JP2005291895A - Composition for measuring residual chlorine - Google Patents
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- JP2005291895A JP2005291895A JP2004106740A JP2004106740A JP2005291895A JP 2005291895 A JP2005291895 A JP 2005291895A JP 2004106740 A JP2004106740 A JP 2004106740A JP 2004106740 A JP2004106740 A JP 2004106740A JP 2005291895 A JP2005291895 A JP 2005291895A
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000000460 chlorine Substances 0.000 title claims abstract description 43
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 42
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 22
- -1 benzidine compound Chemical class 0.000 abstract description 15
- 238000004321 preservation Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 238000002835 absorbance Methods 0.000 description 21
- 238000004040 coloring Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 102100031974 CMP-N-acetylneuraminate-beta-galactosamide-alpha-2,3-sialyltransferase 4 Human genes 0.000 description 6
- 101000703754 Homo sapiens CMP-N-acetylneuraminate-beta-galactosamide-alpha-2,3-sialyltransferase 4 Proteins 0.000 description 6
- BTWUORFYKAZQHW-UHFFFAOYSA-L disodium;2-hydroxy-3-[4-[4-[(2-hydroxy-3-sulfonatopropyl)amino]-3-methylphenyl]-2-methylanilino]propane-1-sulfonate Chemical compound [Na+].[Na+].C1=C(NCC(O)CS([O-])(=O)=O)C(C)=CC(C=2C=C(C)C(NCC(O)CS([O-])(=O)=O)=CC=2)=C1 BTWUORFYKAZQHW-UHFFFAOYSA-L 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000004964 sulfoalkyl group Chemical group 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 125000004181 carboxyalkyl group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- RYKQVXOGIQWCHT-UHFFFAOYSA-N 2-hydroxy-3-[4-[4-[(2-hydroxy-3-sulfopropyl)amino]-3-methylphenyl]-2-methylanilino]propane-1-sulfonic acid Chemical compound C1=C(NCC(O)CS(O)(=O)=O)C(C)=CC(C=2C=C(C)C(NCC(O)CS(O)(=O)=O)=CC=2)=C1 RYKQVXOGIQWCHT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XKCGVXOJQOVXDZ-UHFFFAOYSA-N 2-[2-methyl-4-[3-methyl-4-(2-sulfoethylamino)phenyl]anilino]ethanesulfonic acid Chemical compound C1=C(NCCS(O)(=O)=O)C(C)=CC(C=2C=C(C)C(NCCS(O)(=O)=O)=CC=2)=C1 XKCGVXOJQOVXDZ-UHFFFAOYSA-N 0.000 description 1
- FUALCAMGEPIZCK-UHFFFAOYSA-N 2-[4-(4-amino-3,5-dimethylphenyl)-2,6-dimethylanilino]ethanesulfonic acid Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(NCCS(O)(=O)=O)=C(C)C=2)=C1 FUALCAMGEPIZCK-UHFFFAOYSA-N 0.000 description 1
- BYABUPNXFQPJJS-UHFFFAOYSA-N 2-[4-[3,5-dimethyl-4-(2-sulfoethylamino)phenyl]-2,6-dimethylanilino]ethanesulfonic acid Chemical compound CC1=C(NCCS(O)(=O)=O)C(C)=CC(C=2C=C(C)C(NCCS(O)(=O)=O)=C(C)C=2)=C1 BYABUPNXFQPJJS-UHFFFAOYSA-N 0.000 description 1
- LBHVENJJSMSDGP-UHFFFAOYSA-N 2-hydroxy-3-[4-[4-[(2-hydroxy-3-sulfopropyl)amino]-3,5-dimethylphenyl]-2,6-dimethylanilino]propane-1-sulfonic acid Chemical compound CC1=C(NCC(O)CS(O)(=O)=O)C(C)=CC(C=2C=C(C)C(NCC(O)CS(O)(=O)=O)=C(C)C=2)=C1 LBHVENJJSMSDGP-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- YNAKESQZGPZDDZ-UHFFFAOYSA-N 2-n,2-n-diethylbenzene-1,2-diamine Chemical compound CCN(CC)C1=CC=CC=C1N YNAKESQZGPZDDZ-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- GKBJKGONWWXFTG-UHFFFAOYSA-N 3-[2-methyl-4-[3-methyl-4-(3-sulfopropylamino)phenyl]anilino]propane-1-sulfonic acid Chemical compound C1=C(NCCCS(O)(=O)=O)C(C)=CC(C=2C=C(C)C(NCCCS(O)(=O)=O)=CC=2)=C1 GKBJKGONWWXFTG-UHFFFAOYSA-N 0.000 description 1
