、アンチモン、ゲルマニウムの化合物が好ましく、マンガン、アンチモン、チタン、ゲルマニウムの化合物がより好ましく、酢酸マンガン、三酸化アンチモン、テトラブトキシチタン、二酸化ゲルマニウムが特に好ましい。これらの触媒の使用量は、特に限定は無いが、ポリエステル樹脂に対して金属成分としての量が、好ましくは１〜１０００ｐｐｍ、より好ましくは３〜５００ｐｐｍ、更に好ましくは５〜２５０ｐｐｍ、特に好ましくは７〜１００ｐｐｍである。
熱安定剤としては特に制限はないが、例えばリン酸、亜リン酸、リン酸エステル、亜リン酸エステル等のリン化合物を挙げることができる。これらの中でリン酸トリメチル、リン酸トリエチル等のリン酸エステルが好ましい。これら熱安定剤の使用量は特に制限はないが、ポリエステル樹脂に対してリン原子としての量が、好ましくは１〜３００ｐｐｍ、より好ましくは５〜１００ｐｐｍ、更に好ましくは１０〜６０ｐｐｍである。
There is no restriction | limiting in particular in the method of manufacturing a polyester resin (A), A conventionally well-known method is applicable. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, a solution polymerization method, and a solid phase polymerization method. As the transesterification catalyst, esterification catalyst, polycondensation catalyst, etherification inhibitor, heat stabilizer, light stabilizer and other various stabilizers, polymerization regulators and the like, conventionally known ones can be used.
The transesterification catalyst, esterification catalyst, and polycondensation catalyst are not particularly limited. For example, zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium , Antimony, germanium, tin and other metal compounds (for example, fatty acid salts, carbonates, phosphates, hydroxides, chlorides, oxides, alkoxides) and metal magnesium. These can be used alone or in combination of two or more. As the catalyst, compounds of manganese, cobalt, zinc, titanium, calcium, antimony, and germanium are preferable, and compounds of manganese, antimony, titanium, and germanium are more preferable, and manganese acetate, antimony trioxide, tetrabutoxytitanium, Germanium dioxide is particularly preferred. The amount of these catalysts to be used is not particularly limited, but the amount as a metal component with respect to the polyester resin is preferably 1 to 1000 ppm, more preferably 3 to 500 ppm, still more preferably 5 to 250 ppm, and particularly preferably 7 ~ 100 ppm.
Although there is no restriction | limiting in particular as a heat stabilizer, For example, phosphorus compounds, such as phosphoric acid, phosphorous acid, phosphoric acid ester, phosphorous acid ester, can be mentioned. Of these, phosphate esters such as trimethyl phosphate and triethyl phosphate are preferred. The amount of these heat stabilizers to be used is not particularly limited, but the amount as a phosphorus atom with respect to the polyester resin is preferably 1 to 300 ppm, more preferably 5 to 100 ppm, and still more preferably 10 to 60 ppm.
ポリエステル樹脂（Ａ）の極限粘度は低過ぎると機械強度等の物性が損なわれる事があり、高過ぎると成形性が損なわれる事があり好ましくない。好ましい極限粘度の範囲は、例えば、混合溶媒（重量比：フェノール／１，１，２，２−テトラクロロエタン＝６／４）を用いて２５℃の恒温下、ウベローデ粘度計で測定した値が０．４〜１．５ｄｌ／ｇであり、より好ましくは０．５〜１．０ｄｌ／ｇ、更に好ましくは０．５〜０．９ｄｌ／ｇである。極限粘度が上記０．４ｄｌ／ｇ以上で成形品の強度特性に優れ、上記１．５ｄｌ／ｇ以下の場合に成形性に優れる。 If the intrinsic viscosity of the polyester resin (A) is too low, physical properties such as mechanical strength may be impaired, and if it is too high, moldability may be impaired. The range of preferable intrinsic viscosity is, for example, a value measured with an Ubbelohde viscometer at a constant temperature of 25 ° C. using a mixed solvent (weight ratio: phenol / 1,1,2,2-tetrachloroethane = 6/4). .4 to 1.5 dl / g, more preferably 0.5 to 1.0 dl / g, still more preferably 0.5 to 0.9 dl / g. The intrinsic viscosity is excellent when the intrinsic viscosity is 0.4 dl / g or more, and the moldability is excellent when the intrinsic viscosity is 1.5 dl / g or less.
