JPH0476456A - Oxygen detection agent - Google Patents
Oxygen detection agentInfo
- Publication number
- JPH0476456A JPH0476456A JP18805490A JP18805490A JPH0476456A JP H0476456 A JPH0476456 A JP H0476456A JP 18805490 A JP18805490 A JP 18805490A JP 18805490 A JP18805490 A JP 18805490A JP H0476456 A JPH0476456 A JP H0476456A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- aniline
- aniline polymer
- white
- hue
- 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.)
- Granted
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000001301 oxygen Substances 0.000 title claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 24
- 238000001514 detection method Methods 0.000 title abstract description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 239000004480 active ingredient Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- -1 alcohol compound Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 150000001448 anilines Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VSHTWPWTCXQLQN-UHFFFAOYSA-N N-butyl-N-phenyl-amine Natural products CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- HDVUPIFFKAHPJY-UHFFFAOYSA-N 2-butylaniline Chemical compound CCCCC1=CC=CC=C1N HDVUPIFFKAHPJY-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- RQRKMXABSUYQBV-UHFFFAOYSA-N 2-chloro-3-methylaniline Chemical compound CC1=CC=CC(N)=C1Cl RQRKMXABSUYQBV-UHFFFAOYSA-N 0.000 description 2
- WKURVXXDGMYSDP-UHFFFAOYSA-N 2-propyl-aniline Chemical compound CCCC1=CC=CC=C1N WKURVXXDGMYSDP-UHFFFAOYSA-N 0.000 description 2
- WMIQWIJPGVVMII-UHFFFAOYSA-N 3-butylaniline Chemical compound CCCCC1=CC=CC(N)=C1 WMIQWIJPGVVMII-UHFFFAOYSA-N 0.000 description 2
- IPWGAPCYYMTTLT-UHFFFAOYSA-N 3-propylaniline Chemical compound CCCC1=CC=CC(N)=C1 IPWGAPCYYMTTLT-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- LQKYCMRSWKQVBQ-UHFFFAOYSA-N n-dodecylaniline Chemical compound CCCCCCCCCCCCNC1=CC=CC=C1 LQKYCMRSWKQVBQ-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PEOBJWCWTPZFEH-UHFFFAOYSA-N 2,3,5,6-tetraethylaniline Chemical compound CCC1=CC(CC)=C(CC)C(N)=C1CC PEOBJWCWTPZFEH-UHFFFAOYSA-N 0.000 description 1
- AEYBKXAKCAYYLU-UHFFFAOYSA-N 2,3,5-tripropylaniline Chemical compound C(CC)C1=C(N)C=C(C=C1CCC)CCC AEYBKXAKCAYYLU-UHFFFAOYSA-N 0.000 description 1
- KVZVPRYNVAQUEP-UHFFFAOYSA-N 2-bromo-3-butylaniline Chemical compound BrC1=C(N)C=CC=C1CCCC KVZVPRYNVAQUEP-UHFFFAOYSA-N 0.000 description 1
- RPOZCUVHEOGDCI-UHFFFAOYSA-N 2-bromo-3-ethylaniline Chemical compound CCC1=CC=CC(N)=C1Br RPOZCUVHEOGDCI-UHFFFAOYSA-N 0.000 description 1
- VJNUZLYTGSGDHR-UHFFFAOYSA-N 2-bromo-3-methylaniline Chemical compound CC1=CC=CC(N)=C1Br VJNUZLYTGSGDHR-UHFFFAOYSA-N 0.000 description 1
- SMQJIMVRWBQKRT-UHFFFAOYSA-N 2-chloro-3-ethylaniline Chemical compound CCC1=CC=CC(N)=C1Cl SMQJIMVRWBQKRT-UHFFFAOYSA-N 0.000 description 1
- GJEIKDHQOAYPOX-UHFFFAOYSA-N 2-chloro-3-propylaniline Chemical compound CCCC1=CC=CC(N)=C1Cl GJEIKDHQOAYPOX-UHFFFAOYSA-N 0.000 description 1
- KOVTYTLFAROKNZ-UHFFFAOYSA-N 2-methoxy-n-propylaniline Chemical compound CCCNC1=CC=CC=C1OC KOVTYTLFAROKNZ-UHFFFAOYSA-N 0.000 description 1
- MIRRUJHMAUFGGN-UHFFFAOYSA-N 2-octadecylaniline Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1N MIRRUJHMAUFGGN-UHFFFAOYSA-N 0.000 description 1
- RPHMUHDQXQIFFG-UHFFFAOYSA-N 3-ethyl-2-phenylaniline Chemical compound C1(=CC=CC=C1)C1=C(C=CC=C1N)CC RPHMUHDQXQIFFG-UHFFFAOYSA-N 0.000 description 1
