JP4297425B2 - Polyester resin container with improved weather resistance - Google Patents
Polyester resin container with improved weather resistance Download PDFInfo
- Publication number
- JP4297425B2 JP4297425B2 JP2003336342A JP2003336342A JP4297425B2 JP 4297425 B2 JP4297425 B2 JP 4297425B2 JP 2003336342 A JP2003336342 A JP 2003336342A JP 2003336342 A JP2003336342 A JP 2003336342A JP 4297425 B2 JP4297425 B2 JP 4297425B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- carbon atoms
- butyl
- bis
- resin container
- 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.)
- Expired - Fee Related
Links
- 229920001225 polyester resin Polymers 0.000 title claims description 28
- 239000004645 polyester resin Substances 0.000 title claims description 28
- -1 polyethylene terephthalate Polymers 0.000 claims description 52
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 27
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000012964 benzotriazole Substances 0.000 claims description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 235000013305 food Nutrition 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 7
- 150000002291 germanium compounds Chemical class 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 230000001954 sterilising effect Effects 0.000 claims description 3
- 238000004659 sterilization and disinfection Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 11
- 239000007983 Tris buffer Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- 239000003086 colorant Substances 0.000 description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- FDBMBOYIVUGUSL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FDBMBOYIVUGUSL-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 241001122767 Theaceae Species 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- ONTODYXHFBKCDK-UHFFFAOYSA-N 2-(2,4-dimethylphenyl)-1,3,5-triazine Chemical compound CC1=CC(C)=CC=C1C1=NC=NC=N1 ONTODYXHFBKCDK-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241001483078 Phyto 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
- 230000004888 barrier function Effects 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000014171 carbonated beverage Nutrition 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 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 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 235000014214 soft drink Nutrition 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QGMCRJZYVLHHHB-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 QGMCRJZYVLHHHB-UHFFFAOYSA-N 0.000 description 1
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- JMUOXOJMXILBTE-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 JMUOXOJMXILBTE-UHFFFAOYSA-N 0.000 description 1
- CNIJRTXPAADHAS-UHFFFAOYSA-N (2,4,6-tritert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(OP(O)O)C(C(C)(C)C)=C1 CNIJRTXPAADHAS-UHFFFAOYSA-N 0.000 description 1
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- ABFCPWCUXLLRSC-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C ABFCPWCUXLLRSC-UHFFFAOYSA-N 0.000 description 1
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 description 1
- UTVSTXBMSHWVAR-UHFFFAOYSA-N 1,1-bis(2,5-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=C(C=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=CC(=C1)C(C)(C)C)C(C)(C)C UTVSTXBMSHWVAR-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- FGYJSJUSODGXAR-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-octoxy-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(OCCCCCCCC)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C FGYJSJUSODGXAR-UHFFFAOYSA-N 0.000 description 1
- LFEXFIMXNKZYEX-UHFFFAOYSA-N 1,4-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-2,3-di(tridecyl)butane-1,2,3,4-tetracarboxylic acid Chemical compound CN1C(CC(CC1(C)C)C(C(C(C(C(=O)O)C1CC(N(C(C1)(C)C)C)(C)C)(C(=O)O)CCCCCCCCCCCCC)(C(=O)O)CCCCCCCCCCCCC)C(=O)O)(C)C LFEXFIMXNKZYEX-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- FLSKKFALEYBSJE-UHFFFAOYSA-N 2,6-ditert-butyl-4-[1-(3,5-ditert-butyl-4-hydroxyphenyl)butyl]phenol Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1C(CCC)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLSKKFALEYBSJE-UHFFFAOYSA-N 0.000 description 1
- JMCKNCBUBGMWAY-UHFFFAOYSA-N 2,6-ditert-butyl-4-[[4-(3,5-ditert-butyl-4-hydroxyphenoxy)-6-octylsulfanyl-1,3,5-triazin-2-yl]oxy]phenol Chemical compound N=1C(OC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=NC(SCCCCCCCC)=NC=1OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JMCKNCBUBGMWAY-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- UUINYPIVWRZHAG-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methoxyphenol Chemical compound OC1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 UUINYPIVWRZHAG-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- QCLHBRMEGVMGKL-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC(C(C)(C)CC(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O QCLHBRMEGVMGKL-UHFFFAOYSA-N 0.000 description 1
- ASDMUNZLXRVGMR-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-2-hydroxy-5-methylphenyl]ethyl prop-2-enoate Chemical compound CC1=CC(CCOC(=O)C=C)=C(O)C(N2N=C3C=CC=CC3=N2)=C1 ASDMUNZLXRVGMR-UHFFFAOYSA-N 0.000 description 1
- DYYWBJYAVFTROM-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxy-5-(2-methylbutan-2-yl)phenyl]ethyl 2-methylprop-2-enoate Chemical compound CCC(C)(C)C1=CC(CCOC(=O)C(C)=C)=CC(N2N=C3C=CC=CC3=N2)=C1O DYYWBJYAVFTROM-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- ABNWZMSOVWRPJN-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-5-tert-butyl-2-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O ABNWZMSOVWRPJN-UHFFFAOYSA-N 0.000 description 1
- ZSSVCEUEVMALRD-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 ZSSVCEUEVMALRD-UHFFFAOYSA-N 0.000 description 1
- FBNLLKQNSHIJHE-UHFFFAOYSA-N 2-[4-[4,6-bis(4-methylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]ethyl prop-2-enoate Chemical compound C1=CC(C)=CC=C1C1=NC(C=2C=CC(C)=CC=2)=NC(C=2C(=CC(OCCOC(=O)C=C)=CC=2)O)=N1 FBNLLKQNSHIJHE-UHFFFAOYSA-N 0.000 description 1
- UTNSTOOXQPHXJQ-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyethoxy)phenyl]sulfonylphenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1S(=O)(=O)C1=CC=C(OCCO)C=C1 UTNSTOOXQPHXJQ-UHFFFAOYSA-N 0.000 description 1
- BDBCZPBSCPQMDW-UHFFFAOYSA-N 2-[5-tert-butyl-3-(5-chlorobenzotriazol-2-yl)-2-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O BDBCZPBSCPQMDW-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- NMAGCVWUISAHAP-UHFFFAOYSA-N 3,5-ditert-butyl-2-(2,4-ditert-butylphenyl)-4-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1C1=C(C(O)=O)C=C(C(C)(C)C)C(O)=C1C(C)(C)C NMAGCVWUISAHAP-UHFFFAOYSA-N 0.000 description 1
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- RLWDBZIHAUEHLO-UHFFFAOYSA-N 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propyl 2-methylprop-2-enoate Chemical compound CC(C)(C)C1=CC(CCCOC(=O)C(=C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O RLWDBZIHAUEHLO-UHFFFAOYSA-N 0.000 description 1
- COXVWIFYICVCKC-UHFFFAOYSA-N 3-[4-(benzotriazol-2-yl)-3-hydroxyphenyl]propyl 2-methylprop-2-enoate Chemical compound OC1=CC(CCCOC(=O)C(=C)C)=CC=C1N1N=C2C=CC=CC2=N1 COXVWIFYICVCKC-UHFFFAOYSA-N 0.000 description 1
- UVHLUYZMNUCVJN-UHFFFAOYSA-N 3-methyloctane-4,4-diol Chemical compound CCCCC(O)(O)C(C)CC UVHLUYZMNUCVJN-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