次に本実施形態に使用する環状アセタール骨格を有しないポリエステル樹脂（Ｂ）について説明する。ポリエステル樹脂（Ｂ）は特に制限されるものではないが、ポリエステル樹脂組成物（Ｃ）の耐熱性、透明性、機械的性能、成形加工性等の点から、テレフタル酸、イソフタル酸、１，３−ナフタレンジカルボン酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸から選ばれる１種以上の芳香族ジカルボン酸に由来するジカルボン酸単位とエチレングリコール、トリメチレングリコール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノール、ビスフェノールＡから選ばれる１種以上のジオールに由来するジオール単位からなる芳香族ポリエステル樹脂が好ましい。中でも耐熱性、機械的性能、成形加工性、透明性等の点からＰＥＴ、ポリブチレンテレフタレート、ポリエチレン（２，６−）ナフタレート、ポリエチレンテレフタレートイソフタレートが好ましく、成形加工性、透明性、経済性を特に考慮するとＰＥＴが特に好ましい。 Next, the polyester resin (B) having no cyclic acetal skeleton used in this embodiment will be described. The polyester resin (B) is not particularly limited, but terephthalic acid, isophthalic acid, 1, 3 from the viewpoint of heat resistance, transparency, mechanical performance, moldability, etc. of the polyester resin composition (C). -Derived from one or more aromatic dicarboxylic acids selected from naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid An aromatic polyester resin comprising a dicarboxylic acid unit and a diol unit derived from one or more diols selected from ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and bisphenol A is preferred. Among them, PET, polybutylene terephthalate, polyethylene (2,6-) naphthalate, and polyethylene terephthalate isophthalate are preferable from the viewpoint of heat resistance, mechanical performance, molding processability, transparency, and the like, and the molding processability, transparency, and economy are preferable. In particular, PET is particularly preferable.
本実施形態のポリエステル樹脂組成物（Ｃ）は上記のポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）とを溶融混練することにより得られる。ポリエステル樹脂（Ａ）、（Ｂ）は本発明の要件を満たせばそれぞれ１種類以上であっても良い。ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）のナトリウムＤ線を光源として測定した屈折率差は０．００５以下である事が必要であり、０．００４以下である事が好ましく、０．００３以下である事が更に好ましい。ポリエステル樹脂（Ａ）の屈折率は構成単位の種類、割合を変える事で調整できる。例えば環状アセタール骨格を有するジオールに由来する単位の割合を増やす事でポリエステル樹脂（Ａ）の屈折率は低下し、ナフタレン骨格を有するジカルボン酸単位を増やす事でポリエステル樹脂（Ａ）の屈折率は上昇する。ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）の屈折率差が上記範囲である事で、ポリエステル樹脂組成物（Ｃ）の透明性が優れたものとなる。屈折率はポリエステル樹脂（Ａ）の方が高くても低くても良い。 The polyester resin composition (C) of the present embodiment can be obtained by melt-kneading the polyester resin (A) and the polyester resin (B). One or more polyester resins (A) and (B) may be used as long as they satisfy the requirements of the present invention. The difference in refractive index between the polyester resin (A) and the polyester resin (B) measured using sodium D-line as a light source is required to be 0.005 or less, preferably 0.004 or less, and 0.003 or less. It is further preferable that The refractive index of the polyester resin (A) can be adjusted by changing the type and proportion of the structural unit. For example, increasing the proportion of units derived from a diol having a cyclic acetal skeleton reduces the refractive index of the polyester resin (A), and increasing the number of dicarboxylic acid units having a naphthalene skeleton increases the refractive index of the polyester resin (A). To do. When the difference in refractive index between the polyester resin (A) and the polyester resin (B) is within the above range, the transparency of the polyester resin composition (C) is excellent. The refractive index of the polyester resin (A) may be higher or lower.
本実施形態のポリエステル樹脂組成物（Ｃ）中のポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）の配合割合は、物性や用途によって任意に変えることができるが、ポリエステル樹脂組成物（Ｃ）中の全ジオール構成単位中の環状アセタール骨格を有するジオール単位の割合は０．０５〜２０モル％となるように配合することが好ましい。ポリエステル樹脂組成物（Ｃ）中の全ジオール構成単位中の環状アセタール骨格を有するジオール単位の割合を上記範囲とする事でポリエステル樹脂組成物（Ｃ）に耐熱性を付与する事ができる。 The blending ratio of the polyester resin (A) and the polyester resin (B) in the polyester resin composition (C) of the present embodiment can be arbitrarily changed depending on the physical properties and applications, but in the polyester resin composition (C). The proportion of diol units having a cyclic acetal skeleton in all diol constituent units is preferably 0.05 to 20 mol%. Heat resistance can be imparted to the polyester resin composition (C) by setting the ratio of the diol units having a cyclic acetal skeleton in all the diol constituent units in the polyester resin composition (C) within the above range.
