EP1507771A1 - Composition a base d'isothiazolone et procede de stabilisation d'isothiazolone - Google Patents

Composition a base d'isothiazolone et procede de stabilisation d'isothiazolone

Info

Publication number
EP1507771A1
EP1507771A1 EP03755296A EP03755296A EP1507771A1 EP 1507771 A1 EP1507771 A1 EP 1507771A1 EP 03755296 A EP03755296 A EP 03755296A EP 03755296 A EP03755296 A EP 03755296A EP 1507771 A1 EP1507771 A1 EP 1507771A1
Authority
EP
European Patent Office
Prior art keywords
isothiazolone
group
stabilizing
isothiazolone composition
composition
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.)
Withdrawn
Application number
EP03755296A
Other languages
German (de)
English (en)
Other versions
EP1507771A4 (fr
Inventor
Wan-Pyo 104-1003 Hansin apt. HONG
Jin-Man 306-1303 LG Village apt. KIM
Ki-Seung 103-302 Jindalrae apt. CHOI
Jin-Ho 712-105 Mugunghwa apt. KIM
Ki-Man 102-708 Dongsin apt. PARK
Hi-Weon 649-18 Seryu 2-dong JUNG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SK Chemicals Co Ltd
Original Assignee
SK Chemicals Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from KR1020020062096A external-priority patent/KR20030093086A/ko
Application filed by SK Chemicals Co Ltd filed Critical SK Chemicals Co Ltd
Publication of EP1507771A1 publication Critical patent/EP1507771A1/fr
Publication of EP1507771A4 publication Critical patent/EP1507771A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom

