JP2007230892A - Isothiazolone-based compound-containing water-soluble preparation and method for stabilizing isothiazolone-based compound - Google Patents
Isothiazolone-based compound-containing water-soluble preparation and method for stabilizing isothiazolone-based compound Download PDFInfo
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- JP2007230892A JP2007230892A JP2006052806A JP2006052806A JP2007230892A JP 2007230892 A JP2007230892 A JP 2007230892A JP 2006052806 A JP2006052806 A JP 2006052806A JP 2006052806 A JP2006052806 A JP 2006052806A JP 2007230892 A JP2007230892 A JP 2007230892A
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- Japan
- Prior art keywords
- water
- isothiazolone
- alkali metal
- isothiazolone compound
- soluble preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 32
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical compound O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 230000000087 stabilizing effect Effects 0.000 title abstract description 9
- -1 organic acid alkali metal salt Chemical class 0.000 claims abstract description 89
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims abstract description 22
- 150000007524 organic acids Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 claims description 4
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 17
- 230000035939 shock Effects 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000003899 bactericide agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 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
- 238000004040 coloring Methods 0.000 description 3
- 239000010730 cutting oil Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical class O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- FMNZAHDAULEOSO-UHFFFAOYSA-N 2,2-dibromo-2-nitroethanol Chemical compound OCC(Br)(Br)[N+]([O-])=O FMNZAHDAULEOSO-UHFFFAOYSA-N 0.000 description 1
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- NWPCFCBFUXXJIE-UHFFFAOYSA-N 2-(hydroxymethylamino)ethanol Chemical compound OCCNCO NWPCFCBFUXXJIE-UHFFFAOYSA-N 0.000 description 1
- HUHGPYXAVBJSJV-UHFFFAOYSA-N 2-[3,5-bis(2-hydroxyethyl)-1,3,5-triazinan-1-yl]ethanol Chemical compound OCCN1CN(CCO)CN(CCO)C1 HUHGPYXAVBJSJV-UHFFFAOYSA-N 0.000 description 1
- NCDBYAPSWOPDRN-UHFFFAOYSA-N 2-[dichloro(fluoro)methyl]sulfanylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(SC(Cl)(Cl)F)C(=O)C2=C1 NCDBYAPSWOPDRN-UHFFFAOYSA-N 0.000 description 1
- NCKMMSIFQUPKCK-UHFFFAOYSA-N 2-benzyl-4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1CC1=CC=CC=C1 NCKMMSIFQUPKCK-UHFFFAOYSA-N 0.000 description 1
- KQGMHDNNHXMQST-UHFFFAOYSA-N 2-bromo-2-(bromomethyl)pentanedinitrile;2,2-dibromo-2-cyanoacetamide Chemical compound NC(=O)C(Br)(Br)C#N.BrCC(Br)(C#N)CCC#N KQGMHDNNHXMQST-UHFFFAOYSA-N 0.000 description 1
- HHPJKICDWHTLAV-UHFFFAOYSA-N 2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C=CSN1C1CCCCC1 HHPJKICDWHTLAV-UHFFFAOYSA-N 0.000 description 1
- ASKFWACWQQZSSS-UHFFFAOYSA-N 2-ethyl-1,2-thiazol-3-one Chemical compound CCN1SC=CC1=O ASKFWACWQQZSSS-UHFFFAOYSA-N 0.000 description 1
- HFOCAQPWSXBFFN-UHFFFAOYSA-N 2-methylsulfonylbenzaldehyde Chemical compound CS(=O)(=O)C1=CC=CC=C1C=O HFOCAQPWSXBFFN-UHFFFAOYSA-N 0.000 description 1
- 229940044120 2-n-octyl-4-isothiazolin-3-one Drugs 0.000 description 1
- 229940099451 3-iodo-2-propynylbutylcarbamate Drugs 0.000 description 1
- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 description 1
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IJALWSVNUBBQRA-UHFFFAOYSA-N 4-Isopropyl-3-methylphenol Chemical compound CC(C)C1=CC=C(O)C=C1C IJALWSVNUBBQRA-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- NKEKPBPHPFSSIT-UHFFFAOYSA-N 5-chloro-2-(2,4,4-trimethylpentan-2-yl)-1,2-thiazol-3-one Chemical compound CC(C)(C)CC(C)(C)N1SC(Cl)=CC1=O NKEKPBPHPFSSIT-UHFFFAOYSA-N 0.000 description 1
- MMONDPHQMXRZDG-UHFFFAOYSA-N 5-chloro-2-ethyl-1,2-thiazol-3-one Chemical compound CCN1SC(Cl)=CC1=O MMONDPHQMXRZDG-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- WJLVQTJZDCGNJN-UHFFFAOYSA-N Chlorhexidine hydrochloride Chemical compound Cl.Cl.C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 WJLVQTJZDCGNJN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JGFDZZLUDWMUQH-UHFFFAOYSA-N Didecyldimethylammonium Chemical compound CCCCCCCCCC[N+](C)(C)CCCCCCCCCC JGFDZZLUDWMUQH-UHFFFAOYSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 229920002413 Polyhexanide Polymers 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000005839 Tebuconazole Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- VZLZBGJVQPXXOI-UHFFFAOYSA-N [Cu].[O-][N+]1=CC=CC=C1S Chemical compound [Cu].[O-][N+]1=CC=CC=C1S VZLZBGJVQPXXOI-UHFFFAOYSA-N 0.000 description 1
- XDILZEPJCPEDLT-UHFFFAOYSA-N [Na].[O-][N+]1=CC=CC=C1S Chemical compound [Na].[O-][N+]1=CC=CC=C1S XDILZEPJCPEDLT-UHFFFAOYSA-N 0.000 description 1
- WPZSJJJTNREFSV-UHFFFAOYSA-N [Zn].[O-][N+]1=CC=CC=C1S Chemical compound [Zn].[O-][N+]1=CC=CC=C1S WPZSJJJTNREFSV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 235000016720 allyl isothiocyanate Nutrition 0.000 description 1
- TUFYVOCKVJOUIR-UHFFFAOYSA-N alpha-Thujaplicin Natural products CC(C)C=1C=CC=CC(=O)C=1O TUFYVOCKVJOUIR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960003333 chlorhexidine gluconate Drugs 0.000 description 1
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 description 1