- HPFWYRKGZUGGPB-UHFFFAOYSA-N 4,6-dichloro-n-(2,4,4-trimethylpentan-2-yl)-1,3,5-triazin-2-amine Chemical compound CC(C)(C)CC(C)(C)NC1=NC(Cl)=NC(Cl)=N1 HPFWYRKGZUGGPB-UHFFFAOYSA-N 0.000 description 1
- UQAMDAUJTXFNAD-UHFFFAOYSA-N 4-(4,6-dichloro-1,3,5-triazin-2-yl)morpholine Chemical compound ClC1=NC(Cl)=NC(N2CCOCC2)=N1 UQAMDAUJTXFNAD-UHFFFAOYSA-N 0.000 description 1
- STEYNUVPFMIUOY-UHFFFAOYSA-N 4-Hydroxy-1-(2-hydroxyethyl)-2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CC(O)CC(C)(C)N1CCO STEYNUVPFMIUOY-UHFFFAOYSA-N 0.000 description 1
- OZOAMTISPPUGSQ-UHFFFAOYSA-N 4-[14,16-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-15,15,16,17-tetra(tridecyl)triacontan-14-yl]-2-tert-butyl-5-methylphenol phosphorous acid Chemical compound OP(O)O.OP(O)O.OP(O)O.C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCCCCCCCCCCCC)(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C(CCCCCCCCCCCCC)(CCCCCCCCCCCCC)C(CCCCCCCCCCCCC)(C(CCCCCCCCCCCCC)CCCCCCCCCCCCC)C1=CC(C(C)(C)C)=C(O)C=C1C OZOAMTISPPUGSQ-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- JJHKARPEMHIIQC-UHFFFAOYSA-N 4-octadecoxy-2,6-diphenylphenol Chemical compound C=1C(OCCCCCCCCCCCCCCCCCC)=CC(C=2C=CC=CC=2)=C(O)C=1C1=CC=CC=C1 JJHKARPEMHIIQC-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- OWXXKGVQBCBSFJ-UHFFFAOYSA-N 6-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]ami Chemical compound N=1C(NCCCN(CCN(CCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 OWXXKGVQBCBSFJ-UHFFFAOYSA-N 0.000 description 1
- HNKNVHRXMLUJGX-UHFFFAOYSA-N 6-n-[3-[[4,6-bis[butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[2-[[4,6-bis[butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[3-[[4,6-bis[butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]amino]pro Chemical compound N=1C(NCCCN(CCN(CCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)NC(C)(C)C2)N(CCCC)C2CC(C)(C)NC(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)NC(C)(C)C2)N(CCCC)C2CC(C)(C)NC(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)NC(C)(C)C2)N(CCCC)C2CC(C)(C)NC(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 HNKNVHRXMLUJGX-UHFFFAOYSA-N 0.000 description 1
- VCPLCWRTNGRWDW-UHFFFAOYSA-N 6-n-[6,11-bis[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]amino]undecyl]-2-n,4-n-dibutyl-2-n,4-n-bis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound N=1C(NCCCCCC(CCCCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)NC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 VCPLCWRTNGRWDW-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- AWBZRKRAARZARD-UHFFFAOYSA-N C(C(=C)C)(=O)OCC1CC(NC(C1)(C)C)(C)C.C(C(=C)C)(=O)OCC1CC(N(C(C1)(C)C)C)(C)C Chemical compound C(C(=C)C)(=O)OCC1CC(NC(C1)(C)C)(C)C.C(C(=C)C)(=O)OCC1CC(N(C(C1)(C)C)C)(C)C AWBZRKRAARZARD-UHFFFAOYSA-N 0.000 description 1
- ARRWFANQIONDNH-UHFFFAOYSA-N CC1(NC(CC(C1)C(C(C(C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)(C(=O)O)CCCCCCCCCCCCC)(C(=O)O)CCCCCCCCCCCCC)C(=O)O)(C)C)C.CC1(NC(CC(C1)OC(=O)CC(C(CC(=O)OC1CC(NC(C1)(C)C)(C)C)C(=O)OC1CC(NC(C1)(C)C)(C)C)C(=O)OC1CC(NC(C1)(C)C)(C)C)(C)C)C Chemical compound CC1(NC(CC(C1)C(C(C(C(C(=O)O)C1CC(NC(C1)(C)C)(C)C)(C(=O)O)CCCCCCCCCCCCC)(C(=O)O)CCCCCCCCCCCCC)C(=O)O)(C)C)C.CC1(NC(CC(C1)OC(=O)CC(C(CC(=O)OC1CC(NC(C1)(C)C)(C)C)C(=O)OC1CC(NC(C1)(C)C)(C)C)C(=O)OC1CC(NC(C1)(C)C)(C)C)(C)C)C ARRWFANQIONDNH-UHFFFAOYSA-N 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NLRNNVIIUWJJNL-UHFFFAOYSA-N N1=NN=CC=C1.OC1=C(C=CC(=C1C)OCCCCCC)C1=NC=NC=N1 Chemical class N1=NN=CC=C1.OC1=C(C=CC(=C1C)OCCCCCC)C1=NC=NC=N1 NLRNNVIIUWJJNL-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- SSXHOSJQPWYXJE-UHFFFAOYSA-N OC(CON1C(CC(CC1(C)C)C(C(=O)O)CCCCCCCCCCCCCCCC)(C)C)(C)C Chemical compound OC(CON1C(CC(CC1(C)C)C(C(=O)O)CCCCCCCCCCCCCCCC)(C)C)(C)C SSXHOSJQPWYXJE-UHFFFAOYSA-N 0.000 description 1
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 1
- CJJOQVXAJJJXJD-UHFFFAOYSA-N OP(O)OP(O)O.C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C Chemical compound OP(O)OP(O)O.C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C CJJOQVXAJJJXJD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 description 1
- JWXSMZJIYUUXSV-UHFFFAOYSA-N bis[2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] benzene-1,4-dicarboxylate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=2C=CC(=CC=2)C(=O)OC=2C(=CC(C)=CC=2CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)C(C)(C)C)=C1O JWXSMZJIYUUXSV-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GLOQRSIADGSLRX-UHFFFAOYSA-N decyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCCCC)OC1=CC=CC=C1 GLOQRSIADGSLRX-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- GWWYBYNZFWRRSG-UHFFFAOYSA-N hydroxyphosphanyloxyphosphinous acid;1,2,3,4-tetrakis(2,4-ditert-butylphenyl)biphenylene Chemical compound OPOPO.CC(C)(C)C1=CC(C(C)(C)C)=CC=C1C(C(=C1C=2C(=CC(=CC=2)C(C)(C)C)C(C)(C)C)C=2C(=CC(=CC=2)C(C)(C)C)C(C)(C)C)=C(C=2C3=CC=CC=2)C3=C1C1=CC=C(C(C)(C)C)C=C1C(C)(C)C GWWYBYNZFWRRSG-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000021056 liquid food Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 description 1
- UZUCIYYGGBSFAB-UHFFFAOYSA-N n-hexyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCCCNC1CC(C)(C)NC(C)(C)C1 UZUCIYYGGBSFAB-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- CYCBIVGDSMISKD-UHFFFAOYSA-N o-tridecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanethioate Chemical compound CCCCCCCCCCCCCOC(=S)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CYCBIVGDSMISKD-UHFFFAOYSA-N 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical class [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- GDESWOTWNNGOMW-UHFFFAOYSA-N resorcinol monobenzoate Chemical compound OC1=CC=CC(OC(=O)C=2C=CC=CC=2)=C1 GDESWOTWNNGOMW-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- WWJZWCUNLNYYAU-UHFFFAOYSA-N temephos Chemical compound C1=CC(OP(=S)(OC)OC)=CC=C1SC1=CC=C(OP(=S)(OC)OC)C=C1 WWJZWCUNLNYYAU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- AUPYNGCJRYOPQY-UHFFFAOYSA-N tris(2,5-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=C(C(C)(C)C)C(OP(OC=2C(=CC=C(C=2)C(C)(C)C)C(C)(C)C)OC=2C(=CC=C(C=2)C(C)(C)C)C(C)(C)C)=C1 AUPYNGCJRYOPQY-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- WRSPWQHUHVRNFV-UHFFFAOYSA-N tris[3,5-di(nonyl)phenyl] phosphite Chemical compound CCCCCCCCCC1=CC(CCCCCCCCC)=CC(OP(OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)=C1 WRSPWQHUHVRNFV-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Packages (AREA)
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゲルマニウム化合物を重縮合触媒に用いたポリエステル樹脂に特定の紫外線吸収剤を添加したことを特徴とするポリエステル樹脂製容器に関する。より詳細には、特定のベンゾトリアゾール系紫外線吸収剤を配合したことを特徴とする清涼飲料用ボトルなどの熱殺菌処理が必要な食品包装容器において耐抽出性に優れ、耐候性にも優れるゲルマニウム重縮合触媒を用いて得られた耐熱性、着色性、耐抽出性に優れるポリエステル樹脂製容器に関する。 The present invention relates to a polyester resin container characterized by adding a specific ultraviolet absorber to a polyester resin using a germanium compound as a polycondensation catalyst. More specifically, germanium heavy, which is excellent in extraction resistance and weather resistance in food packaging containers that require heat sterilization treatment, such as soft drink bottles, characterized by blending a specific benzotriazole-based ultraviolet absorber. The present invention relates to a polyester resin container excellent in heat resistance, colorability, and extraction resistance obtained by using a condensation catalyst.
