JP2021154220A - Water treatment agent composition and water treatment method - Google Patents
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011630 iodine Substances 0.000 claims abstract description 47
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 47
- 239000007800 oxidant agent Substances 0.000 claims abstract description 42
- 230000001590 oxidative effect Effects 0.000 claims abstract description 28
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002455 scale inhibitor Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims description 57
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 41
- 150000003839 salts Chemical class 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 150000001340 alkali metals Chemical group 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 8
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 claims description 7
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 230000001629 suppression Effects 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920006027 ternary co-polymer Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000855 fungicidal effect Effects 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- -1 isothiazolone compound Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- MEUIIHOXOWVKNP-UHFFFAOYSA-N phosphanylformic acid Chemical compound OC(P)=O MEUIIHOXOWVKNP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000004436 sodium atom Chemical group 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(C)C(C)(*)C(N*)=O Chemical compound CC(C)(C)C(C)(*)C(N*)=O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 101000597273 Homo sapiens PHD finger protein 11 Proteins 0.000 description 1
- 101000935642 Homo sapiens Phosphoinositide 3-kinase adapter protein 1 Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100025312 Protein BCAP Human genes 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、水系の生物付着等を抑制するための水処理剤組成物、および、その水処理剤組成物を用いた水処理方法に関する。 The present invention relates to a water treatment agent composition for suppressing biofouling of an aqueous system, and a water treatment method using the water treatment agent composition.
冷却水系、冷温水系、純水製造工程水系、排水回収工程水系、紙パルプ工程水系、集塵水系等の様々な水系において、菌類や藻類等に起因する様々な障害が発生することがある。例えば、冷却水系等においては、熱交換器内等でのスライム発生による熱交換率の低下や、配管等のスライム堆積下部で発生する微生物腐食等の障害が知られている。 Various disorders caused by fungi, algae, etc. may occur in various water systems such as cooling water system, cold / hot water system, pure water production process water system, wastewater recovery process water system, paper pulp process water system, and dust collecting water system. For example, in a cooling water system or the like, it is known that the heat exchange rate decreases due to the generation of slime in a heat exchanger or the like, and that microbial corrosion occurs in the lower part of slime deposits such as pipes.
このような菌類や藻類等に起因する障害を抑制する方法としては、殺菌剤組成物を水系に添加する方法が一般に用いられている。殺菌剤としては、イソチアゾロン化合物等の有機系の殺菌剤や、次亜塩素酸等の酸化剤系の殺菌剤等が用いられている。このうち、殺菌効果、コスト等の点から、酸化剤系の殺菌剤組成物が有利となる場合が多く、そのため、これら酸化剤系の殺菌剤組成物は様々な水系において広く使用されている。酸化剤系の殺菌剤組成物の例としては、特許文献１，２のようなクロロスルファミン酸が知られている。 As a method for suppressing damage caused by such fungi, algae and the like, a method of adding a fungicide composition to an aqueous system is generally used. As the disinfectant, an organic disinfectant such as an isothiazolone compound, an oxidizing disinfectant such as hypochlorous acid, and the like are used. Of these, oxidant-based bactericidal compositions are often advantageous in terms of bactericidal effect, cost, and the like, and therefore, these oxidant-based bactericidal compositions are widely used in various water systems. Chlorosulfamic acid as in Patent Documents 1 and 2 is known as an example of an oxidant-based bactericidal composition.
これらの酸化剤系の殺菌剤組成物とスケール抑制剤とを併せて使用する場合、複数の薬液タンクと送液ポンプが必要となり、管理に手間が掛かる問題があった。また、酸化剤系の殺菌剤組成物とスケール抑制剤とを適切な比率で水系に供給する必要があり、例えば酸化剤系の殺菌剤組成物がスケール抑制剤と比べて過剰に添加された場合、その酸化力によりスケール抑制剤が分解し、スケールが発生してしまうおそれがあった。 When these oxidant-based disinfectant compositions and scale inhibitors are used in combination, a plurality of chemical liquid tanks and liquid feed pumps are required, which causes a problem that management is troublesome. Further, it is necessary to supply the oxidant-based fungicide composition and the scale inhibitor in an appropriate ratio to the aqueous system. For example, when the oxidant-based fungicide composition is excessively added as compared with the scale inhibitor. , There was a risk that the scale inhibitor would decompose due to its oxidizing power and scale would be generated.
このため、酸化力の高い酸化剤系の殺菌剤組成物と、スケール抑制剤とができるだけ一定の割合で水系に供給されることが望ましく、酸化剤系の殺菌剤組成物とスケール抑制剤とを一剤化することが最も望ましい。 Therefore, it is desirable that the oxidant-based bactericidal composition having high oxidizing power and the scale inhibitor are supplied to the aqueous system at a constant ratio as much as possible, and the oxidant-based bactericidal composition and the scale inhibitor are used. It is most desirable to make it a single agent.
例えば、特許文献３では、次亜塩素酸ナトリウム等の塩素系酸化剤と、スルファミン酸化合物と、スケール抑制剤であるアニオン性ポリマとを含有してなり、ｐＨ１２以上である一剤化のスライム防止用組成物を提示している。しかしながら、特許文献３のスライム防止用組成物では、塩素系酸化剤とスルファミン酸とを反応させ、クロロスルファミン酸として安定化させているため、組成物の安定性は増すものの、スライム抑制剤の酸化力、すなわちスライム抑制性能が著しく低下してしまう問題があった。 For example, in Patent Document 3, a chlorine-based oxidizing agent such as sodium hypochlorite, a sulfamic acid compound, and an anionic polymer which is a scale inhibitor are contained, and a single agent slime prevention having a pH of 12 or more is prevented. The composition for use is presented. However, in the slime prevention composition of Patent Document 3, since the chlorine-based oxidizing agent and sulfamic acid are reacted and stabilized as chlorosulfamic acid, the stability of the composition is increased, but the oxidation of the slime inhibitor There is a problem that the force, that is, the slime suppression performance is remarkably lowered.
本発明の目的は、酸化剤系殺菌組成物のスライム抑制性能の著しい低下を抑制しつつ、スケール抑制剤を配合した一剤化された水処理剤組成物、およびその水処理剤組成物を用いた水処理方法を提供することにある。 An object of the present invention is to use a one-part water treatment agent composition containing a scale inhibitor while suppressing a significant decrease in slime suppression performance of an oxidizing agent-based bactericidal composition, and a water treatment agent composition thereof. It is to provide a water treatment method that has been used.
本発明は、ヨウ素系酸化剤と、ヨウ化物およびアルカリ剤のうちの少なくとも１つと、スケール抑制剤と、を含む、水処理剤組成物である。 The present invention is a water treatment agent composition containing an iodine-based oxidizing agent, at least one of an iodide and an alkaline agent, and a scale inhibitor.