- 229960004504 chlorhexidine hydrochloride Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- JJKSAEHNIHMQKQ-UHFFFAOYSA-N copper;quinoline Chemical compound [Cu].N1=CC=CC2=CC=CC=C21 JJKSAEHNIHMQKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229940078672 didecyldimethylammonium Drugs 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000750 industrial fungicide Substances 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NFIDBGJMFKNGGQ-UHFFFAOYSA-N isopropylmethylphenol Natural products CC(C)CC1=CC=CC=C1O NFIDBGJMFKNGGQ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- JWZXKXIUSSIAMR-UHFFFAOYSA-N methylene bis(thiocyanate) Chemical compound N#CSCSC#N JWZXKXIUSSIAMR-UHFFFAOYSA-N 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- FJQMEBQMRAFJPW-UHFFFAOYSA-N n-[dichloro(fluoro)methyl]sulfanyl-n-(dimethylsulfamoyl)-2-methylaniline Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=CC=C1C FJQMEBQMRAFJPW-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
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- 229940070805 p-chloro-m-cresol Drugs 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 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
- 239000004300 potassium benzoate Substances 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
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- 229940094037 potassium bromate Drugs 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940095574 propionic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
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- 229940075582 sorbic acid Drugs 0.000 description 1
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- 238000013112 stability test Methods 0.000 description 1
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- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GAAKLDANOSASAM-UHFFFAOYSA-N undec-10-enoic acid;zinc Chemical compound [Zn].OC(=O)CCCCCCCCC=C GAAKLDANOSASAM-UHFFFAOYSA-N 0.000 description 1
- 229940118257 zinc undecylenate Drugs 0.000 description 1
- 229930007845 β-thujaplicin Natural products 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、イソチアゾロン系化合物、アルカリ金属硝酸塩及び水を含有するイソチアゾロン系化合物を含有する水溶性製剤、並びにイソチアゾロン系化合物の安定化方法に関する。 The present invention relates to a water-soluble preparation containing an isothiazolone compound, an alkali metal nitrate and an isothiazolone compound containing water, and a method for stabilizing the isothiazolone compound.
水性塗料、紙用塗工液、ラテックスエマルション、織物エマルション、紡糸油、切削油等の製造等において用いられる工業用水等には微生物が繁殖し易い。微生物が繁殖した水は、悪臭の発生等の原因となって作業環境を悪化させ、また工業製品の生産性を低下させ、工業製品の品質の低下を招く。このため、従来から工業用水等には種々の防腐剤や殺菌剤が使用されている。 Microorganisms tend to propagate in industrial water used in the production of water-based paints, paper coating liquids, latex emulsions, textile emulsions, spinning oils, cutting oils, and the like. The water in which the microorganisms have propagated causes the generation of malodors and the like, worsens the working environment, decreases the productivity of the industrial product, and causes the quality of the industrial product to deteriorate. For this reason, various preservatives and bactericides have been conventionally used for industrial water and the like.
これら工業用水における微生物の発生を抑制ないしは防除する薬剤の１つとして、イソチアゾロン系化合物が知られている。この化合物は工業用殺菌剤、防菌剤として優れた効果を有している。 An isothiazolone compound is known as one of the agents that suppress or control the generation of microorganisms in these industrial waters. This compound has an excellent effect as an industrial fungicide and fungicide.
しかしながら、このイソチアゾロン系化合物は一般的に水に対して不安定であり分解しやすい。そのため、イソチアゾロン系化合物を含む水溶液製剤を製品として安定なまま長期に渡って保存する方法が種々提案されている。 However, this isothiazolone compound is generally unstable to water and easily decomposes. For this reason, various methods have been proposed for preserving an aqueous solution preparation containing an isothiazolone-based compound as a product over a long period of time.
例えば、（ａ）イソチアゾロン系化合物をグリコール系有機溶媒で溶液化して製剤とする方法、（ｂ）イソチアゾロン系化合物の水溶液に、硝酸マグネシウムや塩化マグネシウム等の２価の金属塩を添加する方法、（ｃ）これらの金属塩と錯体を形成させたイソチアゾロン系化合物を利用する方法、（ｄ）金属硝酸塩を含まない３−イソチアゾロン化合物の水溶液に臭素酸塩を添加する方法（特許文献１〜４）、等が知られている。 For example, (a) a method in which an isothiazolone compound is dissolved in a glycol organic solvent to form a preparation, (b) a method in which a divalent metal salt such as magnesium nitrate or magnesium chloride is added to an aqueous solution of an isothiazolone compound, c) a method using an isothiazolone-based compound complexed with these metal salts, (d) a method of adding bromate to an aqueous solution of 3-isothiazolone compounds not containing metal nitrate (Patent Documents 1 to 4), Etc. are known.
しかし、上記（ａ）の方法には、用いるグリコール系溶剤は消防法による危険物の指定を受けており、その取扱いや保存には特別な注意を払う必要があり、グリコール系有機溶媒に溶解した製剤を安全かつ簡単に使用するのは難しいという問題があった。また、安全に使用できるイソチアゾロン系化合物を含有する製剤として、水で希釈してグリコール系有機溶媒の濃度を下げた製剤が提案されているが、工業用殺菌剤として適当な濃度になるようにグリコール系有機溶媒に溶解した製剤を水で希釈した場合、イソチアゾロン系化合物が短期間で分解したり沈殿物が生ずる等の問題があった。 However, in the method (a), the glycol solvent to be used has been designated as a dangerous substance by the Fire Service Act, and special care must be taken for its handling and storage, and it was dissolved in the glycol organic solvent. There was a problem that it was difficult to use the preparation safely and easily. In addition, as a preparation containing an isothiazolone compound that can be used safely, a preparation diluted with water to reduce the concentration of glycol organic solvent has been proposed. When a preparation dissolved in an organic solvent is diluted with water, there is a problem that the isothiazolone compound is decomposed in a short period of time or a precipitate is formed.