- OFFBZMGYNGHBBK-UHFFFAOYSA-N 3-octadecylaniline Chemical compound C(CCCCCCCCCCCCCCCCC)C=1C=C(N)C=CC1 OFFBZMGYNGHBBK-UHFFFAOYSA-N 0.000 description 1
- DPKTVUKEPNBABS-UHFFFAOYSA-N 3-tert-butylaniline Chemical compound CC(C)(C)C1=CC=CC(N)=C1 DPKTVUKEPNBABS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IXCKOXLJNNFOCM-UHFFFAOYSA-N n,n,2-triethylaniline Chemical compound CCN(CC)C1=CC=CC=C1CC IXCKOXLJNNFOCM-UHFFFAOYSA-N 0.000 description 1
- VTHOTOFWYDBNID-UHFFFAOYSA-N n-decylaniline Chemical compound CCCCCCCCCCNC1=CC=CC=C1 VTHOTOFWYDBNID-UHFFFAOYSA-N 0.000 description 1
- IXEGRINNWXKNJO-UHFFFAOYSA-N n-hexadecylaniline Chemical compound CCCCCCCCCCCCCCCCNC1=CC=CC=C1 IXEGRINNWXKNJO-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- UEKWTIYPDJLSKK-UHFFFAOYSA-N n-octadecylaniline Chemical compound CCCCCCCCCCCCCCCCCCNC1=CC=CC=C1 UEKWTIYPDJLSKK-UHFFFAOYSA-N 0.000 description 1
- GCULWAWIZUGXTO-UHFFFAOYSA-N n-octylaniline Chemical compound CCCCCCCCNC1=CC=CC=C1 GCULWAWIZUGXTO-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UMNSMBWAESLVOC-UHFFFAOYSA-N n-pentylaniline Chemical compound CCCCCNC1=CC=CC=C1 UMNSMBWAESLVOC-UHFFFAOYSA-N 0.000 description 1
- CDZOGLJOFWFVOZ-UHFFFAOYSA-N n-propylaniline Chemical compound CCCNC1=CC=CC=C1 CDZOGLJOFWFVOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、酸素の存在下と酸素の不存在下とで、色相を
異にし、その色相差が肉眼で判定可能な酸素検知剤に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxygen detecting agent that has different hues in the presence of oxygen and in the absence of oxygen, and the hue difference can be determined with the naked eye.
酸素の存在を検知するだめの検知剤としては、例えば、
特開昭５４−７０８８６〜７０８８８号公報、同５５−
４２０６８号公報に記載のものが知られている。これら
公報に記載のものは、色素をアルカリ性物質や還元剤等
と組み合わせた組成物よりなり、酸素の存在によって可
逆的に色相変化を引き起こすものである。Examples of detection agents for detecting the presence of oxygen include:
JP-A-54-70886-70888, JP-A No. 55-
The one described in Japanese Patent No. 42068 is known. The compositions described in these publications are composed of a composition in which a dye is combined with an alkaline substance, a reducing agent, etc., and cause a reversible hue change in the presence of oxygen.
ところが、上記従来の酸素検知剤は、酸素の有無に対し
て色相変化が可逆的であるため、−度酸素にさらされて
も、再び無酸素状態に置けば色相が元に戻り、酸素が一
時的に混入した場合等の検知ができないと言う問題があ
った。However, in the conventional oxygen detectors mentioned above, the hue change is reversible depending on the presence or absence of oxygen, so even if exposed to oxygen, the hue will return to its original state if it is placed in an oxygen-free condition again, and the oxygen will temporarily disappear. There was a problem in that it was not possible to detect when substances were mixed in.
したがって、本発明の目的は、酸素の有無に対して色相
変化が不可逆的であり、かつ安定性に優れた酸素検知剤
を提供することにある。Therefore, an object of the present invention is to provide an oxygen sensing agent whose hue changes irreversibly in response to the presence or absence of oxygen and which has excellent stability.
本発明者は、アニリンまたはその誘導体を酸化重合させ
て得られたアニリン重合体が、酸素の存在によって不可
逆的に色相を変化することを見出だし、本発明を完成し
た。The present inventors have completed the present invention by discovering that an aniline polymer obtained by oxidative polymerization of aniline or a derivative thereof changes color irreversibly in the presence of oxygen.
すなわち、本発明の酸素検知剤は、下記一般式（１）で
表わされる繰り返し単位の１種または２種よりなる重合
度８以上のアニリン重合体を活性成分として含有するこ
とを特徴とする。That is, the oxygen sensing agent of the present invention is characterized by containing as an active ingredient an aniline polymer having a degree of polymerization of 8 or more and consisting of one or two types of repeating units represented by the following general formula (1).