前記水処理剤組成物において、前記スケール抑制剤は、式（１）の単量体単位を含む重合体、式（２）の単量体単位を含む重合体、式（１）の単量体単位と式（３）の単量体単位とを含む共重合体、式（１）の単量体単位と式（３）の単量体単位と式（４）の単量体単位とを含む共重合体、式（２）の単量体単位と式（５）の単量体単位と式（６）の単量体単位とを含む共重合体、式（７）のホスフィノカルボン酸共重合体、式（８）のビス（ポリ−２−カルボキシエチル）ホスフィン酸、式（９）の２−ホスホノブタン−１，２，４−トリカルボン酸およびその塩、式（１０）の１−ヒドロキシエチリデン−１，１−ジホスホン酸およびその塩のうちの少なくとも１つであることが好ましい。
（式（１）中、Ｒ１は水素原子またはメチル基を表し、Ｘ１は水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）
（式（２）中、Ｒ２とＲ３はそれぞれ独立に水素原子またはメチル基を表し、Ｘ２とＸ３はそれぞれ独立に水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）
（式（３）中、Ｒ４は水素原子またはメチル基を表し、Ｘ４は炭素数１〜１０のアルキルスルホン酸基もしくはその塩、または、炭素数６〜１０のアリールスルホン酸基もしくはその塩を表し、塩の場合は１価もしくは２価の金属塩、アンモニウム塩または有機アンモニウム塩である。）
（式（４）中、Ｒ５は水素原子またはメチル基を表し、Ｘ５とＸ６はそれぞれ独立に水素原子または炭素数１〜１０のアルキル基を表すが、少なくとも一方が炭素数１〜１０のアルキル基である。）
（式（５）中、Ｒ６は水素原子またはメチル基を表し、Ｘ７は炭素数１〜１０のアルキル基である。）
（式（６）中、Ｒ７は水素原子またはメチル基を表し、Ｘ８は炭素数１〜１０のアルキル基である。）
（式（７）中、Ｙは、水素原子またはアルカリ金属原子を表し、Ｚは、−ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３Ｎａを表し、ｈ，ｌ，ｍ，ｎはそれぞれ０または正の整数であり、ｈ＋ｌ＋ｍ＋ｎは、１〜１００の整数である。）
（式（８）中、Ｙは、水素原子またはアルカリ金属原子を表し、ｍ，ｎはそれぞれ０または正の整数であり、ｍ＋ｎは、１〜１００の整数である。）
（式（９）中、Ｙ１およびＹ２は、それぞれ独立に水素原子またはアルカリ金属原子を表す。）
（式（１０）中、Ｙ３およびＹ４は、それぞれ独立に水素原子またはアルカリ金属原子を表す。）
In the water treatment agent composition, the scale inhibitor is a polymer containing a monomer unit of the formula (1), a polymer containing a monomer unit of the formula (2), and a monomer of the formula (1). A copolymer containing a unit and a monomer unit of the formula (3), a monomer unit of the formula (1), a monomer unit of the formula (3), and a monomer unit of the formula (4). A copolymer containing a monomer unit of the formula (2), a monomer unit of the formula (5), and a monomer unit of the formula (6), and a phosphinocarboxylic acid of the formula (7). Polymer, bis (poly-2-carboxyethyl) phosphinic acid of formula (8), 2-phosphonobutane-1,2,4-tricarboxylic acid of formula (9) and salts thereof, 1-hydroxyethylidene of formula (10). It is preferably at least one of -1,1-diphosphonic acid and a salt thereof.
(In formula (1), R 1 represents a hydrogen atom or a methyl group, and X 1 represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group or an organic ammonium group.)
(In formula (2), R 2 and R 3 independently represent a hydrogen atom or a methyl group, and X 2 and X 3 independently represent a hydrogen atom, a monovalent or divalent metal atom, an ammonium group or an organic ammonium. Represents a group.)
(In the formula (3), R 4 represents a hydrogen atom or a methyl group, and X 4 is an alkyl sulfonic acid group having 1 to 10 carbon atoms or a salt thereof, or an aryl sulfonic acid group having 6 to 10 carbon atoms or a salt thereof. In the case of a salt, it is a monovalent or divalent metal salt, an ammonium salt or an organic ammonium salt.)
(In formula (4), R 5 represents a hydrogen atom or a methyl group, and X 5 and X 6 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but at least one of them has 1 to 10 carbon atoms. It is an alkyl group of.)
(In formula (5), R 6 represents a hydrogen atom or a methyl group, and X 7 is an alkyl group having 1 to 10 carbon atoms.)
(In formula (6), R 7 represents a hydrogen atom or a methyl group, and X 8 is an alkyl group having 1 to 10 carbon atoms.)
(In formula (7), Y represents a hydrogen atom or an alkali metal atom, Z represents −CONHC (CH 3 ) 2 CH 2 SO 3 Na, and h, l, m, and n are 0 or positive, respectively. It is an integer, and h + l + m + n is an integer of 1 to 100.)
(In formula (8), Y represents a hydrogen atom or an alkali metal atom, m and n are 0 or positive integers, respectively, and m + n is an integer of 1 to 100.)
(In formula (9), Y 1 and Y 2 independently represent a hydrogen atom or an alkali metal atom, respectively.)
(In formula (10), Y 3 and Y 4 independently represent a hydrogen atom or an alkali metal atom, respectively.)
前記水処理剤組成物において、前記水処理剤組成物のｐＨが１２未満であることが好ましい。 In the water treatment agent composition, the pH of the water treatment agent composition is preferably less than 12.
前記水処理剤組成物において、前記ヨウ素系酸化剤および前記ヨウ化物の両方を含む場合、前記ヨウ素系酸化剤に対する、前記ヨウ化物の質量の比率が、１．２以上であることが好ましい。 When both the iodine-based oxidant and the iodide are contained in the water treatment agent composition, the ratio of the mass of the iodide to the iodine-based oxidant is preferably 1.2 or more.
本発明は、前記水処理剤組成物を用いて水を処理する水処理方法である。 The present invention is a water treatment method for treating water using the water treatment agent composition.
本発明によって、酸化剤系殺菌組成物のスライム抑制性能の著しい低下を抑制しつつ、スケール抑制剤を配合した一剤化された水処理剤組成物、およびその水処理剤組成物を用いた水処理方法を提供することができる。 According to the present invention, a single-agent water treatment agent composition containing a scale inhibitor and water using the water treatment agent composition while suppressing a significant decrease in slime suppression performance of the oxidant-based bactericidal composition. A processing method can be provided.
本発明の実施の形態について以下説明する。本実施形態は本発明を実施する一例であって、本発明は本実施形態に限定されるものではない。 Embodiments of the present invention will be described below. The present embodiment is an example of carrying out the present invention, and the present invention is not limited to the present embodiment.