また、上記（ｂ）や（ｃ）の方法では、製剤中の金属イオンが対象品に濁りや沈殿を生じさせ易いという問題があった。特にアニオン性高分子水系分散物（例えばエマルション等）中にこのような製剤を添加した場合、共存する金属塩のために分散物が不安定となって、凝集物が発生したり分散状態が崩れたりして分散物の品質にとって致命的な問題が生ずる。 Further, the methods (b) and (c) have a problem that the metal ions in the preparation tend to cause turbidity and precipitation in the target product. In particular, when such a preparation is added to an anionic polymer aqueous dispersion (for example, an emulsion), the dispersion becomes unstable due to the coexisting metal salt, and aggregates are generated or the dispersion state is lost. This can be a fatal problem for the quality of the dispersion.
さらに、上記（ｄ）の方法で用いる水溶性製剤は、通常の市販製品に含まれる３−イソチアゾロンが臭素化されてしまう場合があった。また、高濃度の臭素酸又はヨウ素酸のアルカリ金属塩を含有する製剤では、該製剤が数℃程度以下の低温になるとアルカリ金属塩が析出し、製剤の性能が低下し、臭素酸カリウムの濃度が低下すると、イソチアゾロン系化合物の熱安定性が不十分となり、イソチアゾロン系化合物が分解し易くなるという問題があった。 Furthermore, in the water-soluble preparation used in the method (d), 3-isothiazolone contained in a normal commercial product may be brominated. In addition, in a preparation containing a high concentration of alkali metal salt of bromic acid or iodic acid, the alkali metal salt is precipitated when the preparation is at a low temperature of about several degrees C or less, the performance of the preparation is reduced, the concentration of potassium bromate When is decreased, there is a problem that the thermal stability of the isothiazolone compound becomes insufficient and the isothiazolone compound is easily decomposed.
本発明は、このような従来技術の実情に鑑みてなされたものであり、イソチアゾロン系化合物を含有する水溶性製剤において、製品として長期に亘って安定して保存でき、エマルション系塗料に含有させてもエマルションショックなどを起こすことがない、イソチアゾロン系化合物を含む水溶性製剤、及びイソチアゾロン系化合物を水溶液中で安定化する方法を提供することを課題とする。 The present invention has been made in view of such a state of the art, and in a water-soluble preparation containing an isothiazolone compound, it can be stably stored as a product for a long period of time, and is contained in an emulsion paint. It is an object of the present invention to provide a water-soluble preparation containing an isothiazolone compound and a method for stabilizing the isothiazolone compound in an aqueous solution that does not cause emulsion shock.
本発明者らは上記課題を解決すべく鋭意研究した結果、特に低濃度のイソチアゾロン系化合物を含む水溶液に、所定量のアルカリ金属塩を添加し、かつ、該水溶液のｐＨを３．５〜４．５に調整すると、製品として長期に亘って安定なまま保存できることを見出した。また、得られた製剤は、エマルション系塗料に含有させて使用する場合であっても、エマルションショックなどをひき起こすことがないものであることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have added a predetermined amount of an alkali metal salt to an aqueous solution containing a particularly low concentration of isothiazolone compounds, and the pH of the aqueous solution is adjusted to 3.5 to 4. When adjusted to .5, it was found that the product can be stored stably for a long time. Moreover, even when it was a case where it was made to contain in the emulsion type coating material and used, it discovered that an emulsion shock etc. were not caused, and came to complete this invention.
かくして本発明の第１によれば、下記（１）〜（８）のイソチアゾロン系化合物を含有する水溶性製剤が提供される。
（１）イソチアゾロン系化合物、アルカリ金属硝酸塩及び水を含有し、ｐＨが３．５〜４．５の範囲内に調整されていることを特徴とするイソチアゾロン系化合物を含有する水溶性製剤。
（２）イソチアゾロン系化合物の含有量が、製剤全体に対して、１〜１０重量％である（１）に記載のイソチアゾロン系化合物を含有する水溶性製剤。
（３）アルカリ金属硝酸塩の含有量が、製剤全体に対して、７重量％以上である（１）又は（２）に記載のイソチアゾロン系化合物を含有する水溶性製剤。
Thus, according to the first aspect of the present invention, there is provided a water-soluble preparation containing the following isothiazolone compounds (1) to (8).
(1) A water-soluble preparation containing an isothiazolone compound, comprising an isothiazolone compound, an alkali metal nitrate, and water, wherein the pH is adjusted within a range of 3.5 to 4.5.
(2) The water-soluble preparation containing the isothiazolone compound according to (1), wherein the content of the isothiazolone compound is 1 to 10% by weight with respect to the whole preparation.
(3) The water-soluble preparation containing the isothiazolone compound according to (1) or (2), wherein the content of alkali metal nitrate is 7% by weight or more based on the whole preparation.
（４）イソチアゾロン系化合物が、下記式（１） (4) The isothiazolone compound is represented by the following formula (1)
（式中、Ｙは、水素原子、又は置換されていてもよい炭化水素基を表し、Ｘ１、Ｘ２はそれぞれ独立して、水素原子、ハロゲン原子、又は炭素数１〜６のアルキル基を表す。）で示される化合物である（１）〜（３）のいずれかに記載のイソチアゾロン系化合物を含有する水溶性製剤。
（５）イソチアゾロン系化合物が、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、及び２−メチル−４−イソチアゾリン−３−オンの混合物である（４）に記載のイソチアゾロン系化合物を含有する水溶性製剤。
(In the formula, Y represents a hydrogen atom or an optionally substituted hydrocarbon group, and X 1 and X 2 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms. A water-soluble preparation containing the isothiazolone compound according to any one of (1) to (3), which is a compound represented by:
(5) The isothiazolone compound according to (4), wherein the isothiazolone compound is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one. Contains water-soluble preparation.
（６）アルカリ金属硝酸塩が、硝酸ナトリウム又は硝酸カリウムである（１）〜（５）のいずれかに記載のイソチアゾロン系化合物を含有する水溶性製剤。
（７）有機酸のアルカリ金属塩をさらに含有する（１）〜（６）のいずれかに記載のイソチアゾロン系化合物を含有する水溶性製剤。
（８）有機酸のアルカリ金属塩が、酢酸のアルカリ金属塩である（７）に記載のイソチアゾロン系化合物を含有する水溶性製剤。
(6) A water-soluble preparation containing the isothiazolone compound according to any one of (1) to (5), wherein the alkali metal nitrate is sodium nitrate or potassium nitrate.