従来から、ポリエチレンテレフタレート（ＰＥＴ）樹脂は、優れた透明性、ガスバリヤー性などから飲料用ボトル、化粧品・医薬品容器、洗剤・シャンプー容器などに広く用いられている。 Conventionally, polyethylene terephthalate (PET) resin has been widely used in beverage bottles, cosmetic / pharmaceutical containers, detergent / shampoo containers and the like because of its excellent transparency and gas barrier properties.
一般に、ポリエチレンテレフタレート樹脂は、テレフタル酸もしくはテレフタル酸の低分子量アルキルエステルとエチレングリコールからエステル化やエステル交換反応によりビス（ヒドロキシエチル）フタル酸エステルを製造し、これを触媒の存在下に重縮合することで製造される。該重縮合触媒としては、成形サイクルに優れるアンチモン系触媒が一般的であるが、「飽和ポリエステル樹脂ハンドブック」（例えば、非特許文献１参照）に記載されるように、色調や食品衛生の観点から、我が国ではボトル用途に用いるグレードにおいてはゲルマニウム触媒が用いられるようになっている。（例えば、特許文献１参照）。 In general, polyethylene terephthalate resin produces bis (hydroxyethyl) phthalate ester by esterification or transesterification from terephthalic acid or a low molecular weight alkyl ester of terephthalic acid and ethylene glycol, and this is polycondensed in the presence of a catalyst. It is manufactured by. As the polycondensation catalyst, an antimony catalyst having an excellent molding cycle is generally used. However, as described in “Saturated polyester resin handbook” (for example, see Non-Patent Document 1), from the viewpoint of color tone and food hygiene. In Japan, germanium catalysts are used in grades used for bottles. (For example, refer to Patent Document 1).
食品包装容器は、屋外に長期に放置されることはまれで、高度の耐候性は要求されないものの、販売店の店頭などでは太陽光や蛍光灯の光に曝されるため耐候性の付与が要求されている。ＰＥＴボトルは透明性に優れることが清涼飲料などの容器に利用される一因であり、色調の保持は不可欠である。また、容器には炭酸飲料のような圧力のかかるものや、加熱したお茶等を直接充填する場合に、加熱による変形がないことなど機械強度の保持が不可欠である。 Food packaging containers are rarely left outdoors for a long time and do not require a high level of weather resistance, but they are required to be weather-resistant because they are exposed to sunlight and fluorescent light at stores. Has been. The excellent transparency of PET bottles is one of the factors used for containers such as soft drinks, and it is essential to maintain the color tone. In addition, when the container is filled with a pressure such as carbonated beverages or directly filled with heated tea or the like, it is indispensable to maintain mechanical strength such as no deformation due to heating.
各種合成樹脂の安定化方法としては、フェノール系酸化防止剤、リン系酸化防止剤などの酸化防止剤、紫外線吸収剤、ヒンダードアミン系安定剤などの各種添加剤を樹脂に添加することが知られている。しかし、ただ単に、従来のポリエチレンテレフタレートに従来の添加剤を配合した場合には、発色があり、リン系酸化防止剤では青色に樹脂が着色し、ベンゾトリアゾール系化合物では黄色から褐色に着色するため添加剤の使用は制限されていた。 As a method of stabilizing various synthetic resins, it is known to add various additives such as antioxidants such as phenolic antioxidants and phosphorus antioxidants, ultraviolet absorbers and hindered amine stabilizers to the resin. Yes. However, when the conventional additive is added to the conventional polyethylene terephthalate, there is color development, and the phosphorous antioxidant colors the resin in blue, and the benzotriazole compound colors from yellow to brown. The use of additives has been limited.
また、食品包装容器は食品と接触するため、衛生上および味覚への影響から、添加剤は移行性が小さいことが必要である。また、殺菌のために高温に加熱したお茶などをＰＥＴボトルに直接充填する場合などでは、添加剤が抽出されると安定化効果が損なわれるので、特に、耐抽出性は不可欠である。 In addition, since the food packaging container comes into contact with the food, it is necessary that the additive has a low transferability from the viewpoint of hygiene and taste. In addition, in the case of directly filling a PET bottle with tea or the like heated to high temperature for sterilization, the extraction effect is impaired when the additive is extracted, and thus extraction resistance is particularly essential.
解決しようとする問題点は、ポリエステル樹脂に耐候性を付与し、かつ、着色性、耐抽出性にも優れるポリエステル樹脂製容器を提供することである。 The problem to be solved is to provide a polyester resin container which imparts weather resistance to the polyester resin and is excellent in colorability and extraction resistance.
本発明者らは、上記の課題を解決するために鋭意検討を重ねた結果、（Ａ）ゲルマニウム化合物を重縮合触媒に用いて製造されたポリエチレンテレフタレート樹脂１００重量部に、（Ｂ）下記一般式（Ｉ）で表されるベンゾトリアゾール系紫外線吸収剤０．０１〜１０重量部および（Ｃ）下記一般式（ＩＩ）で表される亜リン酸エステル化合物を添加することにより、上記課題を解決できることを見いだし本発明を完成した。 As a result of intensive studies in order to solve the above problems, the present inventors, as a result of (A) 100 parts by weight of a polyethylene terephthalate resin produced using a germanium compound as a polycondensation catalyst, (B) By adding 0.01 to 10 parts by weight of the benzotriazole-based ultraviolet absorber represented by (I) and (C) a phosphite compound represented by the following general formula (II), the above problems can be solved. The present invention was completed.
即ち、本発明の第１は、（Ａ）ゲルマニウム化合物を重縮合触媒に用いて製造されたポリエチレンテレフタレート樹脂１００重量部に、（Ｂ）下記一般式（Ｉ）で表されるベンゾトリアゾール系紫外線吸収剤０．０１〜１０重量部および（Ｃ）下記一般式（ＩＩ）で表される亜リン酸エステル化合物を添加してなるポリエステル樹脂製容器を提供する。 Specifically, according to the first aspect of the present invention, (A) 100 parts by weight of a polyethylene terephthalate resin produced using a germanium compound as a polycondensation catalyst is combined with (B) a benzotriazole-based ultraviolet absorption represented by the following general formula (I). A polyester resin container comprising 0.01 to 10 parts by weight of an agent and (C) a phosphite compound represented by the following general formula (II) is provided.