また、ポリエステル樹脂組成物（Ｃ）中の全ジカルボン酸構成単位中のナフタレン骨格を有するジカルボン酸単位の割合は、０．１〜３０モル％となるように配合することが好ましい。ポリエステル樹脂組成物（Ｃ）中の全ジカルボン酸構成単位中のナフタレン骨格を有するジカルボン酸単位の割合を上記範囲とする事でポリエステル樹脂組成物（Ｃ）に耐熱性とＵＶバリア性を付与する事ができる。 Moreover, it is preferable to mix | blend so that the ratio of the dicarboxylic acid unit which has a naphthalene skeleton in all the dicarboxylic acid structural units in a polyester resin composition (C) may be 0.1-30 mol%. By imparting heat resistance and UV barrier properties to the polyester resin composition (C), the ratio of the dicarboxylic acid units having a naphthalene skeleton in all the dicarboxylic acid constituent units in the polyester resin composition (C) is within the above range. Can do.
本実施形態のポリエステル樹脂組成物（Ｃ）は、波長３５０ｎｍの光の透過率が３０％／２００μｍ以下である。透過率は好ましくは２０％／２００μｍ以下、より好ましくは１５％／２００μｍ以下、更に好ましくは１０％／２００μｍ以下である。ポリエステル樹脂組成物（Ｃ）の波長３５０ｎｍの光の透過率が上記範囲である事で、本発明のポリエステル樹脂組成物（Ｃ）はＵＶバリア性が良好なものとなる。 The polyester resin composition (C) of the present embodiment has a light transmittance of 30% / 200 μm or less at a wavelength of 350 nm. The transmittance is preferably 20% / 200 μm or less, more preferably 15% / 200 μm or less, and even more preferably 10% / 200 μm or less. When the polyester resin composition (C) has a light transmittance of 350 nm in the above range, the polyester resin composition (C) of the present invention has good UV barrier properties.
ポリエステル樹脂（Ｂ）がＰＥＴである場合に本発明のポリエステル樹脂組成物（Ｃ）が透明性に優れる事が産業的に特に有用である。ポリエステル樹脂（Ａ）とＰＥＴを溶融混練した組成物が、透明性を維持したまま耐熱性、ＵＶバリア性が向上するからである。 When the polyester resin (B) is PET, it is industrially particularly useful that the polyester resin composition (C) of the present invention is excellent in transparency. This is because the composition obtained by melt-kneading the polyester resin (A) and PET improves heat resistance and UV barrier properties while maintaining transparency.
ポリエステル樹脂（Ｂ）がＰＥＴである場合、ＰＥＴの屈折率は約１．５７５である為、透明性に優れるポリエステル樹脂組成物（Ｃ）を得るにはポリエステル樹脂（Ａ）の屈折率は１．５７０〜１．５８０である必要がある。この様な屈折率範囲のポリエステル樹脂（Ａ）を与える組成は多数あるが、ポリエステル樹脂（Ａ）の機械物性、耐熱性、及び経済性を考慮すると環状アセタール骨格を有するジオール以外のジオールがエチレングリコールで、ナフタレン骨格を有するジカルボン酸以外のジカルボン酸がテレフタル酸である事が好ましい。 When the polyester resin (B) is PET, since the refractive index of PET is about 1.575, the refractive index of the polyester resin (A) is 1. for obtaining a polyester resin composition (C) having excellent transparency. It must be 570 to 1.580. There are many compositions that give polyester resin (A) in such a refractive index range, but considering the mechanical properties, heat resistance, and economy of polyester resin (A), diols other than diols having a cyclic acetal skeleton are ethylene glycol. Thus, it is preferable that the dicarboxylic acid other than the dicarboxylic acid having a naphthalene skeleton is terephthalic acid.
本実施形態のポリエステル樹脂組成物（Ｃ）は、本発明の目的を損なわない範囲で各種の成形助剤や添加剤、例えばフィラー、着色剤、補強剤、表面平滑剤、レベリング剤、硬化反応促進剤、光安定化剤、紫外線吸収剤、可塑剤、酸化防止剤、増量剤、つや消し剤、乾燥調節剤、帯電防止剤、沈降防止剤、界面活性剤、流れ改良剤、乾燥油、ワックス類、熱可塑性オリゴマー等を含むこともできる。 The polyester resin composition (C) of the present embodiment has various molding aids and additives such as fillers, colorants, reinforcing agents, surface smoothing agents, leveling agents, and curing reaction accelerations as long as the object of the present invention is not impaired. Agents, light stabilizers, UV absorbers, plasticizers, antioxidants, extenders, matting agents, drying regulators, antistatic agents, antisettling agents, surfactants, flow improvers, drying oils, waxes, A thermoplastic oligomer etc. can also be included.