- PDZPIHCIACYCEI-UHFFFAOYSA-N 3-[4-(4-amino-3,5-diethylphenyl)-2,6-diethylanilino]propane-1-sulfonic acid Chemical compound CCC1=C(N)C(CC)=CC(C=2C=C(CC)C(NCCCS(O)(=O)=O)=C(CC)C=2)=C1 PDZPIHCIACYCEI-UHFFFAOYSA-N 0.000 description 1
- RZCGXNDSQZUYKI-UHFFFAOYSA-N 3-[4-(4-amino-3,5-dimethylphenyl)-2,6-dimethylanilino]-2-hydroxypropane-1-sulfonic acid Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(NCC(O)CS(O)(=O)=O)=C(C)C=2)=C1 RZCGXNDSQZUYKI-UHFFFAOYSA-N 0.000 description 1
- GZNAFYJQMXPVSY-UHFFFAOYSA-N 3-[4-(4-amino-3,5-dimethylphenyl)-2,6-dimethylanilino]propane-1-sulfonic acid Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(NCCCS(O)(=O)=O)=C(C)C=2)=C1 GZNAFYJQMXPVSY-UHFFFAOYSA-N 0.000 description 1
- CNKQMJRJRRDCPZ-UHFFFAOYSA-N 3-[4-[3,5-diethyl-4-(3-sulfopropylamino)phenyl]-2,6-diethylanilino]propane-1-sulfonic acid Chemical compound CCC1=C(NCCCS(O)(=O)=O)C(CC)=CC(C=2C=C(CC)C(NCCCS(O)(=O)=O)=C(CC)C=2)=C1 CNKQMJRJRRDCPZ-UHFFFAOYSA-N 0.000 description 1
- PZNKFYBILBFRRB-UHFFFAOYSA-N 3-[4-[3,5-dimethyl-4-(3-sulfopropylamino)phenyl]-2,6-dimethylanilino]propane-1-sulfonic acid Chemical compound CC1=C(NCCCS(O)(=O)=O)C(C)=CC(C=2C=C(C)C(NCCCS(O)(=O)=O)=C(C)C=2)=C1 PZNKFYBILBFRRB-UHFFFAOYSA-N 0.000 description 1
- OILSUQUKJHWJHA-UHFFFAOYSA-N 3-[n-ethyl-4-[4-[ethyl(3-sulfopropyl)amino]-3-methylphenyl]-2-methylanilino]propane-1-sulfonic acid Chemical compound C1=C(C)C(N(CCCS(O)(=O)=O)CC)=CC=C1C1=CC=C(N(CC)CCCS(O)(=O)=O)C(C)=C1 OILSUQUKJHWJHA-UHFFFAOYSA-N 0.000 description 1
- NVKLBOVBGVTCHI-UHFFFAOYSA-N 4-[4-(4-amino-3,5-dimethylphenyl)-2,6-dimethylanilino]butane-1-sulfonic acid Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(NCCCCS(O)(=O)=O)=C(C)C=2)=C1 NVKLBOVBGVTCHI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- YZOKUHPVENFFGL-UHFFFAOYSA-N S(=O)(=O)(O)CCCCNC=1C(CC(=CC1C)C1=CC=C(NCCCCS(=O)(=O)O)C(=C1)C)(C)C Chemical compound S(=O)(=O)(O)CCCCNC=1C(CC(=CC1C)C1=CC=C(NCCCCS(=O)(=O)O)C(=C1)C)(C)C YZOKUHPVENFFGL-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Abstract
Description
本発明は、水中に含まれる残留塩素の濃度を測定するための組成物に関する。 The present invention relates to a composition for measuring the concentration of residual chlorine contained in water.
生活用水には、殺菌や消毒を目的として次亜塩素酸ナトリウムなどの塩素剤が添加されている。また、工業用水においても、しばしば同様の目的から塩素剤が添加される。この塩素剤は、酸化作用による殺菌効果や消毒効果を有するが、水中においては懸濁物や有機物等との反応、あるいは大気中への拡散などにより、経時的にその効果が低減する。このため、衛生管理の面からは、水中の残留塩素濃度を定期的に検査する必要がある。また、活性炭フィルタなどの残留塩素除去を目的とした水処理機器を使用している場合も、機器の性能や処理水質を管理するため、水中の残留塩素濃度を定期的に検査する必要がある。 Chlorine agents such as sodium hypochlorite are added to domestic water for the purpose of sterilization and disinfection. In industrial water, a chlorine agent is often added for the same purpose. This chlorinating agent has a bactericidal effect and a disinfecting effect due to an oxidizing action, but its effect decreases with time due to reaction with suspensions, organic substances, etc. in water, or diffusion into the atmosphere. For this reason, in terms of hygiene management, it is necessary to periodically check the residual chlorine concentration in the water. In addition, even when using water treatment equipment such as activated carbon filter for the purpose of removing residual chlorine, it is necessary to periodically check the residual chlorine concentration in water in order to manage the performance of the equipment and the quality of the treated water.