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５は、同−又は
互いに異なるものであって、それぞれ水素原子、アルキ
ル基、アルコキシ基、アリール基、ベンジル基又はハロ
ゲン原子を表わす。）本発明の上記アニリン重合体は、
その重合度か８以上であるが、５０〜２００の範囲の重
合度を有するものが特に好ましく使用される。本発明の
アニリン重合体は、下記一般式（ｎ）で示されるアニリ
ン誘導体を酸化重合することによって製造する（式’ｌ
Ｊ％ ＲＩＳＲ２、Ｒ３、Ｒ４及びＲ５は、それぞれ、
上記したものと同一の意味を有する。）Ｒ，−Ｒ，の具
体的例としては、メチル、エチル、ｎ−プロピル、１−
プロピル、ローブチル、５ｏｃ−ブチル、ｔ−ブチル、
ｎ−ペンチル、ｎ−ヘキシル、ローへブチル、ｎ−オク
チル、ｎ−デシル、ｎ〜ドデシル、■−ヘキサデシル、
ｎ−トコシル等のアルキル基；メトキシ、エトキシ、プ
ロポキシ等のアルコキシ基：フェニル基等のアリール基
；ベンジル基：フッ素、塩素、臭素、よう素等のハロゲ
ン原子があげられる。(In the formula, R1, R2, R3, R4 and R5 are the same or different from each other and each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a benzyl group or a halogen atom.) The above aniline polymer is
The degree of polymerization is 8 or more, and those having a degree of polymerization in the range of 50 to 200 are particularly preferably used. The aniline polymer of the present invention is produced by oxidative polymerization of an aniline derivative represented by the following general formula (n) (formula 'l
J% RISR2, R3, R4 and R5 are respectively,
has the same meaning as above. ) Specific examples of R, -R, include methyl, ethyl, n-propyl, 1-
propyl, lobethyl, 5oc-butyl, t-butyl,
n-pentyl, n-hexyl, rhobutyl, n-octyl, n-decyl, n-dodecyl, ■-hexadecyl,
Alkyl groups such as n-tocosyl; alkoxy groups such as methoxy, ethoxy and propoxy; aryl groups such as phenyl; benzyl groups: halogen atoms such as fluorine, chlorine, bromine and iodine.
一般式（ＩＩ）で示されるアニリン誘導体の具体例とし
ては、アニリン、Ｎ−メチルアニリン、Ｎ−エチルアニ
リン、Ｎ−ｎ−プロピルアニリン、Ｎ−ｎ−ブチルアニ
リン、Ｎ−ｎ−ペンチルアニリン、Ｎ−ｎ−オクチルア
ニリン、Ｎ−ｎ−デシルアニリン、Ｎ−ｎ−ドデシルア
ニリン、Ｎ−ｎ−ヘキサデシルアニリン、Ｎ−トコシル
アニリン、Ｎ−ステアリルアニリン、Ｎ−ｎ−プロピル
−２−メトキシアニリン、Ｎ−ｎ−ブチル１− トルイ
ジン、Ｎ−ｎ−ブチル−０−トルイジン、副−トルイジ
ン、０〜トルイジン、２．３−ジェトキシアニリン、２
．５−ジフェニルアニリン、２−フェニル−３−エチル
アニリン、２−クロロ−３−メチルアニリン、２−ブロ
モ−３−メチルアニリン、２−クロロ−３−エチルアニ
リン、２−ブロモ−３−エチルアニリン、２−クロロ−
３−ｎ−プロピルアニリン、２−クロロ−ｇ−ｎ−ブチ
ルアニリン、２−ブロモ−３−ｎ−ブチルアニリン、２
−ｎ−プロピルアニリン、３−ｎ−プロピルアニリン、
２−ｎ−ブチルアニリン、３−ｎ−ブチルアニリン、２
−１−プロピルアニリン、３−１−プロピルアニリン、
２−１−ブチルアニリン、３−１−ブチルアニリン、２
−１−ブチルアニリン、３−ｔ−ブチルアニリン、２−
ステアリルアニリン、３−ステアリルアニリン、２−ト
コシルアニリン、３−トコシルアニリン、２，３．５−
トリエチルアニリン、２，３．５−トリ （ｎ−プロピ
ル）アニリン、２，３，５．６−チトラメチルアニリン
、２，３．５．６−テトラエチルアニリン、ジフェニル
アミン、Ｎ−ヘンシルアニリン等があげられる。Specific examples of the aniline derivative represented by the general formula (II) include aniline, N-methylaniline, N-ethylaniline, N-n-propylaniline, N-n-butylaniline, N-n-pentylaniline, N- -n-octylaniline, N-n-decylaniline, N-n-dodecylaniline, N-n-hexadecylaniline, N-tocosylaniline, N-stearylaniline, N-n-propyl-2-methoxyaniline, N-n-butyl 1-toluidine, N-n-butyl-0-toluidine, sub-toluidine, 0-toluidine, 2,3-jethoxyaniline, 2
．． 5-diphenylaniline, 2-phenyl-3-ethylaniline, 2-chloro-3-methylaniline, 2-bromo-3-methylaniline, 2-chloro-3-ethylaniline, 2-bromo-3-ethylaniline, 2-chloro-
3-n-propylaniline, 2-chloro-g-n-butylaniline, 2-bromo-3-n-butylaniline, 2
-n-propylaniline, 3-n-propylaniline,
2-n-butylaniline, 3-n-butylaniline, 2
-1-propylaniline, 3-1-propylaniline,
2-1-butylaniline, 3-1-butylaniline, 2
-1-butylaniline, 3-t-butylaniline, 2-
Stearylaniline, 3-stearylaniline, 2-tocosylaniline, 3-tocosylaniline, 2,3.5-
Examples include triethylaniline, 2,3.5-tri(n-propyl)aniline, 2,3,5.6-titramethylaniline, 2,3.5.6-tetraethylaniline, diphenylamine, N-hensylaniline, etc. It will be done.