本実施形態に係る水処理剤組成物は、ヨウ素系酸化剤と、ヨウ化物およびアルカリ剤のうちの少なくとも１つと、スケール抑制剤と、を含む組成物である。本実施形態に係る水処理剤組成物は、ヨウ素系酸化剤の溶解性、製剤のｐＨを大幅に上昇させない等の点から、ヨウ素系酸化剤と、ヨウ化物と、アルカリ剤と、スケール抑制剤と、を含むことが好ましい。本実施形態に係る水処理剤組成物は、さらに水を含んでもよい。 The water treatment agent composition according to the present embodiment is a composition containing an iodine-based oxidizing agent, at least one of an iodide and an alkaline agent, and a scale inhibitor. The water treatment agent composition according to the present embodiment has an iodine-based oxidizing agent, an iodide, an alkaline agent, and a scale inhibitor from the viewpoints of solubility of the iodine-based oxidizing agent and not significantly increasing the pH of the preparation. And, preferably. The water treatment agent composition according to the present embodiment may further contain water.
本発明者らは、ヨウ素系酸化剤と、ヨウ化物およびアルカリ剤のうちの少なくとも１つとを、スケール抑制剤と配合することによって、酸化剤系殺菌組成物のスライム抑制性能の著しい低下（すなわち、酸化力の著しい低下）を抑制しつつ、スケール抑制剤を配合した一剤化された水処理剤組成物が得られることを見出した。また、本実施形態に係る水処理剤組成物を用いると、被処理水に添加しても被処理水のｐＨを大幅に上昇させない。 By blending an iodine-based oxidizing agent and at least one of an iodide and an alkaline agent with a scale inhibitor, the present inventors significantly reduce the slime suppressing performance of the oxidizing agent-based bactericidal composition (that is,). It has been found that a single-agent water treatment agent composition containing a scale inhibitor can be obtained while suppressing (significant decrease in oxidizing power). Further, when the water treatment agent composition according to the present embodiment is used, the pH of the water to be treated is not significantly increased even if it is added to the water to be treated.
ヨウ素系酸化剤としては、ヨウ素（Ｉ２）、ヨウ素酸塩、過ヨウ素酸塩等が挙げられる。これらのうち、ヨウ素が、殺菌性能、コスト等の観点から好ましい。 Examples of the iodine-based oxidizing agent include iodine (I 2 ), iodate, and periodate. Of these, iodine is preferable from the viewpoint of sterilization performance, cost and the like.
ヨウ化物としては、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化リチウム、ヨウ化アンモニウムおよびヨウ化水素酸等が挙げられる。これらのうち、溶解性等の点から、ヨウ化カリウムが好ましい。 Examples of the iodide include sodium iodide, potassium iodide, lithium iodide, ammonium iodide, hydroiodic acid and the like. Of these, potassium iodide is preferable from the viewpoint of solubility and the like.
アルカリ剤としては、水酸化ナトリウム、水酸化カリウム等の水酸化アルカリ、炭酸ナトリウム、炭酸カリウム等の炭酸アルカリ等が挙げられる。これらのうち、水酸化アルカリが好ましく、ヨウ素系酸化剤の溶解性等の点から、水酸化カリウムが好ましい。また、アルカリ剤は、固形でなく、水溶液として用いてもよい。 Examples of the alkaline agent include alkali hydroxides such as sodium hydroxide and potassium hydroxide, and alkali carbonates such as sodium carbonate and potassium carbonate. Of these, alkali hydroxide is preferable, and potassium hydroxide is preferable from the viewpoint of solubility of an iodine-based oxidizing agent and the like. Moreover, the alkaline agent may be used as an aqueous solution instead of a solid.
ヨウ化物およびアルカリ剤のうち、ヨウ素系酸化剤の溶解性等の点から、ヨウ化カリウム等のヨウ化物が好ましく、ヨウ化物およびアルカリ剤の両者を含むことがより好ましい。 Of the iodide and the alkaline agent, an iodide such as potassium iodide is preferable from the viewpoint of solubility of the iodine-based oxidizing agent, and it is more preferable to contain both the iodide and the alkaline agent.
スケール抑制剤としては、例えば、下記式（１）の単量体単位を含む重合体、下記式（２）の単量体単位を含む重合体、下記式（１）の単量体単位と下記式（３）の単量体単位とを含む共重合体、下記式（１）の単量体単位と下記式（３）の単量体単位と下記式（４）の単量体単位とを含む共重合体、下記式（２）の単量体単位と下記式（５）の単量体単位と下記式（６）の単量体単位とを含む共重合体、下記式（７）のホスフィノカルボン酸共重合体、下記式（８）のビス（ポリ−２−カルボキシエチル）ホスフィン酸、下記式（９）の２−ホスホノブタン−１，２，４−トリカルボン酸およびその塩、下記式（１０）の１−ヒドロキシエチリデン−１，１−ジホスホン酸およびその塩、アミノトリメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸等が挙げられる。 Examples of the scale inhibitor include a polymer containing a monomer unit of the following formula (1), a polymer containing a monomer unit of the following formula (2), a monomer unit of the following formula (1) and the following. A polymer containing the monomer unit of the formula (3), the monomer unit of the following formula (1), the monomer unit of the following formula (3), and the monomer unit of the following formula (4). A copolymer containing, a polymer containing a monomer unit of the following formula (2), a monomer unit of the following formula (5), and a monomer unit of the following formula (6), of the following formula (7) Phosphinocarboxylic acid copolymer, bis (poly-2-carboxyethyl) phosphinic acid of the following formula (8), 2-phosphonobutane-1,2,4-tricarboxylic acid of the following formula (9) and a salt thereof, the following formula Examples of (10) 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and the like can be mentioned.
スケール抑制剤としては、下記式（１）の単量体単位からなる重合体、下記式（２）の単量体単位からなる重合体、下記式（１）の単量体単位と下記式（３）の単量体単位とからなる二元共重合体、下記式（１）の単量体単位と下記式（３）の単量体単位と下記式（４）の単量体単位とからなる三元共重合体、下記式（２）の単量体単位と下記式（５）の単量体単位と下記式（６）の単量体単位とを含む三元共重合体、下記式（７）のホスフィノカルボン酸共重合体、下記式（８）のビス（ポリ−２−カルボキシエチル）ホスフィン酸、下記式（９）の２−ホスホノブタン−１，２，４−トリカルボン酸およびその塩、下記式（１０）の１−ヒドロキシエチリデン−１，１−ジホスホン酸およびその塩が好ましい。 Examples of the scale inhibitor include a polymer composed of the monomer unit of the following formula (1), a polymer composed of the monomer unit of the following formula (2), the monomer unit of the following formula (1) and the following formula ( From a binary copolymer composed of the monomer unit of 3), the monomer unit of the following formula (1), the monomer unit of the following formula (3), and the monomer unit of the following formula (4). A ternary copolymer comprising the monomer unit of the following formula (2), the monomer unit of the following formula (5), and the monomer unit of the following formula (6), the following formula The phosphinocarboxylic acid copolymer of (7), the bis (poly-2-carboxyethyl) phosphinic acid of the following formula (8), the 2-phosphonobutane-1,2,4-tricarboxylic acid of the following formula (9) and the like thereof. Salts, 1-hydroxyethylidene-1,1-diphosphonic acid of the following formula (10) and salts thereof are preferable.