Definitions

  • US Patent No. 3,870,785 has suggested a method of adding a metal nitrate salt, a nitrite salt, etc. to the composition as a stabilizer.
  • US Patent No. 4,165,318 has suggested a method of adding formaldehyde or a formaldehyde-eluting material to an isothiazolone composition as a stabilizer.
  • US Patent No. 4,824,957 has suggested a method of adding an organic hydroxylic solvent to an isothiazolone composition as a stabilizer.
  • a dispersion or an emulsion such as paint acrylate or latex, etc.
  • a sterilizer comprising salts of divalent ions which cause coagulation.
  • sterilization active ingredients may be incorporated into the coagulation, thus the sterilization active ingredient may be reduced or removed if a product to be stored is filtered.
  • Fig. 1 is a photograph showing salt shock results of isothiazolone compositions of Example 1 , Comparative Example 1 , and a Control according to Experiment 1.
  • Fig. 2 is a photograph showing salt shock results of 10-fold dilutions of the isothiazolone compositions of Example 1 and Comparative Example 1 according to Experiment 1.
  • R-i and R 2 are independently a hydrogen atom, a halogen atom, or a C C alkyl group or aryl group;
  • the (a) 3-isothiazolone compound of the above Chemical Formula 1 is preferably contained in an amount of 0.1 to 20 wt% in the isothiazolone composition of the present invention. If the content of the (a) 3- isothiazolone compound is less than 0.1 wt%, the resulting isothiazolone composition cannot be commercially used because of a low content of sterilizer. And, if the content exceeds 20 wt%, stability becomes deteriorated.
  • the isothiazolone composition of the present invention comprises an alkali metal nitrate salt as a stabilizer, instead of an alkali earth metal salt of a divalent metal such as magnesium nitrate that has been predominantly used as a stabilizer in an isothiazolone composition of the prior art, salt shock is inhibited which makes the isothiazolone composition stable.
  • Magnesium oxide which has been widely used as a pH neutralizing agent of an isothiazolone composition, reacts in the composition to exist in the form of MgCI2 (magnesium chloride). If the content of the MgCI2 exceeds 9 wt% of the composition, solubility of magnesium chloride decreases to cause precipitation of magnesium chloride itself, and more seriously, divalent metal magnesium causes salt shock and thus the aqueous polymer dispersion cannot be stabilized.
  • the (e) iodic acid, periodic acid, iodate, periodate, or a mixture thereof is preferably contained in an amount of 0.0001 to 0.01 wt% of the isothiazolone composition, more preferably 0.001 to 0.005 wt%. If the content is less than 0.0001 wt%, precipitation of the isothiazolone compound cannot be effectively prevented, and if it exceeds 0.01 wt%, production cost increases, thus making the composition uneconomical.
  • the (f) metal bromic acid salt is preferably selected from a group consisting of sodium bromate, potassium bromate and a mixture thereof.
  • the (g) chlorite salt, the other precipitation-preventing agent is preferably contained in an amount of 0.001 to 10 wt%, more preferably 0.01 to 1.0 wt%, and most preferably 0.05 to 0.2 wt%. If the content is less than 0.001 wt%, precipitation of the isothiazolone cannot be effectively prevented, and if it exceeds 10 wt%, the production cost increases, thus making the composition uneconomical.
  • the isothiazolone composition of the present invention preferably comprises (a) 0. to 20 wt% of a 3-isothiazolone compound; (b) 0.1 to 25 wt% of an alkali metal nitrate salt; (c) 0.001 to 20 wt% of an alkali metal chloride salt; and (d) a solvent making up the balance, and the three kinds of precipitation-preventing agents of (e), (f), and (g) alone or in combination.
  • the three kinds of precipitation- preventing agents preferably comprise (e) 0.0001 to 0.01 wt% of iodic acid, periodic acid, iodate, periodate, or a mixture thereof; (f) 0.01 to 1.0 wt% of a metal bromic acid salt; and (g) 0.001 to 10 wt% of chlorite salt.
  • the present invention also provides a method for stabilizing the isothiazolone composition
  • a method for stabilizing the isothiazolone composition comprising the step of (i) adding (a) 0.1 to 20 wt% of a 3-isothiazolone compound represented by the following Chemical Formula 1 ; (b) 0.1 to 25 wt% of an alkali metal nitrate salt; and (c) 0.001 to 20 wt% of an alkali metal carbonate salt to (d) a solvent making up the balance, to prepare a mixed solution of the isothiazolone composition: [Chemical Formula 1]
  • Ri and R 2 are independently a hydrogen atom, a halogen atom, or a C* ⁇ -C 4 alkyl group or aryl group; and, R 3 is a hydrogen atom, a C* ⁇ -C ⁇ 8 alkyl group, a C 2 -C- ⁇ s alkenyl group, a C 2 -Ci 8 alkinyl group, a C 3 -C ⁇ 2 cycloalkyl group having trigonal to ocgonal rings, a C ⁇ 0 -C 24 aralkyl group, or a C* ⁇ 0 -C 24 aryl group.
  • the (a) 3-isothiazolone compound is preferably selected from a group consisting of 5-chloro-2-methyl-4-isothiazolin-3-on, 2-methyl-4- isothiazolin-3-on, 4,5-dichloro-2-methyl-4-isothiazolin-3-on, 5-chloro-2-n- octyl-3-isothiazolone, 4,5-dichloro-2-n-octyl-3-isothiazolone, benzisothiazolone, or a mixture thereof.
  • the (c) alkali metal carbonate salt is added as a pH-neutralizing agent.
  • the introduced alkali metal carbonate salt reacts with chloric acid in the isothiazolone composition to exist in the form of an alkali metal chloride salt.
  • the (c) alkali metal carbonate is preferably introduced in an amount of 0.01 to 15 wt% of the isothiazolone composition, more preferably 0.1 to 10 wt%.
  • the (d) solvent is preferably selected from a group consisting of water, ethyleneglycol, propyleneglycol, dipropyleneglycol, polypropyleneglycol, diethyleneglycol, triethyleneglycol, 1 ,5-pentanediol, 2,4-pentanediol, benzyl alcohol or a mixture thereof.
