JPH02188581A - 2-hydroxyphenylbenzotriazole-based compound and use thereof - Google Patents
2-hydroxyphenylbenzotriazole-based compound and use thereofInfo
- Publication number
- JPH02188581A JPH02188581A JP24862689A JP24862689A JPH02188581A JP H02188581 A JPH02188581 A JP H02188581A JP 24862689 A JP24862689 A JP 24862689A JP 24862689 A JP24862689 A JP 24862689A JP H02188581 A JPH02188581 A JP H02188581A
- Authority
- JP
- Japan
- Prior art keywords
- ultraviolet absorption
- parts
- extraction
- polyester
- behavior
- 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
- 150000001875 compounds Chemical class 0.000 title abstract description 14
- YHCGGLXPGFJNCO-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)phenol Chemical compound OC1=CC=CC=C1C1=CC=CC2=C1N=NN2 YHCGGLXPGFJNCO-UHFFFAOYSA-N 0.000 title abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000004952 Polyamide Substances 0.000 claims description 78
- 229920002647 polyamide Polymers 0.000 claims description 78
- 229920000728 polyester Polymers 0.000 claims description 77
- -1 2-hydroxyphenylbenzotriazole compound Chemical class 0.000 claims description 75
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 95
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229940124543 ultraviolet light absorber Drugs 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 69
- 230000009477 glass transition Effects 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 40
- 238000012360 testing method Methods 0.000 description 36
- 238000002844 melting Methods 0.000 description 25
- 230000008018 melting Effects 0.000 description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 150000004984 aromatic diamines Chemical class 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZZNAYFWAXZJITH-UHFFFAOYSA-N 4-amino-3-nitrobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1[N+]([O-])=O ZZNAYFWAXZJITH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 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 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 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 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 3
- PBGKNXWGYQPUJK-UHFFFAOYSA-N 4-chloro-2-nitroaniline Chemical compound NC1=CC=C(Cl)C=C1[N+]([O-])=O PBGKNXWGYQPUJK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- BMQKHELMNLAASQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)benzotriazole-5-carboxylic acid Chemical compound N1=C2C=C(C(=O)O)C=CC2=NN1C1=CC=CC=C1O BMQKHELMNLAASQ-UHFFFAOYSA-N 0.000 description 2
- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- ZRMXELNTPCSCCJ-UHFFFAOYSA-N 2-(2-hydroxy-5-methylphenyl)benzotriazole-4,6-dicarboxylic acid Chemical compound CC1=CC=C(O)C(N2N=C3C(C(O)=O)=CC(=CC3=N2)C(O)=O)=C1 ZRMXELNTPCSCCJ-UHFFFAOYSA-N 0.000 description 1
- ZTYKISSAWJUKLL-UHFFFAOYSA-N 2-(4,6-dibromobenzotriazol-2-yl)-4-methylphenol Chemical compound CC1=CC=C(O)C(N2N=C3C(Br)=CC(Br)=CC3=N2)=C1 ZTYKISSAWJUKLL-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- IQYRGQNEJQUAFZ-UHFFFAOYSA-N 2h-benzotriazole-4,5-dicarboxylic acid Chemical compound OC(=O)C1=C(C(=O)O)C=CC2=NNN=C21 IQYRGQNEJQUAFZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 241000282376 Panthera tigris Species 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
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 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
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical group BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 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
- 238000005259 measurement Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000006100 radiation absorber Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
不発８Ａは２−ヒドロキシフェニルベンツトリアゾール
系化合物およびその用途に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] Misfire 8A relates to 2-hydroxyphenylbenztriazole compounds and their uses.
多くのポリマーが紫外線により劣化され÷糾ることはよ
く知られている。紫外線１例えば太陽光に長時間さらさ
れると劣化するポリマーとしてポリオレフィン、ポリエ
ステル、ポリアミドなどが挙げられる。It is well known that many polymers are degraded and degraded by ultraviolet light. Ultraviolet rays 1 For example, polymers that deteriorate when exposed to sunlight for a long time include polyolefins, polyesters, polyamides, and the like.
また、近年清涼飲料、アルコール飲料、食用油などの飲
食品、化粧品、医薬品など多種多様の物品が透明プラス
チック容器に入れられ販売され保存されている。透明な
プラスチック容器は約２５０〜約３９０ｎｍの波長を有
する紫外線をかなシの割合で透過することから、内容物
が変質、変色１分解などの悪影響を受ける。In addition, in recent years, a wide variety of products such as soft drinks, alcoholic beverages, edible oils, cosmetics, and pharmaceuticals have been sold and stored in transparent plastic containers. Transparent plastic containers transmit ultraviolet rays having a wavelength of about 250 to about 390 nm at a small rate, so that the contents suffer from adverse effects such as deterioration, discoloration, and decomposition.
そこで紫外線から上記のポリマーの劣化を防ぎ、またプ
ラスチック容器中の物品を保護する目的でそれらのポリ
マーにシアノアクリレート系紫外線吸収剤を含有さする
ことが知られている（特表昭６２−５０１８５６号公報
および特表昭６２−５０１８５７号公報参照）。またベ
ンゾトリアゾール系紫外線吸収剤をポリマーに混和ま九
は共重合によシ配合し、該ポリマーに紫外線吸収性能を
付与することが知られている（特公昭５７−３５２２１
号公報および米国特許第３．２１４．４３６号明細書
参照）。Therefore, it is known that cyanoacrylate-based ultraviolet absorbers are added to these polymers in order to prevent the deterioration of the above-mentioned polymers from ultraviolet rays and to protect articles in plastic containers (Japanese Patent Publication No. 501856/1983). (Refer to the official gazette and Special Publication No. 1983-501857). It is also known that a benzotriazole-based ultraviolet absorber is blended into a polymer or copolymerized to impart ultraviolet absorption performance to the polymer (Japanese Patent Publication No. 57-35221
(see US Pat. No. 3,214,436).
〔発明が解決しようとする課題〕
シアノアクリレート系紫外線吸収剤はベンゾトリアゾー
ル来紫外線吸収剤に比べ熱安定性が悪く。[Problems to be Solved by the Invention] Cyanoacrylate UV absorbers have poor thermal stability compared to benzotriazole UV absorbers.
紫外線吸収性能も劣る。また、特公昭５７−３５２２１
号公報に記載されているベンゾ） ＩＪアゾール系系外
外線吸収剤共重合させて得られるポリマーは耐熱性に劣
り、紫外線吸収効果も満足のいくものではない。さらに
米国特許第３．２１４．４３６号明細書に記載されてい
るベンゾトリアゾール系化合物を共重合させて得られる
ポリマーは紫外線吸収効果において満足のいくものでは
ない。UV absorption performance is also poor. Also, special public service No. 57-35221
The polymer obtained by copolymerizing the benzo) IJ azole external radiation absorber described in the above publication has poor heat resistance and unsatisfactory ultraviolet absorption effect. Furthermore, the polymer obtained by copolymerizing benzotriazole compounds described in US Pat. No. 3,214,436 is not satisfactory in terms of ultraviolet absorption effect.
而して、本発明の１つの目的は、優れた紫外線吸収性能
を有する新規な２−ヒドロキシフェニルベンゾトリアゾ
ール系化合物を提供することにある。１＋本発明の他の
１つの目的は核新規な２−ヒドロキシフェニルベンゾト
リアゾール系化合物の紫外線吸収剤としての用途を提供
することにある。さらに本発明の他の１つの目的は該新
規な２−ヒドロキシフェニルベンゾトリアゾール系化合
物を含有させることによって得られる紫外線吸収性能に
優れたポリマーを提供することにあり、また他の目的の
１つは該新規な２−ヒドロキシフェニルベンゾトリアゾ
ール系化合物を共重合させることによって得られる紫外
線吸収性能に優れたポリ！−を提供することにある。One object of the present invention is to provide a novel 2-hydroxyphenylbenzotriazole compound having excellent ultraviolet absorption performance. Another object of the present invention is to provide a novel 2-hydroxyphenylbenzotriazole compound for use as an ultraviolet absorber. Another object of the present invention is to provide a polymer with excellent ultraviolet absorption performance obtained by incorporating the novel 2-hydroxyphenylbenzotriazole compound; A polyester with excellent ultraviolet absorption performance obtained by copolymerizing the new 2-hydroxyphenylbenzotriazole compound! - to provide.
本発明によれば、上記の目的は、一般式で示される２−
ヒドロキシフェニルベンゾトリアゾール系化合物を提供
することによって達成され、また該２−ヒドロキシフェ
ニルベンゾトリアゾール系化合物を有効成分とする紫外
線吸収剤、該２−ヒドロキシフェニルベンゾトリアゾー
ル系化合物を０．００１−１０重量％含有してなるポリ
マーおよび該２一ヒドロキシフエニルベンゾトリアゾー
ル来化合物を共重合成分として０．００１〜１０重量％
含有してなるポリマーを提供することによって達成され
る。According to the present invention, the above object is achieved by 2-
A UV absorber which is achieved by providing a hydroxyphenylbenzotriazole compound and which contains the 2-hydroxyphenylbenzotriazole compound as an active ingredient; 0.001 to 10% by weight of the polymer containing the compound and the 2-hydroxyphenylbenzotriazole compound as copolymerization components.
This is achieved by providing a polymer comprising:
上記一般式（１）において Ｂ、１ 、 Ｂ２およびＲ
３がそれぞれ表わすハロゲン原子としては１例えば、塩
素原子、臭素原子などが挙げられ、低級アルキル基とし
ては、例えばメチル基、エチル基、ｎ−プロピル基％ｉ
−プロピル１ｌｓｓ ｎ−ブチルａＬｉ−ブチル基、
１ｌｅｅ−ブチル基、ｔａｒｔ−ブチル基などが挙げ
られ、また低級アルコキシル基としては、例えばメトキ
シ基、ニドキシ基、ｎ−プロポキシ基、ｌ−プロポキシ
基、ｎ−ブトキシ基、ｉ−ブトキシ基、５ｅｅ−ブトキ
シ基、ｔｅｒｔ−ブトキシ基などが挙げられる。In the above general formula (1), B, 1 , B2 and R
Examples of the halogen atoms represented by 3 include chlorine atom, bromine atom, etc., and examples of lower alkyl groups include methyl group, ethyl group, n-propyl group, etc.
-propyl 1lss n-butyl aLi-butyl group,
Examples of lower alkoxyl groups include methoxy, nidoxy, n-propoxy, l-propoxy, n-butoxy, i-butoxy, and 5ee-butyl groups. Examples include butoxy group and tert-butoxy group.
上記一般式（１）において％Ｂｌ、 Ｂ２およびＲ３の
りち２つはカルボキシル基であることが必要である。In the above general formula (1), two of %Bl, B2 and R3 must be carboxyl groups.
カルボキシル基を１つ有する２−ヒドロキシフェニルベ
ンゾトリアゾール系化合物を共重合させて得られるポリ
マーは該化合物を共重合成分として有さないボリア一に
比べて重合度が低くなる。A polymer obtained by copolymerizing a 2-hydroxyphenylbenzotriazole compound having one carboxyl group has a lower degree of polymerization than a boria monomer which does not have this compound as a copolymerization component.
またカルボキシル基を３つ有する２−ヒドロキシフェニ
ルベンゾトリアゾール系化合物を共重合させて得られる
ポリマーは架橋しゲル化しやすい。Further, a polymer obtained by copolymerizing a 2-hydroxyphenylbenzotriazole compound having three carboxyl groups is easily crosslinked and gelled.
−ｆｆ式（１）で示される２−ヒドロキシフェニルベン
ゾトリアゾール系化合物の代表例として次の化合物を挙
げることができる。-ff Representative examples of the 2-hydroxyphenylbenzotriazole compound represented by formula (1) include the following compounds.