従来から、水中の残留塩素濃度の測定方法としては、発色色素としてo−トリジンを用いる方法、またはDPD(N,N−ジエチルフェニレンジアミン)を用いる方法が採用されており、近年では、DPDよりも安全性および水溶性に優れたジアルキルベンジジン化合物やテトラアルキルベンジジン化合物を用いる方法が提案されている(特許文献1,2参照)。 Conventionally, as a method for measuring the residual chlorine concentration in water, a method using o-tolidine as a coloring dye or a method using DPD (N, N-diethylphenylenediamine) has been adopted. A method using a dialkylbenzidine compound or a tetraalkylbenzidine compound excellent in safety and water solubility has been proposed (see Patent Documents 1 and 2).
前記特許文献1では、ジアルキルベンジジン化合物の水溶液中での保存安定性を高めて正確に塩素濃度を測定することを目的として、組成物中にジアルキルベンジジン化合物の他に、キレート剤や界面活性剤を含有させている。そして、この組成物を37℃で2時間保存したときに、前記化合物が発色したときの極大吸収である674nmの吸光度の上昇が抑制されることをもって保存安定性の指標としている。したがって、例えば組成物を使用直前まで冷暗所に保存して使用する場合においては、前記組成物は実用上十分な保存安定性を有しているといえる。 In Patent Document 1, a chelating agent or a surfactant is added to the composition in addition to the dialkylbenzidine compound for the purpose of accurately measuring the chlorine concentration by enhancing the storage stability of the dialkylbenzidine compound in an aqueous solution. It is included. And when this composition is stored at 37 ° C. for 2 hours, an increase in absorbance at 674 nm, which is the maximum absorption when the compound is colored, is suppressed, and this is used as an index of storage stability. Therefore, for example, when the composition is stored and used in a cool and dark place until just before use, it can be said that the composition has practically sufficient storage stability.
ところが、例えば組成物を室外で、または温度調整のなされていない屋内で長期間保存して使用する場合には、季節にもよるが通常は5〜50℃の温度条件で保存される。しかしながら、このような過酷な保存条件では、前記組成物の保存安定性は実用上不十分であり、さらに保存安定性の優れた組成物が要望されていた。
本発明は前記問題点に鑑みてなされたものであり、その目的は、5〜50℃の温度条件で長期間保存した場合でも保存安定性に優れた残留塩素測定用組成物を提供することにある。 This invention is made | formed in view of the said problem, The objective is to provide the composition for residual chlorine measurement excellent in storage stability, even when it preserve | saves for a long period of time at 5-50 degreeC temperature conditions. is there.
本発明者は前記課題を解決するため鋭意検討した結果、組成物を酸性領域に調整することで、前記課題が解決できることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by adjusting the composition to an acidic region, and have completed the present invention.
すなわち、請求項1の残留塩素測定用組成物は、ジアルキルベンジジン化合物および/またはテトラアルキルベンジジン化合物と、酸とを含むことを特徴とする。 That is, the residual chlorine measurement composition according to claim 1 is characterized by containing a dialkylbenzidine compound and / or a tetraalkylbenzidine compound and an acid.
本発明の組成物によれば、5〜50℃の温度条件で長期間保存した場合でも保存安定性に優れ、残留塩素濃度の測定に際して、発色色素が発色したときの極大吸収波長付近における吸光度の上昇を抑制することができる。 According to the composition of the present invention, even when stored for a long period of time at a temperature of 5 to 50 ° C., the storage stability is excellent, and when measuring the residual chlorine concentration, the absorbance in the vicinity of the maximum absorption wavelength when the coloring dye develops color. The rise can be suppressed.
本発明の残留塩素測定用組成物は、ジアルキルベンジジン化合物またはテトラアルキルベンジジン化合物から選択される発色色素と、酸とを含む一液の組成物であって、好ましくはpHが3.5以下である点に特徴を有する。 The residual chlorine measurement composition of the present invention is a one-component composition containing a coloring dye selected from a dialkylbenzidine compound or a tetraalkylbenzidine compound and an acid, and preferably has a pH of 3.5 or less. Characterized by points.
ジアルキルベンジジン化合物またはテトラアルキルベンジジン化合物とは、式(I) The dialkylbenzidine compound or the tetraalkylbenzidine compound is a compound represented by the formula (I)
(式中、R1およびR2は、それぞれ独立して、炭素数1〜6のアルキル基を示す。R3およびR4は、それぞれ独立して、炭素数1〜6のアルキル基を示すか、あるいは同時に水素原子を示す。R5およびR6は、それぞれ独立して、水素原子または炭素数1〜6のアルキル基を示す。R7およびR8は、それぞれ独立して、水素原子,1個以上の水酸基を有することもある炭素数1〜6のスルホアルキル基、または1個以上の水酸基を有することもある炭素数1〜6のカルボキシアルキル基を示すが、R7とR8が同時に水素原子であることはない。)で表される化合物をいう。 (In the formula, R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms. Do R 3 and R 4 each independently represent an alkyl group having 1 to 6 carbon atoms? Or R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 7 and R 8 each independently represent a hydrogen atom, 1 A C1-C6 sulfoalkyl group that may have one or more hydroxyl groups, or a C1-C6 carboxyalkyl group that may have one or more hydroxyl groups, but R 7 and R 8 are simultaneously It is not a hydrogen atom.)