（式中、Ｒ１、Ｒ２は各々独立に、水素原子、塩素原子又は炭素原子数１〜４のアルキル基を、Ｒ３、Ｒ４は各々独立に、水素原子又は炭素原子数１〜１８のアルキル基を、Ｒ５、Ｒ６は各々独立に、水素原子又は炭素原子数１〜４のアルキル基を表す。） (In the formula, R 1 and R 2 each independently represent a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms; R 3 and R 4 each independently represent a hydrogen atom or 1 to 18 carbon atoms; R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
（式中、Ｒ７は炭素原子数４〜８のアルキル基または炭素原子数７〜１２のアリールアルキル基を、Ｒ８およびＲ９は各々独立に、水素原子、炭素原子数１〜８のアルキル基または炭素原子数７〜１２のアリールアルキル基を表す。）
本発明の第２は、ポリエステル樹脂製容器がブローボトルである本発明の第１に記載のポリエステル樹脂製容器を提供する。
本発明の第３は、ポリエステル樹脂製容器が熱殺菌処理を施された食品包装容器である本発明の第１または２に記載のポリエステル樹脂製容器を提供する。
(Wherein R 7 is an alkyl group having 4 to 8 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms, and R 8 and R 9 are each independently a hydrogen atom or an alkyl having 1 to 8 carbon atoms. Represents a group or an arylalkyl group having 7 to 12 carbon atoms.)
2nd of this invention provides the container made from a polyester resin as described in 1st of this invention whose polyester resin container is a blow bottle.
3rd of this invention provides the polyester resin container as described in 1 or 2 of this invention which is a food packaging container in which the polyester resin container was heat-sterilized.
本発明により、ゲルマニウム重縮合触媒を用いたポリエステル樹脂を着色することなく、また、飲料容器へ用いた場合に添加物が抽出されることなく、衛生的で、優れた耐候性を付与されたポリエステル樹脂製容器が得られる。 According to the present invention, a polyester that is hygienic and has excellent weather resistance without coloring a polyester resin using a germanium polycondensation catalyst and without being extracted with additives when used in a beverage container. A resin container is obtained.
以下、本発明を詳細に説明する。
（Ａ）ゲルマニウム化合物を重縮合触媒に用いて製造されたポリエステル樹脂
本発明に係るポリエステル樹脂としては、汎用ボトル原料として用いられるポリエチレンテレフタレート樹脂、高価格であるがリターナブルボトルとして用いられるポリエチレンナフタレート樹脂などが挙げられる。
Hereinafter, the present invention will be described in detail.
(A) Polyester resin produced using a germanium compound as a polycondensation catalyst The polyester resin according to the present invention includes a polyethylene terephthalate resin used as a general-purpose bottle raw material, a polyethylene naphthalate resin used as a high-priced but returnable bottle Etc.
本発明に用いられるポリエチレンテレフタレート樹脂としては、テレフタル酸とエチレングリコールを主成分として、必要に応じてイソフタル酸やナフタレンジカルボン酸等のジカルボン酸成分、ｐ−ヒドロキシ安息香酸やヒドロキシナフタレンカルボン酸等のオキシカルボン酸成分、シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド付加体、ビスフェノールＳのエチレンオキサイド付加体、ビス（４−β−ヒドロキシエトキシフェニル）スルホン等のジオール成分等を他の成分として用いてもよい。ただし、他の成分が多くなるとポリエチレンテレフタレートの物性が損なわれるので他の重合成分は２０重量％未満、より好ましくは１０重量％未満である。 The polyethylene terephthalate resin used in the present invention includes terephthalic acid and ethylene glycol as main components, dicarboxylic acid components such as isophthalic acid and naphthalenedicarboxylic acid, and oxy Other components such as a carboxylic acid component, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, and bis (4-β-hydroxyethoxyphenyl) sulfone may be used. However, since the physical properties of polyethylene terephthalate are impaired when the amount of other components increases, the amount of other polymerization components is less than 20% by weight, more preferably less than 10% by weight.
ポリエチレンテレフタレート樹脂の重合方法としては、公知の重合方法のいずれでもよく、例えば、ジメチルテレフタレートとエチレングリコールのエステル交換反応や、テレフタル酸とエチレングリコールの直接エステル化反応により前駆体としてのビス（２−ヒドロキシエチル）テレフタレートを合成し、前駆体をゲルマニウム化合物などの重縮合触媒で、溶融重合することによりポリマーが得られる。
ボトル用には高重合度のものが使用されるので、例えば、溶融重合することにより得られたポリマーを融点より２０〜５０℃低い温度でさらに固相重合させる。
The polymerization method of the polyethylene terephthalate resin may be any of known polymerization methods. For example, bis (2- (2- Hydroxyethyl) terephthalate is synthesized, and the polymer is obtained by subjecting the precursor to melt polymerization with a polycondensation catalyst such as a germanium compound.
Since a bottle having a high degree of polymerization is used for the bottle, for example, the polymer obtained by melt polymerization is further solid-phase polymerized at a temperature 20 to 50 ° C. lower than the melting point.
直接エステル化により製造する場合のエステル化触媒としては、例えば、ナトリウム、マグネシウムのメチラート；ホウ酸亜鉛、酢酸亜鉛など亜鉛、カドミウム、マンガン、コバルト、カルシウム、バリウムなどの脂肪酸塩、炭酸塩；金属マグネシウム；鉛、亜鉛、アンチモン、ゲルマニウムなどの酸化物が挙げられる。エステル交換触媒としては、有機酸カルシウムがチタン触媒やマンガン触媒に比べて着色が少なく、食品衛生上安全であり好ましい。 Examples of the esterification catalyst in the case of producing by direct esterification include, for example, sodium and magnesium methylates; zinc borate, zinc acetate and the like, fatty acid salts and carbonates such as zinc, cadmium, manganese, cobalt, calcium and barium; An oxide such as lead, zinc, antimony or germanium; As the transesterification catalyst, organic acid calcium is preferable because it is less colored compared to titanium catalyst and manganese catalyst, and is safe for food hygiene.
上記ゲルマニウム触媒としては、ゲルマニウムの酸化物、無機酸塩、有機酸塩、ハロゲン化物、硫化物など特に制限はなく、例えば、二酸化ゲルマニウム、四塩化ゲルマニウムなどが用いられる。 The germanium catalyst is not particularly limited, such as germanium oxides, inorganic acid salts, organic acid salts, halides, and sulfides. For example, germanium dioxide and germanium tetrachloride are used.
本発明に用いられるポリエチレンナフタレート樹脂としては、上記ポリエチレンテレフタレート樹脂におけるテレフタル酸の代りに、ナフタレンジカルボン酸を用いて得られる。 The polyethylene naphthalate resin used in the present invention can be obtained using naphthalenedicarboxylic acid instead of terephthalic acid in the polyethylene terephthalate resin.
本発明に用いられるポリエステル樹脂としては、容器用グレードが使用され、極限粘度（Ｉ．Ｖ．）が例えば０．５〜１．５、好ましくは０．６〜１．１、非結晶品では０．６５〜０．７５、結晶品では０．７〜１．０５、共重合品では０．７〜０．８のものが使用される。 As the polyester resin used in the present invention, a container grade is used, and the intrinsic viscosity (IV) is, for example, 0.5 to 1.5, preferably 0.6 to 1.1, and 0 for an amorphous product. .65 to 0.75, 0.7 to 1.05 for the crystal product, and 0.7 to 0.8 for the copolymer product.
（Ｂ）ベンゾトリアゾール系紫外線吸収剤
本発明では、前記一般式（Ｉ）で表される（Ｂ）ベンゾトリアゾール系紫外線吸収剤が用いられる。
一般式（Ｉ）において、Ｒ1、Ｒ2は各々独立に水素原子、塩素原子又は炭素原子数１〜４のアルキル基を、Ｒ3、Ｒ4は各々独立に水素原子又は炭素原子数１〜１８のアルキル基を、Ｒ5、Ｒ6は各々独立に水素原子又は炭素原子数１〜４のアルキル基を表す。
Ｒ1、Ｒ2、Ｒ5、Ｒ6で表されるアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチルなどが挙げられる。
(B) Benzotriazole-based UV absorber In the present invention, (B) benzotriazole-based UV absorber represented by the general formula (I) is used.