一般式（１）で示される２−ヒドロキシフェニルベンゾ
トリアゾール系化合物は、例えば次の方法によシ製造す
ることができる◇
（ｎ） （ＩＩＩ）
（上記式中 Ｂｉ、 Ｒ１およびＲ３は前記定義のとお
シである。）
すなわち、一般式（ＩＩ）て示されるニトロアニリン系
化合物を通常の方法でジアゾ化したのち、−般式（ＩＩ
Ｉ）で示されるフェノール系化合物に１例えば１０％水
酸化ナトリウム水溶液中θ〜５℃の範囲の温度でカップ
リングさせることによシ一般式（ＩＶ）で示されるニト
ロアゾ化合物を得る。このニトロアゾ化合物を亜鉛、錫
などの金属；塩化亜鉛などの還元剤を用いて例えば、水
酸化す）リウム水溶液中４０℃以下の温度でアルカリ還
元を行うことによシ一般式（１）で示される２−ヒドロ
キシフェニルベンゾトリアゾール系化合物を得る。−般
式（ＩＩＩ）で示されるフェノール系化合物は一般式（
Ｉ［）で示されるニトロアニリン系化合物に対してほぼ
等モル量で用いられる。また上記の還元剤は一般式（■
）で示されるニトロアゾ化合物に対して約３〜１０倍モ
ル量で用りられる。The 2-hydroxyphenylbenzotriazole compound represented by the general formula (1) can be produced, for example, by the following method◇ (n) (III) (In the above formula, Bi, R1 and R3 are as defined above) ) That is, after diazotizing the nitroaniline compound represented by general formula (II) by a conventional method, - general formula (II) is diazotized.
A nitroazo compound represented by general formula (IV) is obtained by coupling the phenolic compound represented by I) in a 10% aqueous sodium hydroxide solution at a temperature in the range of θ to 5°C. This nitroazo compound can be reduced by alkaline reduction using a metal such as zinc or tin or a reducing agent such as zinc chloride in an aqueous solution of chlorium hydroxide at a temperature of 40°C or lower to obtain a compound represented by the general formula (1). A 2-hydroxyphenylbenzotriazole compound is obtained. - The phenolic compound represented by the general formula (III) is the general formula (
It is used in an approximately equimolar amount to the nitroaniline compound represented by I[). In addition, the above reducing agent has the general formula (■
) It is used in an amount of about 3 to 10 times the molar amount of the nitroazo compound shown.
（合成法２）
まず、合成法１に従ってカルボキシル基を有しないか、
ま念はカルボキシル基を１個有し、かつ１個ないし３個
のハロゲン原子を有する２−ヒドロキシフェニルベンゾ
トリアゾール系化合物を合成するか、 ｔ′ｆｉ−は合
成法１に従って合成し九カルボキシル基を有しないか、
またはカルボキシル基を１個有する２−ヒドロキシフェ
ニルベンツトリアゾール系化合物に、塩素、臭！！１次
亜塩素酸塩。(Synthesis method 2) First, according to synthesis method 1, whether it has no carboxyl group,
Ideally, a 2-hydroxyphenylbenzotriazole compound having one carboxyl group and 1 to 3 halogen atoms should be synthesized, or t'fi- should be synthesized according to synthesis method 1 with nine carboxyl groups. Do you have or not?
Or 2-hydroxyphenylbenztriazole compounds with one carboxyl group contain chlorine and odor! ! Primary chlorite.
次亜臭素酸基などのハロゲン化剤を１．０〜２．５モル
倍量作用せしめて１個ないし３個のハロゲン原子を導入
し念２−ヒドロキシフェニルベンツトリアゾール系化合
物を合成する。次いでこのハロゲン原子を１個ないし３
個有する２−ヒドロキシフェニルベンゾトリアゾール系
化合物を例えばニッケル、鉄、コバルト、パラジウム、
ロジウムなどの有機金属０．０５〜１モルチの存在下に
一酸化炭素と反応させるか、ｎ−ブチルリチウム１５０
〜３００モルチと反応させ九のち二酸化炭素と反応させ
るか、またはグリニヤール反応などによルノ）ロゲン原
子をカルボキシル基に変換することＫより一般式（１）
で示される２−ヒドロキシフェニルベンゾトリアゾール
系化合物を得る。A halogenating agent such as a hypobromite group is applied in an amount of 1.0 to 2.5 moles to introduce 1 to 3 halogen atoms to synthesize a 2-hydroxyphenylbenztriazole compound. Next, 1 to 3 of these halogen atoms
2-Hydroxyphenylbenzotriazole compounds containing, for example, nickel, iron, cobalt, palladium,
React with carbon monoxide in the presence of 0.05 to 1 mol of an organic metal such as rhodium, or n-butyllithium 150
From K, the general formula (1) is obtained by reacting with ~300 molti and then reacting with carbon dioxide, or by converting the luno)logen atom into a carboxyl group by a Grignard reaction or the like.
A 2-hydroxyphenylbenzotriazole compound represented by is obtained.
一般式（１）で示される２−ヒドロキシフェニルベンゾ
ｌ−ＩＪアゾール系化合物は、紫外線吸収性能が良好で
あシ、シかも熱安定性が良好であることから紫外線吸収
剤として有用である。一般式（１）で示される２−ヒド
ロキシフェニルベンゾトリアゾール系化合物は紫外線吸
収剤としてあらゆるポリマーに対して用いることができ
るが、特に縮合系ポリマー 例えばポリエステル、ポリ
アミドなどに対して好ましく用いられる。The 2-hydroxyphenylbenzo l-IJ azole compound represented by the general formula (1) has good ultraviolet absorption performance and thermal stability, and is therefore useful as an ultraviolet absorber. The 2-hydroxyphenylbenzotriazole compound represented by the general formula (1) can be used as an ultraviolet absorber for all polymers, but is particularly preferably used for condensation polymers such as polyester and polyamide.
上記のポリエステルとしては芳香族ジカルボン酸と芳香
族ジオールからなるポリエステル、芳香族ジカルボン酸
と脂肪族ジオールからなるポリエステル、脂肪族ジカル
ボン酸と芳香族ジオールから危るポリエステル、脂肪族
ジカルボン酸と脂肪族ジオールからなるポリエステルな
どジカルボン酸とジオールからなるポリエステル、オキ
シカルボン酸からなるポリエステル、ラクトンの開環重
合から得られるポリエステルなどが挙げられる。このな
かでもジカルボン酸成分の５０モルチ以上が芳香族ジカ
ルボン酸からなυ、かつジオール成分の８０モルチ以上
が炭素数２〜１０の脂肪族または脂環式ジオールからな
るポリエステルが好ましい。芳香族ジカルボン酸として
例えばテレフタル酸、イソフタル酸、２，６−す７タレ
ンジカルボン酸などが挙げられ、脂肪族ジカルボン酸と
して例えばアジピン酸、アゼライン酸、セバシン酸など
が挙げられる。脂肪族または脂環式ジオールとしては例
えばエチレングリコール、プロピレングリコール、テト
ラメチレングリコール、ヘキサメチレングリコール、ノ
ナメチレングリコール、シクロヘキサンジメタツール、
〜ジエチレングリコフルなどが挙げられ、これらが単独
でま念は２１ｉ以上の組合わせで用いられる。またポリ
エステルは例えばグリセリン、トリメチロールプロパン
、ペンタエリスリトール、トリメリット酸、トリメシン
酸、ピロメリット酸などの３価以上の多官能化合物を溶
融成形が可能な範囲内で共重合成分として含んでいても
よい。ポリエステルは例えばジカルボン酸の低級アルキ
ルエステルとジオールとのエステル交換反応およびこれ
に続く重縮合反応を行う方法、ジカルボン酸とジオール
との脱水エステル化反応およびこれに続く重縮合反応を
行う方法などの通常のポリエステルの製造に用いられる
方法に従って製造される。このようにして得られ念ポリ
エステルはフェノールとテトラクロルエタンの等重量混
合液中、３０℃で測定し九極限粘度が０．３〜１．５、
特に０．４〜１．２の範囲内にあるものが好ましい。The above polyesters include polyesters made of aromatic dicarboxylic acids and aromatic diols, polyesters made of aromatic dicarboxylic acids and aliphatic diols, polyesters that are susceptible to aliphatic dicarboxylic acids and aromatic diols, and polyesters that are dangerous from aliphatic dicarboxylic acids and aromatic diols. Examples include polyesters made of dicarboxylic acids and diols, polyesters made of oxycarboxylic acids, and polyesters obtained from ring-opening polymerization of lactones. Among these, preferred are polyesters in which 50 or more moles of the dicarboxylic acid component are aromatic dicarboxylic acids, and 80 or more moles of the diol component are aliphatic or alicyclic diols having 2 to 10 carbon atoms. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, and 2,6-7tale dicarboxylic acid, and examples of aliphatic dicarboxylic acids include adipic acid, azelaic acid, and sebacic acid. Examples of aliphatic or alicyclic diols include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, nonamethylene glycol, cyclohexane dimetatool,
- diethylene glycofur, etc., and these can be used alone or in combinations of 21i or more. The polyester may also contain a trivalent or higher polyfunctional compound such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, trimesic acid, pyromellitic acid, etc. as a copolymerization component within the range that can be melt-molded. . Polyester can be produced using conventional methods such as a transesterification reaction between a lower alkyl ester of a dicarboxylic acid and a diol, followed by a polycondensation reaction, or a dehydration esterification reaction between a dicarboxylic acid and a diol, followed by a polycondensation reaction. It is produced according to the method used for the production of polyester. The polyester thus obtained has a limiting viscosity of 0.3 to 1.5 when measured at 30°C in an equal weight mixture of phenol and tetrachloroethane.
Particularly preferred is one within the range of 0.4 to 1.2.
上記のポリアミドとしては、芳香族ジカルボン酸と芳香
族ジアミンからなるポリアミド、芳香族ジカルボン酸と
脂肪族シアぽンからなるポリアミド、脂肪族ジカルボン
酸と芳香族ジアミンからなるポリアミド、脂肪族ジカル
ボン酸と脂肪族ジアミンからなるポリアミドなどジカル
ボン酸とジアミンからなるポリアミド、ラクタムの開環
重合から得られるポリアミドなどが挙げられる。この麦
かでも芳香族ジカルボン酸と脂肪族ジアミンからなるポ
リアミド、脂肪族ジカルボン酸と芳香族ジアミンからな
るポリアミドが好ましい。芳香族ジカルボン酸として例
えばテレフタル酸、イソフタル酸、２，６−ナフタレ／
ジカルボン酸などが挙げられ、脂肪族ジカルボン酸とし
て例えばアジピン酸、アゼライン酸、セバシン酸などが
挙げられる。The above polyamides include polyamides made of aromatic dicarboxylic acids and aromatic diamines, polyamides made of aromatic dicarboxylic acids and aliphatic siapones, polyamides made of aliphatic dicarboxylic acids and aromatic diamines, polyamides made of aliphatic dicarboxylic acids and aromatic diamines, and polyamides made of aliphatic dicarboxylic acids and aromatic diamines. Examples include polyamides made of dicarboxylic acids and diamines such as polyamides made of group diamines, and polyamides obtained from ring-opening polymerization of lactams. Preferred are polyamides made of aromatic dicarboxylic acids and aliphatic diamines, and polyamides made of aliphatic dicarboxylic acids and aromatic diamines. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalene/
Examples of the aliphatic dicarboxylic acids include adipic acid, azelaic acid, and sebacic acid.
芳香族ジアミンとして例えばフェニレンジアミン、キシ
リレンジアミンなどが挙げられ、脂肪族ジアミンとして
例えばテトラメチレンジアミン、ヘキサメチレンジアミ
ン、オクタメチレンジアミン力どがそれぞれ挙げられ、
これらが単独でまたは２種以上の組合わせで用いられる
。ま九ポリアミドは例えばトリアオノベンゼン、トリメ
リット酸、トリメシン酸、ピロメリット酸などの３価以
上の多官能化合物を涜融成形が可能な範囲内で共重合成
分として含んでいてもよい。ポリアミドは例えばジカル
ボン酸とジアミンとのナイロン塩合成反応およびこれに
続く重縮合反応を行う方法、ジカルボン酸ハライドとジ
アミンとの界面重合反応を行う方法などの過常のポリア
ミドの製造に用いられる方法に従って製造される。この
ようにして得られたポリアミドは９８チ濃硫酸中、２５
℃で測゛定した相対粘度が１．４〜３゜５．特に１．８
〜３．０の範囲内にあるものが好ましい。Examples of aromatic diamines include phenylene diamine and xylylene diamine, and examples of aliphatic diamines include tetramethylene diamine, hexamethylene diamine, and octamethylene diamine.