本実施形態のポリエステル樹脂組成物（Ｃ）は、本発明の目的を損なわない範囲で溶剤を含んでも良く、また、脂肪族ポリエステル樹脂、熱可塑性ポリエステルエラストマー、ポリオレフィン、ポリスチレン、アクリロニトリル−ブタジエン−スチレン共重合体、ポリメチルメタクリレート、ポリスルホン、ポリエーテル、フェノキシ樹脂、ポリフェニレンオキシド等の樹脂を単独に又は複数含んでいてもよい。 The polyester resin composition (C) of the present embodiment may contain a solvent as long as the object of the present invention is not impaired, and is an aliphatic polyester resin, thermoplastic polyester elastomer, polyolefin, polystyrene, acrylonitrile-butadiene-styrene copolymer. A resin such as a polymer, polymethyl methacrylate, polysulfone, polyether, phenoxy resin, polyphenylene oxide or the like may be contained alone or in combination.
本実施形態のポリエステル樹脂組成物（Ｃ）はポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）を溶融混練する事で得られる。溶融混練は従来既知の方法で行えば良く、例えばポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）を事前に混合しておき、単軸押出し機、二軸押出し機、射出成型機などで溶融混練する方法が挙げられる。樹脂の混合は公知の装置を用いる事ができ、例えばタンブラー、高速ミキサー、ナウターミキサー、リボン型ブレンダー、インテンシブミキサー等を例示する事ができる。 The polyester resin composition (C) of this embodiment is obtained by melt-kneading the polyester resin (A) and the polyester resin (B). The melt kneading may be performed by a conventionally known method. For example, the polyester resin (A) and the polyester resin (B) are mixed in advance and melt kneaded by a single screw extruder, a twin screw extruder, an injection molding machine, or the like. A method is mentioned. A known apparatus can be used for mixing the resin, and examples thereof include a tumbler, a high speed mixer, a nauter mixer, a ribbon blender, and an intensive mixer.
ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）の溶融混練を行う際にポリエステル樹脂間で一部エステル交換反応が起こることがあるが、エステル交換反応の有無やエステル交換反応の度合いにより本発明の効果が損なわれるものではなく、エステル交換反応が起こった樹脂組成物も本発明のポリエステル樹脂組成物に属するものである。 When the polyester resin (A) and the polyester resin (B) are melt-kneaded, a transesterification reaction may occur between the polyester resins. The effect of the present invention depends on the presence or absence of the transesterification reaction and the degree of the transesterification reaction. The resin composition in which the transesterification has occurred also belongs to the polyester resin composition of the present invention.
本実施形態のポリエステル樹脂組成物（Ｃ）は従来公知の方法で成形する事ができる。成形方法は例えば、押出し成形、射出成形、カレンダー成形、押出しブロー成形、射出ブロー成形、インフレーション成形、真空成形、圧空成形、真空圧空成形、一軸延伸、逐次二軸延伸、同時二軸延伸等が挙げられる。これらは、他の樹脂との多層構造とする共押出しや、共射出でも良い。 The polyester resin composition (C) of the present embodiment can be molded by a conventionally known method. Examples of the molding method include extrusion molding, injection molding, calendar molding, extrusion blow molding, injection blow molding, inflation molding, vacuum molding, pressure molding, vacuum pressure molding, uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching. It is done. These may be co-extrusion with other resins or a co-injection.
本実施形態のポリエステル樹脂組成物（Ｃ）の具体的用途としては、特に制限はないが、例えば、飲料水、炭酸飲料、コーヒー飲料、緑茶飲料、紅茶飲料、果汁入り炭酸飲料、スポーツドリンク、乳酸菌飲料、ワイン、ビール、焼酎、日本酒、醤油、ソース、ドレッシング、栄養ドリンク、ハンドクリーム、整髪料、目薬、化粧品、シャンプー、ボディーソープ、医薬品、文具、工具、芳香剤、消臭剤用の中空容器、練りからし、練りワサビ、練りショウガ、練りニンニク、コンデンスミルク、ピーナッツバター、マーガリン、チョコレートクリーム、練り歯磨き等の押出しチューブ容器、ＰＥＴボトル、チーズ、ハム、ソーセージ等の外装フィルム、窓ガラス用ＵＶカットフィルム、ゼリー、プリン、カットフルーツ、味噌、歯ブラシ、電化製品、半導体、乳児用食品の包装容器等が挙げられる。 Although there is no restriction | limiting in particular as a specific use of the polyester resin composition (C) of this embodiment, For example, drinking water, carbonated drink, coffee drink, green tea drink, tea drink, carbonated drink containing fruit juice, sports drink, lactic acid bacteria Hollow containers for beverages, wine, beer, shochu, sake, soy sauce, sauces, dressings, energy drinks, hand creams, hair styling, eye drops, cosmetics, shampoos, body soaps, pharmaceuticals, stationery, tools, fragrances, deodorants , Kneaded, kneaded wasabi, kneaded ginger, kneaded garlic, condensed milk, peanut butter, margarine, chocolate cream, toothpaste and other extruded tube containers, PET bottles, cheese, ham, sausage and other exterior films, window glass UV Cut film, jelly, pudding, cut fruit, miso, toothbrush, electric Products, semiconductor, packaging containers such as infant food, and the like.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明はこれらの実施例によりその範囲を限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by these examples.