In the general formula (I), R 1 and R 2 each independently represent a hydrogen atom, a chlorine atom or an alkyl group having 1 to 4 carbon atoms, and R 3 and R 4 each independently represent a hydrogen atom or 1 to 4 carbon atoms. In the 18 alkyl groups, R 5 and R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group represented by R 1 , R 2 , R 5 and R 6 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl.
Ｒ3、Ｒ4で表されるアルキル基は、炭素原子数１〜１８の直鎖または分岐を有するアルキル基であり、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、ペンチル、第三ペンチル、ヘキシル、ヘプチル、オクチル、２−エチルヘキシル、ノニル、イソノニル、デシル、ウンデシル、ドデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシルなどが挙げられる。 The alkyl group represented by R 3 and R 4 is a linear or branched alkyl group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl. , Pentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like.
一般式（Ｉ）で表される化合物としては、より具体的には、以下の化合物Ｎｏ．１〜５などが挙げられる。ただし、本発明は、以下の化合物によりなんら制限を受けるものではない。 More specifically, examples of the compound represented by the general formula (I) include the following compound Nos. 1-5 etc. are mentioned. However, the present invention is not limited by the following compounds.
上記一般式（Ｉ）で表される（Ｂ）ベンゾトリアゾール系紫外線吸収剤はポリエステル樹脂１００重量部に対して０．０１〜１０重量部、好ましくは０．０５〜５重量部、特に好ましくは０．１〜３重量部添加される。０．０１より少ないと十分な安定加効果が得られず、１０重量部より多いと樹脂表面に浮出したり、樹脂組成物の物性が低下するなど得られる容器の商品性を低下させる。 The (B) benzotriazole ultraviolet absorber represented by the general formula (I) is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, particularly preferably 0, to 100 parts by weight of the polyester resin. Add 1-3 parts by weight. If the amount is less than 0.01, a sufficient stabilizing effect cannot be obtained. If the amount is more than 10 parts by weight, the product properties of the resulting container are lowered, such as being raised on the surface of the resin or the physical properties of the resin composition being lowered.
本発明のポリエステル樹脂製容器は、その加工方法は特に限定されなず、シングルステージ法、ツーステージ法、２軸延伸ブロー法、無延伸法のいずれでもよい。シングルステージ法は、押出ブロー、射出ブロー、射出２軸延伸ブロー（ホットパリソン法）のいずれでもよく、ツーステージ法は押出プリフォームのブロー成形でも射出プリフォームのブロー成形でもよい。 The processing method of the polyester resin container of the present invention is not particularly limited, and any of a single stage method, a two-stage method, a biaxial stretch blow method, and a non-stretch method may be used. The single stage method may be any of extrusion blow, injection blow, and injection biaxial stretch blow (hot parison method), and the two-stage method may be extrusion preform blow molding or injection preform blow molding.
また、ポリエチレンテレフタレート樹脂製容器は、酸素や二酸化炭素に対するガスバリヤー性が不十分であるので、ジュースの色が変色したりビタミンが減るようなおそれがある場合には、ポリエステル樹脂製容器は、エチレン−ビニルアルコール共重合体（例えばクラレ（株）製エバール）や芳香族ポリアミド（例えば三菱ガス化学（株）製ＭＸナイロン）などを中間層に入れた共押出成形品であってもよい。 In addition, since polyethylene terephthalate resin containers have insufficient gas barrier properties against oxygen and carbon dioxide, if there is a risk that the juice color may change or vitamins may decrease, polyester resin containers must be made of ethylene. -It may be a co-extruded product in which an intermediate layer is made of a vinyl alcohol copolymer (for example, Eval manufactured by Kuraray Co., Ltd.) or an aromatic polyamide (for example, MX nylon manufactured by Mitsubishi Gas Chemical Co., Ltd.).
本発明のポリエステル樹脂製容器には、必要に応じて、フェノール系酸化防止剤、リン系酸化防止剤、（Ｃ）着色防止剤、他の紫外線吸収剤、ヒンダードアミン系光安定剤、造核剤、難燃剤、金属石鹸、加工助剤、顔料、充填剤、滑剤などを併用して添加することが好ましい。 In the polyester resin container of the present invention, if necessary, phenolic antioxidant, phosphorus antioxidant, (C) anti-coloring agent, other ultraviolet absorbers, hindered amine light stabilizers, nucleating agents, It is preferable to add flame retardants, metal soaps, processing aids, pigments, fillers, lubricants and the like in combination.
上記フェノール系酸化防止剤としては、２，６−ジ第三ブチル−ｐ−クレゾール、２，６−ジフェニル−４−オクタデシロキシフェノール、ステアリル（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオネート、ジステアリル（３，５−ジ第三ブチル−４−ヒドロキシベンジル）ホスホネート、トリデシル・３，５−ジ第三ブチル−４−ヒドロキシベンジルチオアセテート、チオジエチレンビス［（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオネート］、４，４’−チオビス（６−第三ブチル−ｍ−クレゾール）、２−オクチルチオ−４，６−ジ（３，５−ジ第三ブチル−４−ヒドロキシフェノキシ）−ｓ−トリアジン、２，２’−メチレンビス（４−メチル−６−第三ブチルフェノール）、ビス[３，３−ビス（４−ヒドロキシ−３−第三ブチルフェニル）ブチリックアシッド]グリコールエステル、４，４’−ブチリデンビス（２，６−ジ第三ブチルフェノール）、４，４’−ブチリデンビス（６−第三ブチル−３−メチルフェノール）、２，２’−エチリデンビス（４，６−ジ第三ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−第三ブチルフェニル）ブタン、ビス[２−第三ブチル−４−メチル−６−（２−ヒドロキシ−３−第三ブチル−５−メチルベンジル）フェニル]テレフタレート、１，３，５−トリス（２，６−ジメチル−３−ヒドロキシ−４−第三ブチルベンジル）イソシアヌレート、１，３，５−トリス（３，５−ジ第三ブチル−４−ヒドロキシベンジル）イソシアヌレート、１，３，５−トリス（３，５−ジ第三ブチル−４−ヒドロキシベンジル）−２，４，６−トリメチルベンゼン、１，３，５−トリス[（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオニルオキシエチル]イソシアヌレート、テトラキス[メチレン−３−（３’，５’−ジ第三ブチル−４’−ヒドロキシフェニル）プロピオネート]メタン、２−第三ブチル−４−メチル−６−（２−アクリロイルオキシ−３−第三ブチル−５−メチルベンジル）フェノール、３，９−ビス[２−（３−第三ブチル−４−ヒドロキシ−５−メチルヒドロシンナモイルオキシ）−１，１−ジメチルエチル]−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカン、トリエチレングリコールビス［β−（３−第三ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート］等が挙げられる。 Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxyphenyl). ) Propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di Tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4 -Hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4 -Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methyl) Phenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2- Tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4- Tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5- Tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [Methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl) -5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8, 10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. I can get lost.