  • the method for stabilizing isothiazolone further adds a compound selected from a group consisting of (e) iodic acid, periodic acid, iodate, periodate or a mixture thereof; (f) a metal bromate; (g) chlorite salt, and a mixture thereof to the isothiazolone composition as a precipitation-preventing agent to further stabilize the isothiazolone composition.
  • a compound selected from a group consisting of (e) iodic acid, periodic acid, iodate, periodate or a mixture thereof; (f) a metal bromate; (g) chlorite salt, and a mixture thereof to the isothiazolone composition as a precipitation-preventing agent to further stabilize the isothiazolone composition.
  • the mixture of two or more kinds of precipitation-preventing agents, which have different operation mechanisms, are preferably added in appropriate ratios.
  • the (e) iodic acid, periodic acid, iodate, periodate, or a mixture thereof is preferably added in an amount of 0.0001 to 0.01 wt% of the isothiazolone composition, more preferably 0.001 to 0.005 wt%. If the content is less than 0.0001 wt%, precipitation of isothiazolone cannot be effectively prevented, and if it exceeds 0.01 wt%, the color changes with the passage of time, and production cost increases thus making the method uneconomical.
  • the (e) iodic acid, periodic acid, iodate, periodate or a mixture thereof is preferably selected from a group consisting of lithium iodate, sodium iodate, potassium iodate, ammonium iodate, lithium periodate, sodium periodate, potassium periodate, ammonium periodate, iodic acid, periodic acid dihydrate or a mixture thereof, and iodic acid, periodic acid dihydrate, sodium iodic acid, potassium iodic acid or a mixture thereof are more preferable.
  • the isothiazolone composition of the present invention can be stably used in a dispersion or emulsion such as paint acrylate or latex, etc. because it does not comprise a divalent metal alkali earth metal salt such as magnesium chloride, which causes salt shock, therefore effectively inhibiting the growth of harmful microorganisms.
  • the isothiazolone composition of the present invention can be used for a microorganism inhibitor in microorganism habitats such as a cooling water tower, an air washer, a boiler, a mineral slurry, a wastewater disposal plant, a decorative fountain, a reversed osmotic filtration system, an ultrafiltration system, ballast water, an evaporation condenser, a heat exchanger, and for pulp and paper processing oils, plastics, emulsions and dispersants, paint, latex, coating agents metal processing oils, etc., to effectively inhibit the growth of harmful microorganisms such as bacteria, mold, algae, etc.
  • a microorganism inhibitor in microorganism habitats such as a cooling water tower, an air washer, a boiler, a mineral slurry, a wastewater disposal plant, a decorative fountain, a reversed osmotic filtration system, an ultrafiltration system, ballast water, an evaporation condenser, a heat exchanger, and for pulp and paper processing oils
  • 3-isothiazolone solutions were prepared with the compositions and contents given in the following Table 1.
  • 3- isothiazolone compound a mixture of 5-chloro-2-methyl-4-isothiazolin-3-on (CMI) and 2-methyl-4-isothiazolin-3-on (Ml) with the mixing ratio of approximately 3:1 was used.
  • the alkali metal carbonate (sodium chloride, potassium chloride) and magnesium chloride are those produced in the composition by sodium carbonate, potassium carbonate, magnesium nitrate and magnesium oxide introduced for pH neutralization.
  • an isothiazolone composition causing salt shock comprises many magnesium ions as a stabilizer. It was confirmed whether or not samples prepared according to Examples 1 to 13 and Comparative Example 1 can be used as a sterilizer for a dispersion or emulsion such as paint acrylate or latex, etc. that sensitively reacts with divalent ions and coagulates, that is, whether or not they can stabilize a polymer aqueous dispersion.
  • Fig. 2 is a photo showing the salt shock results of 10- fold dilutions of isothiazolone composition samples of Example 1, and Comparative Example 1 in Experiment 1.
  • the isothiazolone composition that does not comprise an alkali earth metal salt of a divalent metal such as magnesium chloride that is, an isothiazolone composition stabilized by an alkali metal nitrate salt, can stabilize a polymer aqueous dispersion of a high concentration.
  • Fig. 3 is a photo showing the salt shock results of isothiazolone composition samples of Example 1 and Comparative Example 1.
  • the sample of Comparative Example 1 showed a large change in concentration of main ingredients after being stored at 65 ° C for 28 days, thus the ratio of CMI/MI decreased and precipitate formed. Since, of the two main ingredients of the isothiazolone solution, i.e. CMIT and MIT, the stability of CMIT is lower than that of MIT, the result that the initial ratio of 3:1 decreased means that CMI precipitated by the amount of decrease.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition à base d'isothiazolone et un procédé de stabilisation de cette composition et notamment une composition à base d'isothiazolone qui est exempte de sels de métaux alcalino-terreux d'un métal bivalent tel que le chlorure de magnésium, qui provoquent un choc salin; elle peut ainsi être utilisée de manière stable en tant que stérilisateur dans une dispersion ou une émulsion telle qu'une peinture acrylate ou un latex, ce qui permet de freiner efficacement toute croissance de micro-organismes; et elle présente une stabilité de stockage supérieure grâce à son faible taux de formation de précipitations grâce à l'inclusion d'agent de prévention de précipitations. L'invention concerne également un procédé de stabilisation de cette composition.
EP03755296A 2002-05-29 2003-05-28 Composition a base d'isothiazolone et procede de stabilisation d'isothiazolone Withdrawn EP1507771A4 (fr)

