EP0773281B1 - Préparations pour refrigerants Inbrifiants stabilisées - Google Patents

Préparations pour refrigerants Inbrifiants stabilisées Download PDF

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Publication number
EP0773281B1
EP0773281B1 EP96250190A EP96250190A EP0773281B1 EP 0773281 B1 EP0773281 B1 EP 0773281B1 EP 96250190 A EP96250190 A EP 96250190A EP 96250190 A EP96250190 A EP 96250190A EP 0773281 B1 EP0773281 B1 EP 0773281B1
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EP
European Patent Office
Prior art keywords
additive mixture
oxide
mercaptopyridine
mixture according
cooling lubricant
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.)
Expired - Lifetime
Application number
EP96250190A
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German (de)
English (en)
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EP0773281A2 (fr
EP0773281A3 (fr
Inventor
Wolfgang Siegert
Wolfgang Dr. Beilfuss
Klaus Dr. Weber
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Schuelke and Mayr GmbH
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Schuelke and Mayr GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/061—Carbides; Hydrides; Nitrides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/16—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/18—Ammonia
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/102—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon only in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working

Definitions

  • the present invention relates to additive mixtures for cooling lubricant products and cooling lubricant products containing a Isothiazolone and one against chemical decomposition of isothiazolone effective stabilizer included.
  • Isothiazolone compounds are effective as bactericidal and / or fungicidal active ingredients in cooling lubricants for metal processing known.
  • certain components tend to be in Metalworking fluids for the destruction of isothiazolones and thus eliminate their microbiological protective activity. This is especially the case when the metal processing fluids in concentrated form.
  • Isothiazolones can attack.
  • An example for this is the sodium salt of 2-mercapto-pyridine-N-oxide (sodium omadine), that 5-chloro-2-methylisothiazolone decomposes in each system, in which both exist together.
  • EP-A-0 425 143, US-A-4 150 026 and US-A-4 241 214 disclose that metal salt complexes of isothiazolones due to their improved thermal stability are used while the biological activity is maintained.
  • EP-B-0 443 821 are additive mixtures for cooling lubricant products known, according to the preamble of claim 1 isothiazolone and one against chemical decomposition of the isothiazolone effective stabilizer.
  • isothiazolone there is the use of sulfur Compounds or salts thereof disclosed with the EP 96 25 0190.4
  • Isothiazolone can reversibly form an adduct, in particular Compounds in which a sulfur atom is added to a nitrogen, is bound aromatic ring.
  • suitable compounds in EP-B-0 443 821) 4-mercaptopyridine, the Sodium salt of 2-mercaptopyridine, 2-mercaptobenzothiazole and 4-methyl-4-H-1,2,4-triazole-3-thiol called.
  • the stabilizer effective ratio of stabilizer to isothiazolone is at least 0.1: 1 according to EP-B-0 443 821, in particular between 0.5: 1 to 1.5: 1.
  • compositions known from EP-B-0 443 821 Isothiazolone and stabilizer can additionally solvents contain.
  • Preferred solvents are so-called "capped polyols", such as. Triethylene.
  • the present invention is based on the object
  • Additive mixtures for cooling lubricant products available which isothiazolones as bactericidal and / or fungicidal Active ingredients contain, the cooling lubricant concentrates or from it manufactured cooling lubricant from microbial attack protect and the durability and life of the cooling lubricant products improve.
  • the additive mixtures according to the invention should themselves be sufficiently stable and under practical conditions storable and durable.
  • the metered addition should be in a cooling lubricant concentrate or in a cooling lubricant, preferably a water-mixed Coolant, can be done.
  • the tasks are characterized by the characterizing features of Claims 1 and 11 solved.
  • claim 1 is in the additive mixtures additionally provided a solubilizer, that of phenoxyethanol, phenoxypropanols, 1-methoxy-2-propanol, and mixtures thereof are selected.
  • the solver is for example in an amount of 30 to 91.7 wt .-%, for example 30 to 75, preferably 40 to 70 Wt .-%, more preferably 50 to 65 wt .-% and in particular about 58 wt .-% in the additive mixture.
  • the cooling lubricant products contain in addition to the usual Ingredients an additive mixture according to the invention.
  • the cooling lubricant products can be used as cooling lubricant concentrate or contain the cooling lubricant concentrate. Accordingly, can the additives of the invention in cooling lubricant concentrates are introduced, which then to coolants be diluted.