上記リン系酸化防止剤としては、トリフェニルホスファイト、トリス（２，４−ジ第三ブチルフェニル）ホスファイト、トリス（２，５−ジ第三ブチルフェニル）ホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（ジノニルフェニル）ホスファイト、トリス（モノ、ジ混合ノニルフェニル）ホスファイト、ジフェニルアシッドホスファイト、２，２'−メチレンビス（４，６−ジ第三ブチルフェニル）オクチルホスファイト、ジフェニルデシルホスファイト、ジフェニルオクチルホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、フェニルジイソデシルホスファイト、トリブチルホスファイト、トリス（２−エチルヘキシル）ホスファイト、トリデシルホスファイト、トリラウリルホスファイト、ジブチルアシッドホスファイト、ジラウリルアシッドホスファイト、トリラウリルトリチオホスファイト、ビス（ネオペンチルグリコール）・１，４−シクロヘキサンジメチルジホスファイト、ビス（２，４−ジ第三ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，５−ジ第三ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ第三ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、テトラ（Ｃ１２−１５混合アルキル）−４，４’−イソプロピリデンジフェニルホスファイト、ビス[２，２’−メチレンビス(４，６−ジアミルフェニル)]・イソプロピリデンジフェニルホスファイト、テトラトリデシル・４，４’−ブチリデンビス(２−第三ブチル−５−メチルフェノール)ジホスファイト、ヘキサ（トリデシル）・１，１，３−トリス（２−メチル−５−第三ブチル−４−ヒドロキシフェニル）ブタン・トリホスファイト、テトラキス（２，４−ジ第三ブチルフェニル）ビフェニレンジホスホナイト、トリス（２−〔（２，４，７，９−テトラキス第三ブチルジベンゾ〔ｄ，ｆ〕〔１，３，２〕ジオキサホスフェピン−６−イル）オキシ〕エチル）アミン、９，１０−ジハイドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド、２−ブチル−２−エチルプロパンジオール・２，４，６−トリ第三ブチルフェノールモノホスファイト等が挙げられる。 Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,5-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite. Phyto, Tris (dinonylphenyl) phosphite, Tris (mono, dimixed nonylphenyl) phosphite, Diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite, Diphenyl Decyl phosphite, diphenyl octyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibu Tyracid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphos Phyto, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidenediphenyl phosphite, bis [2,2'-methylenebis (4,6-dia) Milphenyl)]-isopropyl Dendiphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert- Butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis tert-butyldibenzo [d , F] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2- And butyl-2-ethylpropanediol. 2,4,6-tritert-butylphenol monophosphite.
上記（Ｃ）着色防止剤は、好ましくはリン系酸化防止剤であり、さらに前記一般式（II）で表される亜リン酸エステル化合物が好ましい。具体的には、ビス（２，４−ジ第三ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ第三ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイト等が挙げられる。 The (C) anti-coloring agent is preferably a phosphorus antioxidant, and more preferably a phosphite compound represented by the general formula (II). Specifically, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4 -Dicumylphenyl) pentaerythritol diphosphite and the like.
上記他の紫外線吸収剤としては、例えば、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−オクトキシベンゾフェノン、５，５’−メチレンビス（２−ヒドロキシ−４−メトキシベンゾフェノン）等の２−ヒドロキシベンゾフェノン類；２−（２−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、２−（２−ヒドロキシ−５−第三オクチルフェニル）ベンゾトリアゾール、２−（２−ヒドロキシ−３，５−ジ第三ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２−ヒドロキシ−３−第三ブチル−５−メチルフェニル）−５−クロロベンゾトリアゾール、２−（２−ヒドロキシ−３，５−ジクミルフェニル）ベンゾトリアゾール、２−（２−ヒドロキシ−３−第三ブチル−５−カルボキシフェニル）ベンゾトリアゾールのポリエチレングリコールエステル、２−〔２−ヒドロキシ−３−（２−アクリロイルオキシエチル）−５−メチルフェニル〕ベンゾトリアゾール、２−〔２−ヒドロキシ−３−（２−メタクリロイルオキシエチル）−５−第三ブチルフェニル〕ベンゾトリアゾール、２−〔２−ヒドロキシ−３−（２−メタクリロイルオキシエチル）−５−第三オクチルフェニル〕ベンゾトリアゾール、２−〔２−ヒドロキシ−３−（２−メタクリロイルオキシエチル）−５−第三ブチルフェニル〕−５−クロロベンゾトリアゾール、２−〔２−ヒドロキシ−５−（２−メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２−〔２−ヒドロキシ−３−第三ブチル−５−（２−メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２−〔２−ヒドロキシ−３−第三アミル−５−（２−メタクリロイルオキシエチル）フェニル〕ベンゾトリアゾール、２−〔２−ヒドロキシ−３−第三ブチル−５−（３−メタクリロイルオキシプロピル）フェニル〕−５−クロロベンゾトリアゾール、２−〔２−ヒドロキシ−４−（２−メタクリロイルオキシメチル）フェニル〕ベンゾトリアゾール、２−〔２−ヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロピル）フェニル〕ベンゾトリアゾール、２−〔２−ヒドロキシ−４−（３−メタクリロイルオキシプロピル）フェニル〕ベンゾトリアゾール等の２−（２−ヒドロキシフェニル）ベンゾトリアゾール類；２−（２−ヒドロキシ−４−メトキシフェニル）−４，６−ジフェニル−１，３，５−トリアジン、２−（２−ヒドロキシ−４−ヘキシロキシフェニル）−４，６−ジフェニル−１，３，５−トリアジン、２−（２−ヒドロキシ−４−オクトキシフェニル）−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン、２−〔２−ヒドロキシ−４−（３−Ｃ１２〜１３混合アルコキシ−２−ヒドロキシプロポキシ）フェニル〕−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン、２−〔２−ヒドロキシ−４−（２−アクリロイルオキシエトキシ）フェニル〕−４，６−ビス（４−メチルフェニル）−１，３，５−トリアジン、２−（２，４−ジヒドロキシ−３−アリルフェニル）−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン、２，４，６−トリス（２−ヒドロキシ−３−メチル−４−ヘキシロキシフェニル）−１，３，５−トリアジン等の２−（２−ヒドロキシフェニル）−４，６−ジアリール−１，３，５−トリアジン類；フェニルサリシレート、レゾルシノールモノベンゾエート、２，４−ジ第三ブチルフェニル−３，５−ジ第三ブチル−４−ヒドロキシベンゾエート等のベンゾエート類；２−エチル−２’−エトキシオキザニリド、２−エトキシ−４’−ドデシルオキザニリド等の置換オキザニリド類；エチル−α−シアノ−β，β−ジフェニルアクリレート、メチル−２−シアノ−３−メチル−３−（ｐ−メトキシフェニル）アクリレート等のシアノアクリレート類；各種の金属塩又は金属キレート、特にニッケル又はクロムの塩又はキレート類等が挙げられる。 Examples of the other ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4- 2-hydroxybenzophenones such as methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-) 3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3) , 5-Dicumylphenyl) benzotriazole, 2- (2-hydroxy-3- Polyethylene glycol ester of tributyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- ( 2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy -3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2 -Hydroxy-3-tert-butyl-5- (2-methacrylic) Yloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5 -(3-Methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3- 2- (2-hydroxyphenyl) benzotriazoles such as methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole; 2- ( 2-hydroxy-4-methoxyphenyl) -4 , 6-Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4- Octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis ( 4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine , 2, 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5- such as 1,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5-triazine Triazines; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, Substituted oxanilides such as 2-ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, etc. And various metal salts or metal chelates, particularly nickel or chromium salts or chelates.