〔ポリエステル樹脂（Ａ）の合成（製造例１〜３）〕
充填塔式精留塔、分縮器、全縮器、コールドトラップ、撹拌機、加熱装置、窒素導入管を備えた０．１５立方メートルのポリエステル製造装置に表１に記載量の原料モノマーを仕込み、ジカルボン酸成分１００モルに対し酢酸マンガン４水和物０．０３モルの存在下、窒素雰囲気下で２１５℃迄昇温してエステル交換反応を行った。メタノールの留出量が理論量に対して９０％以上に達した後、ジカルボン酸成分１００モルに対し、酸化アンチモン（ＩＩＩ）０．０１モルとリン酸トリエチル０．０６モルを加え、昇温と減圧を徐々に行い、最終的に２８０℃、１００Ｐａ以下で重合を行った。適度な溶融粘度になった時点で反応を終了し、ポリエステル樹脂（Ａ）を得た。得られたポリエステル樹脂（Ａ）の評価結果を表１に示す。
尚、表中の略記は下記を意味する。
ＤＭＴ：ジメチルテレフタレート
ＮＤＣＭ：２，６−ナフタレンジカルボン酸ジメチル
ＥＧ：エチレングリコール
ＳＰＧ：３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン
[Synthesis of polyester resin (A) (Production Examples 1 to 3)]
A 0.15 cubic meter polyester production apparatus equipped with a packed tower type rectification tower, a partial condenser, a full condenser, a cold trap, a stirrer, a heating device, and a nitrogen introduction tube is charged with the raw material monomer in the amount shown in Table 1. In the presence of 0.03 mol of manganese acetate tetrahydrate with respect to 100 mol of the dicarboxylic acid component, the temperature was raised to 215 ° C. in a nitrogen atmosphere to conduct a transesterification reaction. After the amount of distilled methanol reached 90% or more of the theoretical amount, 0.01 mol of antimony (III) oxide and 0.06 mol of triethyl phosphate were added to 100 mol of the dicarboxylic acid component, The pressure was gradually reduced, and polymerization was finally performed at 280 ° C. and 100 Pa or less. The reaction was terminated when an appropriate melt viscosity was reached, and a polyester resin (A) was obtained. Table 1 shows the evaluation results of the obtained polyester resin (A).
Abbreviations in the table mean the following.
DMT: dimethyl terephthalate NDCM: dimethyl 2,6-naphthalenedicarboxylate EG: ethylene glycol SPG: 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [ 5.5] Undecane
〔他のポリエステル樹脂〕
本実施例中で使用した環状アセタール骨格を有しないポリエステル樹脂を以下に記す。また、これらのポリエステル樹脂に関する評価結果を表２に示す。
（１）ＰＥＴ：ポリエチレンテレフタレート（日本ユニペット（株）製、商品名：ＵＮＩＰＥＴ ＲＴ５５３Ｃ）
（２）ＰＥＮ：ポリエチレンナフタレート（東洋紡績（株）製、商品名：ＰＮ−５１０）
[Other polyester resins]
The polyester resin having no cyclic acetal skeleton used in this example is described below. In addition, Table 2 shows the evaluation results regarding these polyester resins.
(1) PET: Polyethylene terephthalate (manufactured by Nippon Unipet Co., Ltd., trade name: UNIPET RT553C)
(2) PEN: Polyethylene naphthalate (Toyobo Co., Ltd., trade name: PN-510)
〔各ポリエステル樹脂の評価方法〕
（１）共重合組成
各構成単位の組成を１Ｈ−ＮＭＲ測定にて算出した。測定はＢＲＵＫＥＲ製ＢＲＵＫＥＲ ＡＤＶＡＮＣＥ−５００IIIを用い、５００ＭＨｚで測定した。溶媒には重クロロホルムを用いた。ＰＥＴ、ＰＥＮの評価の際は重クロロホルム／重トリフルオロ酢酸混合溶媒（容量比：９／１）を用いた。
（２）ガラス転移温度
（株）島津製作所製ＤＳＣ／ＴＡ−６０ＷＳを使用し、ポリエステル樹脂約１０ｍｇをアルミニウム製非密封容器に入れ、窒素ガス（３０ｍｌ／ｍｉｎ）気流中、昇温速度２０℃／ｍｉｎで２８０℃まで加熱、溶融したものを急冷して測定用試料とした。該試料を同条件で測定し、ＤＳＣ曲線の転移前後における基線の差の１／２だけ変化した温度をガラス転移温度とした。
（３）極限粘度
混合溶媒（重量比：フェノール／１，１，２，２−テトラクロロエタン＝６／４）を用いて２５℃で測定した。測定はＶＩＳＣＯＴＥＫ社製ＲＥＬＡＴＩＶＥ ＶＩＳＣＯＭＥＴＥＲ Ｙ５０１Ｃを用いて行った。
（４）屈折率
ポリエステル樹脂を射出成形にて、一辺が２０ｍｍの直角二等辺三角形（３ｍｍ厚）に成形した。射出成形は住友重機械工業（株）製ＳＥ１３０を用いた。この成形片をＴｇ−２０℃のオーブンで１０時間アニール処理した物を測定サンプルとし、ＡＴＡＧＯ（株）製屈折率計を用い、５８９ｎｍ（ナトリウムD線）で屈折率を測定した。
[Evaluation method of each polyester resin]
(1) Copolymer composition The composition of each structural unit was calculated by 1 H-NMR measurement. The measurement was performed at 500 MHz using a BRUKER ADVANCE-500III manufactured by BRUKER. Deuterated chloroform was used as the solvent. In the evaluation of PET and PEN, a deuterated chloroform / deuterated trifluoroacetic acid mixed solvent (volume ratio: 9/1) was used.
