WO2019120602A1 - Formulation de tmad/bit stable au stockage - Google Patents

Formulation de tmad/bit stable au stockage Download PDF

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Publication number
WO2019120602A1
WO2019120602A1 PCT/EP2018/000551 EP2018000551W WO2019120602A1 WO 2019120602 A1 WO2019120602 A1 WO 2019120602A1 EP 2018000551 W EP2018000551 W EP 2018000551W WO 2019120602 A1 WO2019120602 A1 WO 2019120602A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc
bit
tmad
composition according
mixtures
Prior art date
Application number
PCT/EP2018/000551
Other languages
German (de)
English (en)
Inventor
Rüdiger Baum
Thomas Wunder
Original Assignee
Thor Gmbh
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
Application filed by Thor Gmbh filed Critical Thor Gmbh
Priority to EP18830381.2A priority Critical patent/EP3726993A1/fr
Publication of WO2019120602A1 publication Critical patent/WO2019120602A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof

Definitions

  • the present invention relates to a storage-stable aqueous biocide composition in the form of a dispersion comprising the components: (a) 1 to 20 l, 2-benzisothiazolin-3-one (BIT) and / or its alkali metal salts, (b) 10 to 70 wt. -%
  • Tetramethylolacetylenediurea (c) 0.5 to 20% by weight of one or more zinc component (s) selected from the group consisting of zinc oxide (ZnO), zinc hydroxide (Zn (OH) 2 ), zinc carbonate (ZnC0 3 ) and Mixtures thereof and ad. 100% water.
  • the invention further relates to processes for the preparation of these biocidal compositions and their use for the protection of industrial materials and products against attack and destruction by microorganisms.
  • 2-Benzisothiazolin-3-one (BIT) or its sodium, potassium and lithium salts is a long-used in practice drug for the preparation of microbicidally active formulations.
  • 1,2-Benzisothiazolin-3-one (BIT) is characterized by good chemical and thermal stability and basically has a broad antimicrobial effect against bacteria, fungi and yeasts.
  • BIT-containing concentrates or biocidal products are generally formulated in the form of alkali metal salts at high pH.
  • co-solvents in the form of water-miscible solvents such as propylene glycol, have to be used in most cases despite the high pH values (compare U.S. 4,188,376).
  • BESTATIGUNGSKOPIE To reduce unwanted effects that can be caused by free formaldehyde BIT is usually used in combination with so-called Formaldehyddepotitatien, such as tetramethylolacetylenediurea (TMAD) (see, EP 1 249 166 Al).
  • TMAD tetramethylolacetylenediurea
  • a disadvantage of these known from the prior art synergistic mixtures of BIT and TMAD is that such mixtures with high active ingredient content can be formulated as storage-stable mixtures either with the aid of co-solvents or at a high pH of pH> 10 (see. W02006 / 102994 Al).
  • the corresponding formulations do not have too high a pH. Reasons for this are a less problematic handling and a lower degradation of formaldehyde (Cannizzarro reaction).
  • the object of the present invention was therefore to provide long-term stable compositions, in the form of a dispersion, containing BIT and TMAD, which are preferably solvent-free and preferably have a pH in the weakly acidic to slightly alkaline range.
  • a storage-stable aqueous biocide composition in the form of a dispersion, comprising the components:
  • TMAD tetramethylolacetylenediurea
  • (C) 0.5 to 20, preferably 1 to 10 wt .-% of one or more zinc component (s) selected from the group consisting of zinc oxide (ZnO), zinc hydroxide (Zn (OH) 2 ), zinc carbonate (ZnC0 3 ) and Mixtures thereof and
  • aqueous biocide compositions or dispersions defined above, the 1,2-benzisothiazolin-3-one (BIT) and / or its alkali metal salts and Tetramethylolacetylendihamstoff (TMAD), by the addition of the zinc component (s) have a satisfactory long-term stability during storage.
  • the biocidal compositions according to the invention are characterized in that their pH is in the range from 4 to 7, preferably in the range from 5.5 to 6.5.
  • such compositions are less problematic because of the almost neutral pH in their handling and are also characterized by a lower degradation of formaldehyde (Cannizzarro reaction).
  • the biocide composition is characterized in that the total sum of components (a), (b) and (c) is generally 11.5 to 70% by weight. preferably 15 to 60 wt .-%, particularly preferably 20 to 40 wt .-% is.
  • compositions according to the invention contain 1,2-benzisothiazolin-3-one (BIT) and / or its sodium, potassium or lithium salts or mixtures thereof.
  • BIT 1,2-benzisothiazolin-3-one
  • TMAD tetramethylolacetylenediurea
  • the ratio of 1,2-benzisothiazolin-3-one (BIT) and / or its sodium, potassium or lithium salts or mixtures thereof to tetramethylolacetylenediurea (TMAD) in the formulations according to the invention is in a weight ratio of 1: 1 to 1: 50, preferably from 1: 2 to 1: 20, more preferably from 1: 3 to 1:10.