上記ヒンダードアミン化合物としては、例えば、２，２，６，６−テトラメチル−４−ピペリジノール−１−オキシ、２，２，６，６−テトラメチル−４−ピペリジルステアレート、１，２，２，６，６−ペンタメチル−４−ピペリジルステアレート、２，２，６，６−テトラメチル−４−ピペリジルベンゾエート、１−（２−ヒドロキシ−２−メチルプロピルオキシ）−２，２，６，６−テトラメチル−４−ピペリジルステアレート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、ビス（１−オクトキシ−２，２，６，６−テトラメチル−４−ピペリジル）セバケート、１，２，２，６，６−ペンタメチル−４−ピペリジルメチルメタクリレート、２，２，６，６−テトラメチル−４−ピペリジルメチルメタクリレート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）・ビス（トリデシル）−１，２，３，４−ブタンテトラカルボキシレート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）・ビス（トリデシル）−１，２，３，４−ブタンテトラカルボキシレート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）−２−ブチル−２−（３，５−ジ第三−ブチル−４−ヒドロキシベンジル）マロネート、１−（２−ヒドロキシエチル）−２，２，６，６−テトラメチル−４−ピペリジノール／コハク酸ジエチル重縮合物、１，６−ビス（２，２，６，６−テトラメチル−４−ピペリジルアミノ）ヘキサン／ジブロモエタン重縮合物、１，６−ビス（２，２，６，６−テトラメチル−４−ピペリジルアミノ）ヘキサン／２，４−ジクロロ−６−モルホリノ−ｓ−トリアジン重縮合物、１，６−ビス（２，２，６，６−テトラメチル−４−ピペリジルアミノ）ヘキサン／２，４−ジクロロ−６−第三オクチルアミノ−ｓ−トリアジン重縮合物、１，５，８，１２−テトラキス[２，４−ビス（Ｎ−ブチル−Ｎ−（２，２，６，６−テトラメチル−４−ピペリジル）アミノ）−ｓ−トリアジン−６−イル]−１，５，８，１２−テトラアザドデカン、１，５，８，１２−テトラキス[２，４−ビス（Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ピペリジル）アミノ）−ｓ−トリアジン−６−イル]−１，５，８，１２−テトラアザドデカン、１，６，１１−トリス[２，４−ビス（Ｎ−ブチル−Ｎ−（２，２，６，６−テトラメチル−４−ピペリジル）アミノ）−ｓ−トリアジン−６−イルアミノ]ウンデカン、１，６，１１−トリス[２，４−ビス（Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ピペリジル）アミノ）−ｓ−トリアジン−６−イルアミノ]ウンデカン、３，９−ビス〔１，１−ジメチル−２−[トリス（２，２，６，６−テトラメチル−４−ピペリジルオキシカルボニルオキシ）ブチルカルボニルオキシ]エチル〕−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、３，９−ビス〔１，１−ジメチル−２−[トリス（１，２，２，６，６−ペンタメチル−４−ピペリジルオキシカルボニルオキシ）ブチルカルボニルオキシ]エチル〕−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン等が挙げられる。 Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidinol-1-oxy, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2, 6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, 1- (2-hydroxy-2-methylpropyloxy) -2,2,6,6- Tetramethyl-4-piperidylstearate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis ( 1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate 2,2,6,6-tetramethyl-4-piperidylmethyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate Bis (2,2,6,6-tetramethyl-4-piperidyl) -bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl -4-piperidyl) -bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- ( 3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, , 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) ) Hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro- 6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4- Piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1 , 2,2,6,6-pentamethyl-4-piperidyl) Amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6) , 6-Tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl) -4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris ( 1,2,2,6,6-pentamethyl-4 Piperidyl oxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10-spiro [5.5] undecane.
上記各種添加剤の添加量はポリエステル樹脂１００重量部に対し０．００１〜１０、好ましくは０．０１〜５重量部の範囲である。 The addition amount of the above various additives is in the range of 0.001 to 10, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyester resin.
本発明のポリエチレンテレフタレート樹脂製容器としては、ジュース、炭酸飲料、お茶、調味料、食用油、アルコール飲料など、液状の飲食物用容器が挙げられる。また、洗剤などの非食品用途や工業用容器へも使用可能である。
上記容器には、内容物が加圧、常圧；低温、高温で、充填されたり保存されたりしてもよい。
Examples of the polyethylene terephthalate resin container of the present invention include liquid food and drink containers such as juice, carbonated drink, tea, seasoning, edible oil, and alcoholic drink. It can also be used for non-food applications such as detergents and industrial containers.
In the container, the contents may be filled or stored under pressure, normal pressure, low temperature or high temperature.
本発明のポリエステル樹脂製容器は、後述する試験法による耐候性が７，０００時間以上、好ましくは８，０００時間以上である。
耐候性が上記時間より短すぎると、内容物の賞味期限内で機械強度が十分保持できずに破損したり、色調が保持できずに商品性が損なわれるなどの問題となる。
また、色調は無色であることが必要である。無色でないと内容物の本来の色調とは異なる色調に誤解されて、商品性を損なう。
また、耐抽出性は０．３％未満が好ましく、特に好ましくは未検出である。
耐抽出性が上記範囲より大きすぎると、衛生上問題がある他、味覚への影響、さらには樹脂に対する添加剤の安定化効果の低下などの問題がある。
The polyester resin container of the present invention has a weather resistance of 7,000 hours or more, preferably 8,000 hours or more, according to a test method described later.
If the weather resistance is too short than the above time, the mechanical strength may not be sufficiently maintained within the shelf life of the contents, and the product may be damaged because the color tone cannot be maintained.
Also, the color tone needs to be colorless. If it is not colorless, it will be misunderstood as a color tone different from the original color tone of the contents, and the merchantability will be impaired.
Further, the extraction resistance is preferably less than 0.3%, particularly preferably undetected.
If the extraction resistance is larger than the above range, there are problems in terms of hygiene, taste influence, and further problems such as a decrease in the stabilizing effect of the additive on the resin.
（実施例）
以下、実施例により本発明を詳細に説明する。しかし、以下の実施例により本発明はなんら制限されるものではない。
以下に実施例に用いた樹脂（Ａ）、紫外線吸収剤（Ｂ）および（Ｃ）着色防止剤の略号を示す。
樹脂（Ａ）
Ｇｅ−ＰＥＴ：ポリエチレンテレフタレート樹脂（帝人（株）製ＴＲ−８５５０：ゲルマニウム触媒により重縮合したポリエチレンテレフタレート）
Ｓｂ−ＰＥＴ：ポリエチレンテレフタレート樹脂（デュポン社製Ｍｅｌｉｎａｒ Ｌａｓｅｒ＋：アンチモン触媒により重縮合したポリエチレンテレフタレート）
紫外線吸収剤（Ｂ）
ＬＡ−１：２，２’−メチレンビス（４−第三オクチル−６−（ベンゾトリアゾール−２−イル）フェノール）（旭電化工業（株）社製：アデカスタブ ＬＡ−３１（化合物NO.１））
ＬＡ−２：２−（２−ヒドロキシ−５−第三オクチルフェニル）ベンゾトリアゾール
ＬＡ−３：２−（２−ヒドロキシ−３，５−ジ第三ブチルフェニル）−５−クロロベンゾトリアゾール
着色防止剤（Ｃ）
ビス（２，６−ジ第三ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト
(Example)
Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited by the following examples.
The abbreviations of the resin (A), ultraviolet absorber (B) and (C) anti-coloring agent used in the examples are shown below.
Resin (A)
Ge-PET: Polyethylene terephthalate resin (TR-8550 manufactured by Teijin Limited: Polyethylene terephthalate polycondensed with germanium catalyst)
Sb-PET: Polyethylene terephthalate resin (DuPont's Melinar Laser +: Polyethylene terephthalate polycondensed with antimony catalyst)
UV absorber (B)
LA-1: 2,2′-methylenebis (4-tert-octyl-6- (benzotriazol-2-yl) phenol) (Asahi Denka Kogyo Co., Ltd .: ADK STAB LA-31 (Compound No. 1))
LA-2: 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole LA-3: 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole anti-coloring agent (C)
Bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite
容器の試験
耐候性：得られた容器の側面から２ｃｍ×４ｃｍの試験片を各配合ごとに５枚切り取り、サンシャインウェザオメータでヘーズが５０％になるまでの時間を耐候性として評価した。
着色性：耐候性評価に用いた試験片５枚を重ねて目視による着色性評価を行った。
耐抽出性：試験片の表面積１平方インチ（２．５４ｃｍ×２．５４ｃｍ）につき抽出溶媒１０ｍｌを用いて、抽出溶媒が１０％エタノール水溶液では２１２゜Ｆ（１００℃）で２時間、および５０％エタノール水溶液では１７８゜Ｆ（８１℃）で２時間抽出した。抽出物が検出されない場合をＮＤ、０．３％未満を△、０．３％以上抽出されたものを×とした。
Test of container Weather resistance: Five test pieces of 2 cm × 4 cm were cut out from the side surface of the obtained container for each formulation, and the time until the haze reached 50% was evaluated as weather resistance with a sunshine weatherometer.