上記のアニリン誘導体の酸化重合法としては、アニリン
誘導体を酸性水溶液、又は有機溶媒中で定電位、定電流
、又は定電圧条件下で電解酸化する方法、及び過硫酸塩
、重クロム酸塩、過酸化水素、塩化鉄等の酸化剤を用い
る方法等が使用できるが、後者の酸化重合法の方が、安
価でかつ容易な方法であるので有利である。The oxidative polymerization method of the above-mentioned aniline derivatives includes a method of electrolytically oxidizing the aniline derivative in an acidic aqueous solution or an organic solvent under constant potential, constant current, or constant voltage conditions; A method using an oxidizing agent such as hydrogen oxide or iron chloride can be used, but the latter oxidative polymerization method is advantageous because it is cheaper and easier.
上記のようにして得られるアニリン重合体は、反応系中
に存在する酸をドーパントとして取り込んで着色してい
るため、脱色する必要がある。すなわち、まず、得られ
たアニリン重合体を、電気化学的に処理したり、或いは
アンモニア水につける等、公知の方法によって脱ドープ
を行ない、さらに、ヒドラジンで還元して、白色或いは
灰白色のアニリン重合体（還元型アニリン重合体）とす
る。Since the aniline polymer obtained as described above is colored by incorporating the acid present in the reaction system as a dopant, it is necessary to decolorize it. That is, first, the obtained aniline polymer is dedoped by a known method such as electrochemical treatment or soaked in aqueous ammonia, and then reduced with hydrazine to obtain a white or gray-white aniline polymer. Combined (reduced aniline polymer).
この還元型アニリン重合体は、酸素を含まない還元雰囲
気下（酸素濃度０．１％未満）で白色或いは灰白色を呈
し、また、酸素存在下（酸素濃度０゜１％以上）で酸化
状態の色相（青ないし緑）を呈する性質を有するもので
あって、それ等の色相の差が、肉眼で明確に区別できる
。This reduced aniline polymer exhibits a white or grayish color in a reducing atmosphere that does not contain oxygen (oxygen concentration of less than 0.1%), and exhibits an oxidized hue in the presence of oxygen (oxygen concentration of 0.1% or more). (blue to green), and the difference in hue can be clearly distinguished with the naked eye.
このアニリン重合体を酸素検知剤として使用する場合、
その使用量は、酸素検知機能を４える口であれば特に制
限はないが、酸素検知機能量に対して、０．１〜１００
重量％含有させることが可能である。特に１〜９５重量
％の範囲含有させることが好ましい。When using this aniline polymer as an oxygen sensing agent,
The amount used is not particularly limited as long as it has an oxygen detection function of 4, but it is 0.1 to 100% of the oxygen detection function.
It is possible to contain it by weight%. In particular, it is preferably contained in a range of 1 to 95% by weight.
本発明の酸素検知剤においては、上記アニリン重合体を
、適当な担体に担持させて用いることができる。これ等
の担体は、白色顔料を兼ねてもよく、例えば、酸化アル
ミニウム、二酸化チタン、酸化亜鉛、シリカゲル、シリ
カ・アルミナゲル、合成ゼオライト、天然ゼオライト、
カオリン、活性白土等の例で示される金属酸化物、硫酸
カルシウム、硫酸マグネシウム、けい酸マグネシウム、
塩化マグネシウム、リン酸カルシウム、炭酸バリウム、
炭酸マグネシウムのようなアルカリ土類金属塩等の無機
酸塩、ステアリン酸マグネシウム、シュウ酸カルシウム
、安息香酸カルシウム等の有機酸塩、イオン交換樹脂、
セルロース、セルロース性物質、その他有機高分子化合
物等があげられる。アニリン重合体をこれ等担体に担持
させる方法は、周知の方法が利用できる。In the oxygen detecting agent of the present invention, the above aniline polymer can be supported on a suitable carrier. These carriers may also serve as white pigments, such as aluminum oxide, titanium dioxide, zinc oxide, silica gel, silica/alumina gel, synthetic zeolite, natural zeolite,
Metal oxides such as kaolin, activated clay, calcium sulfate, magnesium sulfate, magnesium silicate,
Magnesium chloride, calcium phosphate, barium carbonate,
Inorganic acid salts such as alkaline earth metal salts such as magnesium carbonate, organic acid salts such as magnesium stearate, calcium oxalate, calcium benzoate, ion exchange resins,
Examples include cellulose, cellulosic substances, and other organic polymer compounds. A well-known method can be used to support the aniline polymer on these carriers.
本発明の酸素検知剤が良好がっ敏速に作用するためには
、水又はアルコール系化合物が共存することが望ましい
。したがって、本発明の酸素検知剤には、水又はアルコ
ール系化合物を含有させることか好ましい。In order for the oxygen sensing agent of the present invention to act well and quickly, it is desirable that water or an alcoholic compound be present. Therefore, it is preferable that the oxygen detecting agent of the present invention contains water or an alcohol compound.