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
KR2002030023 2002-05-29
KR20020030023 2002-05-29
KR1020020062096A KR20030093086A (ko) 2002-05-29 2002-10-11 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR2002062096 2002-10-11
KR2002076857 2002-12-05
KR1020020076857A KR20030093087A (ko) 2002-05-29 2002-12-05 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR1020030018624A KR100975372B1 (ko) 2002-05-29 2003-03-25 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR1020030018625A KR100975373B1 (ko) 2002-05-29 2003-03-25 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR2003018624 2003-03-25
KR2003018625 2003-03-25
KR2003028973 2003-05-07
KR1020030028973A KR100975374B1 (ko) 2002-05-29 2003-05-07 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
KR2003028974 2003-05-07
KR1020030028974A KR100975375B1 (ko) 2002-05-29 2003-05-07 이소티아졸론 조성물 및 이소티아졸론의 안정화 방법
PCT/KR2003/001047 WO2003099799A1 (fr) 2002-05-29 2003-05-28 Composition a base d'isothiazolone et procede de stabilisation d'isothiazolone

Publications (2)

Publication Number Publication Date
EP1507771A1 true EP1507771A1 (fr) 2005-02-23
EP1507771A4 EP1507771A4 (fr) 2006-08-30

Family

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Family Applications (1)

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EP03755296A Withdrawn EP1507771A4 (fr) 2002-05-29 2003-05-28 Composition a base d'isothiazolone et procede de stabilisation d'isothiazolone

Country Status (5)

Country Link
EP (1) EP1507771A4 (fr)
JP (1) JP2005527626A (fr)
CN (1) CN100400521C (fr)
AU (1) AU2003232654B2 (fr)
WO (1) WO2003099799A1 (fr)

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JP5194205B2 (ja) * 2004-02-19 2013-05-08 住化エンビロサイエンス株式会社 工業用抗菌組成物
JP5101826B2 (ja) * 2006-02-28 2012-12-19 日本曹達株式会社 イソチアゾロン系化合物を含有する水溶性製剤およびイソチアゾロン系化合物の安定化方法
AU2007202261B2 (en) * 2006-06-02 2012-06-28 Rohm And Haas Company Microbicidal composition
JPWO2008146436A1 (ja) * 2007-05-31 2010-08-19 株式会社ケミクレア 安定な殺微生物組成物
CN103570642B (zh) * 2012-08-01 2015-03-18 中国中化股份有限公司 一种异噻唑啉酮类化合物及其作为杀菌剂的用途
CN103030733B (zh) * 2012-12-06 2014-12-10 青岛大学 一种侧链含苯异噻唑啉酮的聚丙烯酸酯防污共聚树脂及其制备方法
CN103319433A (zh) * 2013-07-08 2013-09-25 王建国 一种cmi工业杀菌剂的生产工艺
CN106472520A (zh) * 2016-09-23 2017-03-08 江苏辉丰农化股份有限公司 一种农药组合物
EP3606345B1 (fr) * 2017-04-04 2021-06-30 THOR GmbH Composition biocide stabilisée
KR102541313B1 (ko) 2018-01-12 2023-06-13 후지필름 가부시키가이샤 약액, 기판의 처리 방법
JP7043366B2 (ja) * 2018-08-08 2022-03-29 エステー株式会社 固形揮散製剤
CN109964947A (zh) * 2019-04-12 2019-07-05 嘉兴沃特泰科环保科技有限公司 非氧化杀菌剂
CN110037041A (zh) * 2019-04-30 2019-07-23 三河市霍夫曼化学品制造有限公司 一种异噻唑啉酮类复配微乳型杀菌防霉剂、其制备方法及应用
CN111087653A (zh) * 2019-11-13 2020-05-01 嘉兴学院 一种水性聚氨酯乳液用防腐剂及其制备方法
CN113549358A (zh) * 2021-07-28 2021-10-26 陕西省石油化工研究设计院 一种涂料用复合防腐剂及其制备方法与应用

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EP0540213A1 (fr) * 1991-10-30 1993-05-05 Rohm And Haas Company Bromate utilisé comme inhibiteur de formation de nitrosamine dans des isothiazolones stabilisés avec du nitrate

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KR100703997B1 (ko) * 2001-05-08 2007-04-04 에스케이케미칼주식회사 이소티아졸론 조성물과 안정화 방법, 및 이를 이용하는미생물의 생장 억제방법

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See also references of WO03099799A1 *

Also Published As

Publication number Publication date
EP1507771A4 (fr) 2006-08-30
AU2003232654B2 (en) 2007-05-17
JP2005527626A (ja) 2005-09-15
CN100400521C (zh) 2008-07-09
CN1671674A (zh) 2005-09-21
AU2003232654A1 (en) 2003-12-12
WO2003099799A1 (fr) 2003-12-04

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