前記一般式(I)のR1およびR2における炭素数1〜6のアルキル基としては、例えばメチル基,エチル基,プロピル基,イソプロピル基,ブチル基,イソブチル基、sec-ブチル基,tert-ブチル基,ペンチル基,1−メチルブチル基,2−メチルブチル基,3−メチルブチル基,1−エチルプロピル基,ヘキシル基等が挙げられる。これらの中では、ジアルキルベンジジン化合物の場合、R1およびR2のいずれかがメチル基であることが好ましく、R1およびR2がともにメチル基であることがより好ましい。また、テトラアルキルベンジジン化合物の場合、R1およびR2がともにメチル基またはエチル基であることがより好ましい。 Examples of the alkyl group having 1 to 6 carbon atoms in R 1 and R 2 of the general formula (I) include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- Examples include butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, hexyl group and the like. Among these, in the case of the dialkyl benzidine compound, it is preferable that one of R 1 and R 2 are methyl groups, and more preferably R 1 and R 2 are both methyl groups. In the case of a tetraalkylbenzidine compound, it is more preferable that both R 1 and R 2 are a methyl group or an ethyl group.
前記一般式(I)のR3およびR4における炭素数1〜6のアルキル基としては、前記R1およびR2と同じものが挙げられる。これらの中では、テトラアルキルベンジジン化合物の場合、R3およびR4がともにメチル基またはエチル基であることが好ましい。 Examples of the alkyl group having 1 to 6 carbon atoms in R 3 and R 4 in the general formula (I) include the same as those in R 1 and R 2 . Among these, in the case of a tetraalkylbenzidine compound, it is preferable that R 3 and R 4 are both a methyl group or an ethyl group.
前記一般式(I)のR5およびR6における炭素数1〜6のアルキル基としては、前記R1およびR2と同じものが挙げられ、これらの中では、R5およびR6がともにメチル基またはエチル基であることが好ましい。本発明では、R5およびR6がともに水素原子である場合、またはR5およびR6がともにエチル基である場合が特に好ましい。 Examples of the alkyl group having 1 to 6 carbon atoms in R 5 and R 6 of the general formula (I) include the same groups as those in R 1 and R 2. Among these, R 5 and R 6 are both methyl. It is preferably a group or an ethyl group. In the present invention, it is particularly preferred that R 5 and R 6 are both hydrogen atoms, or that R 5 and R 6 are both ethyl groups.
前記一般式(I)のR7およびR8における1個以上の水酸基を有することもある炭素数1〜6のスルホアルキル基とは、前記R1およびR2と同じアルキル基がスルホン酸基で置換された誘導体をいう。スルホン酸基の置換位置は特に限定されないが、通常はアルキル基の末端に置換されていることが好ましい。前記スルホアルキル基は、1個以上の水酸基を有してもよい。該水酸基の置換位置およびその個数は特に限定されない。また、水酸基を有しない炭素数1〜6のスルホアルキル基も本発明に好適に用いることができる。本発明に好適なスルホアルキル基としては、例えば2−スルホエチル基,3−スルホプロピル基,2−ヒドロキシ−3−スルホプロピル基,2−ヒドロキシ−2−スルホエチル基,4−スルホブチル基等が挙げられる。 The sulfoalkyl group having 1 to 6 carbon atoms which may have one or more hydroxyl groups in R 7 and R 8 of the general formula (I) is a sulfonic acid group in which the same alkyl group as R 1 and R 2 is Refers to a substituted derivative. The substitution position of the sulfonic acid group is not particularly limited, but it is usually preferred that the sulfonic acid group is substituted at the terminal of the alkyl group. The sulfoalkyl group may have one or more hydroxyl groups. The substitution position of the hydroxyl group and the number thereof are not particularly limited. Moreover, the C1-C6 sulfoalkyl group which does not have a hydroxyl group can also be used suitably for this invention. Examples of the sulfoalkyl group suitable for the present invention include 2-sulfoethyl group, 3-sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 2-hydroxy-2-sulfoethyl group, 4-sulfobutyl group and the like. .
前記一般式(I)のR7およびR8における1個以上の水酸基を有することもある炭素数1〜6のカルボキシアルキル基とは、前記R1およびR2と同じアルキル基がカルボキシル基で置換された誘導体をいう。カルボキシル基の置換位置は特に限定されないが、通常はアルキル基の末端に置換されていることが好ましい。該カルボキシアルキル基は、1個以上の水酸基を有していてもよい。該水酸基の置換位置およびその個数は特に限定されない。水酸基を有しない炭素数1〜6のカルボキシアルキル基も本発明に好適に用いることができる。 The carboxyalkyl group having 1 to 6 carbon atoms which may have one or more hydroxyl groups in R 7 and R 8 of the general formula (I) is the same alkyl group as in R 1 and R 2 is substituted with a carboxyl group Derivatives. The substitution position of the carboxyl group is not particularly limited, but it is usually preferable that the carboxyl group is substituted at the terminal of the alkyl group. The carboxyalkyl group may have one or more hydroxyl groups. The substitution position of the hydroxyl group and the number thereof are not particularly limited. A C1-C6 carboxyalkyl group which does not have a hydroxyl group can also be used suitably for this invention.