酸素検知７１ｉ＋１に水を含有させる場合の水の使用量
は、特に制限はなく、使用条件及び使用形態に応して調
整すればよい。酸素検知剤が固体状の場合には、通常、
酸素検知機能量に対し、０．１〜２０重量％の範囲で存
在させるのが好ましい。但し、ここで用いる水は、予め
、煮沸、減圧下での超音波脱気、又は窒素やヘリウム等
の不活性ガスによるバブリング等の方法で、溶存酸素を
除いておく必要がある。The amount of water used when the oxygen sensor 71i+1 contains water is not particularly limited and may be adjusted depending on the usage conditions and usage pattern. When the oxygen detection agent is in solid form, usually
It is preferably present in an amount of 0.1 to 20% by weight based on the amount of oxygen detection function. However, it is necessary to remove dissolved oxygen from the water used here by a method such as boiling, ultrasonic deaeration under reduced pressure, or bubbling with an inert gas such as nitrogen or helium.
マタ、アルコール系化合物とは、アルコール性水酸基を
有する化合物を意味し、常温液状のものが好ましい。具
体的には、メタノール、エタノール、プロパツール等の
飽和−価アルコール、グリセリン、エチレングリコール
のような飽和多価アルコール等が使用可能であり、その
使用量は、前記の水の場合と同様、適宜決定される。ま
た、高沸点のアルコールと水を併用することも可能であ
り、この場合、アルコール系化合物は、水の保持にも役
立つ。The alcoholic compound means a compound having an alcoholic hydroxyl group, and is preferably liquid at room temperature. Specifically, saturated-hydric alcohols such as methanol, ethanol, and propatool, and saturated polyhydric alcohols such as glycerin and ethylene glycol can be used, and the amount used is determined as appropriate, as in the case of water. It is determined. It is also possible to use a high boiling point alcohol and water together, in which case the alcoholic compound also helps retain water.
本発明において、酸素検知剤の使用形態には特に制限は
なく、スラリー状でも懸濁液状でも使用することができ
る。しかしながら、安定性、取扱いの簡便さ１．適用範
囲の広さ等の点を考えれば、酸素検知剤は固体状で使用
するのが好ましく、その場合、水を嫌うような系でも好
適に用いることができる。固形状で使用する場合には、
上記のアニリン重合体及び所望により添加されるその他
の成分を、通常の機械的手法で不活性気体下で混合し、
得られた粉末をそのまま、或いは錠剤などに成形して使
用することか可能である。In the present invention, there is no particular restriction on the form in which the oxygen detecting agent is used, and it can be used in either a slurry or suspension form. However, stability, ease of handling, 1. Considering the wide range of application, it is preferable to use the oxygen detecting agent in solid form, and in that case, it can be suitably used even in systems that dislike water. When used in solid form,
The above aniline polymer and other components added as desired are mixed by a conventional mechanical method under an inert gas,
The obtained powder can be used as it is or after being formed into a tablet or the like.
本発明の酸素検知剤は、上記のように、水又はアルコー
ル系化合物が共存する場合に良好がっ敏速に作用するの
で、水蒸気が存在する系内で使用するのが好ましい。し
たがって、酸素検知剤を、例えば、含有水分の多い食料
品と同一の系内に置く場合などが、本発明の酸素検知剤
の好適な使用例としてあげることができる。As mentioned above, the oxygen detecting agent of the present invention works well and quickly when water or an alcoholic compound coexists, so it is preferable to use it in a system where water vapor is present. Therefore, an example of a suitable use of the oxygen detecting agent of the present invention is when the oxygen detecting agent is placed in the same system as food products containing a large amount of moisture.
アニリン５ｇを、１モル／ＩＩの硫酸水溶液１００−に
溶解し、過硫酸アンモニウム３ｇを溶解した硫酸水溶液
１００ ｌ１１１を、０℃で撹拌しながら加えた。5 g of aniline was dissolved in 100 l of a 1 mol/II sulfuric acid aqueous solution, and 100 l111 of a sulfuric acid aqueous solution in which 3 g of ammonium persulfate was dissolved was added with stirring at 0°C.
４時間反応させた後、析出した固形物を濾別し、これを
十分に水洗した後、１ｏｏ−の水に分散し、アンモニア
水１００ｍ１ｌを加えて４時間攪拌した。固彫物を濾別
し、十分に水洸した後、１００−の水に分散し、ヒドラ
ジン２５ｇを加えて、８時間撹拌した。分散している固
形物が白色になったので、これを窒素中で濾別し、乾燥
してアニリン重合体４ｇを得た。このアニリン重合体の
分子量をＧＰＣで測定したところ、ポリスチレン換算で
数平均分子量１２０００． （ＮＭＰ用カシカラム使用
ｈｏｄｅｙ Ｋｌ）−８０Ｍ）であった。このアニリン
重合体（重合度−１３０）の粉末を、窒素中から空気中
に出したところ、直ちに白色から淡青色に変化した。After reacting for 4 hours, the precipitated solid was filtered out, thoroughly washed with water, dispersed in 100ml of water, 100ml of aqueous ammonia was added, and the mixture was stirred for 4 hours. After the hard carvings were filtered and washed thoroughly, they were dispersed in 100% water, 25 g of hydrazine was added, and the mixture was stirred for 8 hours. Since the dispersed solid matter became white, it was filtered under nitrogen and dried to obtain 4 g of aniline polymer. When the molecular weight of this aniline polymer was measured by GPC, the number average molecular weight was 12,000. (Hodey Kl using Kashi column for NMP)-80M). When the powder of this aniline polymer (degree of polymerization -130) was taken out from nitrogen into air, the color immediately changed from white to light blue.