(7) A water-soluble preparation containing the isothiazolone compound according to any one of (1) to (6), which further contains an alkali metal salt of an organic acid.
(8) The water-soluble preparation containing the isothiazolone compound according to (7), wherein the alkali metal salt of an organic acid is an alkali metal salt of acetic acid.
本発明の第２によれば、下記（９）のイソチアゾロン系化合物の安定化方法が提供される。
（９）イソチアゾロン系化合物、アルカリ金属硝酸塩、及び水を含有する水溶液に、有機酸のアルカリ金属塩を添加して、ｐＨを３．５〜４．５の範囲内に調整することを特徴とするイソチアゾロン系化合物の安定化方法。
According to a second aspect of the present invention, there is provided a method for stabilizing an isothiazolone compound of the following (9).
(9) It is characterized in that an alkali metal salt of an organic acid is added to an aqueous solution containing an isothiazolone compound, an alkali metal nitrate, and water, and the pH is adjusted within a range of 3.5 to 4.5. A method for stabilizing an isothiazolone compound.
本発明の第１によれば、製品として長期に亘って安定して保存でき、エマルション系塗料に含有させてもエマルションショックなどを起こすことがない、イソチアゾロン系化合物を含有する水溶性製剤が提供される。
本発明の第２によれば、イソチアゾロン系化合物を水溶液中で、長期に亘って安定化することができるイソチアゾロン系化合物の安定化方法が提供される。
According to the first aspect of the present invention, there is provided a water-soluble preparation containing an isothiazolone compound that can be stably stored as a product for a long period of time and does not cause emulsion shock or the like even if it is contained in an emulsion paint. The
According to the second aspect of the present invention, there is provided a method for stabilizing an isothiazolone compound, which can stabilize the isothiazolone compound in an aqueous solution over a long period of time.
以下、本発明を詳細に説明する。
１）イソチアゾロン系化合物を含有する水溶性製剤
本発明のイソチアゾロン系化合物を含有する水溶性製剤は、イソチアゾロン系化合物、アルカリ金属硝酸塩及び水を含有し、ｐＨが３．５〜４．５の範囲内に調整されていることを特徴とする。
Hereinafter, the present invention will be described in detail.
1) Water-soluble preparation containing isothiazolone compound The water-soluble preparation containing the isothiazolone compound of the present invention contains an isothiazolone compound, an alkali metal nitrate and water, and the pH is in the range of 3.5 to 4.5. It is characterized by being adjusted to.
（１）イソチアゾロン系化合物
本発明に用いるイソチアゾロン系化合物としては、イソチアゾロン骨格を有する殺菌活性を有する化合物であれば、特に制限されないが、下記式（１）
(1) Isothiazolone-based compound The isothiazolone-based compound used in the present invention is not particularly limited as long as it has a bactericidal activity having an isothiazolone skeleton, but the following formula (1)
で示される化合物が好ましい。
式（１）中、Ｙは、水素原子、又は置換されていてもよい炭化水素基を表す。
Ｙの置換されていてもよい炭化水素基の炭化水素基としては、炭素数１〜１０のアルキル基、炭素数２〜６のアルケニル基、炭素数２〜６のアルキニル基、炭素数３〜１０のシクロアルキル基、炭素数６〜１４のアリール基等が挙げられる。
これらの中で、炭素数１〜１０のアルキル基、炭素数３〜１０のシクロアルキル基が好ましく、炭素数１〜１０のアルキル基がより好ましい。
The compound shown by these is preferable.
In formula (1), Y represents a hydrogen atom or an optionally substituted hydrocarbon group.
Examples of the hydrocarbon group that may be substituted for Y include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, and 3 to 10 carbon atoms. Cycloalkyl group, an aryl group having 6 to 14 carbon atoms, and the like.
Among these, a C1-C10 alkyl group and a C3-C10 cycloalkyl group are preferable, and a C1-C10 alkyl group is more preferable.
前記炭素数１〜１０のアルキル基としては、たとえばメチル基、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、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−へプチル基、ｎ−オクチル基、イソオクチル基、ｓｅｃ−オクチル基、ｔｅｒｔ−オクチル基、ｎ−ノニル基、ｎ−デシル基等が挙げられる。 Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. N-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, n-decyl group and the like.
前記Ｙの置換基を有していてもよい炭化水素基の置換基としては、ヒドロキシル基；塩素原子、フッ素原子、臭素原子、ヨウ素原子等のハロゲン原子；シアノ基；アミノ基；カルボキシル基；メトキシ基、エトキシ基等の炭素数１〜４のアルコキシ基；フェノキシ基等の炭素数６〜１０のアリールオキシ基；メチルチオ基、エチルチオ基等の炭素数１〜４のアルキルチオ基；フェニルチオ基等の炭素数６〜１０のアリールチオ基；等が挙げられる。 Examples of the substituent of the hydrocarbon group which may have a substituent of Y include hydroxyl group; halogen atom such as chlorine atom, fluorine atom, bromine atom and iodine atom; cyano group; amino group; carboxyl group; Alkoxy groups having 1 to 4 carbon atoms such as ethoxy groups; aryloxy groups having 6 to 10 carbon atoms such as phenoxy groups; alkylthio groups having 1 to 4 carbon atoms such as methylthio groups and ethylthio groups; carbons such as phenylthio groups A 6-6 arylthio group; and the like.
これらの中でも、Ｙとしては、メチル基、エチル基、プロピル基、ｎ−オクチル基、tｅｒｔ−オクチル基等の炭素数１〜１０のアルキル基が特に好ましい。 Among these, as Y, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-octyl group, and a tert-octyl group is particularly preferable.
Ｘ１、Ｘ２はそれぞれ独立して、水素原子；塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メチル基、エチル基等の炭素数１〜６のアルキル基；を表す。
これらの中でも、Ｘ１、Ｘ２としては、Ｘ１、Ｘ２が共に水素原子である場合、Ｘ１、Ｘ２のうち、一方が水素原子で、他方がハロゲン原子である場合、Ｘ１、Ｘ２が共にハロゲン原子である場合のいずれかであるのが好ましい。また、ハロゲン原子としては、塩素原子が特に好ましい。
X 1 and X 2 each independently represent a hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group.