前記一般式(I)で表されるジアルキルベンジジン化合物の好ましい例としては、例えばN,N’−ビス(2−スルホエチル)−3,3’−ジメチルベンジジン、N,N’−ビス(3−スルホプロピル)−3,3’−ジメチルベンジジン、N,N’−ビス(2−ヒドロキシ−3−スルホプロピル)−3,3’−ジメチルベンジジン、N,N’−ビス(4−スルホブチル)−3,3’−ジメチルベンジジン、N,N’−ビス(3−スルホプロピル)−N,N’−ジエチル−3,3’−ジメチルベンジジン等が挙げられる。 Preferable examples of the dialkylbenzidine compound represented by the general formula (I) include, for example, N, N′-bis (2-sulfoethyl) -3,3′-dimethylbenzidine, N, N′-bis (3-sulfo Propyl) -3,3′-dimethylbenzidine, N, N′-bis (2-hydroxy-3-sulfopropyl) -3,3′-dimethylbenzidine, N, N′-bis (4-sulfobutyl) -3, Examples thereof include 3′-dimethylbenzidine, N, N′-bis (3-sulfopropyl) -N, N′-diethyl-3,3′-dimethylbenzidine and the like.
また、前記一般式(I)で表されるテトラアルキルベンジジン化合物の好ましい例としては、例えばN−(2−スルホエチル)−3,3’,5,5’−テトラメチルベンジジン、N−(3−スルホプロピル)−3,3’,5,5’−テトラメチルベンジジン、N−(4−スルホブチル)−3,3’,5,5’−テトラメチルベンジジン、N−(3−スルホプロピル)−3,3’,5,5’−テトラエチルベンジジン、N−(2−ヒドロキシ−3−スルホプロピル)−3,3’,5,5’−テトラメチルベンジジン、N,N’−ビス(2−スルホエチル)−3,3’,5,5’−テトラメチルベンジジン、N,N’−ビス(3−スルホプロピル)−3,3’,5,5’−テトラメチルベンジジン、N,N’−ビス(4−スルホブチル)−3,3’,5,5’−テトラメチルベンジジン、N,N’−ビス(3−スルホプロピル)−3,3’,5,5’−テトラエチルベンジジン、N,N’−ビス(2−ヒドロキシ−2−スルホエチル)−3,3’,5,5’−テトラメチルベンジジン、N,N’−ビス(2−ヒドロキシ−3−スルホプロピル)−3,3’,5,5’−テトラメチルベンジジン等が挙げられる。 Preferred examples of the tetraalkylbenzidine compound represented by the general formula (I) include N- (2-sulfoethyl) -3,3 ′, 5,5′-tetramethylbenzidine, N- (3- Sulfopropyl) -3,3 ′, 5,5′-tetramethylbenzidine, N- (4-sulfobutyl) -3,3 ′, 5,5′-tetramethylbenzidine, N- (3-sulfopropyl) -3 , 3 ′, 5,5′-tetraethylbenzidine, N- (2-hydroxy-3-sulfopropyl) -3,3 ′, 5,5′-tetramethylbenzidine, N, N′-bis (2-sulfoethyl) -3,3 ', 5,5'-tetramethylbenzidine, N, N'-bis (3-sulfopropyl) -3,3', 5,5'-tetramethylbenzidine, N, N'-bis (4 -Sulfobutyl) -3,3 , 5,5′-tetramethylbenzidine, N, N′-bis (3-sulfopropyl) -3,3 ′, 5,5′-tetraethylbenzidine, N, N′-bis (2-hydroxy-2-sulfoethyl) ) -3,3 ′, 5,5′-tetramethylbenzidine, N, N′-bis (2-hydroxy-3-sulfopropyl) -3,3 ′, 5,5′-tetramethylbenzidine and the like. .
前記ジアルキルベンジジン化合物および前記テトラアルキルベンジジン化合物は、それぞれ単独で、あるいは混合して用いることができる。また、前記ジアルキルベンジジン化合物および前記テトラアルキルベンジジン化合物は、塩の形態でも用いることができる。塩としては、例えばナトリウム塩等が代表的なものとして挙げられる。 The dialkylbenzidine compound and the tetraalkylbenzidine compound can be used alone or in combination. The dialkylbenzidine compound and the tetraalkylbenzidine compound can also be used in the form of a salt. As a salt, a sodium salt etc. are mentioned as a typical thing, for example.
前記発色色素の配合割合は特に限定されず、通常は組成物中0.1〜2.0重量%である。 The mixing ratio of the coloring dye is not particularly limited, and is usually 0.1 to 2.0% by weight in the composition.