これらのうち、下記式（１）の単量体単位を含む重合体、下記式（２）の単量体単位を含む重合体、下記式（１）の単量体単位と下記式（３）の単量体単位とを含む共重合体、下記式（１）の単量体単位と下記式（３）の単量体単位と下記式（４）の単量体単位とを含む共重合体、下記式（２）の単量体単位と下記式（５）の単量体単位と下記式（６）の単量体単位とを含む共重合体、下記式（７）のホスフィノカルボン酸共重合体、下記式（８）のビス（ポリ−２−カルボキシエチル）ホスフィン酸、下記式（９）の２−ホスホノブタン−１，２，４−トリカルボン酸およびその塩、下記式（１０）の１−ヒドロキシエチリデン−１，１−ジホスホン酸およびその塩は、通常、スケール抑制剤としての機能の他に、鉄系金属用の金属防食剤としても機能する。 Among these, a polymer containing a monomer unit of the following formula (1), a polymer containing a monomer unit of the following formula (2), a monomer unit of the following formula (1) and the following formula (3) Polymer containing the above-mentioned monomer unit, the following formula (1), the following formula (3), and the following formula (4). , A copolymer containing a monomer unit of the following formula (2), a monomer unit of the following formula (5), and a monomer unit of the following formula (6), and a phosphinocarboxylic acid of the following formula (7). Copolymer, bis (poly-2-carboxyethyl) phosphinic acid of the following formula (8), 2-phosphonobutane-1,2,4-tricarboxylic acid of the following formula (9) and a salt thereof, of the following formula (10) 1-Hydroxyethylidene-1,1-diphosphonic acid and salts thereof usually function not only as a scale inhibitor but also as a metal anticorrosive agent for iron-based metals.
（式（１）中、Ｒ１は水素原子またはメチル基を表し、Ｘ１は水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）
(In formula (1), R 1 represents a hydrogen atom or a methyl group, and X 1 represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group or an organic ammonium group.)
（式（２）中、Ｒ２とＲ３はそれぞれ独立に水素原子またはメチル基を表し、Ｘ２とＸ３はそれぞれ独立に水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）
(In formula (2), R 2 and R 3 independently represent a hydrogen atom or a methyl group, and X 2 and X 3 independently represent a hydrogen atom, a monovalent or divalent metal atom, an ammonium group or an organic ammonium. Represents a group.)
（式（３）中、Ｒ４は水素原子またはメチル基を表し、Ｘ４は炭素数１〜１０のアルキルスルホン酸基もしくはその塩、または、炭素数６〜１０のアリールスルホン酸基もしくはその塩を表し、塩の場合は１価もしくは２価の金属塩、アンモニウム塩または有機アンモニウム塩である。）
(In the formula (3), R 4 represents a hydrogen atom or a methyl group, and X 4 is an alkyl sulfonic acid group having 1 to 10 carbon atoms or a salt thereof, or an aryl sulfonic acid group having 6 to 10 carbon atoms or a salt thereof. In the case of a salt, it is a monovalent or divalent metal salt, an ammonium salt or an organic ammonium salt.)
（式（４）中、Ｒ５は水素原子またはメチル基を表し、Ｘ５とＸ６はそれぞれ独立に水素原子または炭素数１〜１０のアルキル基を表すが、少なくとも一方が炭素数１〜１０のアルキル基である。）
(In formula (4), R 5 represents a hydrogen atom or a methyl group, and X 5 and X 6 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but at least one of them has 1 to 10 carbon atoms. It is an alkyl group of.)
（式（５）中、Ｒ６は水素原子またはメチル基を表し、Ｘ７は炭素数１〜１０のアルキル基である。）
(In formula (5), R 6 represents a hydrogen atom or a methyl group, and X 7 is an alkyl group having 1 to 10 carbon atoms.)
（式（６）中、Ｒ７は水素原子またはメチル基を表し、Ｘ８は炭素数１〜１０のアルキル基である。）
(In formula (6), R 7 represents a hydrogen atom or a methyl group, and X 8 is an alkyl group having 1 to 10 carbon atoms.)
（式（７）中、Ｙは、水素原子またはアルカリ金属原子を表し、Ｚは、−ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３Ｎａを表し、ｈ，ｌ，ｍ，ｎはそれぞれ０または正の整数であり、ｈ＋ｌ＋ｍ＋ｎは、１〜１００の整数である。）
(In formula (7), Y represents a hydrogen atom or an alkali metal atom, Z represents −CONHC (CH 3 ) 2 CH 2 SO 3 Na, and h, l, m, and n are 0 or positive, respectively. It is an integer, and h + l + m + n is an integer of 1 to 100.)
（式（８）中、Ｙは、水素原子またはアルカリ金属原子を表し、ｍ，ｎはそれぞれ０または正の整数であり、ｍ＋ｎは、１〜１００の整数である。）
(In formula (8), Y represents a hydrogen atom or an alkali metal atom, m and n are 0 or positive integers, respectively, and m + n is an integer of 1 to 100.)
（式（９）中、Ｙ１およびＹ２は、それぞれ独立に水素原子またはアルカリ金属原子を表す。）
(In formula (9), Y 1 and Y 2 independently represent a hydrogen atom or an alkali metal atom, respectively.)
（式（１０）中、Ｙ３およびＹ４は、それぞれ独立に水素原子またはアルカリ金属原子を表す。）
(In formula (10), Y 3 and Y 4 independently represent a hydrogen atom or an alkali metal atom, respectively.)
なお、式（１）〜（３）における有機アンモニウム塩としては、例えば、炭素原子数が１〜４のアルキル基またはヒドロキシアルキル基を有するアルキルアンモニウム基または（ヒドロキシ）アルキルアンモニウム基が好ましい。 As the organic ammonium salt in the formulas (1) to (3), for example, an alkylammonium group or a (hydroxy) alkylammonium group having an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group is preferable.
式（１）〜（３）における１価もしくは２価の金属塩としては、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩等が挙げられる。 Examples of the monovalent or divalent metal salt in the formulas (1) to (3) include sodium salt, potassium salt, calcium salt, magnesium salt and the like.
式（３）におけるＸ４がアルキルスルホン酸基もしくはその塩である場合のアルキル基としては、炭素原子数が１〜８のアルキル基が好ましい。Ｘ４がアリールスルホン酸基もしくはその塩である場合のアリール基としては、炭素原子数が６〜１０のアリール基またはアリールアルキル基が好ましい。 When X 4 in the formula (3) is an alkyl sulfonic acid group or a salt thereof, the alkyl group preferably has an alkyl group having 1 to 8 carbon atoms. When X 4 is an aryl sulfonic acid group or a salt thereof, the aryl group is preferably an aryl group having 6 to 10 carbon atoms or an arylalkyl group.