  • the cooling lubricant products can be used as Solution or as an emulsion. Preferably, water-mixed Coolant produced.
  • the isothiazolones used in the additive mixture according to the invention are halogen-free and are represented by the formula reproduced in the Y is a (C 1 -C 18 ) alkyl or (C 3 -C 12 ) cycloalkyl group containing one or more hydroxy, cyano, alkylamino, dialkylamino, aryl, amino, carboxy, Carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, cycloalkylamino, carbamoxy or isothiazolonyl groups, an unsubstituted (C 2 -C 8 ) alkenyl or alkynyl group, a (C 7 -C 10 ) -Aralkyl distr which may be substituted with one or more (C 1 -C 4 ) alkyl or (C 1 -C 4 ) alkoxy groups, or an aryl group which is reacted with one or more nitro, (C 1 -
  • heterocyclic are Sulfur-nitrogen compounds such as 2-mercaptopyridine N-oxide and corresponding salts, preferably alkali metal or ammonium salts such as.
  • Pyrion-Na (40% aqueous solution of 2-mercaptopyridine N-oxide sodium salt), 2-mercaptopyridine N-oxide metal salt complexes such as zinc pyrithione (e.g., as a 48% aqueous dispersion), 2,2'-dithiobis (pyridine N-oxide) (pyrion disulfide), as well as Mixtures thereof.
  • 2-mercaptopyridine N-oxide sodium salt such as zinc pyrithione (e.g., as a 48% aqueous dispersion), 2,2'-dithiobis (pyridine N-oxide) (pyrion disulfide), as well as Mixtures thereof.
  • pyrion-Na, zinc pyrithione and pyrion disulfide preferred.
  • oxidants such as iodopropynyl butyl carbamate, hydrogen peroxide, t-butyl hydroperoxide, sodium bromate and Cu (II) salts as co-stabilizers, with sodium bromate, hydrogen peroxide, 2-tert-butyl-6-methylphenol and pyrion disulfide are preferred as co-stabilizers.
  • the isothiazolone content in the additive mixture 2.25 to 20.25% by weight, for example 6.75 to 20.25% by weight, preferably 9 to 13.5% by weight and in particular about 11% by weight be.
  • the stabilizer content in the additive mixture may be about 1.3 to 10 wt .-%, for example 4 to 10 wt .-%, preferably 6 to 8 Wt .-% and in particular about 7 wt .-% amount, for example also 0.05 to 1.0, preferably 0.5 to 0.1 wt.%, in particular 0.2 wt .-% co-catalyst may be present.
  • the molar ratio isothiazolone compound: stabilizer is for example at least 10: 1, preferably between 1.5: 1 and 1: 1.5 and especially about 1: 1, such as between 1.1: 1 and 1: 1.27.
  • the additive mixtures are preferably in commercial Incorporated cooling lubricant concentrates, from which then Dilutions may be made with water, e.g. 4% dilutions.
  • the liquid preparations may optionally contain further additives contain the functional properties of the cooling lubricant or cooling lubricant additive.
  • the active ingredient isothiazolone
  • the Stabilizer for example, Pyrion-Na
  • the preparation is well dosed and can be stored under practical conditions and durable. Also advantageous is the good handling of the preparation, compared to storage, preparation and dosing of active substances present in two-component systems and stabilizers.
  • the additive mixtures according to the invention can be coolants concentrates be added effectively, so that their durability and the lifetime of the finished cooling lubricant products, is improved compared to known systems.
  • the raised Stability of the preparations according to the invention is evident especially in the lower tendency to form sediments.
  • Kathon RH 893 designates a 45% n-Octylisothiazolone solution in 1,2-propylene glycol and pyrione-Na a 40% aqueous 2-mercaptopyridine N-oxide sodium salt solution.
  • Formulations based on Kathon 893 and Pyrion-Na were in the molar ratio 1: 1 to 1: 5 in different Solver and solved for compatibility and stability examined.
  • Total drug content (sum of N-octylisothiazolone and 2-mercaptopyridine N-oxide-Na salt) was about 18%.
  • the Kathon 893 content is in all the same.
  • the samples were at 40 ° C or Room temperature stored in clear glass and daily about 7 to Stirred for 8 hours. From the optically stable concentrates were prepared with deionized water 4% solutions or emulsions whose NOITZ content was determined by HPLC. Null values were not determined.
  • N-octylisothiazolone content after storage Coolant concentrate: Kutwell 40
  • the concentrates and emulsions plus additives were optical practically unchanged, even after storage.
  • the concentrates differed partly due to different compositions.
  • the products A to C differed in the stabilizing Effect of isothiazolone - with the exception of C at Coolant concentrate SA 2146 - not significant, too not versus a separate addition of Kathon 893 and Pyrion-Na.
  • the preparations or active ingredients were each in the Concentrates incorporated from which then 4% dilutions in Norderstedter town water were used.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Lubricants (AREA)