本発明の組成物に含有される酸は、該組成物のpHを酸性領域、好ましくは3.5以下、より好ましくは3.0以下、特に好ましくは1.9以下に調整するために用いられる。前記組成物のpHを酸性領域に調整することにより、5〜50℃の温度条件で長期間保存した場合でも発色色素が発色したときの極大吸収波長付近における吸光度の経時的な上昇を抑制し、安定した残留塩素濃度の測定を行うことができる。より具体的には、5〜50℃の温度条件で長期間保存した場合でも、組成物を検水に添加したときのバックグラウンド値を残留塩素濃度0.1mg/リットル相当以下に抑制して測定することができる。酸としては、無機酸または有機酸を単独で、またはこれらを適宜組み合わせて用いることができる。無機酸としては、例えば硫酸,塩酸,リン酸等の酸化性や還元性を示さない酸が挙げられる。有機酸としては、例えばクエン酸,酢酸,コハク酸,シュウ酸等が挙げられる。 The acid contained in the composition of the present invention is used to adjust the pH of the composition to the acidic region, preferably 3.5 or less, more preferably 3.0 or less, and particularly preferably 1.9 or less. . By adjusting the pH of the composition to an acidic region, even when stored for a long period of time at a temperature of 5 to 50 ° C., it suppresses the increase in absorbance in the vicinity of the maximum absorption wavelength when the coloring dye develops color, Stable residual chlorine concentration can be measured. More specifically, even when the composition is stored for a long time at a temperature of 5 to 50 ° C., the background value when the composition is added to the test water is suppressed to a residual chlorine concentration of 0.1 mg / liter or less. can do. As the acid, an inorganic acid or an organic acid can be used alone or in combination. Examples of inorganic acids include acids that do not exhibit oxidizing or reducing properties such as sulfuric acid, hydrochloric acid, and phosphoric acid. Examples of the organic acid include citric acid, acetic acid, succinic acid, oxalic acid and the like.
本発明では、前記組成物のpHを微調整するために、必要に応じて、例えば酸のアルカリ金属塩を含有させることができる。酸のアルカリ金属塩としては、例えばリン酸ナトリウム,クエン酸ナトリウム等が挙げられる。例えば、組成物のpHを1.0以下(例えば0.6)に設定したい場合、硫酸とリン酸でpH0.6未満の組成物を調製し、ついでリン酸ナトリウムを加えることで簡単に所望のpHとすることができる。 In the present invention, in order to finely adjust the pH of the composition, for example, an alkali metal salt of an acid can be contained as necessary. Examples of the alkali metal salt of acid include sodium phosphate and sodium citrate. For example, when it is desired to set the pH of the composition to 1.0 or less (for example, 0.6), a composition having a pH of less than 0.6 is prepared with sulfuric acid and phosphoric acid, and then sodium phosphate is added to obtain a desired composition. The pH can be set.
本発明の組成物は、発色色素,酸,必要に応じて酸のアルカリ金属塩を均一に混合することで製造することができる。例えば、酸の水溶液に発色試薬を溶解し、必要に応じて酸のアルカリ金属塩を溶解することにより製造することができる。 The composition of the present invention can be produced by uniformly mixing a coloring dye, an acid, and, if necessary, an alkali metal salt of an acid. For example, it can be produced by dissolving a coloring reagent in an aqueous acid solution and, if necessary, dissolving an alkali metal salt of the acid.
本発明の組成物は、水中の残留塩素濃度の測定に用いることができる。残留塩素を含む水の種類は特に限定されず、例えば工業用水や生活用水に広く適用することができる。 The composition of the present invention can be used for measurement of residual chlorine concentration in water. The kind of water containing residual chlorine is not specifically limited, For example, it can apply widely to industrial water and domestic water.