実施例２
アニリン０．１モル／ｆｌ、過塩素酸０．２モル／ｇを
含む水溶液中で、白金板をそれぞれ作用極、対極として
、飽和カロメル電極に対し、０．８Ｖの定電位で３０分
間電解重合した。それにより、緑色のアニリン重合体を
作用極に得た。この作用極に０．３ｖの逆電位を１時間
かけて脱ドープし、さらに２モル／Ｉのヒドラジン水溶
液に４時間浸漬した後、窒素気流下で乾燥し、白色のア
ニリン重合体０．０５ｇを得た。このアニリン重合体の
分子量をＧＰＣてＡｌ１ｊ定したところ、ポリスチレン
換算て数平均分子ＱＩ５０００ （ＮＭＰ用カシカラム
使用ｈｏｄｅｘＫｌ）−８０Ｍ）であった。このアニリ
ン重合体（重合度−１６０）の粉末を、窒素中がら空気
中に出したところ、直ちに白色から淡緑色に変化した。Example 2 In an aqueous solution containing 0.1 mol/fl of aniline and 0.2 mol/g of perchloric acid, a platinum plate was used as a working electrode and a counter electrode, respectively, and a constant potential of 0.8 V was applied to the saturated calomel electrode. Electrolytic polymerization was carried out for minutes. As a result, a green aniline polymer was obtained as a working electrode. This working electrode was dedoped with a reverse potential of 0.3 V for 1 hour, and then immersed in a 2 mol/I hydrazine aqueous solution for 4 hours, dried under a nitrogen stream, and 0.05 g of a white aniline polymer was added to the working electrode. Obtained. When the molecular weight of this aniline polymer was determined by Al1j by GPC, it was found to be a number average molecular QI of 5000 (hodex Kl using Kashi column for NMP) -80M) in terms of polystyrene. When this powder of aniline polymer (degree of polymerization -160) was taken out into the air under nitrogen, the color immediately changed from white to light green.
実施例３
実施例１において、アニリンの代わりに２−メＩ・キシ
アニリン５ｇを用いた以外は、実施例１と同様に処理を
行ない、３．５ｇの白色アニリン重合体を１！Ｉだ。こ
のアニリン重合体の分子量をＧＰＣでΔＩＩＩ定したと
ころ、ポリスチレン換算で数平均分子２５０００ （Ｎ
ＭＰ用カシカラム使用ｈｏｄｃｘ Ｋｌ）−８０Ｍ）で
あった。このアニリン重合体（重合度−４０）の粉末を
、窒素中から空気中に出したところ、直ちに白色から淡
青色に変化した。Example 3 The same procedure as in Example 1 was carried out except that 5 g of 2-MeI xyaniline was used instead of aniline in Example 1, and 3.5 g of white aniline polymer was mixed into 1! It's I. When the molecular weight of this aniline polymer was determined by ΔIII by GPC, the number average molecular weight was 25,000 (N
Kashi column for MP was used (hodcx Kl)-80M). When the powder of this aniline polymer (degree of polymerization -40) was taken out into the air from nitrogen, the color immediately changed from white to light blue.
実施例４
実施例２において、アニリンの代わりにＮ−ｎ−ブチル
アニリン０．１モル／ｇを用いた以外は実施例２と同様
に処理を行ない、０．０２ｇの白色アニリン重合体を得
た。このアニリン重合体の分子量をＧＰＣで測定したと
ころ、ポリスチレン換算で数平均分子量１００００
（Ｎ Ｍ Ｐ用カラム使用、Ｓ ｈ Ｏｄ ＯＸＫＤ−
８０Ｍ）であった。このアニリン重合体（重合度−９０
）の粉末を、窒素中から空気中に出したところ、直ちに
白色から淡緑色に変化した。Example 4 The same process as in Example 2 was carried out except that 0.1 mol/g of N-n-butylaniline was used instead of aniline, and 0.02 g of a white aniline polymer was obtained. . When the molecular weight of this aniline polymer was measured by GPC, the number average molecular weight was 10,000 in terms of polystyrene.
(Using NMP column, Sh Od OXKD-
80M). This aniline polymer (degree of polymerization -90
) When the powder was taken out from nitrogen into air, the color immediately changed from white to light green.