Among these, X 1, X 2, when X 1, X 2 are both hydrogen atoms, of X 1, X 2, one is a hydrogen atom, the other is halogen atom, X 1, X 2 is preferably any of halogen atoms. Moreover, as a halogen atom, a chlorine atom is especially preferable.
上記式（１）で表されるイソチアゾロン系化合物の具体例としては、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン、４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オン、２−エチル−４−イソチアゾリン−３−オン、４，５−ジクロロ−２−シクロヘキシル−４−イソチアゾリン−３−オン、５−クロロ−２−エチル−４−イソチアゾリン−３−オン、５−クロロ−２−ｔ−オクチル−４−イソチアゾリン−３−オン等が挙げられる。これらの化合物は一種単独で、あるいは二種以上からなる混合物で用いることができる。
これらの中でも、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オンが好ましい。
Specific examples of the isothiazolone compound represented by the above formula (1) include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n- Octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 4,5-dichloro-2- Examples include cyclohexyl-4-isothiazolin-3-one, 5-chloro-2-ethyl-4-isothiazolin-3-one, and 5-chloro-2-t-octyl-4-isothiazolin-3-one. These compounds can be used alone or in a mixture of two or more.
Among these, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferable.
これらのイソチアゾロン系化合物はいずれも公知化合物であり、たとえば米国特許第３７６１４８８号明細書、米国特許第３８４９４３０号明細書、米国特許第３８７０７９５号明細書、米国特許第４０６７８７８号明細書、米国特許第４１５００２６号明細書、米国特許第４２４１２１４号明細書、米国特許第３５１７０２２号明細書、米国特許第３０６５１２３号明細書、米国特許第３７６１４８９号明細書、および米国特許第３８４９４３０号明細書等に記載の方法またはそれらに準ずる方法によって製造することができる。 These isothiazolone compounds are all known compounds, for example, US Pat. No. 3,761,488, US Pat. No. 3,849,430, US Pat. No. 3,870,795, US Pat. No. 4,067,878, US Pat. Or US Pat. No. 4,241,214, US Pat. No. 3,571,022, US Pat. No. 3,065,123, US Pat. No. 3,761,489, US Pat. No. 3,849,430, or the like, It can be produced by a method according to them.
イソチアゾロン系化合物の含有量は、特に限定されないが、通常、製剤全体に対して、０．１〜３０重量％、好ましくは１〜１０重量％、より好ましくは２〜６重量％である。 The content of the isothiazolone compound is not particularly limited, but is usually 0.1 to 30% by weight, preferably 1 to 10% by weight, and more preferably 2 to 6% by weight with respect to the whole preparation.
（２）アルカリ金属硝酸塩
本発明の製剤は、アルカリ金属硝酸塩を含有する。アルカリ金属硝酸塩は、水溶液中のイソチアゾロン系化合物を安定化する機能を有する。また、硝酸マグネシウムなどのマグネシウム塩等をエマルション系塗料に大量に含有させると、エマルションショックを引き起こすことがあるが、本発明においては、アルカリ金属硝酸塩を使用するため、エマルション系塗料に大量に含有させ場合であっても、エマルションショックを引き起こすことがない。
(2) Alkali metal nitrate The preparation of the present invention contains an alkali metal nitrate. The alkali metal nitrate has a function of stabilizing the isothiazolone compound in the aqueous solution. In addition, if a large amount of magnesium salt such as magnesium nitrate is contained in an emulsion paint, emulsion shock may be caused. However, in the present invention, since an alkali metal nitrate is used, the emulsion paint may contain a large amount. Even if it does not cause emulsion shock.
アルカリ金属硝酸塩のアルカリ金属としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム等が挙げられ、ナトリウム又はカリウムが好ましく、ナトリウムが特に好ましい。 Examples of the alkali metal of the alkali metal nitrate include lithium, sodium, potassium, rubidium, and cesium. Sodium or potassium is preferable, and sodium is particularly preferable.
アルカリ金属硝酸塩の含有量は、特に制約されないが、優れた保存安定性を有する水溶性製剤を得る上では、水溶性製剤全体に対して７重量％以上であるのが好ましく、製造コストなどを考慮すれば、７〜３０重量％がより好ましく、７〜１５重量％が更に好ましい。 The content of the alkali metal nitrate is not particularly limited, but in order to obtain a water-soluble preparation having excellent storage stability, it is preferably 7% by weight or more based on the whole water-soluble preparation, and the production cost is considered. If it does, 7 to 30 weight% is more preferable, and 7 to 15 weight% is still more preferable.
（３）水
本発明の水溶性製剤に用いる水としては、特に制約されず、水道水、蒸留水、脱イオン水等を使用することができる。より安定性に優れる水溶性製剤を得る上では、不純物の少ない蒸留水、脱イオン水等の使用が好ましい。
(3) Water The water used in the water-soluble preparation of the present invention is not particularly limited, and tap water, distilled water, deionized water, and the like can be used. In order to obtain a water-soluble preparation having more excellent stability, it is preferable to use distilled water, deionized water or the like with less impurities.
（４）ｐＨ
本発明の水溶性製剤は、ｐＨが３．５〜４．５の範囲内、好ましくは３．７〜４．３の範囲内、より好ましくは３．９〜４．１の範囲内に調整されていることを特徴とする。ｐＨをこのような範囲内に調整することにより、水溶液中において、長期に亘って安定した水溶性製剤を得ることができる。
(4) pH
The water-soluble preparation of the present invention has a pH adjusted within the range of 3.5 to 4.5, preferably within the range of 3.7 to 4.3, and more preferably within the range of 3.9 to 4.1. It is characterized by. By adjusting the pH within such a range, it is possible to obtain a water-soluble preparation that is stable for a long time in an aqueous solution.
ｐＨを３．５〜４．５に調整する方法としては、水溶性製剤のｐＨを３．５〜４．５の範囲に調整できる方法であれば、特に制約されない。より長期に亘って安定して保存できる水溶性製剤を得る上では、イソチアゾロン系化合物及びアルカリ金属硝酸塩を含有する水溶液に、有機酸のアルカリ金属塩を添加して、水溶液のｐＨが３．５〜４．５の範囲とする方法が好ましい。 The method for adjusting the pH to 3.5 to 4.5 is not particularly limited as long as the method can adjust the pH of the water-soluble preparation to a range of 3.5 to 4.5. In order to obtain a water-soluble preparation that can be stably stored for a longer period of time, an alkali metal salt of an organic acid is added to an aqueous solution containing an isothiazolone compound and an alkali metal nitrate, and the pH of the aqueous solution is 3.5 to 3.5. The method which makes it the range of 4.5 is preferable.