(2) Glass transition temperature Using DSC / TA-60WS manufactured by Shimadzu Corporation, about 10 mg of polyester resin is put in an aluminum non-sealed container, and the temperature rising rate is 20 ° C. in a nitrogen gas (30 ml / min) stream. A sample heated and melted at 280 ° C. for min was rapidly cooled to obtain a measurement sample. The sample was measured under the same conditions, and the temperature at which the difference between the baselines before and after the transition of the DSC curve changed by 1/2 was taken as the glass transition temperature.
(3) Intrinsic viscosity The intrinsic viscosity was measured at 25 ° C. using a mixed solvent (weight ratio: phenol / 1,1,2,2-tetrachloroethane = 6/4). The measurement was performed using RELATIVE VISCOMETER Y501C manufactured by Viscotek.
(4) Refractive index Polyester resin was formed into a right-angled isosceles triangle (3 mm thickness) having a side of 20 mm by injection molding. For injection molding, SE130 manufactured by Sumitomo Heavy Industries, Ltd. was used. The molded piece was annealed in an oven at Tg-20 ° C. for 10 hours as a measurement sample, and the refractive index was measured at 589 nm (sodium D line) using an ATAGO refractometer.
〔実施例１〕
ポリエステル樹脂（Ａ）として製造例１で合成したポリエステル樹脂を使用し、ポリエステル樹脂（Ｂ）として表２に示すＰＥＴ樹脂を使用し、表３に記載する割合でポリエステル樹脂（Ａ）、ポリエステル樹脂（Ｂ）をタンブラーにてドライブレンドした後、単軸押出機（スクリュー径：３２ｍｍφ、Ｌ／Ｄ：３２）で溶融混練し、厚さ０．２ｍｍのポリエステル樹脂組成物（Ｃ）のシートを作製した。製膜条件は、シリンダー温度２３５〜２６５℃、Ｔダイ温度２６５℃、スクリュー回転数４０ｒｐｍ、冷却ロール温度７５℃である。各種評価は以下に示す方法により行った。評価結果を表３に示す。
[Example 1]
The polyester resin synthesized in Production Example 1 was used as the polyester resin (A), the PET resin shown in Table 2 was used as the polyester resin (B), and the polyester resin (A) and polyester resin ( After B) was dry blended with a tumbler, it was melt-kneaded with a single screw extruder (screw diameter: 32 mmφ, L / D: 32) to prepare a sheet of polyester resin composition (C) having a thickness of 0.2 mm. . The film forming conditions are a cylinder temperature of 235 to 265 ° C., a T die temperature of 265 ° C., a screw rotation speed of 40 rpm, and a cooling roll temperature of 75 ° C. Various evaluations were performed by the following methods. The evaluation results are shown in Table 3.