Claims (16)

  1. Mélange d'additifs pour des produits réfrigérants lubrifiants comprenant :
    a. un isothiazolone non halogéné de formule :
    Figure 00280001
    dans lequel
    Y est un groupe alkyle en C1-C18 ou un groupe cycloalkyle en C3-C12 qui peut être substitué avec un ou plusieurs groupes hydroxy, cyano, alkylamino, dialkylamino, aryle, amino, carboxy, carbalcoxy, alcoxy, aryloxy, alkylthio, arylthio, cycloalkylamino, carbamoxy ou isothiazolonyle, un groupe non substitué alcynyle ou alcényle en C2-C8, un groupe aralkyle en C7-C10, qui peut être substitué avec un ou plusieurs groupes alkyle en C1-C4 ou groupes alcoxy en C1-C4, ou est un groupe aryle qui peut être substitué avec un ou plusieurs groupes nitro, alkyle en C1-C4, alkyle-acrylamino en C1-C4, carb-(C1-C4)-alcoxy ou sulfamyle, et
    R et R' sont respectivement indépendamment l'un de l'autre hydrogène, un groupe alkyle en C1-C4, un groupe cycloalkyle en C4-C8, ou sont liés ensemble en formant un groupe benzoisothiazolonyle,
    b. un stabilisant efficace contre la décomposition chimique de l'isothiazolone, choisi parmi le N-oxyde de la pyridinethiol-2, les sels métalliques ou d'ammonium du N-oxyde de la pyridinethiol-2, les complexes de sels métalliques du N-oxyde de la pyridinethiol-2, le 2,2'-dithiobis (pyridine N-oxyde) et des mélanges de ceux-ci, ainsi que le cas échéant un co-stabilisant, et
    c. un agent de solubilisation, choisi parmi le phénoxyéthanol, les phénoxypropanols, le 1-méthoxypropanol-2 et les mélanges de ceux-ci.
  2. Mélange d'additifs selon la revendication 1, caractérisé en ce que l'agent de solubilisation est contenu dans une quantité allant de 30 à 91,7 % en poids par rapport au mélange d'additifs.
  3. Mélange d'additifs selon la revendication 2, caractérisé en ce que l'agent de solubilisation est contenu dans une quantité allant de 30 à 75 % en poids par rapport au mélange d'additifs.
  4. Mélange d'additifs selon la revendication 3, caractérisé en ce que l'agent de solubilisation est contenu dans une quantité allant de 50 à 65 % en poids par rapport au mélange d'additifs.
  5. Mélange d'additifs selon l'une des revendications 1 à 4, caractérisé en ce que le co-stabilisant est un agent d'oxydation doux.
  6. Mélange d'additifs selon l'une des revendications 1 à 5, caractérisé en ce que le co-stabilisant est choisi parmi le butylcarbamate d'iodopropynyle, le peroxyde d'hydrogène, le tert-butylperoxyde, le bromate de sodium, les sels cuivriques, le 2-tert-butyl-6-méthylphénol et le bisulfure de pyrione.
  7. Mélange d'additifs selon l'une des revendications 1 à 6 qui comprend les composants suivants par rapport au mélange :