用いる有機酸のアルカリ金属塩としては、特に制限されない。
有機酸のアルカリ金属塩としては、無機酸、カルボキシル基を有する有機化合物、スルホン酸、フェノール系化合物等が挙げられ、酢酸、トリフルオロ酢酸、フタル酸、クエン酸、ギ酸、シュウ酸、酒石酸等のカルボキシル基を有する有機化合物が好ましい。また、有機酸のアルカリ金属塩のアルカリ金属としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウムが挙げられ、ナトリウム又はカリウムが好ましい。
The alkali metal salt of the organic acid to be used is not particularly limited.
Examples of alkali metal salts of organic acids include inorganic acids, organic compounds having a carboxyl group, sulfonic acids, phenolic compounds, and the like, such as acetic acid, trifluoroacetic acid, phthalic acid, citric acid, formic acid, oxalic acid, and tartaric acid. Organic compounds having a carboxyl group are preferred. Moreover, as an alkali metal of the alkali metal salt of an organic acid, lithium, sodium, potassium, rubidium, and cesium are mentioned, Sodium or potassium is preferable.
これらの中でも、長期に亘って安定して保存できる水溶性製剤を得ることできること、及び製造コストの観点から、酢酸ナトリウム又は酢酸カリウムの使用がより好ましく、酢酸ナトリウムが特に好ましい。 Among these, the use of sodium acetate or potassium acetate is more preferable, and sodium acetate is particularly preferable from the viewpoints of obtaining a water-soluble preparation that can be stably stored for a long period of time and manufacturing cost.
用いる有機酸のアルカリ金属塩の使用量は、水溶性製剤のｐＨを３．５〜４．５の範囲に調整できる量であれば、特に制限されないが、通常、水溶性製剤全体に対して、０．０１〜１．０重量％程度となる範囲である。 The amount of the alkali metal salt of the organic acid to be used is not particularly limited as long as it is an amount that can adjust the pH of the water-soluble preparation to a range of 3.5 to 4.5. The range is about 0.01 to 1.0% by weight.
本発明の水溶性製剤は、その目的、用途等に応じて、公知の添加剤、たとえば界面活性剤、酸化防止剤等を含有していてもよい。
また、保存安定性に影響を与えない範囲であれば、硝酸マグネシウム塩などのアルカリ土類金属塩、グリコール系有機溶媒等を少量含有していてもよい。
The water-soluble preparation of the present invention may contain a known additive, for example, a surfactant, an antioxidant and the like, depending on the purpose and application.
In addition, as long as the storage stability is not affected, a small amount of an alkaline earth metal salt such as a magnesium nitrate salt, a glycol organic solvent, or the like may be contained.
さらに本発明の水溶性製剤は、イソチアゾロン系化合物以外の他の殺菌剤を含有していても良い。他の殺菌剤としては、１，２−ベンゾイソチアゾリン−３−オン、Ｎ−ｎ−ブチル−１，２−ベンゾイソチアゾリン−３−オン、イソチオシアン酸アリル、２−（４‘−チアゾリル）−ベンツイミダゾール、２−ベンツイミダゾリルカルバミン酸メチル、２−（４−チオシアノメチルチオ）ベンツチアゾール、３−ヨード−２−プロピニルブチルカーバメート、４−クロロフェニル−３−ヨードプロパギルホルマール、ジヨードメチル−ｐ−トリルスルホン、ｐ−クロロ−ｍ−クレゾール、安息香酸、ソルビン酸、カプリル酸、プロピオン酸、１０−ウンデシレン酸、ソルビン酸カリウム、プロピオン酸カリウム、安息香酸カリウム、フタル酸モノマグネシウム、ウンデシレン酸亜鉛、８−ヒドロキシキノリン、キノリン銅、ビス（ジメチルジチオカルバモイル）ジスルフィド、２，４，４’−トリクロロ−２’−ヒドロオキシジフェニルエーテル、Ｎ−（フルオロジクロロメチルチオ）フタルイミド、Ｎ，Ｎ−ジメチル−Ｎ’−（ジクロロフルオロメチルチオ）−Ｎ’−フェニルスルファミド、Ｎ，Ｎ−ジメチル−Ｎ’−（ジクロロフルオロメチルチオ）−Ｎ’−トリルスルファミド、ヘキサヒドロ−１，３，５−トリス（２−ヒドロキシエチル）−Ｓ−トリアジン、２−（ヒドロキシメチルアミノ）エタノール、テブコナゾール、ヒノキチオール、２，３，５，６，−テトラクロロイソフタロニトリル、２−ブロモ−２−ニトロ−１，３−プロパンジオール、２，２−ジブロモ−３−ニトリロプロピオンアミド、１，２−ジブロモ−２，４−ジシアノブタン、２，２−ジブロモ−２−ニトロエタノール、２−ピリジンチオール−１−オキシドナトリウム、２−ピリジンチオール−１−オキシド亜鉛、２−ピリジンチオール−１−オキシド銅、２，３，５，６−テトラクロロ−４−（メチルスルホニル）ピリジン、ジデシルジメチルアンモニウムクロリド、ジデシルジメチルアンモニウムアジペート、塩化ベンザルコニウム、塩化ベンゼトニウム、テトラデシルジメチルベンジルアンモニウムクロリド、グルコン酸クロルヘキシジン、塩酸クロルヘキシジン、ポリヘキサメチレンビグアナイド塩酸塩、メチレンビスチオシアネート、イソプロピルメチルフェノール、フェノール、ブチルバラペン、エチルパラベン、メチルパラペン、プロピルパラペン、メタクレゾール、オルトクレゾール、パラクレゾール、オルトフェニルフェノールナトリウム、クロロフェン、パラクロルフェノール、パラクロロメタキシレート、パラクロロクレゾール、ポリリジン、塩化銀、酸化チタン、銀等が挙げられる。 Furthermore, the water-soluble preparation of the present invention may contain other bactericides other than isothiazolone compounds. Other fungicides include 1,2-benzisothiazolin-3-one, Nn-butyl-1,2-benzisothiazolin-3-one, allyl isothiocyanate, 2- (4′-thiazolyl) -benzimidazole. Methyl 2-benzimidazolylcarbamate, 2- (4-thiocyanomethylthio) benzthiazole, 3-iodo-2-propynylbutyl carbamate, 4-chlorophenyl-3-iodopropargyl formal, diiodomethyl-p-tolylsulfone, p -Chloro-m-cresol, benzoic acid, sorbic acid, caprylic acid, propionic acid, 10-undecylenic acid, potassium sorbate, potassium propionate, potassium benzoate, monomagnesium phthalate, zinc undecylenate, 8-hydroxyquinoline, Quinoline copper, bis (dimethyl Thiocarbamoyl) disulfide, 2,4,4′-trichloro-2′-hydroxydiphenyl ether, N- (fluorodichloromethylthio) phthalimide, N, N-dimethyl-N ′-(dichlorofluoromethylthio) -N′-phenylsulfur Famide, N, N-dimethyl-N ′-(dichlorofluoromethylthio) -N′-tolylsulfamide, hexahydro-1,3,5-tris (2-hydroxyethyl) -S-triazine, 2- (hydroxy Methylamino) ethanol, tebuconazole, hinokitiol, 2,3,5,6, -tetrachloroisophthalonitrile, 2-bromo-2-nitro-1,3-propanediol, 2,2-dibromo-3-nitrilopropionamide 1,2-dibromo-2,4-dicyanobutane, 2,2-dibromo 2-nitroethanol, 2-pyridinethiol-1-oxide sodium, 2-pyridinethiol-1-oxide zinc, 2-pyridinethiol-1-oxide copper, 2,3,5,6-tetrachloro-4- (methyl) (Sulfonyl) pyridine, didecyldimethylammonium chloride, didecyldimethylammonium adipate, benzalkonium chloride, benzethonium chloride, tetradecyldimethylbenzylammonium chloride, chlorhexidine gluconate, chlorhexidine hydrochloride, polyhexamethylene biguanide hydrochloride, methylene bis thiocyanate, isopropyl Methylphenol, phenol, butylbarapene, ethylparaben, methylparapen, propylparapen, metacresol, orthocresol, paracresol, orthopheny Examples include ruphenol sodium, chlorophene, parachlorophenol, parachlorometaxylate, parachlorocresol, polylysine, silver chloride, titanium oxide, silver and the like.
本発明の水溶性製剤を調製する方法は、特に限定されず、各化合物の配合はどのような順序で行ってもよいが、イソチアゾロン系化合物、アルカリ金属硝酸塩、及び水を含有する水溶性製剤に、有機酸のアルカリ金属塩を添加して、ｐＨを３．５〜４．５の範囲内に調整する方法が好ましい。この方法によれば、本発明の水溶性製剤を簡便かつ効率よく製造することができる。 The method for preparing the water-soluble preparation of the present invention is not particularly limited, and each compound may be blended in any order, but the water-soluble preparation containing an isothiazolone compound, alkali metal nitrate, and water may be used. A method of adjusting the pH within the range of 3.5 to 4.5 by adding an alkali metal salt of an organic acid is preferable. According to this method, the water-soluble preparation of the present invention can be produced simply and efficiently.
２）イソチアゾロン系化合物の安定化方法
本発明のイソチアゾロン系化合物の安定化方法は、イソチアゾロン系化合物、アルカリ金属硝酸塩及び水を含有する水溶液に、有機酸のアルカリ金属塩を添加して、ｐＨを３．５〜４．５の範囲内に調整することを特徴とする。本発明の安定化方法によれば、水溶液中において、長期に亘ってイソチアゾロン系化合物を安定して存在させることができる。
2) Stabilization method of isothiazolone compound The stabilization method of the isothiazolone compound according to the present invention comprises adding an alkali metal salt of an organic acid to an aqueous solution containing an isothiazolone compound, an alkali metal nitrate and water to adjust the pH to 3 Adjusting within the range of 5 to 4.5. According to the stabilization method of the present invention, an isothiazolone compound can be stably present in an aqueous solution over a long period of time.
また、イソチアゾロン系化合物、アルカリ金属硝酸塩及び水を含有する水溶液に有機酸のアルカリ金属塩を添加して、ｐＨを３．５〜４．５の範囲内に調整した後であっても、経時的に水溶液のｐＨが変化する場合がある。従って、イソチアゾロン系化合物を水溶液中で長期に亘って安定化させたい場合には、定期的に水溶液のｐＨを測定し、ｐＨが３．５〜４．５に維持されるように、前記水溶液に有機酸のアルカリ金属塩を添加することも好ましい。 Even after the alkali metal salt of an organic acid is added to an aqueous solution containing an isothiazolone compound, alkali metal nitrate and water, and the pH is adjusted within the range of 3.5 to 4.5, The pH of the aqueous solution may change. Therefore, when it is desired to stabilize the isothiazolone compound in an aqueous solution over a long period of time, the pH of the aqueous solution is periodically measured, and the aqueous solution is adjusted so that the pH is maintained at 3.5 to 4.5. It is also preferable to add an alkali metal salt of an organic acid.
本発明の水溶性製剤は、従来から使用されている種々の分野の産業において、工業用殺菌剤等として使用することができる。なかでも、製紙工程における白水、ラテックス、合成高分子エマルション、顔料、塗料、印刷版用処理液、接着剤、冷却用水、インキ、切削油、化粧用品、不織布、紡糸油、皮革等の用途等に適しており、合成高分子エマルション、紡糸油、切削油、インキ等により適している。 The water-soluble preparation of the present invention can be used as an industrial disinfectant or the like in various industries that have been used conventionally. Especially for white water, latex, synthetic polymer emulsion, pigment, paint, printing plate treatment liquid, adhesive, cooling water, ink, cutting oil, cosmetics, nonwoven fabric, spinning oil, leather, etc. in the papermaking process. Suitable for synthetic polymer emulsions, spinning oils, cutting oils, inks and the like.