〔ポリエステル樹脂組成物（Ｃ）のシートの評価方法〕
（１）組成
各構成単位の組成を１Ｈ−ＮＭＲ測定にて算出した。測定はＢＲＵＫＥＲ製ＢＲＵＫＥＲ ＡＤＶＡＮＣＥ−５００IIIを用い、５００ＭＨｚで測定した。溶媒には重クロロホルム／重トリフルオロ酢酸混合溶媒（容量比：９／１）を用いた。
（２）ガラス転移温度
（株）島津製作所製ＤＳＣ／ＴＡ−６０ＷＳを使用し、ポリエステル樹脂組成物のシート約１０ｍｇをアルミニウム製非密封容器に入れ、窒素ガス（３０ｍｌ／ｍｉｎ）気流中、昇温速度２０℃／ｍｉｎで２８０℃まで加熱、溶融したものを急冷して測定用試料とした。該試料を同条件で測定し、ＤＳＣ曲線の転移前後における基線の差の１／２だけ変化した温度をガラス転移温度とした。
（３）曇価
曇価は、ＪＩＳ Ｋ−７１０５、ＡＳＴＭ Ｄ１００３に準じて０．２ｍｍ厚のシートを測定した。使用した測定装置は、日本電色工業社製の曇価測定装置（型式：ＣＯＨ−３００Ａ）である。
（４）波長３５０ｎｍの光の透過率
波長３５０ｎｍの光の透過率は島津製作所性紫外可視近赤外分光光度計ＵＶ−３１００ＰＣ、マルチパーパス大型試料室ユニットＭＰＣ−３１００形を用いて、０．２ｍｍ厚のシートを測定した。
[Evaluation Method for Polyester Resin Composition (C) Sheet]
(1) Composition The composition of each structural unit was calculated by 1 H-NMR measurement. The measurement was performed at 500 MHz using a BRUKER ADVANCE-500III manufactured by BRUKER. A deuterated chloroform / deuterated trifluoroacetic acid mixed solvent (volume ratio: 9/1) was used as the solvent.
(2) Glass transition temperature Using DSC / TA-60WS manufactured by Shimadzu Corporation, about 10 mg of a polyester resin composition sheet is placed in an aluminum non-sealed container and heated in a nitrogen gas (30 ml / min) stream. A sample heated and melted to 280 ° C. at a rate of 20 ° C./min was rapidly cooled to obtain a measurement sample. The sample was measured under the same conditions, and the temperature at which the difference between the baselines before and after the transition of the DSC curve changed by 1/2 was taken as the glass transition temperature.
(3) Haze value The haze value was determined by measuring a 0.2 mm thick sheet according to JIS K-7105 and ASTM D1003. The measuring apparatus used is a fog value measuring apparatus (model: COH-300A) manufactured by Nippon Denshoku Industries Co., Ltd.
(4) Transmittance of light having a wavelength of 350 nm The transmittance of light having a wavelength of 350 nm is 0.2 mm using a Shimadzu UV-visible near-infrared spectrophotometer UV-3100PC, a multipurpose large sample chamber unit MPC-3100. Thick sheets were measured.
〔実施例２〜３〕
実施例１において、ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）の溶融混練の割合を表３に記載する割合に変更した以外は、実施例１と同様にしてポリエステル樹脂組成物（Ｃ）のシートの作製を行い、各種の評価を実施した。評価結果を表３に示す。
[Examples 2-3]
In Example 1, a sheet of the polyester resin composition (C) was prepared in the same manner as in Example 1 except that the melt kneading ratio of the polyester resin (A) and the polyester resin (B) was changed to the ratio described in Table 3. And various evaluations were performed. The evaluation results are shown in Table 3.
〔実施例４〜６〕
実施例１において、ポリエステル樹脂（Ａ）として製造例２で合成したポリエステル樹脂を使用し、ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）の溶融混練の割合を表４に記載する割合とした以外は、実施例１と同様にしてポリエステル樹脂組成物（Ｃ）のシートの作製を行い、各種の評価を実施した。評価結果を表４に示す。
[Examples 4 to 6]
In Example 1, the polyester resin synthesized in Production Example 2 was used as the polyester resin (A), and the ratio of the melt kneading of the polyester resin (A) and the polyester resin (B) was changed to the ratio described in Table 4. In the same manner as in Example 1, a sheet of the polyester resin composition (C) was prepared, and various evaluations were performed. The evaluation results are shown in Table 4.
〔実施例７、８〕
実施例１において、ポリエステル樹脂（Ａ）として製造例３で合成したポリエステル樹脂を使用し、ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）の溶融混練の割合を表５に記載する割合とした以外は、実施例１と同様にしてポリエステル樹脂組成物（Ｃ）のシートの作製を行い、各種の評価を実施した。評価結果を表５に示す。
[Examples 7 and 8]
In Example 1, the polyester resin synthesized in Production Example 3 was used as the polyester resin (A), and the ratio of the melt kneading of the polyester resin (A) and the polyester resin (B) was changed to the ratio described in Table 5. In the same manner as in Example 1, a sheet of the polyester resin composition (C) was prepared, and various evaluations were performed. The evaluation results are shown in Table 5.