    a. de 2,25 à 20,25 % en poids de N-octyl-isothiazolone,
    b. environ de 1,3 à 10 % en poids de sel de sodium du N-oxyde de la pyridinethiol et
    c. de 30 à 91,7% en poids de 2-phénoxyéthanol, 2-phénoxypropanol ou 1-méthoxypropanol-2.
  8. Mélange d'additifs selon la revendication 7 qui comprend les composants suivants par rapport au mélange :
    a. de 6,75 à 20,25 % en poids de N-octyl-isothiazolone,
    b. de 4 à 10 % en poids de sel de sodium du N-oxyde de la pyridinethiol etc. de 30 à 75 % en poids de 2-phénoxyéthanol, 2-phénoxypropanol ou 1-méthoxypropanol-2.
  9. Mélange d'additifs selon la revendication 8 qui comprend les composants suivants par rapport au mélange :
    a. de 9 à 13,5 % en poids de N-octyl-isothiazolone,
    b. de 6 à 8 % en poids de sel de sodium du N-oxyde de la pyridinethiol et
    c. de 50 à 65 % en poids de 2-phénoxyéthanol, 2-phénoxypropanol ou 1-méthoxypropanol-2.
  10. Mélange d'additifs selon la revendication 9 qui comprend les composants suivants par rapport au mélange :
    a. environ 11 % en poids de N-octyl-isothiazolone,
    b. environ 7 % en poids de sel de sodium du N-oxyde de la pyridinethiol et
    c. environ 58% en poids de 2-phénoxyéthanol, 2-phénoxypropanol ou 1-méthoxypropanol-2.
  11. Produits réfrigérants lubrifiants caractérisés en ce qu'ils contiennent, outre des composants usuels, un mélange d'additifs selon l'une des revendications 1 à 10.
  12. Produits réfrigérants lubrifiants selon la revendication 11, caractérisé en ce qu'ils se présentent sous forme de concentrés d'agents réfrigérants lubrifiants ou sous une forme prête à l'emploi.
  13. Produits réfrigérants lubrifiants selon la revendication 11 ou 12, caractérisés en ce qu'ils se présentent sous forme de solution ou d'émulsion.
  14. Utilisation d'un mélange d'additifs selon l'une des revendications 1 à 10 pour préparer des produits réfrigérants lubrifiants.
  15. Utilisation selon la revendication 14, caractérisée en ce qu'un concentré d'agent réfrigérant lubrifiant est préparé.
  16. Utilisation selon la revendication 15, caractérisée en ce qu'un agent réfrigérant lubrifiant mélangé avec de l'eau est préparé.
EP96250190A 1995-09-08 1996-09-05 Préparations pour refrigerants Inbrifiants stabilisées Expired - Lifetime EP0773281B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19534532 1995-09-08
DE19534532A DE19534532C2 (de) 1995-09-08 1995-09-08 Additivmischungen für Kühlschmiermittelprodukte und deren Verwendung

Publications (3)

Publication Number Publication Date
EP0773281A2 EP0773281A2 (fr) 1997-05-14
EP0773281A3 EP0773281A3 (fr) 1998-05-13
EP0773281B1 true EP0773281B1 (fr) 2005-10-19