These may be used alone or in combination of two or more. The polyamide may contain, for example, a trivalent or higher polyfunctional compound such as trianobenzene, trimellitic acid, trimesic acid, pyromellitic acid, etc. as a copolymer component within a range that allows melt molding. Polyamides can be manufactured according to conventional methods used to produce polyamides, such as a nylon salt synthesis reaction between a dicarboxylic acid and a diamine followed by a polycondensation reaction, or an interfacial polymerization reaction between a dicarboxylic acid halide and a diamine. Manufactured. The polyamide thus obtained was dissolved in 98% concentrated sulfuric acid at 25%
The relative viscosity measured at °C is 1.4-3°5. Especially 1.8
-3.0 is preferable.
本発明によシ提供される紫外線吸収剤はポリマーに対し
０．００１〜１０重量％の範囲内で配合される。その配
合量は０．０１〜２重ｆ！Ｌ％の範囲内にあることが好
ましく、０．０５〜２ｆｆｔ％の範囲内にあることがよ
シ好ましい。配合量が０．００１重量％未満の場合はポ
リマーの紫外線吸収効果が低く、また１０重量％を越え
る場合はポリマーの物性が低下するおそれがある。The ultraviolet absorber provided by the present invention is blended into the polymer in an amount of 0.001 to 10% by weight. Its blending amount is 0.01 to 2 times f! It is preferably within the range of L%, and more preferably within the range of 0.05 to 2 fft%. If the amount is less than 0.001% by weight, the ultraviolet absorption effect of the polymer will be low, and if it exceeds 10% by weight, the physical properties of the polymer may deteriorate.
本発明の紫外線吸収剤はポリマーにその製造工程の任意
の段階で配合することが可能であり、ｔたポリマーの成
形前または成形中に常法によって配合することも可能で
ある。紫外線吸収剤はポリマー中に混和された状態また
は共重合された状態で存在する。The ultraviolet absorber of the present invention can be blended into the polymer at any stage of its manufacturing process, and can also be blended by a conventional method before or during molding of the polymer. The UV absorber is present in a mixed or copolymerized state in the polymer.
ま九本発明によ〕提供される紫外線吸収剤は必要に応じ
て他の添加剤、例えば着色剤、帯電防止剤、難燃剤、充
填剤、可塑剤などと併用して用いることもできる。Furthermore, the ultraviolet absorber provided by the present invention can be used in combination with other additives such as colorants, antistatic agents, flame retardants, fillers, plasticizers, etc., if necessary.
このようにして本発明の紫外線吸収剤を配合してなるポ
リマーとしては、一般式（１）で示される２−ヒドロキ
シフェニルベンゾトリアゾール系化合物が例えばその末
端でエステル結合、アミド結合などによシ主鎖部または
側鎖部に共重合されているポリマーが好ましい。In the polymer containing the ultraviolet absorber of the present invention, a 2-hydroxyphenylbenzotriazole compound represented by the general formula (1) is used, for example, as a polymer with an ester bond, an amide bond, etc. at its terminal. Preferably, the polymer is copolymerized in the chain portion or side chain portion.
上記の一般式（１）で示される２−ヒドロキシフェニル
ベンゾトリアゾール系化合物を配合してなるポリマーを
該ポリマーと相溶性のある他のポリマーで希釈する場合
、希釈後のポリマー中の一般式（１）テ示すレル２−ヒ
ドロキシフェニルベンツトリアゾール系化合物の配合量
が前記の範囲内となるように希釈する。When diluting a polymer formed by blending the 2-hydroxyphenylbenzotriazole compound represented by the above general formula (1) with another polymer that is compatible with the polymer, the general formula (1 ) The compound is diluted so that the amount of the 2-hydroxyphenylbenztriazole compound to be used falls within the above range.
本発明によシ提供されるポリマーは優れた紫外線吸収性
能を有する。本発明により提供されるポリマーのなかで
も、一般式（１）で示される２−ヒドロキシフェニルベ
ンゾトリアゾール系化合物を共重合成分として含有する
ポリマーは紫外線吸収成分がポリマーから抽出される辷
とがないので好ましい。また、本発明のポリマーは溶融
成形が可能であル、公知の成形法１例えば射出成形、プ
ロー成形、二軸延伸プロー成形、真空成形、圧縮成形な
どによ〕成形される。さらに本発明のポリマーハ他のポ
リマーとブレンドまたは積層して用いることもできる。The polymer provided by the present invention has excellent UV absorption performance. Among the polymers provided by the present invention, a polymer containing a 2-hydroxyphenylbenzotriazole compound represented by general formula (1) as a copolymerization component has no possibility of extracting the ultraviolet absorbing component from the polymer. preferable. Further, the polymer of the present invention can be melt-molded by known molding methods such as injection molding, blow molding, biaxial stretch blow molding, vacuum forming, and compression molding. Furthermore, the polymer of the present invention can also be used by blending or laminating with other polymers.
本発明のポリマーを成形して得られる例えば包装材、容
器などは紫外線吸収性能に優れておシ、紫外線の透過を
遮断することでそれらの内容物の紫外線による劣化、変
貿などを有効に防ぐことができる。For example, packaging materials, containers, etc. obtained by molding the polymer of the present invention have excellent ultraviolet absorption performance, and by blocking the transmission of ultraviolet rays, they effectively prevent the contents from deteriorating due to ultraviolet rays and changing trade. be able to.
以下、本発明を実施例によシ具体的に説明するが、本発
明はこれらの実施例によシ限定されるものではない。な
お、実施例中の「部」は「重量部」を表し、物性値は下
記の方法に従って測定した。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. In addition, "parts" in the examples represent "parts by weight", and physical property values were measured according to the following method.
（１） 紫外スペクトル
高滓製作所製ＵＶ−２１００型分光光度計を用い、２−
ヒドロキシフェニルベンゾトリアゾール系化合物はｌＯ
り／ぶのエタノール溶液として、またポリマーは１０
ｔ／１１のフェノール−テトラクロルエタン等重量混合
溶媒溶液として測定した。(1) Ultraviolet Spectrum Using a UV-2100 spectrophotometer manufactured by Takashi Seisakusho, 2-
Hydroxyphenylbenzotriazole compounds are lO
As an ethanol solution of R/B, the polymer was
It was measured as a mixed solvent solution of equal weight of phenol and tetrachloroethane at t/11.
（２） 抽出性
ポリマーＩｆをフェノール−テトラクロルエタン尋重量
混合−溶媒約２００ＩＩＬｌに溶解し、得られた溶液を
約２１のメタノールに加え、析出したポリマーを濾別し
たのち、ポリマーの紫外スペクトルを測定し、抽出操作
前のポリマーのスペクトルと比較した。(2) Extractable polymer If was dissolved in approximately 200 IIL of phenol-tetrachloroethane weight mixture-solvent, the resulting solution was added to approximately 21 kg of methanol, the precipitated polymer was filtered out, and the ultraviolet spectrum of the polymer was determined. It was measured and compared with the spectrum of the polymer before the extraction operation.
（８） 極限粘度〔υ〕
フェノール−テトラクロルエタン等重量混合溶媒を用い
５ｌｏｆ／Ｊ！の濃度、３０”Ｃで測定した。(8) Intrinsic viscosity [υ] 5lof/J using an equal weight mixed solvent of phenol and tetrachloroethane! The concentration was measured at 30''C.
（４） 相対粘度 ηｒｅｌ
ＪＩＳ Ｋ６８１０に従い９８チ濃硫酸中、１゜ｙ／
１の濃度、２５℃で測定した。(4) Relative viscosity ηrel 1゜y/in 98% concentrated sulfuric acid according to JIS K6810
1 concentration at 25°C.
（６） 融点翫およびガラス転移点 Ｔｔメトラー社
製ＴＡ−３０００型ＤＳＣを用いて、急冷非晶状態の試
料に対し１０”Ｃ／分の昇温速度にて測定した。(6) Melting point and glass transition point Using a TA-3000 DSC manufactured by Tt Mettler, measurement was performed on a sample in a rapidly cooled amorphous state at a heating rate of 10''C/min.
４−アミノ−３−ニトロ安息香酸３６．４ ｆ（２００
ｒｎｍｏｌｅ ）を濃塩酸６０ Ｆ （６００ｍｍｏｌ
ｅ ）と亜硝酸ナトリウム１３．８９ （２００ｍｍｏ
ｌｅ ）を用いて通常の方法によシジアゾ化し、ジアゾ
ニウム塩溶液を調整し念。０〜５℃の温度範囲に保念れ
念ｐ−ヒドロ・キシ安息香酸２７．６ ｔ （２００ｍ
ｍｏｌｅ ）を含む１０重量慢水酸化ナトリウム水溶液
２００ｔｘｌに得られ次ジアゾニウム塩溶液を徐々に添
加し。4-amino-3-nitrobenzoic acid 36.4 f (200
rnmole) in concentrated hydrochloric acid 60 F (600 mmol
e) and sodium nitrite 13.89 (200 mmo
diazotization using a conventional method to prepare a diazonium salt solution. 27.6 t (200 m
The resulting diazonium salt solution was gradually added to 200 txl of a 10 weight aqueous solution of sodium hydroxide containing 1 mole of sodium hydroxide.
２時間攪拌したのち析出し次ニトロアゾ化合物を濾別し
念。収率は６４俤であった。After stirring for 2 hours, the precipitated nitroazo compound was filtered off. The yield was 64 yen.
得られ念ニトロアゾ化合物２８．７Ｆ（１００工１ｅ）
を２Ｎの水酸化ナトリツム水溶液１００−に溶解し、こ
の溶液を亜鉛粉末３０ ｔ （４６０ｍｍｏｌｅ ）を
含む２５俤水酸化ナトリウム水溶液５ Ｑ ｔｔｌに４
０℃以下の温度に保ちながら徐々に添加し之。反応混合
物を３０℃以下の温度に冷却してから濃塩酸で酸性（田
＝１〜２）にしたのち２時間攪拌した。Obtained nitroazo compound 28.7F (100 steps 1e)
was dissolved in a 2N sodium hydroxide aqueous solution (100-100 kg), and this solution was added to 25 ttl of a sodium hydroxide aqueous solution (5 Q ttl) containing 30 t (460 mmole) of zinc powder.
Add it gradually while keeping the temperature below 0°C. The reaction mixture was cooled to a temperature of 30°C or less, acidified with concentrated hydrochloric acid (temperature = 1-2), and stirred for 2 hours.
次いで１反応混合物を水酸化す） ＩＪウムを用いてア
ルカリ性（…＝１３〜１４）にしたのちグラスフィルタ
ーで濾過し、得られた濾液を再び濃塩酸で酸性（ｍ＝ｔ
〜２）にし、析出した沈殿物を濾別し念。この沈殿物を
冷水で洗浄、乾燥後水−メタノールから再結晶して淡褐
色の結晶として２−（２−ヒドロキシフェニル）ベンゾ
トリアゾール−５，５−ジカルボン酸を１６．１Ｆ得た
。収率は５４％であった。Then, the reaction mixture was made alkaline (...=13-14) using IJum, filtered through a glass filter, and the obtained filtrate was acidified again with concentrated hydrochloric acid (m=t
~2), and filter out the precipitate. This precipitate was washed with cold water, dried, and then recrystallized from water-methanol to obtain 16.1F of 2-(2-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid as pale brown crystals. The yield was 54%.
生成物のエタノール中での紫外線最大吸収波長は３３４
ｒｍであった。The maximum UV absorption wavelength of the product in ethanol is 334
It was rm.
生成中の物性値を次に示す。The physical properties during production are shown below.
元素分析値
理論値 実験値
（Ｃｘ４ＨｅＮｓＯｓとして）
Ｃ％ ５６．１９ ５ａ９５Ｈ％
３，０３ ３．０ＯＮチ １４．
０４ １３．８９質量分析値 ２９９（Ｍ
”）
δ−ニトロアニリン５５．２ ｆ （４００ｍｍｏｌｅ
） ヲ氷酢酸中で臭素１５０．２２（９４０ｍｍｏｌ
ｅ ）と反応させ、２．４−ジブクモ−６−ニトロアニ
リン８５．２ｔ （２８８ｍｍｏｌｅ ）を得た。Elemental analysis value Theoretical value Experimental value (as Cx4HeNsOs) C% 56.19 5a95H%
3,03 3.0ONchi 14.
04 13.89 Mass spectrometry value 299 (M
”) δ-nitroaniline 55.2 f (400 mmole
) Bromine 150.22 (940 mmol) in glacial acetic acid
e) to obtain 85.2t (288 mmole) of 2,4-dibucumo-6-nitroaniline.