式（４）〜（６）におけるアルキル基としては、炭素原子数が１〜８のアルキル基が好ましい。 As the alkyl group in the formulas (4) to (6), an alkyl group having 1 to 8 carbon atoms is preferable.
式（１）の単量体単位と式（３）の単量体単位とからなる二元共重合体における単量体単位の重量比率としては、１〜９９：９９〜１であることが好ましい。 The weight ratio of the monomer unit in the binary copolymer composed of the monomer unit of the formula (1) and the monomer unit of the formula (3) is preferably 1 to 99: 99 to 1. ..
式（１）の単量体単位と式（３）の単量体単位と式（４）の単量体単位とからなる三元共重合体における単量体単位の重量比率としては、１〜９８：１〜９８：１〜９８であることが好ましい。 The weight ratio of the monomer unit in the ternary copolymer composed of the monomer unit of the formula (1), the monomer unit of the formula (3) and the monomer unit of the formula (4) is 1 to 1. It is preferably 98: 1 to 98: 1 to 98.
式（２）の単量体単位と式（５）の単量体単位と式（６）の単量体単位とからなる三元共重合体における単量体単位の重量比率としては、１〜９８：１〜９８：１〜９８であることが好ましい。 The weight ratio of the monomer unit in the ternary copolymer composed of the monomer unit of the formula (2), the monomer unit of the formula (5) and the monomer unit of the formula (6) is 1 to 1. It is preferably 98: 1 to 98: 1 to 98.
式（１）〜（６）の単量体単位を含む重合体の重量平均分子量は、５００〜１００，０００の範囲が好ましい。重量平均分子量が５００未満あるいは１００，０００を超えると、スケール抑制性能が低下する場合がある。 The weight average molecular weight of the polymer containing the monomer units of the formulas (1) to (6) is preferably in the range of 500 to 100,000. If the weight average molecular weight is less than 500 or more than 100,000, the scale suppression performance may be deteriorated.
式（７）のホスフィノカルボン酸共重合体の重量平均分子量は、５００〜１００，０００の範囲が好ましい。重量平均分子量が５００未満あるいは１００，０００を超えると、スケール抑制性能が低下する場合がある。式（８）のビス（ポリ−２−カルボキシエチル）ホスフィン酸の重量平均分子量は、５００〜１００，０００の範囲が好ましい。重量平均分子量が５００未満あるいは１００，０００を超えると、スケール抑制性能が低下する場合がある。 The weight average molecular weight of the phosphinocarboxylic acid copolymer of the formula (7) is preferably in the range of 500 to 100,000. If the weight average molecular weight is less than 500 or more than 100,000, the scale suppression performance may be deteriorated. The weight average molecular weight of the bis (poly-2-carboxyethyl) phosphinic acid of the formula (8) is preferably in the range of 500 to 100,000. If the weight average molecular weight is less than 500 or more than 100,000, the scale suppression performance may be deteriorated.
式（７），（８），（９），（１０）におけるアルカリ金属原子としては、ナトリウム原子、カリウム原子が好ましく、ナトリウム原子がより好ましい。式（９）のＹ１およびＹ２が水素原子である２−ホスホノブタン−１，２，４−トリカルボン酸は、以下の化合物である。
式（１０）のＹ３およびＹ４が水素原子である１−ヒドロキシエチリデン−１，１−ジホスホン酸は、以下の化合物である。
本実施形態に係る水処理剤組成物に含まれる全ヨウ素濃度は、組成物全体の量に対して０．７重量％〜５．０重量％の範囲であることが好ましい。全ヨウ素濃度が組成物全体の量に対して０．７重量％未満であると、生物付着の制御に劣る場合があり、５．０重量％を超えると、保存性等の製剤安定性が損なわれる場合がある。 The total iodine concentration contained in the water treatment agent composition according to the present embodiment is preferably in the range of 0.7% by weight to 5.0% by weight with respect to the total amount of the composition. If the total iodine concentration is less than 0.7% by weight based on the total amount of the composition, the control of biofouling may be inferior, and if it exceeds 5.0% by weight, the pharmaceutical stability such as storage stability is impaired. May occur.
本実施形態に係る水処理剤組成物の製剤ｐＨは、１２未満であることが好ましく、３以上１２未満の範囲であることがより好ましく、５以上１０以下の範囲がさらに好ましい。製剤ｐＨが１２以上であると、被処理水のｐＨが上昇しスケール成分が析出しやすくなる。また、製剤ｐＨが３未満であると、被処理水のｐＨが低下し鉄系や銅系金属が腐食しやすくなる。 The pharmaceutical pH of the water treatment agent composition according to the present embodiment is preferably less than 12, more preferably 3 or more and less than 12, and even more preferably 5 or more and 10 or less. When the pH of the preparation is 12 or more, the pH of the water to be treated rises and scale components are likely to precipitate. Further, when the pH of the preparation is less than 3, the pH of the water to be treated is lowered and iron-based and copper-based metals are easily corroded.
本実施形態に係る水処理剤組成物において、ヨウ素系酸化剤およびヨウ化物の両方を含む場合、ヨウ素系酸化剤に対する、ヨウ化物の質量の比率（ヨウ化物／ヨウ素系酸化剤）は、１．０以上であることが好ましく、１．２以上であることがより好ましく、１．７以上５．０以下であることがさらに好ましい。上記比率が１．０未満であると、不溶化物の量が増える場合があり、５．０を超えると、配合量に見合うほどの製剤安定化効果が得られず不経済になる場合がある。 When both the iodine-based oxidant and the iodide are contained in the water treatment agent composition according to the present embodiment, the ratio of the mass of the iodide to the iodine-based oxidant (iodine / iodine-based oxidant) is 1. It is preferably 0 or more, more preferably 1.2 or more, and further preferably 1.7 or more and 5.0 or less. If the above ratio is less than 1.0, the amount of the insoluble matter may increase, and if it exceeds 5.0, the formulation stabilizing effect commensurate with the blending amount may not be obtained, which may be uneconomical.
本実施形態に係る水処理剤組成物において、ヨウ素系酸化剤およびヨウ化物の両方を含む場合、ヨウ素系酸化剤とヨウ化物との和に対するアルカリ剤の質量の比率［アルカリ剤／（ヨウ素系酸化剤＋ヨウ化物）］は、製剤中のヨウ素保存安定性を向上させるため、０．４未満であることが好ましく、０．３未満であることがより好ましい。上記比率が０．４を超えると、ヨウ素系酸化剤成分の無効消費量が増え、また、製剤の保存中にヨウ素濃度が低下してしまう場合がある。 When both the iodine-based oxidizing agent and the iodide are contained in the water treatment agent composition according to the present embodiment, the ratio of the mass of the alkaline agent to the sum of the iodine-based oxidizing agent and the iodide [alkali agent / (iodine-based oxidation). Agent + iodide)] is preferably less than 0.4, more preferably less than 0.3, in order to improve the iodine storage stability in the formulation. If the above ratio exceeds 0.4, the ineffective consumption of the iodine-based oxidant component increases, and the iodine concentration may decrease during the storage of the pharmaceutical product.