また、残留塩素濃度の測定にあたっては、典型的には、測定対象の水から採取した検水に対して発色色素が残留塩素の当量以上含まれるように本発明の組成物が添加される。そして、発色色素が発色したときの極大吸収波長付近の吸光度を測定し、あらかじめ求めておいた残留塩素濃度と吸光度の検量線に基づいて、検水中の残留塩素濃度が測定される。さらに、残留塩素の測定精度を高めるためには、組成物に含まれる発色色素の濃度、測定時における組成物の添加量および採取する検水の容量等の測定条件をあらかじめ決めた上で測定することが好ましい。 In measuring the residual chlorine concentration, typically, the composition of the present invention is added so that the coloring dye is contained in an amount equal to or greater than the residual chlorine with respect to the sample water collected from the water to be measured. Then, the absorbance near the maximum absorption wavelength when the coloring dye develops color is measured, and the residual chlorine concentration in the test water is measured based on the previously determined residual chlorine concentration and absorbance calibration curve. Furthermore, in order to increase the measurement accuracy of residual chlorine, measurement is performed after determining the measurement conditions such as the concentration of the coloring dye contained in the composition, the amount of the composition added at the time of measurement, and the volume of sample water to be collected. It is preferable.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
(組成物を高温で長期間保存したときの吸収スペクトルに及ぼす組成物調製時のpHの影響)
発色色素としてN,N’−ビス(2−ヒドロキシ−3−スルホプロピル)−3,3’−ジメチルベンジジンのナトリウム塩(株式会社同仁化学研究所;商品名SAT−3)を0.5重量%,硫酸(47%)を7.5重量%,リン酸を5重量%,リン酸ナトリウムを4重量%,水を83重量%配合した組成物を調製した。この組成物のpHは0.59であった。つぎに、前記組成物に水酸化ナトリウム水溶液を加えて、pH0.69〜1.49の組成物をさらに調製した。調製した組成物20ミリリットルをポリプロピレン製容器に入れ、40℃で4ヶ月保存したときの波長400〜800nmにおける吸光度を分光光度計(株式会社日立製作所製U−2010、石英セル長:10mm)で測定した。得られた吸収スペクトルを図1に示す。図1から、組成物調製時のpHが大きくなるほど、SAT−3が発色したときの極大吸収である674nm前後の吸光度が上昇することが分かった。
(Effect of pH at the time of preparing the composition on the absorption spectrum when the composition is stored at a high temperature for a long period of time)
0.5% by weight of sodium salt of N, N′-bis (2-hydroxy-3-sulfopropyl) -3,3′-dimethylbenzidine (Dojindo Laboratories, Inc .; trade name SAT-3) as a coloring dye A composition containing 7.5% by weight of sulfuric acid (47%), 5% by weight of phosphoric acid, 4% by weight of sodium phosphate and 83% by weight of water was prepared. The pH of this composition was 0.59. Next, an aqueous sodium hydroxide solution was added to the composition to further prepare a composition having a pH of 0.69 to 1.49. 20 ml of the prepared composition was put into a polypropylene container, and the absorbance at a wavelength of 400 to 800 nm when stored at 40 ° C. for 4 months was measured with a spectrophotometer (U-2010 manufactured by Hitachi, Ltd., quartz cell length: 10 mm). did. The obtained absorption spectrum is shown in FIG. From FIG. 1, it was found that the absorbance at around 674 nm, which is the maximum absorption when SAT-3 was colored, increased as the pH during composition preparation increased.
(pHの上限値の決定)
図1の吸収スペクトルから、市販LEDで測定可能な波長655nmにおける吸光度の実測値を用いて、組成物のpHと吸光度の三次近似式を求め、この式を用いてpH0.59〜3.9の吸光度を近似計算した。つぎに、検水4ミリリットルに対して組成物60マイクロリットルを添加する測定条件を設定し、組成物添加時の検水の吸光度を、pH0.59〜3.9について計算により求めた。すなわち、この吸光度は、組成物が添加された残留塩素濃度0mg/リットルの検水が示す吸光度に相当する。さらに、この吸光度に対し、あらかじめ求めておいたpH0.6の組成物を用いたときの検量線に基づいて検水の残留塩素濃度判定値を計算した。結果を表1に示す。
(Determination of the upper limit of pH)
From the absorption spectrum of FIG. 1, the measured value of the absorbance at a wavelength of 655 nm that can be measured with a commercial LED is used to obtain a third-order approximation of the pH and absorbance of the composition, and this formula is used to determine the pH of 0.59 to 3.9. Absorbance was approximated. Next, measurement conditions for adding 60 microliters of the composition to 4 milliliters of the test water were set, and the absorbance of the test water at the time of adding the composition was determined by calculation for pH 0.59 to 3.9. That is, this absorbance corresponds to the absorbance indicated by the test water having a residual chlorine concentration of 0 mg / liter to which the composition has been added. Furthermore, the residual chlorine concentration judgment value of test water was calculated with respect to this absorbance based on a calibration curve obtained using a composition having a pH of 0.6 determined in advance. The results are shown in Table 1.
表1に記載されている吸光度(計算値)は、組成物を検水に添加したときの吸光度のバックグラウンドを示し、この吸光度のバックグラウンドが小さいほど、発色色素の酸化劣化度合いが小さいことを意味する。ここで、本発明の組成物を使用する残留塩素濃度測定においては、測定精度を確保する観点から、バックグラウンドの残留塩素濃度判定値が0.1mg/リットル以下であることが好ましい。組成物のpHが小さくなるほど波長655nmの吸光度が小さくなることを考慮すると、表1より、バックグラウンドの吸光度が0.05以下ないし0.08以下であれば、0.1mg/リットル以下の誤差で測定できることが分かる。したがって、組成物のpHを3.0以下ないし3.5以下に調整すれば、発色色素の酸化劣化による残留塩素濃度判定値への影響を抑制することができる。 The absorbance (calculated value) shown in Table 1 indicates the background of absorbance when the composition is added to the test water. The smaller the background of absorbance, the smaller the degree of oxidative degradation of the coloring dye. means. Here, in the measurement of residual chlorine concentration using the composition of the present invention, the background residual chlorine concentration determination value is preferably 0.1 mg / liter or less from the viewpoint of ensuring measurement accuracy. Considering that the absorbance at a wavelength of 655 nm decreases as the pH of the composition decreases, from Table 1, if the background absorbance is 0.05 to 0.08, an error of 0.1 mg / liter or less occurs. It can be seen that it can be measured. Therefore, by adjusting the pH of the composition to 3.0 or less to 3.5 or less, it is possible to suppress the influence on the residual chlorine concentration judgment value due to the oxidative deterioration of the coloring dye.