〔比較例１〜３〕
ポリエステル樹脂（Ａ）に代えて表２に示すＰＥＮ樹脂を使用し、ポリエステル樹脂（Ｂ）として表２に示すＰＥＴ樹脂を使用し、表６に記載する割合でＰＥＮ、ポリエステル樹脂（Ｂ）をタンブラーにてドライブレンドした後、単軸押出機（スクリュー径：３２ｍｍφ、Ｌ／Ｄ：３２）で溶融混練し、厚さ０．２ｍｍのポリエステル樹脂組成物（Ｃ）のシートを作製した。製膜条件は、シリンダー温度２３５〜２８５℃、Ｔダイ温度２８５℃、スクリュー回転数４０ｒｐｍ、冷却ロール温度７５℃である。各種評価は下記に示す方法により行った。
得られたポリエステル樹脂組成物（Ｃ）のシートを表５に記載の温度、予熱温度３０秒で３．０×３．０倍に同時二軸延伸してポリエステル系二次加工成形体（Ｄ）の作製を行い、各種の評価を実施した。樹脂組成物（Ｃ）、及び二次加工成形体（Ｄ）の評価結果を表６に示す。
[Comparative Examples 1-3]
The PEN resin shown in Table 2 is used instead of the polyester resin (A), the PET resin shown in Table 2 is used as the polyester resin (B), and the PEN and the polyester resin (B) are tumbled in the ratios shown in Table 6. After dry blending, a single-screw extruder (screw diameter: 32 mmφ, L / D: 32) was melt-kneaded to prepare a 0.2 mm thick polyester resin composition (C) sheet. The film forming conditions are a cylinder temperature of 235 to 285 ° C., a T die temperature of 285 ° C., a screw rotation speed of 40 rpm, and a cooling roll temperature of 75 ° C. Various evaluations were performed by the methods shown below.
The obtained polyester resin composition (C) sheet is simultaneously biaxially stretched 3.0 × 3.0 times at a temperature shown in Table 5 and a preheating temperature of 30 seconds to obtain a polyester-based secondary processed molded article (D). And various evaluations were performed. Table 6 shows the evaluation results of the resin composition (C) and the secondary processed molded body (D).
本発明のポリエステル樹脂組成物は、耐熱性、透明性、ＵＶバリア性に優れたポリエステル樹脂組成物であり、シート、フィルム、シート成形体、中空容器等に好適に用いることができる。 The polyester resin composition of the present invention is a polyester resin composition excellent in heat resistance, transparency and UV barrier properties, and can be suitably used for sheets, films, sheet molded articles, hollow containers and the like.
Claims (6)
（１）ポリエステル樹脂（Ａ）とポリエステル樹脂（Ｂ）のナトリウムＤ線を光源として測定した屈折率差が０．００５以下である。
（２）ポリエステル樹脂組成物（Ｃ）中の全ジオール構成単位中の環状アセタール骨格を有するジオールに由来する単位の割合が０．０５〜２０モル％である。
（３）ポリエステル樹脂組成物（Ｃ）中の全ジカルボン酸単位中のナフタレン骨格を有するジカルボン酸に由来する単位の割合が０．１〜３０モル％である。
（４）波長３５０ｎｍの光の透過率が３０％／２００μｍ以下である。 A polyester resin (A) containing a unit derived from a diol having a cyclic acetal skeleton as a diol unit and a unit derived from a dicarboxylic acid having a naphthalene skeleton as a dicarboxylic acid unit; and a polyester resin having no cyclic acetal skeleton ( B) and a polyester resin composition (C) having the following characteristics (1) to (4).
(1) The refractive index difference measured using the sodium D line of the polyester resin (A) and the polyester resin (B) as a light source is 0.005 or less.
(2) The ratio of the unit derived from the diol which has a cyclic acetal skeleton in all the diol structural units in the polyester resin composition (C) is 0.05 to 20 mol%.
(3) The ratio of the unit derived from the dicarboxylic acid having a naphthalene skeleton in all the dicarboxylic acid units in the polyester resin composition (C) is 0.1 to 30 mol%.
(4) The transmittance of light having a wavelength of 350 nm is 30% / 200 μm or less.
又は一般式（２）：
で表されるジオールに由来する単位である請求項１に記載のポリエステル樹脂組成物（Ｃ）。 The unit derived from the diol having a cyclic acetal skeleton in the polyester resin (A) is represented by the general formula (1):
Or general formula (2):
The polyester resin composition (C) according to claim 1, which is a unit derived from a diol represented by the formula:
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117283957A (en) * | 2023-08-16 | 2023-12-26 | 杭州井羽科技有限公司 | Wear-resistant antibacterial down jacket fabric suitable for children and production process thereof |
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| CN117283957A (en) * | 2023-08-16 | 2023-12-26 | 杭州井羽科技有限公司 | Wear-resistant antibacterial down jacket fabric suitable for children and production process thereof |
| CN117283957B (en) * | 2023-08-16 | 2024-06-07 | 杭州井羽科技有限公司 | Wear-resistant antibacterial down jacket fabric suitable for children and production process thereof |
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