実施例１において４−アミノ−３−ニトロ安息香酸３６
．４り（２００ｍｍｏｌｅ ）の代わシに２．４−ジブ
ｏ ％ −５−＝ ） ａアニリン５９．２ ｆ （２
００ｍｍｏｌｅ ）を用い、かつｐ−ヒドロキシ安息香
酸２７．６ Ｆ（２００ｍｍｏｌｅ ）の代わシにｐ−
メチルフェノール２１、６ ｆ （２００ｍｍｏｌｅ
）を用いる以外ハ同様にして４．６−ジブロモ−２−（
２’−ヒドロキシ−５′−メチルフェニル）ベンゾトリ
アゾールを得た。収率は６０チであった。In Example 1, 4-amino-3-nitrobenzoic acid 36
．． 2.4-zib o % -5-= ) a aniline 59.2 f (2
00 mmole), and p-hydroxybenzoic acid 27.6 F (200 mmole) was used.
Methylphenol 21,6f (200mmole
) except that 4,6-dibromo-2-(
2'-Hydroxy-5'-methylphenyl)benzotriazole was obtained. The yield was 60 cm.
得られた４、６−ジプロモー２−（２−ヒドロキシ−５
−メチルフェニル）ベンゾトリアソール３８．３ ｆ
（１００ｍｍｏｌｅ、）を石油：Ｃ−？ ル中”ｔ”
ｎ −ブチルリチウム１４．１ ？ （２２０ｍｍｏｌ
ｅ ）を加えて２４時間還流したのちドライアイスと反
応させ、２−（２−ヒドロキシ−５′−メチルフェニル
）ベンゾトリアゾール−４，６−ジカルボン酸を２２．
２ｆ得九。収率は７１チであった。The obtained 4,6-dipromo-2-(2-hydroxy-5
-methylphenyl)benzotriazole 38.3 f
(100 mmole,) petroleum: C-? “t” in le
n-butyllithium 14.1? (220 mmol
e) was added and refluxed for 24 hours, and then reacted with dry ice to form 2-(2-hydroxy-5'-methylphenyl)benzotriazole-4,6-dicarboxylic acid.
2f gain nine. The yield was 71 inches.
生成物のエタノール中での紫外線最大吸収波長は３３４
ｎｍであった。The maximum UV absorption wavelength of the product in ethanol is 334
It was nm.
生成物の物性値軸度に示す。The physical properties of the product are shown in the axis degree.
元素分析値
Ｃチ
Ｈチ
Ｎチ
買置分析値
５７．５１
３．５４
１３．４１
３１３（Ｍ”）
５７．１８
３．４３
１３．０３
４−クロル−２−ニトロアニリン５１゜８ｔ（３００ｍ
ｍｏｌｅ ）を氷酢酸中で臭素５７．５ Ｆ （３６０
ｍｍｏｌｅ）と反ろさせ、６−ブロモ−４−クロル−２
−ニトロアニリン６１．６ ｔ （２４３ｍｍｏｌｅ
）を得た。Elemental analysis value C Chi H Chi N Chi purchase analysis value 57.51 3.54 13.41 313 (M”) 57.18 3.43 13.03 4-chloro-2-nitroaniline 51° 8t (300m
57.5 F (360 mole) of bromine in glacial acetic acid
mmole) and 6-bromo-4-chloro-2
- 61.6 t (243 mmole) of nitroaniline
) was obtained.
実施例１において４−アミノ−３−ニトロ安息香酸３６
．４ ｆ （２００ｍｍｏｌｅ ）の代わシに６−ブロ
ー１ニー４−クロル−２−ニトロアニリン５０．３Ｆ（
２００ｍｍｏｌｅ ）を用いる以外は同様にして４−プ
１’％−６−／ロルー２−（２’−ヒドロキシフェニル
）ベンゾトリアゾール−５−カルボン酸を得た。In Example 1, 4-amino-3-nitrobenzoic acid 36
．． 4 F (200 mmole) was replaced with 6-blow 1 knee 4-chloro-2-nitroaniline 50.3 F (
4-P1'%-6-/Lo-2-(2'-hydroxyphenyl)benzotriazole-5-carboxylic acid was obtained in the same manner except that 200 mmole) was used.
収率は５８チであった。The yield was 58 cm.
得られ念４−プロモー６−クロル−２−（２’−ヒドロ
ヤシフェニル）ベンゾトリアゾール−５−カルボン酸３
６．８ ｆ （１００ｍｍｏｌｅ）を石油エーテに中で
−ｆ）ｎ−７”ｆｋすｆラム９．６ ｆ （１５Ｑｍｍ
ｏｌｅ）を加えて１０分間還流したのちドライアイスと
反応させ、６−クロル−２−（２−ヒドロキシフェニル
）ベンゾトリアゾール−４，５−ジカルボン酸２Ｚ、８
ｆを得た。収率は４５チであった。Obtained 4-promo-6-chloro-2-(2'-hydrocyphenyl)benzotriazole-5-carboxylic acid 3
6.8 f (100 mmole) in petroleum ether
After adding ole) and refluxing for 10 minutes, it was reacted with dry ice to produce 6-chloro-2-(2-hydroxyphenyl)benzotriazole-4,5-dicarboxylic acid 2Z,8
I got f. The yield was 45 cm.
生成物のエタノール中での紫外線最大吸収波長は３３３
ｎｍであった。The maximum UV absorption wavelength of the product in ethanol is 333
It was nm.
生成物の物性値な次に示す。The physical properties of the product are shown below.
以下余白
Ｃチ
ｑ６
Ｎチ
α慢
質景分析値
５０．３９
２．４２
１２□５９
１０．６２
３３４ＣＭ”）
５０．１０
２．３８
１２．７７
１０．９１
Ｃチ ６１．１７ ６０．９２Ｈ％
３．５５ ３．５２Ｎ％
１６．４６ １６．２５質量分析
値 ２５５（Ｍ”）
実施例１において４−アミノ−３−ニトロ安息香酸３６
．４ ｆ （２００ｍｍｏｌｅ ）の代わりにｏ’ −
ニトロアニリン２７．６ ｆ （２００ｍｍｏｌｅ ）
を用いる以外ハ同様ニジて２− （２’−ヒドロキシフ
ェニル）ベンゾトリアゾール−５−カルボン酸１３．３
Ｆを得た。収率は５２チであつ九。Below margin Cchi q6 Nchi α arrogance analysis value 50.39 2.42 12□59 10.62 334CM”) 50.10 2.38 12.77 10.91 Cchi 61.17 60.92H%
3.55 3.52N%
16.46 16.25 Mass spectrometry value 255 (M”) 4-Amino-3-nitrobenzoic acid 36 in Example 1
．． 4 o' − instead of f (200 mmole)
Nitroaniline 27.6 f (200 mmole)
2-(2'-hydroxyphenyl)benzotriazole-5-carboxylic acid 13.3
I got an F. The yield was 52 cm.
生成物のエタノール中での紫外線最大吸収波長は３３２
ｎｍであった。The maximum UV absorption wavelength of the product in ethanol is 332
It was nm.
生成物の物性値を次に示す。The physical properties of the product are shown below.
実施例１において４−アミノ−３−ニトロ安息香酸３６
．４ Ｆ （２００ｍｍｏｌｅ ）の代わりに４−クロ
ル−２−ニトロアニリン３４．５ ＰＣ２００ｍｍｏｌ
ｅ ）を用いる以外は同様にして５−クロル−２−（２
’−ヒドロキシフェニル）ベンゾトリアゾール−５−カ
ルボン酸１７．４ｆを得た。収率は３０膚であった。In Example 1, 4-amino-3-nitrobenzoic acid 36
．． 4-chloro-2-nitroaniline 34.5 PC200 mmol instead of 4 F (200 mmole)
5-chloro-2-(2
'-Hydroxyphenyl)benzotriazole-5-carboxylic acid 17.4f was obtained. Yield was 30 skins.
生成物のエタノール中での紫外線最大吸収波長は３３２
１′１ｒｒｌであツタ。The maximum UV absorption wavelength of the product in ethanol is 332
Ivy at 1'1rrl.
生成物の物性を次に示す。The physical properties of the product are shown below.
Ｃチ
Ｈチ
ｔｓ
αチ
質量分析値
５３．９０
２．７８
１４．５１
１２．２４
２９０（Ｍ”）
５３．７５
２．６０
１４．２２
１２．２３
０％
Ｈ％
Ｎチ
質量分析値
５６．１９
３．０３
１４．０４
２９９（Ｍ＋）
５６．２８
３．２９
１４．０８
比較例Ｉにおいて、ｐ−ヒドロキシ安息香酸２７、６
ｆ （２００ｍｒｎｏｌｅ ）の代わりに４−ヒドロキ
シイソフタル酸３６．４ ｔ （２００ｒｎｍｏｌｅ
）を用イル以外は同様にして２−（２−ヒドロキシフェ
ニル）ベンゾトリアゾール−３，５−ジカルボン酸２６
，９ｆを得た。収率は４５％であった。CchiHchits αchi mass spectrometry value 53.90 2.78 14.51 12.24 290 (M”) 53.75 2.60 14.22 12.23 0% H% Nchi mass spectrometry value 56. 19 3.03 14.04 299 (M+) 56.28 3.29 14.08 In Comparative Example I, p-hydroxybenzoic acid 27,6
f (200 mrnole) instead of 4-hydroxyisophthalic acid 36.4 t (200 mrnole
) was prepared in the same manner except that 2-(2-hydroxyphenyl)benzotriazole-3,5-dicarboxylic acid 26
,9f was obtained. The yield was 45%.
生成物のエタノール中での紫外線最大吸収波長は３１０
ｎｍであった。The maximum UV absorption wavelength of the product in ethanol is 310
It was nm.
生成物の物性値を次に示す。The physical properties of the product are shown below.
比較例３においてＯ−ニトロアニリン２７．６ｆ（２０
０ｍｍｏｌｅ ）の代わｆｉＫ４−クロ／Ｉ／ −２−
二）ロアニリン３４．５ ｆ （２００ｍｍｏｌｅ ）
を用イル以外は同様にして５−クロル−２−（２’−ヒ
ドロキシフェニル）ペンツトリアゾール−３；５−ジカ
ルボン酸３０．７ｆを得た。収率は４６チであった。In Comparative Example 3, O-nitroaniline 27.6f (20
0mmole) instead of fiK4-black/I/-2-
2) Roaniline 34.5 f (200 mmole)
30.7f of 5-chloro-2-(2'-hydroxyphenyl)penztriazole-3;5-dicarboxylic acid was obtained in the same manner except that . The yield was 46 cm.
生成物のエタノール中での紫外線最大吸収波長は３２０
１ｍであった。The maximum UV absorption wavelength of the product in ethanol is 320
It was 1m.
生成物の物性値を次に示す。The physical properties of the product are shown below.
０％ ５０．３９ ５０．０２Ｈ
チ ２．４２ ２．４８Ｎチ
１２．５９ １２．９０αチ
１０．６２ １０．５５質量分析値
３３４（Ｍ＋）
実施例１〜３および比較例１〜４て得られた一般式（Ｉ
）で示される２−ヒドロキシフェニルベンゾトリアゾー
ル系化合物を表−１に示す。0% 50.39 50.02H
Chi 2.42 2.48N Chi
12.59 12.90αchi
10.62 10.55 Mass spectrometry value
334 (M+) General formula (I) obtained in Examples 1 to 3 and Comparative Examples 1 to 4
) 2-hydroxyphenylbenzotriazole compounds are shown in Table 1.