(保存安定性試験)
SAT−3を0.5重量%,硫酸(47%)を7.5重量%,リン酸を5重量%,リン酸ナトリウムを4重量%,水を83重量%配合した組成物を調製した。この組成物のpHは0.59であった。この調製した組成物を5℃,25℃,40℃,50℃の4通りの温度条件下で保存した。そして、組成物の調製時,74日および120日経過時の組成物を残留塩素濃度の測定用組成物とした。残留塩素濃度の測定に際しては、残留塩素濃度0mg/リットルの検水および残留塩素濃度約1.6mg/リットルの検水4ミリリットルに対して前記組成物を60マイクロリットル添加し、波長655nmの吸光度を分光光度計(株式会社日立製作所製U−2010、石英セル長:10mm)で測定した。そして、あらかじめ求めておいた検量線から検水中の残留塩素濃度判定値を計算した。また、比較例として、測定時に使用した検水中の残留塩素濃度をハック社(HACH Company)製ポケット水質計Cl2(DPD法による残留塩素測定キット)を用いて測定した。ここで、DPD法は発色色素を粉末で保存するため酸化劣化がほとんどなく、また水道法で指定された方法であるため、実施例との比較対象として選定した。結果を表2と表3に示す。
(Storage stability test)
A composition containing 0.5% by weight of SAT-3, 7.5% by weight of sulfuric acid (47%), 5% by weight of phosphoric acid, 4% by weight of sodium phosphate, and 83% by weight of water was prepared. The pH of this composition was 0.59. The prepared composition was stored under four temperature conditions of 5 ° C, 25 ° C, 40 ° C and 50 ° C. Then, at the time of preparation of the composition, the composition after 74 days and 120 days elapsed was used as a composition for measuring the residual chlorine concentration. In measuring the residual chlorine concentration, 60 microliters of the above composition was added to 4 ml of test water having a residual chlorine concentration of 0 mg / liter and 4 ml of test water having a residual chlorine concentration of about 1.6 mg / liter, and the absorbance at a wavelength of 655 nm was measured. The measurement was made with a spectrophotometer (U-2010 manufactured by Hitachi, Ltd., quartz cell length: 10 mm). And the residual-chlorine density | concentration judgment value in test water was computed from the analytical curve calculated | required beforehand. Moreover, as a comparative example, the residual chlorine concentration in the test water used at the time of measurement was measured using a pocket water quality meter Cl 2 (residual chlorine measurement kit by DPD method) manufactured by HACH Company. Here, since the DPD method preserves the coloring dye as a powder, there is almost no oxidative deterioration, and since it is a method specified by the water supply method, it was selected as a comparison target with the examples. The results are shown in Tables 2 and 3.
表2から、SAT−3を配合した組成物を5〜50℃で120日保存した場合、残留塩素濃度の測定に際して、波長655nmにおける吸光度の上昇がほぼゼロを示し、残留塩素濃度判定値もほぼゼロとなった。このことは、前記組成物は、5〜50℃で120日保存した場合でも保存安定性に極めて優れ、残留塩素濃度の測定に際して、バックグラウンドの上昇をほぼゼロにできること示している。また、表3から、SAT−3を用いる方法で得られた残留塩素濃度判定値と、DPD法により得られた残留塩素濃度判定値との差は保存温度によらずほぼ一致していた。したがって、SAT−3を配合した組成物によれば、5〜50℃で120日保存した場合でも、検水中の残留塩素濃度を精度良く測定できることが分かった。 From Table 2, when the composition containing SAT-3 was stored at 5 to 50 ° C. for 120 days, when measuring the residual chlorine concentration, the increase in absorbance at a wavelength of 655 nm showed almost zero, and the residual chlorine concentration judgment value was almost the same. It became zero. This indicates that the composition is extremely excellent in storage stability even when stored at 5 to 50 ° C. for 120 days, and the background increase can be made almost zero when measuring the residual chlorine concentration. Further, from Table 3, the difference between the residual chlorine concentration judgment value obtained by the method using SAT-3 and the residual chlorine concentration judgment value obtained by the DPD method was almost the same regardless of the storage temperature. Therefore, according to the composition which mix | blended SAT-3, even when it preserve | saved at 5-50 degreeC for 120 days, it turned out that the residual chlorine density | concentration in test water can be measured with a sufficient precision.
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