本実施形態に係る水処理剤組成物において、ヨウ化物およびアルカリ剤のうちアルカリ剤のみを含む場合、水処理剤組成物の製剤直後のｐＨが８．４以上１０．０以下であることが好ましく、９．０以上９．７以下であることがより好ましい。上記ｐＨが８．４未満であると、不溶化物の量が増える場合があり、１０．０を超えると、製剤中のヨウ素濃度が低下する場合がある。 When the water treatment agent composition according to the present embodiment contains only the alkaline agent among the iodide and the alkaline agent, the pH immediately after the preparation of the water treatment agent composition is preferably 8.4 or more and 10.0 or less. , 9.0 or more and 9.7 or less is more preferable. If the pH is less than 8.4, the amount of insoluble matter may increase, and if it exceeds 10.0, the iodine concentration in the preparation may decrease.
＜水処理剤組成物の製造方法＞
本実施形態に係る水処理剤組成物は、例えば、ヨウ素系酸化剤と、ヨウ化物およびアルカリ剤のうちの少なくとも１つと、スケール抑制剤とを混合することにより得られ、例えば、ヨウ素系酸化剤と、ヨウ化物およびアルカリ剤のうちの少なくとも１つと、スケール抑制剤と、水とを混合することにより得られる。
<Manufacturing method of water treatment agent composition>
The water treatment agent composition according to the present embodiment is obtained by mixing, for example, an iodine-based oxidizing agent, at least one of an iodide and an alkaline agent, and a scale inhibitor, for example, an iodine-based oxidizing agent. And at least one of iodide and alkaline agents, scale inhibitors and water.
＜水処理剤組成物を用いた水処理方法＞
本実施形態に係る水処理剤組成物は、冷却水系、冷温水系、純水製造工程水系、排水回収工程水系、紙パルプ工程水系、集塵水系等の様々な水系において、用いることができる。本実施形態に係る水処理剤組成物は、例えば、冷却水等の工業用水システムの水処理や、生物付着汚染の進んだ配管洗浄等の水処理方法等に用いることができる。
<Water treatment method using a water treatment agent composition>
The water treatment agent composition according to the present embodiment can be used in various water systems such as a cooling water system, a cold / hot water system, a pure water production process water system, a wastewater recovery process water system, a paper pulp process water system, and a dust collecting water system. The water treatment agent composition according to the present embodiment can be used, for example, for water treatment of industrial water systems such as cooling water, water treatment methods such as pipe cleaning with advanced biofouling and contamination.
本実施形態に係る水処理剤組成物を添加した水系における全ヨウ素濃度は、０．１〜１５０ｍｇ／Ｌであることが好ましい。水処理剤組成物を添加した水系における全ヨウ素濃度が０．１ｍｇ／Ｌ未満であると、十分なスライム抑制効果を得ることができない場合があり、１５０ｍｇ／Ｌより多いと、系内の金属材質を腐食させる場合がある。 The total iodine concentration in the water system to which the water treatment agent composition according to the present embodiment is added is preferably 0.1 to 150 mg / L. If the total iodine concentration in the water system to which the water treatment agent composition is added is less than 0.1 mg / L, a sufficient slime suppressing effect may not be obtained, and if it is more than 150 mg / L, the metal material in the system. May corrode.
以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
＜実施例１〜１８＞
実施例については、表１〜表４に示す配合組成（重量％）および順番で添加（表の上から順番に添加）して製剤化を行った。製剤化は、ＰＴＦＥ（ポリテトラフルオロエチレン）製の容器内で、室温（２５℃）以下に冷却し、スターラで撹拌しながら各薬剤を添加して行った。
<Examples 1 to 18>
Examples were formulated by adding the compounding compositions (% by weight) shown in Tables 1 to 4 in order (added in order from the top of the table). The formulation was carried out in a container made of PTFE (polytetrafluoroethylene), cooled to room temperature (25 ° C.) or lower, and each drug was added while stirring with a stirrer.
表１〜表４において、「ＰＡＡ」は、アクリル酸単独重合体（重量平均分子量約４，５００）、「ＡＡＢＩ」は、アクリル酸と、２−アクリルアミド−２−メチルプロパンスルホン酸のアクリル酸系二元共重合体（重量平均分子量約４，５００）、「ＡＡＴＥＲ」は、アクリル酸と、２−アクリルアミド−２−メチルプロパンスルホン酸と、アルキルアクリルアミドのアクリル酸系三元共重合体（重量平均分子量約４，５００）、「ＰＭＡＡ」は、マレイン酸単独重合体（重量平均分子量約１，０００）、「ＰＭＡＶＡ」は、マレイン酸と、アクリル酸エチルと、ビニルアセテートのマレイン酸系三元重合体（重量平均分子量約１，０００）である。「ＰＣＡＢＩ」は、式（７）のホスフィノカルボン酸共重合体（ｈ＋ｌ＋ｍ＋ｎの平均値が約１６）、「ＢＣＡＰ」は、式（８）のビス（ポリ−２−カルボキシエチル）ホスフィン酸（ｍ＋ｎの平均値が約１６）、「ＰＢＴＣ」は、２−ホスホノブタン−１，２，４−トリカルボン酸、「ＨＥＤＰ」は、１−ヒドロキシエチリデン−１，１−ジホスホン酸である。水酸化カリウムは、関東化学社製の特級試薬、ヨウ化カリウムとヨウ素は、富士フィルム和光純薬社製の特級試薬を用いた。 In Tables 1 to 4, "PAA" is an acrylic acid homopolymer (weight average molecular weight of about 4,500), and "AABI" is an acrylic acid system of acrylic acid and 2-acrylamide-2-methylpropanesulfonic acid. Binary copolymer (weight average molecular weight about 4,500), "AATER" is an acrylic acid-based ternary copolymer of acrylic acid, 2-acrylamide-2-methylpropansulfonic acid, and alkylacrylamide (weight average). Molecular weight of about 4,500), "PMAA" is a maleic acid homopolymer (weight average molecular weight of about 1,000), and "PMAVA" is a maleic acid-based ternary weight of maleic acid, ethyl acrylate, and vinyl acetate. It is a coalescence (weight average molecular weight of about 1,000). "PCABI" is a phosphinocarboxylic acid copolymer of formula (7) (the average value of h + l + m + n is about 16), and "BCAP" is bis (poly-2-carboxyethyl) phosphinic acid (m + n) of formula (8). "PBTC" is 2-phosphonobutane-1,2,4-tricarboxylic acid, and "HEDP" is 1-hydroxyethylidene-1,1-diphosphonic acid. For potassium hydroxide, a special grade reagent manufactured by Kanto Chemical Co., Inc. was used, and for potassium iodide and iodine, a special grade reagent manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was used.