実施例５
実施例１において、アニリン５ｆの代わりに、アニリン
２．５ｇ及びｏ−トルイジン２．５ｇの混合物を用いた
以外は、実施例１と同様に処理を行ない、３．６ｇの白
色アニリン重合体を得た。このアニリン重合体の分子量
をＧＰＣで測定したところ、ポリスチレン換算で数平均
分子ｆｆ１７０００ （ＮＭＰ用カシカラム使用ｈｏｄ
ｅｘ ＫＤ−８０Ｍ）であった。また、元素分析値（Ｃ
： ７９．７１％、）Ｉ ： ５．８３％、Ｎ。Example 5 The same procedure as in Example 1 was carried out except that a mixture of 2.5 g of aniline and 2.5 g of o-toluidine was used instead of aniline 5f, and 3.6 g of white aniline heavy Obtained union. When the molecular weight of this aniline polymer was measured by GPC, it was found that the number average molecular weight was 17,000 in terms of polystyrene (using a Kashi column for NMP).
ex KD-80M). In addition, elemental analysis value (C
: 79.71%,) I: 5.83%, N.
１４．４６％）より、アニリンと０−）ルイジンの比率
は、４：３であることが確認された。このアニリン重合
体（重合度−９０）の粉末を、窒素中がら空気中に出し
たところ、直ちに白色から淡青色に変化した。14.46%), it was confirmed that the ratio of aniline to 0-)luidine was 4:3. When the powder of this aniline polymer (degree of polymerization -90) was taken out into the air from a nitrogen atmosphere, the color immediately changed from white to light blue.
実施例６
実施例１において、アニリン５ｇの代わりに、アニリン
２．５ｇ及び２−クロロ−３−メチルアニリン２．５ｇ
の混合物を用いた以外は、実施例１と同様に処理を行な
い、３．１ｇの白色アニリン重合体を得た。このアニリ
ン重合体の分子ｍをＧＰＣで測定したところ、ポリスチ
レン換算で数平均分子ｍ８０００（ＮＭＰ用カシカラム
使用ｈｏｄａｘ Ｋｌ）−８０Ｍ）であった。また、元
素分析値（Ｃ： ７２．５２％、Ｈ：４．４６％、Ｎ
： １４．１０％）より、アニリンと２−クロロ−３−
メチルアニリンの比率は、３：１であることか確認され
た。このアニリン重合体（重合度−８０）の粉末を、窒
素中から空気中に出したところ、直ちに白色から淡青色
に変化した。Example 6 In Example 1, 2.5 g of aniline and 2.5 g of 2-chloro-3-methylaniline were used instead of 5 g of aniline.
The treatment was carried out in the same manner as in Example 1, except that a mixture of 3.1 g of white aniline polymer was obtained. When the molecule m of this aniline polymer was measured by GPC, it was found to be a number average molecule m8000 (hodax Kl using Kashi column for NMP -80M) in terms of polystyrene. In addition, elemental analysis values (C: 72.52%, H: 4.46%, N
: 14.10%), aniline and 2-chloro-3-
The ratio of methylaniline was confirmed to be 3:1. When the powder of this aniline polymer (degree of polymerization -80) was taken out into the air from nitrogen, the color immediately changed from white to light blue.
実施例７
実施例１において、アニリン５ｇの代わりに、アニリン
２．０ｇ及びＮ−ｎ−ドデシルアニリン２．５ｇの混合
物を用いた以外は、実施例１と同様に処理を行ない、３
．１ｇの白色アニリン重合体を得た。Example 7 The same procedure as in Example 1 was carried out except that a mixture of 2.0 g of aniline and 2.5 g of N-n-dodecylaniline was used instead of 5 g of aniline in Example 1, and 3
．． 1 g of white aniline polymer was obtained.
このアニリン重合体の分子量をＧＰＣでΔｐ１定したと
ころ、ポリスチレン換算で数平均分子ｆｆ１ｌｌｏｏ。When the molecular weight of this aniline polymer was determined by Δp1 by GPC, the number average molecular weight was ff1lloo in terms of polystyrene.
（ＮＭＰ用カシカラム使用ｈｏｄｃｘ Ｋｌ）−８［Ｉ
Ｍ ）であった。また、元素分析値（Ｃ： ８１．３８
％、Ｈ： １１．０８９６、Ｎ ： １０．５４％）よ
り、アニリンとＮ−ロードデシルアニリンの比率は、３
、ｌであることか確認された。このアニリン重合体（重
合度−８０）の粉末を、窒素中から空気中に出したとこ
ろ、直ちに白色から淡青色に変化した。(Hodcx Kl using Kashi column for NMP)-8[I
M). In addition, elemental analysis value (C: 81.38
%, H: 11.0896, N: 10.54%), the ratio of aniline and N-rhodecylaniline is 3.
, l. When the powder of this aniline polymer (degree of polymerization -80) was taken out into the air from nitrogen, the color immediately changed from white to light blue.
実施例８
実施例］の白色アニリン重合体１．６ｇ、脱気した水０
．２ｇ、及び酸化亜鉛０．２ｇを窒素雰囲気下でよく混
合して錠剤に成形した。この錠剤を空気中に出したとこ
ろ、直ちに白色から淡青色に変化した。Example 8 1.6 g of the white aniline polymer of Example], 0 degassed water
．． 2 g and 0.2 g of zinc oxide were mixed well under a nitrogen atmosphere and formed into tablets. When this tablet was taken out into the air, the color immediately changed from white to pale blue.