以下余白
表
実施例４
ジメチルテレフタレー）１０００部、エチレングリコー
ル７２０部（エチレングリコール対ジメチルテレフタレ
ートのモル比＝２．２５対１）および酢酸マンガン四水
和物０．３部を室温で反応器に仕込み、−１＝：１４０
″Ｃｔで昇温し念の５、さらに十
攪拌下約３時間かけて徐々に２４０℃昇温し、理論量の
９９チ以上のメタノールを留去し九。次いで、亜リン酸
０．１部、二酸化ゲルマニウム０．５部および実施例１
で得られ＊２−（２’−ヒドロキシフェニル）ベンゾト
リアゾール−５，５−ジカルボン酸４．９部を添加し、
２８０℃、０．５■ＨＰ以下の条件下で約２時間７ｉ縮
合せしめ念。得られ念ポリエステルの極限粘度〔で〕は
０．８２であシ、融点は２４８．１℃であシ、ガラス転
移温度は８０．２℃であつ念。Below is a blank table. Example 4 1000 parts of dimethyl terephthalate), 720 parts of ethylene glycol (molar ratio of ethylene glycol to dimethyl terephthalate = 2.25:1), and 0.3 part of manganese acetate tetrahydrate were placed in a reactor at room temperature. Preparation, -1=:140
The temperature was gradually raised to 240°C over a period of about 3 hours with further stirring, and the theoretical amount of 99 or more methanol was distilled off.Next, 0.1 part of phosphorous acid was added. , 0.5 part of germanium dioxide and Example 1
Adding 4.9 parts of *2-(2'-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid obtained in
Condensation was carried out for about 2 hours at 280°C and 0.5 HP or less. The intrinsic viscosity of the obtained polyester was 0.82, the melting point was 248.1°C, and the glass transition temperature was 80.2°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
実施例５
実施例４において、２−（２−ヒドロキシフェニル）ペ
ンツトリアゾール−５，ｓ −ジカルボン酸４．９部の
代わりに０．５部用いる以外は同様にしてポリエステル
を得喪。得られたポリエステルの極限粘度〔マ〕は０．
８３であり、融点は２５０、−１℃であり、ガラス転移
温度は８０．５℃であった。Example 5 A polyester was obtained in the same manner as in Example 4, except that 0.5 part of 2-(2-hydroxyphenyl)penztriazole-5,s-dicarboxylic acid was used instead of 4.9 parts. The intrinsic viscosity [ma] of the obtained polyester was 0.
83, the melting point was 250, -1°C, and the glass transition temperature was 80.5°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較し九結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared.The results showed that the behavior of both samples was exactly the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
実施例６
実施例４において、２−（２−ヒドロキシフェニル）ベ
ンゾトリアゾール−５，５−ジカルボン酸４．９部の代
わシに９．８部用いる以外は同様にしてポリエステルを
得た。得られたポリエステルの極限粘度〔η〕は０．７
４であり、融点は２４６．２℃であり、ガラス転移温度
は７９，６℃であった。Example 6 A polyester was obtained in the same manner as in Example 4, except that 9.8 parts of 2-(2-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid was used instead of 4.9 parts. The intrinsic viscosity [η] of the obtained polyester is 0.7
4, the melting point was 246.2°C, and the glass transition temperature was 79.6°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外＃ｉ！吸収挙動を比較した結果１両者の
挙動は全く同じで６つ九。抽出後の試料の紫外１ｆｓｅ
、集挙動を表−２に示す。An extractability test was conducted on this polyester, and ultraviolet #i! was measured for each sample before and after extraction. As a result of comparing the absorption behavior, the behavior of both is exactly the same. Ultraviolet 1fse of sample after extraction
, the collection behavior is shown in Table 2.
実施例７
実施例４において、２−（２’−ヒドロキシフェニル）
ベンゾトリアゾール−５，５′−ジカルボン酸４．９部
の代わ）に４９部用いる以外は同様にしてポリエステル
を得た。得られたポリエステルの極限粘度〔η〕は０．
７６であシ、融点は２４５．６℃であシ、ガラス転移温
度は７９．３℃であった。Example 7 In Example 4, 2-(2'-hydroxyphenyl)
A polyester was obtained in the same manner except that 49 parts of benzotriazole-5,5'-dicarboxylic acid (instead of 4.9 parts) was used. The intrinsic viscosity [η] of the obtained polyester was 0.
The melting point was 245.6°C, and the glass transition temperature was 79.3°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであり九。抽出後の試料の紫外線吸収挙動を
表−２に示す。We conducted an extractability test on this polyester and compared the ultraviolet absorption behavior of each sample before and after extraction, and found that the behavior of both samples was exactly the same9. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
実施例８
実施例４において、２−（２’−ヒドロキシフェニル）
ベンゾトリアゾール−５，５′−ジカルボン酸４．９部
の代わ）に７３．５部用いる以外は同様にしてポリエス
テルを得た。得られたポリエステルの極限粘度〔η〕は
０．７４であり、融点は２４２．１’Ｃであシ、ガラス
１移温度は７８．９℃であった。Example 8 In Example 4, 2-(2'-hydroxyphenyl)
A polyester was obtained in the same manner except that 73.5 parts of benzotriazole-5,5'-dicarboxylic acid (instead of 4.9 parts) was used. The intrinsic viscosity [η] of the obtained polyester was 0.74, the melting point was 242.1'C, and the glass 1 transfer temperature was 78.9°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであつ念。抽出後の試料の紫外線吸収挙動を
表−２に示す。We conducted an extractability test on this polyester and compared the ultraviolet absorption behavior of each sample before and after extraction, and found that the behavior of both samples was exactly the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
実施例９
実Ｍ例４において、２−（２−ヒドロキシフェニル）ベ
ンゾトリアゾール−５，５−ジカルボン酸４．９部の代
わＪ）Ｋ実施例２で得られた２−（２’−ヒドロキシ−
５−メチルフェニル）ベンゾトリアゾール−４，６−ジ
カルボン酸４．９部を用いる以外は同様にしてポリエス
テルを得た。得られたポリエステルの極限粘度〔η〕は
０．７７であり、融点は２５０．２℃であシ、ガラス転
移温度は７９．９℃であった。Example 9 In Example 4, 4.9 parts of 2-(2-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid was replaced with 2-(2'-hydroxy-
A polyester was obtained in the same manner except that 4.9 parts of 5-methylphenyl)benzotriazole-4,6-dicarboxylic acid was used. The obtained polyester had an intrinsic viscosity [η] of 0.77, a melting point of 250.2°C, and a glass transition temperature of 79.9°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１０
実施例４において、ジメチルテレフタレート１０００部
の代わりにジメチルインフタレート１０００部を用いる
以外は同様にしてポリエステルを得た。得られたポリエ
ステルの極限粘度〔η〕は０．７８であシ、ガラス転移
温度は６４．５℃であった。Example 10 A polyester was obtained in the same manner as in Example 4, except that 1000 parts of dimethyl inphthalate was used instead of 1000 parts of dimethyl terephthalate. The intrinsic viscosity [η] of the obtained polyester was 0.78, and the glass transition temperature was 64.5°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較し九結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared.The results showed that the behavior of both samples was exactly the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１１
実施例４において、２−（２−ヒドロキシフェニル）ベ
ンゾトリアゾール−５，５−ジカルボン酸４．９部の代
わりに実施例３で得た６−クロル−２−（２′−ヒドロ
キシフェニル）ベンゾトリアソール−４，５−ジカルボ
ン酸を用いる以外は同様にしてポリエステルを得念。得
られたポリエステルの極限粘度〔η〕は０．７９であり
、融点は２５０．６℃であり、ガラス転移温度は８０．
０℃であった。Example 11 In Example 4, 6-chloro-2-(2'-hydroxyphenyl obtained in Example 3) was used instead of 4.9 parts of 2-(2-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid. ) Polyester was prepared in the same manner except that benzotriazole-4,5-dicarboxylic acid was used. The obtained polyester had an intrinsic viscosity [η] of 0.79, a melting point of 250.6°C, and a glass transition temperature of 80.
It was 0°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
比較例５
実ｊ［４において、２−（２−ヒドロキシフェニル）ペ
ンツトリアゾール−５，５−ジカルボン酸を用いない以
外は同様にしてポリエステルを得た。Comparative Example 5 A polyester was obtained in the same manner as in Example J [4, except that 2-(2-hydroxyphenyl)penztriazole-5,5-dicarboxylic acid was not used.
得られたポリエステルの極限粘度〔η〕は０．７５でｓ
ｂ、融点は２５２．９℃であシ、ガラス転移温度比較例
６
比較例５において、ジメチルテレフタレート１０００部
を用いる以外は同様にしてポリエステルを得な。得られ
たポリエステルの極限粘度〔υ〕は０．７０であり、ガ
ラス転移温度は６５．０℃であった。The intrinsic viscosity [η] of the obtained polyester is 0.75 and s
b. The melting point was 252.9°C. Glass transition temperature Comparative Example 6 A polyester was obtained in the same manner as in Comparative Example 5 except that 1000 parts of dimethyl terephthalate was used. The intrinsic viscosity [υ] of the obtained polyester was 0.70, and the glass transition temperature was 65.0°C.
このポリエステルの紫外線吸収挙動を表−２に示す。Table 2 shows the ultraviolet absorption behavior of this polyester.
比較例７
実施例４において、２−（２−ヒドロキシフェニル）ベ
ンゾトリアゾール−５，５−ジカルボン酸４．９部の代
わりに比較例１で得られ＆２−（２’−ヒドロキシフェ
ニル）ベンゾトリアソール−５−カルボン酸４．９部を
用いる以外は同様にしてポリエステルを得た。得られた
ポリエステルの極限粘度〔マ〕は０．８０であり、融点
は２４８．１℃であり。Comparative Example 7 In Example 4, &2-(2'-hydroxyphenyl)benzotriazole obtained in Comparative Example 1 was substituted for 4.9 parts of 2-(2-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid. A polyester was obtained in the same manner except that 4.9 parts of -5-carboxylic acid was used. The obtained polyester had an intrinsic viscosity of 0.80 and a melting point of 248.1°C.
ガラス転移温度は７９．７℃であった。The glass transition temperature was 79.7°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較し次結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared.The results showed that the behavior of both samples was exactly the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
比較例８
実ｊｌＪ４において、２−（２−ヒドロキシフェニル）
ベンゾトリアゾール−５，５′−ジカルボン酸４．９部
の代わりに比較例２で得られた５−クロル−２−（２’
−ヒドロキシフェニル）ベンゾトリアゾール−５′−カ
ルボン酸４．９部を用いる以外は同様にしてポリエステ
ルを得た。得られたポリエステルの極限粘度〔マ〕は０
，７４であシ、融点は２４９．４℃であシ、ガラス転移
温度は７９．５℃であった。Comparative Example 8 In actual jlJ4, 2-(2-hydroxyphenyl)
5-chloro-2-(2'
A polyester was obtained in the same manner except that 4.9 parts of -hydroxyphenyl)benzotriazole-5'-carboxylic acid was used. The intrinsic viscosity [ma] of the obtained polyester is 0
, 74, the melting point was 249.4°C, and the glass transition temperature was 79.5°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果、両者の挙動
は全く同じでありな。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of the two samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
比較例９
実施例４において、２−（２−ヒドロキシフェニル）ベ
ンゾトリアゾール−５，５−ジカルボン酸４．９部の代
わシに比較例３で得られた２−（２’−ヒドロキシフェ
ニル）ペンシトＩ）１ソーＡ’−３’、５−ジカルボン
酸４．９部を用いる以外は同様にしてポリエステルを得
た。得られたポリエステルの極限粘度〔η〕は０．７８
であシ、融点は２５２．１ ’Ｃであシ、゛ガラス転移
温度は８０．０℃であった。Comparative Example 9 In Example 4, 2-(2'-hydroxyphenyl)pensitide obtained in Comparative Example 3 was used instead of 4.9 parts of 2-(2-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid. I) A polyester was obtained in the same manner except that 4.9 parts of 1soA'-3',5-dicarboxylic acid was used. The intrinsic viscosity [η] of the obtained polyester was 0.78
The melting point was 252.1°C, and the glass transition temperature was 80.0°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果５両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared.5 The behavior of both samples was exactly the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
比較例１０
実施例４において、２−（２−ヒドロキシフェニル）ヘ
ンジトリアゾール−５，５−ジカルボン酸４．９部の代
わシに比較例４で得られｆｃ５−クロル−２−（２’−
ヒドロキシフエニ・ル）ペンツトリアゾール−３１５−
ジカルボン酸４．９部を用いる以外は同様にしてポリエ
ステルを得た。得られたポリエステルの極限粘度〔マ〕
は０．７６であυ、融点は２４９．７℃であシ、ガラス
転移温度は７９．９℃でおった。Comparative Example 10 In Example 4, fc5-chloro-2-(2'-
Hydroxyphenylenepenztriazole-315-
A polyester was obtained in the same manner except that 4.9 parts of dicarboxylic acid was used. Intrinsic viscosity of the obtained polyester
was 0.76, the melting point was 249.7°C, and the glass transition temperature was 79.9°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較し友結果、両者の′挙
動は全く同じであった。抽出後の試料の紫外線吸収挙動
を表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared.The results showed that the behavior of both samples was exactly the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
比較例１１
実施例７において、２−（２−ヒドロキシフェニル）ヘ
ンシトリアゾール−５，５−ジカルボン酸４９部の代わ
シに比較例１で得られた２−（２−ヒドロキシフェニル
）ペンシト＋）７ゾーに−５−カルボン酸４９部を用い
る以外は同様にしてポリエステルを得念。得られたポリ
エステルの極限粘度〔η〕は０．３３であり、融点は２
５３．４℃であり、ガラス転移温度は７１．２℃であっ
た。Comparative Example 11 In Example 7, 2-(2-hydroxyphenyl)pencyto+)7 obtained in Comparative Example 1 was used instead of 49 parts of 2-(2-hydroxyphenyl)hencytriazole-5,5-dicarboxylic acid. A polyester was prepared in the same manner except that 49 parts of -5-carboxylic acid was used as the solvent. The intrinsic viscosity [η] of the obtained polyester was 0.33, and the melting point was 2.