なお、ｐＨの測定は、以下の条件で行った。
電極タイプ：ガラス電極式
ｐＨ測定計：東亜ディーケーケー社製、ＩＯＬ−３０型
電極の校正：関東化学社製フタル酸塩ｐＨ（４．０１）、標準液（第２種）、同社製中性リン酸塩ｐＨ（６．８６）標準液（第２種）の２点校正で行った
測定温度：２５℃
測定値：測定液に電極を浸漬し、安定後の値を測定値とし、３回測定の平均値
The pH was measured under the following conditions.
Electrode type: Glass electrode type pH meter: Toa DKK, IOL-30 type Electrode calibration: Kanto Chemical Co., Ltd. Phosphate pH (4.01), standard solution (type 2), neutral phosphorus manufactured by the same company Measurement temperature performed by two-point calibration of phosphate pH (6.86) standard solution (type 2): 25 ° C.
Measured value: The electrode is immersed in the measuring solution, and the value after stabilization is used as the measured value, which is the average value of three measurements.
実施例において、遊離ハロゲン濃度および全ハロゲン濃度は、試料を１万倍希釈し、ＨＡＣＨ社の多項目水質分析計ＤＲ／３９００を用いて、有効塩素測定法（ＤＰＤ（ジエチル−ｐ−フェニレンジアミン）法）により測定した。なお、遊離ヨウ素濃度および全ヨウ素濃度は、遊離塩素濃度、全塩素濃度として値を求めた後、塩素とヨウ素の分子量から算出した値を用いた。また、各水処理剤組成物について、２５℃、遮光下で１０日間保存したあとの全ヨウ素濃度を測定し、製剤化直後の全ヨウ素濃度に対する残存率を算出した。また、表１，２，３，４の組成物については、不溶化物の有無を目視で確認した。 In the examples, the free halogen concentration and the total halogen concentration were obtained by diluting the sample 10,000 times and using a multi-item water quality analyzer DR / 3900 manufactured by HACH to measure effective chlorine (DPD (diethyl-p-phenylenediamine)). Measured by method). For the free iodine concentration and the total iodine concentration, the values calculated from the molecular weights of chlorine and iodine were used after obtaining the values as the free chlorine concentration and the total chlorine concentration. In addition, the total iodine concentration of each water treatment agent composition after being stored at 25 ° C. in the dark for 10 days was measured, and the residual ratio with respect to the total iodine concentration immediately after the formulation was calculated. Further, with respect to the compositions shown in Tables 1, 2, 3 and 4, the presence or absence of insoluble matter was visually confirmed.
実施例の組成物では、酸化剤系スライム抑制剤であるヨウ素系酸化剤と、特定のポリマとをｐＨ１０未満で配合することにより、無機系スライム抑制剤のスライム抑制性能の著しい低下（酸化力の著しい低下）を抑制しつつ、一剤化することができた。また、表１，２のヨウ素系酸化剤およびヨウ化物の両方を含む組成物については、ヨウ素系酸化剤に対するヨウ化物の質量比が１．２以上である場合に、不溶化物を生成させずにヨウ素系酸化剤とポリマとを一剤化することができ、製剤化直後の全ヨウ素濃度は２．８重量％以上と、高濃度のヨウ素を含有する組成物が得られた。表３，４のヨウ化物およびアルカリ剤のうちアルカリ剤のみを含む組成物については、製剤化直後のｐＨが９．０以上９．７以下の場合に、製剤化直後の全ヨウ素濃度は０．６重量％以上と、高濃度のヨウ素を含有する組成物が得られた。なお、いずれの実施例についても、全ヨウ素における遊離ヨウ素の割合は９０％以上と、酸化力が高い状態のまま一剤化できていることもわかった。 In the composition of the example, by blending an iodine-based oxidizing agent, which is an oxidizing agent-based slime inhibitor, and a specific polymer at a pH of less than 10, the slime suppressing performance of the inorganic slime inhibitor is significantly reduced (oxidizing power). It was possible to make it a single agent while suppressing a significant decrease). Further, for the compositions containing both the iodine-based oxidant and the iodide in Tables 1 and 2, when the mass ratio of the iodide to the iodine-based oxidant is 1.2 or more, insoluble matter is not generated. The iodine-based oxidizing agent and the polymer could be unified, and the total iodine concentration immediately after formulation was 2.8% by weight or more, and a composition containing a high concentration of iodine was obtained. For the compositions containing only the alkaline agent among the iodides and alkaline agents in Tables 3 and 4, when the pH immediately after the formulation is 9.0 or more and 9.7 or less, the total iodine concentration immediately after the formulation is 0. A composition containing a high concentration of iodine, which is 6% by weight or more, was obtained. In each of the examples, the ratio of free iodine to total iodine was 90% or more, and it was also found that the product could be unified with high oxidizing power.
このように、酸化剤系殺菌組成物のスライム抑制性能の著しい低下を抑制しつつ、スケール抑制剤を配合した一剤化された水処理剤組成物が得られ、その水処理剤組成物を用いた水処理方法を提供することができた。
In this way, a single-agent water treatment agent composition containing a scale inhibitor can be obtained while suppressing a significant decrease in slime suppression performance of the oxidant-based bactericidal composition, and the water treatment agent composition is used. We were able to provide the existing water treatment method.
Claims (5)
ヨウ化物およびアルカリ剤のうちの少なくとも１つと、
スケール抑制剤と、
を含むことを特徴とする水処理剤組成物。 Iodine-based oxidizer and
With at least one of the iodide and alkaline agent,
Scale inhibitor and
A water treatment agent composition comprising.
前記スケール抑制剤は、式（１）の単量体単位を含む重合体、式（２）の単量体単位を含む重合体、式（１）の単量体単位と式（３）の単量体単位とを含む共重合体、式（１）の単量体単位と式（３）の単量体単位と式（４）の単量体単位とを含む共重合体、式（２）の単量体単位と式（５）の単量体単位と式（６）の単量体単位とを含む共重合体、式（７）のホスフィノカルボン酸共重合体、式（８）のビス（ポリ−２−カルボキシエチル）ホスフィン酸、式（９）の２−ホスホノブタン−１，２，４−トリカルボン酸およびその塩、式（１０）の１−ヒドロキシエチリデン−１，１−ジホスホン酸およびその塩のうちの少なくとも１つであることを特徴とする水処理剤組成物。
（式（１）中、Ｒ１は水素原子またはメチル基を表し、Ｘ１は水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）
（式（２）中、Ｒ２とＲ３はそれぞれ独立に水素原子またはメチル基を表し、Ｘ２とＸ３はそれぞれ独立に水素原子、１価もしくは２価の金属原子、アンモニウム基または有機アンモニウム基を表す。）
（式（３）中、Ｒ４は水素原子またはメチル基を表し、Ｘ４は炭素数１〜１０のアルキルスルホン酸基もしくはその塩、または、炭素数６〜１０のアリールスルホン酸基もしくはその塩を表し、塩の場合は１価もしくは２価の金属塩、アンモニウム塩または有機アンモニウム塩である。）
（式（４）中、Ｒ５は水素原子またはメチル基を表し、Ｘ５とＸ６はそれぞれ独立に水素原子または炭素数１〜１０のアルキル基を表すが、少なくとも一方が炭素数１〜１０のアルキル基である。）
（式（５）中、Ｒ６は水素原子またはメチル基を表し、Ｘ７は炭素数１〜１０のアルキル基である。）
（式（６）中、Ｒ７は水素原子またはメチル基を表し、Ｘ８は炭素数１〜１０のアルキル基である。）
（式（７）中、Ｙは、水素原子またはアルカリ金属原子を表し、Ｚは、−ＣＯＮＨＣ（ＣＨ３）２ＣＨ２ＳＯ３Ｎａを表し、ｈ，ｌ，ｍ，ｎはそれぞれ０または正の整数であり、ｈ＋ｌ＋ｍ＋ｎは、１〜１００の整数である。）
（式（８）中、Ｙは、水素原子またはアルカリ金属原子を表し、ｍ，ｎはそれぞれ０または正の整数であり、ｍ＋ｎは、１〜１００の整数である。）
（式（９）中、Ｙ１およびＹ２は、それぞれ独立に水素原子またはアルカリ金属原子を表す。）
（式（１０）中、Ｙ３およびＹ４は、それぞれ独立に水素原子またはアルカリ金属原子を表す。） The water treatment agent composition according to claim 1.