Colorability: Five test pieces used for weather resistance evaluation were overlapped, and visual colorability was evaluated.
Extraction resistance: using 10 ml of extraction solvent per square inch (2.54 cm × 2.54 cm) of surface area of the test piece, 2 hours at 212 ° F. (100 ° C.) in a 10% ethanol aqueous solution, and 50% In an aqueous ethanol solution, extraction was performed at 178 ° F. (81 ° C.) for 2 hours. The case where no extract was detected was indicated as ND, the case where less than 0.3% was indicated by Δ, and the case where 0.3% or more was extracted was indicated by ×.
（実施例Ｉ−１）
Ｇｅ−ＰＥＴ１００重量部に表１記載の紫外線吸収剤及び着色防止剤０．０５重量部を添加して、日本製鋼所製ダイレクトブロー成形機「電動式小型中空成形機ＪＥＢ−７／Ｐ５０／ＷＳ６０Ｓ」を使用して、シリンダー温度２８０℃で金型温度１５℃、１３秒サイクルで容量７００ｍｌの容器を作成し、各種試験を行った。結果を表１に示す。
(Example I-1)
Direct blow molding machine “Electric small size hollow molding machine JEB-7 / P50 / WS60S” manufactured by Nippon Steel Works, with the addition of 0.05 part by weight of UV absorber and anti-coloring agent listed in Table 1 to 100 parts by weight of Ge-PET. Was used to prepare a container having a capacity of 700 ml at a cylinder temperature of 280 ° C., a mold temperature of 15 ° C., and a 13-second cycle, and various tests were conducted. The results are shown in Table 1.
（比較例Ｉ−１〜Ｉ−３）
紫外線吸収剤を表１のようにした以外は、実施例Ｉ−１と同様に行った。結果を表１に示す。
(Comparative Examples I-1 to I-3)
The same procedure as in Example I-1 was carried out except that the ultraviolet absorber was changed as shown in Table 1. The results are shown in Table 1.
（比較例Ｉ−４）
ポリエチレンテレフタレートをＧｅ−ＰＥＴからＳｂ−ＰＥＴに変えた以外は、実施例Ｉ−１と同様に行った。結果を表１に示す。
(Comparative Example I-4)
The same procedure as in Example I-1 was carried out except that the polyethylene terephthalate was changed from Ge-PET to Sb-PET. The results are shown in Table 1.
実施例Ｉ−１では、耐候性に優れ、抽出試験において添加剤の抽出もなく、色調にも優れる。しかし、比較例Ｉ−１の紫外線吸収剤を添加していない配合で耐候性が低いことは当然であるが、比較例Ｉ−２やＩ−３でも耐候性が低く、また、アンチモン系触媒で重縮合したポリエチレンテレフタレートを用いた比較例Ｉ−４では、耐候性や抽出性は優れるものの、色調が悪く、容器に用いるには不適当である。 In Example I-1, the weather resistance is excellent, the additive is not extracted in the extraction test, and the color tone is also excellent. However, it is a matter of course that the weather resistance is low in the formulation without adding the ultraviolet absorbent of Comparative Example I-1, but the weather resistance is low in Comparative Examples I-2 and I-3, and the antimony catalyst is used. Comparative Example I-4 using polycondensed polyethylene terephthalate is excellent in weather resistance and extractability, but has poor color tone and is unsuitable for use in containers.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003336342A JP4297425B2 (en) | 2003-09-26 | 2003-09-26 | Polyester resin container with improved weather resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003336342A JP4297425B2 (en) | 2003-09-26 | 2003-09-26 | Polyester resin container with improved weather resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005105004A JP2005105004A (en) | 2005-04-21 |
| JP4297425B2 true JP4297425B2 (en) | 2009-07-15 |
Family
ID=34532507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003336342A Expired - Fee Related JP4297425B2 (en) | 2003-09-26 | 2003-09-26 | Polyester resin container with improved weather resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4297425B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7884146B2 (en) | 2007-02-20 | 2011-02-08 | Fujifilm Corporation | Polymer material containing ultraviolet absorbent |
| US20100130638A1 (en) | 2007-03-30 | 2010-05-27 | Fujifilm Corporation | Ultraviolet absorbent composition |
| US8039532B2 (en) | 2007-08-16 | 2011-10-18 | Fujifilm Corporation | Heterocyclic compound, ultraviolet absorbent and composition containing the same |
| JP5244437B2 (en) | 2008-03-31 | 2013-07-24 | 富士フイルム株式会社 | UV absorber composition |
| JP5250289B2 (en) | 2008-03-31 | 2013-07-31 | 富士フイルム株式会社 | UV absorber composition |
| JP2009270062A (en) | 2008-05-09 | 2009-11-19 | Fujifilm Corp | Ultraviolet absorbent composition |
| JP5360969B2 (en) * | 2009-03-16 | 2013-12-04 | 大和製罐株式会社 | Polyester resin composition, polyester container and polyester laminated paper container using the same |
| JP2011074295A (en) * | 2009-09-30 | 2011-04-14 | Adeka Corp | Polyester resin composition |
| US20120189793A1 (en) * | 2009-09-30 | 2012-07-26 | Adeka Corporation | Polyester resin composition, polyester fiber, polyester resin molded article, and process for production of nucleating agent for polyester resin |
-
2003
- 2003-09-26 JP JP2003336342A patent/JP4297425B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005105004A (en) | 2005-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7132499B2 (en) | Polyester resin container with improved weatherability | |
| US6599994B2 (en) | Polyester blends and heat shrinkable films made therefrom | |
| US7169880B2 (en) | Shaped articles from cycloaliphatic polyester compositions | |
| EP2484725B1 (en) | Polyester resin composition, polyester fiber, polyester resin molded article, and process for production of nucleating agent for polyester resin | |
| AU780351B2 (en) | Method of content protection with durable UV absorbers | |
| JP4297425B2 (en) | Polyester resin container with improved weather resistance | |
| US4814366A (en) | Thermoplastic polyester resin composition | |
| US5985389A (en) | Polyester and optical brightener blend having improved properties | |
| EP2647668B1 (en) | Polyester resin composition and molded body of same | |
| JP2003534424A (en) | Carbonate polymer compositions containing low volatility UV absorbing compounds | |
| US20050171253A1 (en) | Containers or films comprising hydroxyphenlbenzotriazole uv absorbers for protecting contents against the effects of uv radiation | |
| JP2016033021A (en) | Ultraviolet blocking container | |
| JP4243893B2 (en) | Polycarbonate resin molding | |
| JPH11510112A (en) | Amorphous transparent sheet of crystallizable thermoplastic resin with high standard viscosity | |
| JP2011137127A (en) | Polyester resin molding and manufacturing method therefor | |
| JPH10330607A (en) | Thermoplastic thermosetting molding product and its production | |
| JP2017154286A (en) | Method for manufacturing plastic bottle | |
| JPH05156138A (en) | Thermoplastic polyester resin composition | |
| JPH089687B2 (en) | Polyester resin composition | |
| JP2002020592A (en) | Polyester resin composition | |
| JP2004099704A (en) | Polyester resin composition | |
| MXPA98000940A (en) | Lamina amorfa transparent of a crystallized thermoplastic with a normal viscosity a | |
| KR20000007995A (en) | Copolymerized polyester resin | |
| MXPA97010294A (en) | Lamina amorfa transparente stabilizado of ultraviolet light of a crystallized thermoplastic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20050829 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060522 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081218 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090127 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090220 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090410 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090410 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4297425 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120424 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130424 Year of fee payment: 4 |
|
| LAPS | Cancellation because of no payment of annual fees |