The temperature was 53.4°C, and the glass transition temperature was 71.2°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
比較例１２
実施例４において、２−（２’−ヒドロキシフェニル）
ベンゾトリアゾール−５，５−ジカルボン酸４．９部の
代わ！＞ＫＯ，００５部用いる以外は同様にしてポリエ
ステルを得た。得られたポリエステルの極限粘度〔１〕
は０．７６であシ、融点は２５２．１℃であり、ガラス
転移温度は８０．４℃であつ九。Comparative Example 12 In Example 4, 2-(2'-hydroxyphenyl)
Instead of 4.9 parts of benzotriazole-5,5-dicarboxylic acid! Polyester was obtained in the same manner except that >KO,005 parts were used. Intrinsic viscosity of the obtained polyester [1]
is 0.76, the melting point is 252.1°C, and the glass transition temperature is 80.4°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果１両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared.1 The behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
比較例１３
実施例４において、２−（２−ヒドロキシフェニル）ベ
ンゾトリアゾール−５，５−ジカルボン酸４．９部の代
わりに下記の構造式で表わされる紫外線吸収剤４．９部
を用いる以外は同様にしてポリエステルを得た。得られ
たポリエステルの極限粘度〔η〕は０．７８であ夛、融
点は２５２．７℃であシ、ガラス転移温度は８０．３℃
であつ九。Comparative Example 13 Example 4 except that 4.9 parts of an ultraviolet absorber represented by the following structural formula was used instead of 4.9 parts of 2-(2-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid. Polyester was obtained in the same manner. The intrinsic viscosity [η] of the obtained polyester was 0.78, the melting point was 252.7°C, and the glass transition temperature was 80.3°C.
Atatsu nine.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果を表−２に示
す。An extractability test was conducted on this polyester, and the results of comparing the ultraviolet absorption behavior of each sample before and after extraction are shown in Table 2.
比較例１４
実施例４において％ ２−（２’−ヒドロキシフェニ
ル）ベンゾトリアゾール−ｓ、 ｓ −ジカルボン酸４
．９部の代わｆｉＫ下記の構造式で表される紫外線吸収
剤４．９部を用いる以外は同様にしてポリエステルを得
念。得られたポリエステルの極限粘度〔マ〕は０．７７
であシ、融点は２５２．９℃であシ、ガラス転移温度は
８０．０℃であった。Comparative Example 14 In Example 4, % 2-(2'-hydroxyphenyl)benzotriazole-s, s-dicarboxylic acid 4
．． Polyester was prepared in the same manner except that 4.9 parts of an ultraviolet absorber represented by the structural formula below was used instead of 9 parts of fiK. The intrinsic viscosity [ma] of the obtained polyester is 0.77
The melting point was 252.9°C, and the glass transition temperature was 80.0°C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較し之結果を表−２に示
す。This polyester was subjected to an extractability test, and the ultraviolet absorption behavior of each sample before and after extraction was compared, and the results are shown in Table 2.
比較例１５
実Ｍ例４において、２−（２’−ヒドロキシフェニル）
ベンゾトリアゾール−５，５−ジカルボン酸４．９部の
代わシに下記の構造式で表される紫外線吸収剤４．９部
を用いる以外は同様にしてポリエステルを得な。得られ
たポリエステルの極限粘度〔η〕は０．７５であり、融
点は２５０．３℃であシ、ガラス転移温度は７９．７°
Ｃであった。Comparative Example 15 In Example M 4, 2-(2'-hydroxyphenyl)
A polyester was obtained in the same manner except that 4.9 parts of an ultraviolet absorber represented by the following structural formula was used instead of 4.9 parts of benzotriazole-5,5-dicarboxylic acid. The intrinsic viscosity [η] of the obtained polyester was 0.75, the melting point was 250.3°C, and the glass transition temperature was 79.7°.
It was C.
このポリエステルの抽出性試験を行い、抽出前後の各試
料について紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−２に示す。表−２から明らかなようＫこのポリエス
テルは実施例ｌ５１１よシ得られたポリエステルに比べ
、紫外線吸収性能は著しく劣っていた。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction. As is clear from Table 2, this polyester had significantly inferior ultraviolet absorption performance compared to the polyester obtained in Example 1511.
比較例１Ｇ
実施例７において、２−（２−ヒドロキシフェニル）ベ
ンゾトリアゾール−５，５−ジカルボン酸４９部の代わ
りに下記の構造式で表される紫外線吸収剤２０部を用い
る以外は同様にしてポリエステルを得た。得られなポリ
エステルの極限粘度〔η〕は０．６２であシ、融点は２
４５．２℃であった。そのガラス転移温度は７０．８℃
であり、実施例１〜９および実施例１１で得られたポリ
エステルに比べ耐熱性の著しい低下が認められた。Comparative Example 1G The same procedure as in Example 7 was carried out except that 20 parts of an ultraviolet absorber represented by the following structural formula was used instead of 49 parts of 2-(2-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid. Polyester was obtained. The intrinsic viscosity [η] of the resulting polyester was 0.62, and the melting point was 2.
The temperature was 45.2°C. Its glass transition temperature is 70.8℃
, and a significant decrease in heat resistance was observed compared to the polyesters obtained in Examples 1 to 9 and Example 11.
このポリエステルの抽出性試験を行い、抽出前後の各試
料についての紫外線吸収挙動を比較した結果、両者の挙
動は全く同じであった。抽出後の試料の紫外線吸収挙動
を表−２に示す。An extractability test was conducted on this polyester, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 2 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１２
テレフタル酸４２９部、インフタル酸１０００部、実施
例１で得られ几２−（２−ヒドロキシフェニル）ベンゾ
トリアゾール−５，５′−ジカルボン酸１０．６部、ヘ
キサメチレンジアミン１０５０ｍ、安息香酸１０．５部
、イオン交換水６１４部および次亜リン酸ナトリウム１
．８部をオートクレーブに仕込み、窒素置換を十分行っ
たの５．密閉状態のまま加熱し、内圧９〜ｌＯ神／−１
内温１９０〜２００℃に制御しながら１時間攪拌し反応
を行った。次いで内圧が１８ｋｆ／ｃｒＡになるまで加
熱し。Example 12 429 parts of terephthalic acid, 1000 parts of inphthalic acid, 10.6 parts of 2-(2-hydroxyphenyl)benzotriazole-5,5'-dicarboxylic acid obtained in Example 1, 1050 m of hexamethylene diamine, benzoic acid 10.5 parts, 614 parts of ion exchange water and 1 part of sodium hypophosphite
．． 5. Pour 8 parts into an autoclave and thoroughly purge with nitrogen. Heat it in a sealed state to an internal pressure of 9 to 10/-1
The reaction was carried out by stirring for 1 hour while controlling the internal temperature to 190 to 200°C. Then, it was heated until the internal pressure became 18 kf/crA.
その圧力を保持するように放圧させながら攪拌し重合反
応を開始させた。２００℃から２５０℃まで５時間かけ
てゆるやかに昇温し、水の留出がなくなり比時点で放圧
しポリアミドを取ル出した。The polymerization reaction was started by stirring while releasing the pressure to maintain the same pressure. The temperature was gradually raised from 200° C. to 250° C. over 5 hours, and when no water was distilled off, the pressure was released and the polyamide was taken out.
得られたポリアミドの相対粘度ηｒｅｌは２．２６であ
り、ガラス転移温度は１２６．４℃であった。The relative viscosity ηrel of the obtained polyamide was 2.26, and the glass transition temperature was 126.4°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果。The results of an extractability test of this polyamide and a comparison of the ultraviolet absorption behavior of each sample before and after extraction.
両者の挙動は全（く同じであり念。抽出後の試料の紫外
線吸収挙動を表−３に示す。Note that the behavior of both is exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１３
実施例１２において、２−（２’−ヒドロキシフェニル
）ペンソートリアシーＡ−５，５’−ジカルボン酸１０
．６部の代わりに２．１部用いる以外は同様にしてボリ
アずドを得た。得られたポリアミドの相対粘度ｒＩｒｅ
ｌは２．１０であり、ガラス転移温度は１２７．０℃で
あった。Example 13 In Example 12, 2-(2'-hydroxyphenyl)pensortriacee A-5,5'-dicarboxylic acid 10
．． Boriazudo was obtained in the same manner except that 2.1 parts were used instead of 6 parts. Relative viscosity rIre of the obtained polyamide
1 was 2.10, and the glass transition temperature was 127.0°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較１−た結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１４
実施例１２においてｓ ２− （２’−ヒドロキシフェ
ニル）ペンツトリアゾール−５，５−ジカルボン酸１０
．６部の代わりに２１．２部用いる以外は同様にしてポ
リアミドを得た。得られたポリアミドの相対粘度ηｒｅ
ｌは２．１０であり、ガラス転移温度は１２７．０℃で
あった。Example 14 In Example 12, s2-(2'-hydroxyphenyl)penztriazole-5,5-dicarboxylic acid 10
．． A polyamide was obtained in the same manner except that 21.2 parts were used instead of 6 parts. Relative viscosity ηre of the obtained polyamide
1 was 2.10, and the glass transition temperature was 127.0°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
についての紫外線吸収挙動を比較し九結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared.The results showed that the behavior of both samples was exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１５
実施例１２において、２−（２−ヒドロキシフェニル）
ベンシト）アゾール−５，５−ジカルボン酸１０．６部
の代わＪ）Ｋ１００部用いる以外は同様にしてポリアミ
ドを得念。得られ九ポリアミドの相対粘度ｙｒｅｌは２
．０８であシ、ガラス転移ｙｂｅは１２６．６℃であっ
た。Example 15 In Example 12, 2-(2-hydroxyphenyl)
A polyamide was prepared in the same manner, except that 100 parts of J)K was used instead of 10.6 parts of benzito)azole-5,5-dicarboxylic acid. The relative viscosity yrel of the nine polyamides obtained is 2
．． In 2008, the glass transition temperature was 126.6°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
についての紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１６
実施例１２において、２−（２−ヒドロキシフェニル）
ベンゾトリアゾール−５，５−ジカルボン酸１Ｏ１６部
の代わシに実施例２で得られた２−（２−ヒ）’ＣＩ？
シー５−メチルフェニル）ベンゾトリアゾール４４，６
−ジカルポン酸１０．６部を用いる以外は同様にしてポ
リアミドを得意。得られ九ポリアミドの相対粘度ｙｒｅ
ｌは２．０８であり、ガラス転移温度は１２６．６℃で
６つ念。Example 16 In Example 12, 2-(2-hydroxyphenyl)
2-(2-H)'CI? obtained in Example 2 in place of 1016 parts of benzotriazole-5,5-dicarboxylic acid.