本発明の水溶性製剤を使用する際には、たとえば滴下法、間欠添加法、塗布法、噴霧法、浸漬法等の公知の方法を使用することができ、使用の対象となる物や目的等により前記の方法を使い分ければよい。
またその使用量も、使用の対象となる物や目的等により適宜定めることができる。
When using the water-soluble preparation of the present invention, for example, known methods such as a dropping method, an intermittent addition method, a coating method, a spraying method, a dipping method, etc. can be used. The above method may be properly used.
In addition, the amount of use can be determined as appropriate depending on the object to be used and the purpose.
以下、実施例及び比較例により本発明をさらに具体的に説明する。本発明は、以下の実施例により何ら制限されない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited at all by the following examples.
（実施例１〜８、比較例１〜４）水溶性製剤の調製
適当量のイオン交換水に、市販のイソチアゾロン系殺菌剤（商品名：ＫＡＴＨＯＮ ＷＴ、ローム＆ハース社製、５−クロロ−２−メチル−４−イソチアゾリン−３−オンを約１０重量％、２−メチル−４−イソチアゾリン−３−オンを約３重量％含有、以下、「殺菌剤Ａ」と略記）及び硝酸ナトリウム（ＮａＮＯ３）を第１表及び第２表に示す量添加して水溶液を得た。得られた水溶液に酢酸ナトリウムを少量加えて、所定のｐＨに調整した後、さらに、製剤全体が１００重量部となるように少量のイオン交換水を添加して、実施例１〜８、比較例１〜４の水溶性製剤を調製した。実施例１〜８、比較例１〜４の水溶性製剤中の殺菌剤Ａ及び硝酸ナトリウム（ＮａＮＯ３）の含有量（重量部）、並びに、得られた各水溶性製剤のｐＨを第１表及び第２表にまとめて示す。
(Examples 1-8, Comparative Examples 1-4) Preparation of water-soluble preparations To a suitable amount of ion-exchanged water, commercially available isothiazolone fungicides (trade name: KATHON WT, manufactured by Rohm & Haas, 5-chloro-2) -Containing about 10% by weight of methyl-4-isothiazolin-3-one and about 3% by weight of 2-methyl-4-isothiazolin-3-one, hereinafter abbreviated as "bactericidal agent A") and sodium nitrate (NaNO 3 ) Was added in the amounts shown in Tables 1 and 2 to obtain an aqueous solution. After adding a small amount of sodium acetate to the obtained aqueous solution and adjusting to a predetermined pH, a small amount of ion-exchanged water was further added so that the whole preparation was 100 parts by weight, and Examples 1 to 8 and Comparative Examples 1-4 water-soluble formulations were prepared. Table 1 shows the contents (parts by weight) of the bactericidal agent A and sodium nitrate (NaNO 3 ) in the water-soluble preparations of Examples 1 to 8 and Comparative Examples 1 to 4, and the pH of each water-soluble preparation obtained. And are summarized in Table 2.
（保存安定性試験）
実施例１〜８、比較例１〜４で得た水溶性製剤の５０ｍｌをそれぞれサンプル瓶に入れ、密栓して室温で７日間放置した。その後、水溶性製剤の着色度を肉眼で観察した。着色が濃くなるほど、イソチアゾリン系化合物の分解が進んでいることを示す。
観察した結果、無色透明である場合を◎、ほとんど着色がない場合を○、うすく茶色に着色している場合を△、茶色に着色している場合を×で評価した。評価結果を第１表及び第２表に示す。
(Storage stability test)
50 ml of the water-soluble preparations obtained in Examples 1 to 8 and Comparative Examples 1 to 4 were placed in sample bottles, sealed, and left at room temperature for 7 days. Thereafter, the degree of coloring of the water-soluble preparation was observed with the naked eye. It shows that decomposition | disassembly of an isothiazoline type compound is progressing, so that coloring is dark.
As a result of the observation, the case of being colorless and transparent was evaluated as ◎, the case of being hardly colored as ◯, the case of being colored light brown as Δ, and the case of being colored as brown as ×. The evaluation results are shown in Tables 1 and 2.
第１表より、ｐＨを４．０に固定して、硝酸ナトリウムの添加量を２重量％〜１０重量％とした実施例１〜６の水溶性製剤では着色がほとんど見られず、保存安定性が優れていた。特に、硝酸ナトリウムの添加量を７重量％以上とした実施例１〜３の水溶性製剤では着色がまったく見られず、保存安定性に極めて優れていた。また、第１表には示していないが、実施例１の水溶性製剤は、１４日間放置した後であっても、外観上まったく変化が見られず、無色透明を維持していた。 From Table 1, the water-soluble preparations of Examples 1 to 6 in which the pH was fixed at 4.0 and the amount of sodium nitrate added was 2 wt% to 10 wt% showed little coloration and storage stability. Was excellent. In particular, in the water-soluble preparations of Examples 1 to 3 in which the amount of sodium nitrate added was 7% by weight or more, no coloring was observed, and the storage stability was extremely excellent. Further, although not shown in Table 1, the water-soluble preparation of Example 1 remained colorless and transparent without any change in appearance even after being left for 14 days.
第２表より、ｐＨが３．５〜４．５である水溶性製剤（実施例１、７、８）は、保存安定性に優れていることが分かる。上述したように、ｐＨを４．０とした実施例１の水溶性製剤は特に保存安定性に優れていた。
From Table 2, it can be seen that the water-soluble preparations (Examples 1, 7 and 8) having a pH of 3.5 to 4.5 are excellent in storage stability. As described above, the water-soluble preparation of Example 1 having a pH of 4.0 was particularly excellent in storage stability.
Claims (9)
An isothiazolone-based compound comprising an isothiazolone-based compound, an alkali metal nitrate and an aqueous solution containing water, and an alkali metal salt of an organic acid added to adjust the pH to a range of 3.5 to 4.5. Stabilization method.
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| JP2018121945A (en) * | 2017-02-02 | 2018-08-09 | エステー株式会社 | Solid volatile formulation |
| JP2020022662A (en) * | 2018-08-08 | 2020-02-13 | エステー株式会社 | Solid volatilization formulation |
| CN112400871A (en) * | 2020-11-30 | 2021-02-26 | 洛阳市兽药厂 | Isothiazolinone compound soluble powder and preparation process thereof |
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