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DE (2) DE19534532C2 (fr)
ES (1) ES2247597T3 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2320026B (en) * 1996-12-05 2000-01-26 Sunkyong Ind Ltd Stabilized isothiazolone solution
GB9708267D0 (en) 1997-04-24 1997-06-18 Johnson & Johnson Chemical composition
DE60000804T2 (de) * 1999-04-16 2003-09-11 Rohm And Haas Co., Philadelphia Stabile mikrobizide Formulierung
DE19961621C2 (de) * 1999-12-13 2002-11-14 Schuelke & Mayr Gmbh Bakterizide und fungizide flüssige Zubereitungen für technische Produkte
WO2002067685A1 (fr) * 2001-02-26 2002-09-06 Lonza Inc. Preparations de conservateurs stables comprenant des composes halopropynyle et un solvant butoxydiglycol
EP1527684B1 (fr) * 2002-01-31 2013-02-27 Rohm And Haas Company Association microbicide synergique
US9034905B2 (en) 2003-02-05 2015-05-19 Rohm And Haas Company Synergistic microbicidal combinations
DE10340829A1 (de) * 2003-09-04 2005-04-07 Schülke & Mayr GmbH Salzarme oder salzfreie mikrobizide Zusammensetzung auf Basis von Isothiazolon-Derivaten und Pyriondisulfid
DE102004052878A1 (de) 2004-11-02 2006-05-04 Schülke & Mayr GmbH Isothiazolonhaltige Konservierungsmittel mit verbesserter Stabilität
DE102006045066B4 (de) * 2006-09-21 2010-07-01 Schülke & Mayr GmbH Mikrobizide Zubereitung auf der Basis von 1,2-Benzisothiazolin-3-on mit einem Gehalt an aromatischem Alkohol
DE102009048189A1 (de) 2009-10-02 2011-04-07 Schülke & Mayr GmbH Lagerstabile mikrobizide Konzentrate und deren Verwendung als Konservierungsmittel

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870795A (en) * 1973-02-28 1975-03-11 Rohm & Haas Stabilization of solutions of 3-isothiazolones employing certain metal nitrates and nitrites
DE3904099C1 (fr) * 1989-02-11 1990-07-12 Schuelke & Mayr Gmbh, 2000 Norderstedt, De
DE3911808A1 (de) * 1989-04-11 1990-10-18 Riedel De Haen Ag Fluessiges konservierungsmittel
ES2061890T5 (es) * 1989-11-10 2002-04-16 Thor Gmbh Soluciones acuosas estabilizadas de 3-isotiazolinonas.
GB9003871D0 (en) * 1990-02-21 1990-04-18 Rohm & Haas Stabilization of isothiazolones
US5037989A (en) * 1990-04-05 1991-08-06 Rohm And Haas Company Phenoxyalkanol as a stabilizer for isothiazolone concentrates
US5108500A (en) * 1990-12-10 1992-04-28 Rohm And Haas Company Stabilization of water insoluble 3-isothiazolones
JP3524937B2 (ja) * 1992-02-10 2004-05-10 日本エンバイロケミカルズ株式会社 工業用殺菌剤
GB9300936D0 (en) * 1993-01-19 1993-03-10 Zeneca Ltd Stable liquid compositions and their use
JPH07133205A (ja) * 1993-11-08 1995-05-23 Shinto Paint Co Ltd 木材用防カビ組成物
US5478797A (en) * 1994-11-21 1995-12-26 Rohm And Haas Company Bromate stabilization of nitrate-free 3-isothiazolones at pH 4-5.1
US5599827A (en) * 1995-05-16 1997-02-04 Rohm And Haas Company Stable microemulsions of certain 3-isothiazolone compounds

Also Published As

Publication number Publication date
EP0773281A2 (fr) 1997-05-14
DE59611282D1 (de) 2006-03-02
DE19534532C2 (de) 1999-04-08
EP0773281A3 (fr) 1998-05-13
DE19534532A1 (de) 1997-03-20
ES2247597T3 (es) 2006-03-01

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