5-methylphenyl)benzotriazole 44,6
- Polyamide was produced in the same manner except that 10.6 parts of dicarboxylic acid was used. Relative viscosity of the obtained nine polyamides
l is 2.08, and the glass transition temperature is 126.6°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
についての紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１７
アジビン酸１０００部、実施例１で得られた２−（２−
ヒドロキシフェニル）ヘンシトリアゾール−５，５−ジ
カルボン酸８４部、ｍ−キシリレンジアミン９５５部、
安息香酸７．０部、イオン交換水４０９部および次亜リ
ン酸ナトリウム１．２部をオートクレーブに仕込み％窒
素置換を十分行ったのち、密閉状態のｔま加熱し、内圧
９〜１０ｋｙ／ｄ、内温１９０〜２００℃に制御しなが
ら１時間攪拌し反応を行つ念。次いで内圧が１８１＃／
−になるまで加熱し、その圧力を保持するように放圧さ
せながら攪拌し重合反応を開始させた。２００℃から２
７０℃まで５時間かけてゆるやかに昇温−し。Example 17 1000 parts of adivic acid, 2-(2-
84 parts of hydroxyphenyl)hencytriazole-5,5-dicarboxylic acid, 955 parts of m-xylylenediamine,
After charging 7.0 parts of benzoic acid, 409 parts of ion-exchanged water, and 1.2 parts of sodium hypophosphite into an autoclave and thoroughly replacing the autoclave with nitrogen, the autoclave was heated in a closed state until t, and the internal pressure was 9 to 10 k/d. Stir for 1 hour while controlling the internal temperature to 190-200°C to carry out the reaction. Then the internal pressure was 181#/
The mixture was heated to - and stirred while releasing the pressure to maintain that pressure to initiate the polymerization reaction. 2 from 200℃
Gently raise the temperature to 70℃ over 5 hours.
水の留出がなくなった時点で放圧しポリアミドを取シ出
した。得られ念ポリアミドの相対粘度ｙｒｅｌは２．１
９であり、ガラス転移温度は８６．１℃であシ、融点は
２３０．２℃であつ念。When water stopped distilling out, the pressure was released and the polyamide was taken out. The relative viscosity yrel of the obtained polyamide is 2.1
9, the glass transition temperature is 86.1°C, and the melting point is 230.2°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
についての紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
実施例１８
ヘキサメチレンジアミン１０００部、アジピン酸１２５
４部および実施例１で得られた２−（２′−ヒドロキシ
フェニル）ベンゾトリアゾール−５，５−シカルホン酸
８．３部を各々メタノールに２５重量％の濃度になるよ
うに溶解したのち、これらの溶液をゆりくシと混合しナ
イロン塩を得念。得られ念ナイロン塩と等重量倍の水と
をオートクレーブに仕込み窒素ｔｉｔ換を十分行ったの
ち、密閉状態のまま加熱し、内圧１０〜１７．５ｋｆ／
ｄｌ内温２００〜２３０℃で４時間攪拌し、次いで１時
間かけて圧力を解放すると同時に内温を２５０〜２７０
’ＣＫ昇温させ十分に加熱したのち冷却してポリアミド
を取シ出しな。得られたボリアずドの相対粘度ηｒｅｌ
は２．４３であり、ガラス転移温度は５４．３℃であシ
、融点は２６０℃であった。Example 18 1000 parts of hexamethylene diamine, 125 parts of adipic acid
4 parts and 8.3 parts of 2-(2'-hydroxyphenyl)benzotriazole-5,5-cyclophonic acid obtained in Example 1 were each dissolved in methanol to a concentration of 25% by weight. Mix the solution with Yurikushi to obtain nylon salt. The obtained nylon salt and the same weight of water were placed in an autoclave, and after sufficient nitrogen exchange, the autoclave was heated in a sealed state, and the internal pressure was 10 to 17.5 kf/
Stir for 4 hours at an internal temperature of 200-230°C, then release the pressure for 1 hour and simultaneously lower the internal temperature to 250-270°C.
'CK Raise the temperature and heat it sufficiently, then cool it and take out the polyamide. Relative viscosity ηrel of the obtained boriazudo
was 2.43, the glass transition temperature was 54.3°C, and the melting point was 260°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果、両者の挙動は
全く同じであった。抽出後の試料の紫外線吸収挙動を表
−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例１７
実施例１２においてｂ ２− （２−ヒドロキシフェニ
ル）ベンゾトリアゾール−５，５−シｆｙルボン酸を用
いない以外は同様にしてポリアミドを得た。Comparative Example 17 A polyamide was obtained in the same manner as in Example 12 except that b2-(2-hydroxyphenyl)benzotriazole-5,5-sifylboxylic acid was not used.
得られたポリアミドの相対粘度ηｒｅｌは２．３５であ
シ、ガラス転移温度は１２６．７℃であつ念。このポリ
アミドの紫外線吸収挙動を表−３に示す。The relative viscosity ηrel of the obtained polyamide was 2.35, and the glass transition temperature was 126.7°C. Table 3 shows the ultraviolet absorption behavior of this polyamide.
比較例１８
実施例１７において、２−（２−ヒドロキシフェニル）
ベンゾトリアゾール−５，５’ −ジカルボン酸を用い
ない以外は同様にしてポリアミドを得た。Comparative Example 18 In Example 17, 2-(2-hydroxyphenyl)
A polyamide was obtained in the same manner except that benzotriazole-5,5'-dicarboxylic acid was not used.
得られたボリアオドの相対粘度ηｒｅｌは２．２２であ
シ、ガラス転移温度は８６．３℃であり、融点は２３３
．２℃であつ念。このポリアミドの紫外線吸収挙動を表
−３に示す。The relative viscosity ηrel of the obtained boriad was 2.22, the glass transition temperature was 86.3°C, and the melting point was 233.
．． I hope it's 2℃. Table 3 shows the ultraviolet absorption behavior of this polyamide.
比較例１９
実施例１８において、２−（２−ヒドロキシフェニル）
ベンゾトリアゾール−５，５’−ジカルボン酸を用いな
い以外は同様にしてポリアミドを得た。Comparative Example 19 In Example 18, 2-(2-hydroxyphenyl)
A polyamide was obtained in the same manner except that benzotriazole-5,5'-dicarboxylic acid was not used.
得られ九ポリアミドの相対粘度ηｒｅｌは２．４２であ
シ、ガラス転移温度は５４．６℃であシ、融点は２６２
．２℃であった。このポリアミドの紫外線吸収挙動を表
−３に示す。The relative viscosity ηrel of the obtained nine polyamides was 2.42, the glass transition temperature was 54.6°C, and the melting point was 262.
．． The temperature was 2°C. Table 3 shows the ultraviolet absorption behavior of this polyamide.
比較例２０
’ｊｌｌｌＪ１２においてｂ ２−Ｃ２−ヒドロキシ
フェニル）ベンゾトリアゾール−５，５−ジカルボン酸
１０．６部の代わりに比較例１で得られた２−（２′−
ヒドロキシフェニル）ベンゾトリアゾール−５−カルボ
ン酸１Ｏ０６部を用いる以外は同様にしてポリアミドを
得た。得られ虎ボリアずドの相対粘度ｙｒｅｌは２，２
５であシ、ガラス転移温度は１２６．６℃であった。Comparative Example 20 In JlllJ12, 2-(2'-
A polyamide was obtained in the same manner except that 1006 parts of hydroxyphenylbenzotriazole-5-carboxylic acid was used. The relative viscosity yrel of the obtained tiger borer is 2,2
5 and the glass transition temperature was 126.6°C.
このボリアオドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果、両者の挙動は
全く同じであった。抽出後の試料の紫外線吸収挙動を表
−３に示す。An extractability test was conducted on this boriaod, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例２１
実施例１２において、２−（２’−ヒドロキシフェニル
）ベンゾトリアゾール−ｓ、ｓ’−ジカルボン酸１Ｏ０
６部の代わシに比較例１で得られた２−（２−ヒドロキ
シフェニル）ベンゾトリアゾール−５−カルボン酸１０
６１部を用いる以外は同様にしてポリアミドを得意が１
重合度がほとんど上がっていなかりな。Comparative Example 21 In Example 12, 2-(2'-hydroxyphenyl)benzotriazole-s,s'-dicarboxylic acid 100
2-(2-hydroxyphenyl)benzotriazole-5-carboxylic acid obtained in Comparative Example 1 in place of 6 parts
Polyamide was prepared in the same manner except that 61 parts were used.
The degree of polymerization has hardly increased.
比較例２２
実ｔｌＡ例ｘ ２において、２−（２−ヒドロキシフェ
ニル）ヘンシトリアゾール−５，５−ジカルボン酸１０
．６部の代わシに比較例２で得られ念５−クロ＃−２−
（２−ヒドロキシフェニル）ヘンシトリアゾール−５−
カルボン酸１０．６部を用いる以外は同様にしてポリア
ミドを得な。得られたボリアオドの相対粘′１Ｈｅｌは
２．２１であシ、ガラス転移温度は１２６．３℃であっ
た。Comparative Example 22 In Actual tlA Example x 2, 2-(2-hydroxyphenyl)hensitriazole-5,5-dicarboxylic acid 10
．． In place of 6 parts, the amount obtained in Comparative Example 2 was 5-Cl#-2-
(2-hydroxyphenyl)hencytriazole-5-
A polyamide was obtained in the same manner except that 10.6 parts of carboxylic acid was used. The relative viscosity '1Hel of the obtained boliaod was 2.21, and the glass transition temperature was 126.3°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果、両者の挙動は
全く同じであった。抽出後の試料の紫外線吸収挙動を表
−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例２３
実施例１２において、２−（２’−ヒドロキシフェニル
）ベンゾトリアゾール−５，５−ジカルボン酸１０．６
部の代わシに比較例３で得られた２−（２′−ヒドロキ
シフェニル）ヘンシトリアソール−、／ ５／−ジカル
ボン酸１０．６部を用いる以外は同様にしてポリアミド
を得喪。得られ九ポリアミドの相対粘度ηｒｅｌは２．
２８であ＃）、ガラス転移温度は１２６．４℃であった
。Comparative Example 23 In Example 12, 2-(2'-hydroxyphenyl)benzotriazole-5,5-dicarboxylic acid 10.6
A polyamide was obtained in the same manner except that 10.6 parts of the 2-(2'-hydroxyphenyl)hensitriazole,/5/-dicarboxylic acid obtained in Comparative Example 3 was used in place of 1 part. The relative viscosity ηrel of the nine polyamides obtained was 2.
The glass transition temperature was 126.4°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較し几結果。We conducted an extractability test on this polyamide and compared the ultraviolet absorption behavior of each sample before and after extraction.
両者の挙動は全く同じであった。抽出後の試料の紫外線
吸収挙動を表−３に示す。The behavior of both was exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例２４
実施例１２において、２−（２’−ヒドロキシフェニル
）ペンツトリアゾール−５，５’ −ジカルボン酸１０
．６部の代わりに比較例４で得られ之５−りｏ ／Ｉ／
−２−（２−ヒドロキシフェニル）ペンツトリアゾー
ル−３，５−ジカルボン酸１Ｏ０６部を用いる以外は同
様にしてポリアミドを得た。得られ九ポリアミドの相対
粘度ηｒｅｌは２．１２であシ、ガラス転移温度は１２
６．２℃であつ九。Comparative Example 24 In Example 12, 2-(2′-hydroxyphenyl)penztriazole-5,5′-dicarboxylic acid 10
．． 5 parts obtained in Comparative Example 4 instead of 6 parts /I/
A polyamide was obtained in the same manner except that 1006 parts of -2-(2-hydroxyphenyl)penztriazole-3,5-dicarboxylic acid was used. The relative viscosity ηrel of the nine polyamides obtained was 2.12, and the glass transition temperature was 12.
At 6.2℃.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果、両者の挙動は
全く同じであった。抽出後の試料の紫外線吸収挙動を表
−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例２５
実施例１７において、２−（２−ヒドロキシフェニル）
ヘンジトリアゾール−５，５−ジカルボン酸８．４部の
代わシに比較例１で得られた２ −（２’−ヒドロキシ
フェニル）ベンゾトリアゾール−５′−カルボン酸８．
４部を用いる以外は同様にしてポリアミドを得た。得ら
れたポリアミドの相対粘度ηｒｅｌは２．０１であシ、
ガラス転移温度は８６．５℃であシ、融点は゛捻３１．
８℃であった。Comparative Example 25 In Example 17, 2-(2-hydroxyphenyl)
8.4 parts of 2-(2'-hydroxyphenyl)benzotriazole-5'-carboxylic acid obtained in Comparative Example 1 was used instead of 8.4 parts of hengetriazole-5,5-dicarboxylic acid.
A polyamide was obtained in the same manner except that 4 parts were used. The relative viscosity ηrel of the obtained polyamide was 2.01,
The glass transition temperature is 86.5°C, and the melting point is 31°C.