実施例９
実施例１の白色アニリン重合体１．５ｇ、エチレングリ
コール０．２に、及びシリカゲル０．３ｇを窒素雰囲気
下でよく混合して錠剤に成形した。この錠剤を空気中に
出したところ、直ちに白色から淡青色に変化した。また
、粉末のままでも空気中で直ちに白色から淡青色に変化
した。Example 9 1.5 g of the white aniline polymer of Example 1, 0.2 g of ethylene glycol, and 0.3 g of silica gel were thoroughly mixed under a nitrogen atmosphere and formed into tablets. When this tablet was taken out into the air, the color immediately changed from white to pale blue. In addition, even in the form of a powder, the color immediately changed from white to light blue in the air.
実施例１０
実施例４の白色アニリン重合体１．３ｇ、脱気した水０
，２ｇ、及び酸化アルミニウム０．５Ｋを窒素雰囲気下
でよく混合して錠剤に成形した。この錠剤を空気中に出
したところ、直ちに白色から淡緑色に変化した。また、
粉末のままでも空気中で直ちに白色から淡緑色に変化し
た。Example 10 1.3 g of the white aniline polymer of Example 4, 0 degassed water
, 2g, and 0.5K of aluminum oxide were mixed well under a nitrogen atmosphere and formed into tablets. When this tablet was taken out into the air, its color immediately changed from white to light green. Also,
Even as a powder, it immediately changed from white to light green in the air.
本発明の酸素検知剤は、酸素の存在によって鋭敏に作用
し、発色する。したがって、生鮭食料品や加重食品等の
保存、有機薬品や金属等の酸化防等のために、真空包装
、窒素シール法、脱酸素剤法等によってそれらを密閉容
器に封入する場合に併用することができ、それによって
、密閉容器内の酸素の有無を容易に確認することが可能
になる。したがってまた、脱気の不完全さや容器の密閉
不良による空気洩れなどに起因するトラブルを未然に防
止することが可能になる。The oxygen detecting agent of the present invention acts sensitively and develops color due to the presence of oxygen. Therefore, in order to preserve raw salmon foods, weighted foods, etc., and to prevent oxidation of organic chemicals and metals, etc., it is used in combination when sealing them in airtight containers using vacuum packaging, nitrogen sealing methods, oxygen scavenger methods, etc. This makes it possible to easily check the presence or absence of oxygen in the closed container. Therefore, it is also possible to prevent troubles caused by air leakage due to incomplete degassing or improper sealing of the container.
また、本発明の酸素検知剤の色相変化は不可逆であるた
め、本発明の酸素検知剤を用いれば、酸素にさらされた
履歴の有無を判定することができる。Moreover, since the hue change of the oxygen detecting agent of the present invention is irreversible, if the oxygen detecting agent of the present invention is used, it is possible to determine whether there is a history of exposure to oxygen.
さらにまた、本発明の酸素検知剤は、安定性に優れてお
り、無酸素状態で１年以上の保存が可能であるという利
点も有している。Furthermore, the oxygen detecting agent of the present invention has the advantage that it has excellent stability and can be stored in an oxygen-free state for one year or more.
Claims (3)
１種または２種よりなる重合度８以上のアニリン重合体
を活性成分として含有することを特徴とする酸素検知剤
。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４及びＲ＿５は
、同一又は互いに異なるものであって、それぞれ水素原
子、アルキル基、アルコキシ基、アリール基、ベンジル
基又はハロゲン原子を表わす。）(1) An oxygen sensing agent characterized by containing as an active ingredient an aniline polymer having a degree of polymerization of 8 or more and consisting of one or two types of repeating units represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1, R_2, R_3, R_4 and R_5 are the same or different, and each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, (represents a benzyl group or a halogen atom)
（１）記載の酸素検知剤。(2) The oxygen detecting agent according to claim (1), which contains water or an alcohol compound.
項（１）又は（２）記載の酸素検知剤。(3) The oxygen sensing agent according to claim (1) or (2), wherein the aniline polymer is supported on a carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18805490A JP2949515B2 (en) | 1990-07-18 | 1990-07-18 | Oxygen detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18805490A JP2949515B2 (en) | 1990-07-18 | 1990-07-18 | Oxygen detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0476456A true JPH0476456A (en) | 1992-03-11 |
| JP2949515B2 JP2949515B2 (en) | 1999-09-13 |
Family
ID=16216883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18805490A Expired - Fee Related JP2949515B2 (en) | 1990-07-18 | 1990-07-18 | Oxygen detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2949515B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2368908A (en) * | 2000-11-09 | 2002-05-15 | Secr Defence | Exposure sensor for oxygen or water |
-
1990
- 1990-07-18 JP JP18805490A patent/JP2949515B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2368908A (en) * | 2000-11-09 | 2002-05-15 | Secr Defence | Exposure sensor for oxygen or water |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2949515B2 (en) | 1999-09-13 |
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