The scale inhibitor is a polymer containing a monomer unit of the formula (1), a polymer containing a monomer unit of the formula (2), a monomer unit of the formula (1) and a simple unit of the formula (3). A polymer containing a metric unit, a polymer containing a monomer unit of the formula (1), a monomer unit of the formula (3), and a monomer unit of the formula (4), the formula (2). A copolymer containing the monomer unit of the formula (5), the monomer unit of the formula (6), and the phosphinocarboxylic acid copolymer of the formula (7), of the formula (8). Bis (poly-2-carboxyethyl) phosphinic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid of formula (9) and salts thereof, 1-hydroxyethylidene-1,1-diphosphonic acid of formula (10) and A water treatment agent composition characterized by being at least one of the salts.
(In formula (1), R 1 represents a hydrogen atom or a methyl group, and X 1 represents a hydrogen atom, a monovalent or divalent metal atom, an ammonium group or an organic ammonium group.)
(In formula (2), R 2 and R 3 independently represent a hydrogen atom or a methyl group, and X 2 and X 3 independently represent a hydrogen atom, a monovalent or divalent metal atom, an ammonium group or an organic ammonium. Represents a group.)
(In the formula (3), R 4 represents a hydrogen atom or a methyl group, and X 4 is an alkyl sulfonic acid group having 1 to 10 carbon atoms or a salt thereof, or an aryl sulfonic acid group having 6 to 10 carbon atoms or a salt thereof. In the case of a salt, it is a monovalent or divalent metal salt, an ammonium salt or an organic ammonium salt.)
(In formula (4), R 5 represents a hydrogen atom or a methyl group, and X 5 and X 6 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but at least one of them has 1 to 10 carbon atoms. It is an alkyl group of.)
(In formula (5), R 6 represents a hydrogen atom or a methyl group, and X 7 is an alkyl group having 1 to 10 carbon atoms.)
(In formula (6), R 7 represents a hydrogen atom or a methyl group, and X 8 is an alkyl group having 1 to 10 carbon atoms.)
(In formula (7), Y represents a hydrogen atom or an alkali metal atom, Z represents −CONHC (CH 3 ) 2 CH 2 SO 3 Na, and h, l, m, and n are 0 or positive, respectively. It is an integer, and h + l + m + n is an integer of 1 to 100.)
(In formula (8), Y represents a hydrogen atom or an alkali metal atom, m and n are 0 or positive integers, respectively, and m + n is an integer of 1 to 100.)
(In formula (9), Y 1 and Y 2 independently represent a hydrogen atom or an alkali metal atom, respectively.)
(In formula (10), Y 3 and Y 4 independently represent a hydrogen atom or an alkali metal atom, respectively.)
前記水処理剤組成物のｐＨが１２未満であることを特徴とする水処理剤組成物。 The water treatment agent composition according to claim 1 or 2.
A water treatment agent composition characterized in that the pH of the water treatment agent composition is less than 12.
前記水処理剤組成物が前記ヨウ素系酸化剤および前記ヨウ化物の両方を含む場合、前記ヨウ素系酸化剤に対する、前記ヨウ化物の質量の比率が、１．２以上であることを特徴とする水処理剤組成物。 The water treatment agent composition according to any one of claims 1 to 3.
When the water treatment agent composition contains both the iodine-based oxidant and the iodide, the ratio of the mass of the iodide to the iodine-based oxidant is 1.2 or more. Treatment agent composition.
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| US4386005A (en) * | 1981-01-06 | 1983-05-31 | Chemical Sciences, Inc. | Scale inhibitor for reverse osmosis water purification system |
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| JP2013128927A (en) * | 2013-02-14 | 2013-07-04 | Miura Co Ltd | Chemicals feeding control method of circulating water system and chemicals feeding control device of circulating water system |
| JP2013213234A (en) * | 2012-03-30 | 2013-10-17 | Kurita Water Ind Ltd | Method for preventing scaling in steam generation equipment |
| JP2014079719A (en) * | 2012-10-18 | 2014-05-08 | Japan Organo Co Ltd | Scale cleaning liquid composition and scale cleaning method |
| JP2018030132A (en) * | 2017-11-16 | 2018-03-01 | 三浦工業株式会社 | Method for treating service water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4386005A (en) * | 1981-01-06 | 1983-05-31 | Chemical Sciences, Inc. | Scale inhibitor for reverse osmosis water purification system |
| JPS61257206A (en) * | 1985-05-04 | 1986-11-14 | ザ ビ−．エフ．グツドリツチ カンパニ− | Method of preventing growth of organism in reverse osmosis water purification system |
| JP2001129554A (en) * | 1999-11-02 | 2001-05-15 | Japan Organo Co Ltd | Method and apparatus for making deionized water |
| JP2002193711A (en) * | 2000-12-22 | 2002-07-10 | Mitsubishi Gas Chem Co Inc | Multi-function type water-treating agent |
| JP2013213234A (en) * | 2012-03-30 | 2013-10-17 | Kurita Water Ind Ltd | Method for preventing scaling in steam generation equipment |
| JP2014079719A (en) * | 2012-10-18 | 2014-05-08 | Japan Organo Co Ltd | Scale cleaning liquid composition and scale cleaning method |
| JP2013128927A (en) * | 2013-02-14 | 2013-07-04 | Miura Co Ltd | Chemicals feeding control method of circulating water system and chemicals feeding control device of circulating water system |
| JP2018030132A (en) * | 2017-11-16 | 2018-03-01 | 三浦工業株式会社 | Method for treating service water |
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