The temperature was 8°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果、両者の挙動は
全く同じであり九。抽出後の試料の紫外線吸収挙動を表
−３に示す。We conducted an extractability test on this polyamide and compared the ultraviolet absorption behavior of each sample before and after extraction, and found that the behavior of the two was exactly the same9. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例２６
実ｍ例１８において、２−（２−ヒドロキシフェニル）
ベンゾトリアゾール−ｓ、 ｓ −ジカルボン酸８．３
部の代わシに比較例１で得られ７’ｔ２−（２’−ヒド
ロキシフェニル）ベンゾトリアゾール−５′−カルボン
酸８．３部を用いる以外は同様にしてポリアミドを得た
。得られたポリアミドの相対粘度ηｒｅｌは２．４３で
あシ、ガラス転移温度は５４．３℃であシ、融点は２６
０．２℃であった。Comparative Example 26 In Example 18, 2-(2-hydroxyphenyl)
Benzotriazole-s, s-dicarboxylic acid 8.3
A polyamide was obtained in the same manner except that 8.3 parts of 7't2-(2'-hydroxyphenyl)benzotriazole-5'-carboxylic acid obtained in Comparative Example 1 was used instead of 8.3 parts of 7't2-(2'-hydroxyphenyl)benzotriazole-5'-carboxylic acid. The relative viscosity ηrel of the obtained polyamide was 2.43, the glass transition temperature was 54.3°C, and the melting point was 26.
The temperature was 0.2°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果。The results of an extractability test of this polyamide and a comparison of the ultraviolet absorption behavior of each sample before and after extraction.
両者の挙動は全く同じであった。抽出後の試料の紫外線
吸収挙動を表−３に示す。The behavior of both was exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例２７
実施例１２において＋ｚ−Ｃｚ−ヒドロキシフェニル）
ベンゾトリアゾール−５，５−ジカルボン酸１０．６部
の代わシに０．０１部用いる以外は同様にしてボリアば
ドを得た。得られたポリアミドの相対粘度ηｒｅｌは２
．３３であシ、ガラス転移温度は１２６．３℃であった
。Comparative Example 27 +z-Cz-hydroxyphenyl in Example 12)
Boriabad was obtained in the same manner except that 0.01 part of benzotriazole-5,5-dicarboxylic acid was replaced with 10.6 parts of benzotriazole-5,5-dicarboxylic acid. The relative viscosity ηrel of the obtained polyamide is 2
．． The glass transition temperature was 126.3°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
についての紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例２８
実ｍ例１２において、２−（２−ヒドロキシフェニル）
ペンツトリアゾール−５，５−ジカルボン酸１０．６部
の代わルに下記の構造式で表される紫外線吸収剤１０．
６部を用いる以外は同様にしてポリアミドを得た。得ら
れたポリアミドの相対粘度ｙｒｅｌは２．２０であシ、
ガラス転移温度は１２６．４℃であった。Comparative Example 28 In Example 12, 2-(2-hydroxyphenyl)
10. Ultraviolet absorber represented by the following structural formula in place of 10.6 parts of penztriazole-5,5-dicarboxylic acid.
A polyamide was obtained in the same manner except that 6 parts were used. The relative viscosity yrel of the obtained polyamide was 2.20,
The glass transition temperature was 126.4°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
についての紫外線吸収挙動を比較した結果、両者の挙動
は全く同じであった。抽出後の紫外線吸収挙動を表−３
に示す。表−３から明らかなようにこのポリアミドは実
施例１２〜１８より得られ念ポリアミドに比べ、紫外線
吸収性能は著しく劣っていた。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared. As a result, the behavior of both samples was completely the same. Table 3 shows the ultraviolet absorption behavior after extraction.
Shown below. As is clear from Table 3, the ultraviolet absorption performance of this polyamide was significantly inferior to that of the polyamides obtained in Examples 12 to 18.
比較例２９
実施例１２において、２−（２’−ヒドロヤシフェニル
）ベンゾトリアゾール−５，５−ジカルボン酸１０．６
部の代わシに下記の構造式て表される紫外線吸収剤４２
．４部を用いる以外は同様にしてポリアミドを得た。得
られ九ポリアミドの相対粘度ηｒｅｌは１．６０であっ
た。そのガラス転移温度は１１５．８℃であり、実施例
１２〜１６より得られ念ポリアミドに比べ耐熱性の著し
い低下が認められ念。Comparative Example 29 In Example 12, 10.6
Ultraviolet absorber 42 represented by the following structural formula in place of part:
．． A polyamide was obtained in the same manner except that 4 parts were used. The relative viscosity ηrel of the nine polyamides obtained was 1.60. Its glass transition temperature was 115.8°C, and it was observed that the heat resistance was significantly lower than that of the polyamides obtained in Examples 12 to 16.
このポリアミドの抽出性試験を行い、抽出前後の各試料
についての紫外線吸収挙動を比較し九結果、両者の挙動
は全く同じであった。抽出後の試料の紫外線吸収挙動を
表−３に示す。An extractability test was conducted on this polyamide, and the ultraviolet absorption behavior of each sample before and after extraction was compared.The results showed that the behavior of both samples was exactly the same. Table 3 shows the ultraviolet absorption behavior of the sample after extraction.
比較例３０
実施例１２において、２−（２−ヒドロキシフェニル）
ベンゾトリアゾール−５，５−ジカルボン酸１０．６部
の代わシに下記の構造式で表わされる紫外線吸収剤１Ｏ
１６部を用いる以外は同様にしてポリアミドを得た。得
られたポリアミドの相対粘度ηｒｅｌは２．１９であシ
、ガラス転移温度は１２６．５℃であった。Comparative Example 30 In Example 12, 2-(2-hydroxyphenyl)
In place of 10.6 parts of benzotriazole-5,5-dicarboxylic acid, an ultraviolet absorber 1O represented by the structural formula below
A polyamide was obtained in the same manner except that 16 parts were used. The relative viscosity ηrel of the obtained polyamide was 2.19, and the glass transition temperature was 126.5°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果を表−３に示す
。An extractability test was conducted on this polyamide, and the results of comparing the ultraviolet absorption behavior of each sample before and after extraction are shown in Table 3.
比較例３１
実施例１２において、２−（２’−ヒドロキシフェニル
）ヘンゾ＋ｙアゾールー５．５−ジカルボン酸１Ｏ１６
部の代わりに下記の構造式で表わされる紫外線吸収剤１
０．６部を用いる以外は同様にしてポリアミドを得比。Comparative Example 31 In Example 12, 2-(2'-hydroxyphenyl)henzo+yazole-5.5-dicarboxylic acid 1O16
Ultraviolet absorber 1 represented by the following structural formula instead of
Polyamide was obtained in the same manner except that 0.6 part was used.
得られたボリアミドＯ相対粘度ηｒｅｌは２．１０であ
シ、ガラス転移温度は１２６゜４℃であった。The relative viscosity ηrel of the obtained polyamide O was 2.10, and the glass transition temperature was 126°4°C.
このポリアミドの抽出性試験を行い、抽出前後の各試料
について紫外線吸収挙動を比較した結果を表−３に示す
。An extractability test was conducted on this polyamide, and the results of comparing the ultraviolet absorption behavior of each sample before and after extraction are shown in Table 3.
以下余白
〔発明の効果〕
本発明によシ提供される一般式（１）で示される２−ヒ
ドロキシフェニルベンゾトリアゾール系化合物は紫外線
吸収性能が良好であり、しかも熱安定性が良好であるな
どの特長を有してお〕、紫外線吸収剤として有用である
。また一般式（１）で示される２−ヒドロキシフェニル
ベンゾトリアゾール系化合物が配合されたポリマーは優
れ要素外線吸収性能を有する。Blank space below [Effects of the Invention] The 2-hydroxyphenylbenzotriazole compound represented by the general formula (1) provided by the present invention has good ultraviolet absorption performance and good thermal stability. ] and is useful as an ultraviolet absorber. Further, a polymer containing a 2-hydroxyphenylbenzotriazole compound represented by the general formula (1) has excellent elemental external ray absorption performance.
特許出願人 株式会社 り ラ しPatent applicant RiRashi Co., Ltd.
Claims (1)
ハロゲン原子、低級アルキル基また は低級アルコキシル基を表し、Ｒ＾２はカルボキシル基
、水素原子、ハロゲン原子、低級 アルキル基または低級アルコキシル基を表 す。ただし、Ｒ＾１、Ｒ＾１およびＲ＾３のうち２つは
カルボキシル基である。 で示される２−ヒドロキシフェニルベンゾトリアゾール
系化合物。 ２、請求項１記載の２−ヒドロキシフェニルベンゾトリ
アゾール系化合物を有効成分とする紫外線吸収剤。 ３、請求項１記載の２−ヒドロキシフェニルベンゾトリ
アゾール系化合物を０．００１〜１０重量％含有してな
るポリマー。 ４、請求項１記載の２−ヒドロキシフェニルベンゾトリ
アゾール系化合物を共重合成分として０．００１〜１０
重量％含有してなるポリマー。 ５、ポリマーがポリエステルであることを特徴とする請
求項４記載のポリマー。 ６、ポリマーがポリアミドであることを特徴とする請求
項４記載のポリマー。[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ In the formula, R^1 and R^3 are respectively carboxyl groups,
It represents a halogen atom, a lower alkyl group or a lower alkoxyl group, and R^2 represents a carboxyl group, a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxyl group. However, two of R^1, R^1 and R^3 are carboxyl groups. A 2-hydroxyphenylbenzotriazole compound represented by: 2. An ultraviolet absorber containing the 2-hydroxyphenylbenzotriazole compound according to claim 1 as an active ingredient. 3. A polymer containing 0.001 to 10% by weight of the 2-hydroxyphenylbenzotriazole compound according to claim 1. 4. 0.001 to 10% of the 2-hydroxyphenylbenzotriazole compound according to claim 1 as a copolymerization component
Polymer containing % by weight. 5. The polymer according to claim 4, wherein the polymer is a polyester. 6. The polymer according to claim 4, wherein the polymer is a polyamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24862689A JPH02188581A (en) | 1988-10-07 | 1989-09-25 | 2-hydroxyphenylbenzotriazole-based compound and use thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-254656 | 1988-10-07 | ||
| JP25465688 | 1988-10-07 | ||
| JP24862689A JPH02188581A (en) | 1988-10-07 | 1989-09-25 | 2-hydroxyphenylbenzotriazole-based compound and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02188581A true JPH02188581A (en) | 1990-07-24 |
Family
ID=26538872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24862689A Pending JPH02188581A (en) | 1988-10-07 | 1989-09-25 | 2-hydroxyphenylbenzotriazole-based compound and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02188581A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0464522A2 (en) * | 1990-06-30 | 1992-01-08 | Cheil Synthetics Inc. | Copolyester elastomer having good weather resistance |
| KR100383919B1 (en) * | 2001-01-15 | 2003-05-14 | 주식회사 엘지화학 | Preparation of 2-(2-hydro xyphenyl)-2h-benzotriazoles |
| JP2012512304A (en) * | 2008-12-17 | 2012-05-31 | エクソンモービル ケミカル パテンツ，インコーポレイティド | Stabilized and dynamically vulcanized thermoplastic elastomer compositions useful in fluid barrier applications |
| JP2016113622A (en) * | 2009-11-02 | 2016-06-23 | イノレックス インベストメント コーポレイション | Uv absorbing complex polyester polymers, compositions containing uv absorbing complex polyester polymers, and related methods |
-
1989
- 1989-09-25 JP JP24862689A patent/JPH02188581A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0464522A2 (en) * | 1990-06-30 | 1992-01-08 | Cheil Synthetics Inc. | Copolyester elastomer having good weather resistance |
| KR100383919B1 (en) * | 2001-01-15 | 2003-05-14 | 주식회사 엘지화학 | Preparation of 2-(2-hydro xyphenyl)-2h-benzotriazoles |
| JP2012512304A (en) * | 2008-12-17 | 2012-05-31 | エクソンモービル ケミカル パテンツ，インコーポレイティド | Stabilized and dynamically vulcanized thermoplastic elastomer compositions useful in fluid barrier applications |
| JP2016113622A (en) * | 2009-11-02 | 2016-06-23 | イノレックス インベストメント コーポレイション | Uv absorbing complex polyester polymers, compositions containing uv absorbing complex polyester polymers, and related methods |
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