  • the biocidal compositions of the invention contain the 1,2-benzisothiazolin-3-one (BIT) and / or its sodium, potassium or lithium metal salts or mixtures thereof.
  • the amounts of BIT and / or its alkali metal salts in the compositions are generally from 1 to 20 wt .-%, preferably from 2 to 15 wt .-%, each based on the total weight of the composition.
  • the biocide compositions according to the invention generally comprise TMAD in an amount of 10 to 70% by weight, preferably in an amount of 15 to 30% by weight, based in each case on the total weight of the composition.
  • the biocidal compositions of the invention further contain the zinc component (s) selected from the group consisting of zinc oxide (ZnO), zinc hydroxide (Zn (OH) 2 ), zinc carbonate (ZnC0 3 ) and mixtures thereof, generally in an amount of from 0.5 to 20 wt .-%, preferably in an amount of 1 to 10 wt .-% and particularly preferably in an amount of 2 to 5 wt .-%, each based on the total weight of the composition.
  • the zinc component (s) selected from the group consisting of zinc oxide (ZnO), zinc hydroxide (Zn (OH) 2 ), zinc carbonate (ZnC0 3 ) and mixtures thereof, generally in an amount of from 0.5 to 20 wt .-%, preferably in an amount of 1 to 10 wt .-% and particularly preferably in an amount of 2 to 5 wt .-%, each based on the total weight of the composition.
  • ZnO zinc oxide
  • Zn (OH) 2 zinc hydroxide
  • ZnC0 3 zinc carbonate
  • the biocidal compositions according to the invention are characterized in that they contain zinc oxide as component (c).
  • compositions according to the invention are distinguished by good long-term stability. No significant drug degradation was observed during storage, nor did crystal formation or precipitation or stronger pH shifts occur. Furthermore, it was found that the proportion of free formaldehyde in the composition is very low and is generally ⁇ 1%, in particular ⁇ 0.5%, and does not change significantly during storage.
  • the biocidal compositions according to the invention contain, in addition to the components (a), (b) and (c) ad. 100% water. That is, in addition to the components (a), (b), (c) and optionally further components such as thickeners, defoamers and dispersants, water is the main solvent of the compositions.
  • the biocidal compositions according to the invention contain about 10 to 90% by weight, preferably about 30 to 60 wt .-% water, each based on the total weight of the composition.
  • compositions according to the invention are free of co-solvents according to a preferred embodiment.
  • the compositions according to the invention may also contain co-solvents in amounts of from 0 to 5% by weight, preferably from 0 to 3% by weight.
  • co-solvents are generally used with water-miscible solvents such as alcohols such as butanol, glycerol, glycols and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone ,
  • the biocidal compositions according to the invention can be prepared by dissolving (a) BIT and / or its sodium salt and / or its potassium salt and / or its lithium salt in water, if appropriate with the addition of sodium hydroxide, potassium hydroxide, lithium hydroxide or mixtures thereof, and b), a solution of tetramethylol diurea (TMAD) in water and (c) the at least one zinc component selected from the group consisting of zinc oxide (ZnO), zinc hydroxide (Zn (OH) 2 ), zinc carbonate (ZnC0 3 ) and mixtures thereof ,
  • the zinc component preferably ZnO
  • TMAD preferably ZnO
  • a commercial solution of TMAD such as Acticide ® F (N)
  • the BIT in form of an aqueous dispersion as ACTICIDE ® BW33
  • the pH of the biocide composition may be adjusted to a value in the range of pH 4 to pH 9, preferably Ph 4 to pH 7, by adding sodium hydroxide, potassium hydroxide, lithium hydroxide or mixtures thereof or, if appropriate, with the aid of hydrochloric acid become.
  • the alkaline 1,2-benzisothiazolin-3-one (BIT) solution used to prepare the biocidal compositions according to the invention can be prepared, for example, by dissolving l, 2-benzisothiazolin-3-one in water, sodium, potassium or lithium salt and optionally NaOH, KOH or LiOH added or by starting from 1,2-benzisothiazolin-3-one and preparing its salts by addition of NaOH, KOH or LiOH, or mixtures thereof in water.
  • BIT 1,2-benzisothiazolin-3-one
  • TM AD tetramethylolacetylenediurea
  • the solution of tetramethylolacetylenediurea (TM AD) used to produce the biocide of the invention can either be prepared analogously to that described in EP 0060471 Al method or adding standard solutions of tetramethylolacetylenediurea (TM AD) as Acticide ® F (N).
  • the at least one zinc component selected from the group consisting of zinc oxide (ZnO), zinc hydroxide (Zn (OH) 2 ), zinc carbonate (ZnC0 3 ) and mixtures thereof used in the preparation of the biocidal compositions according to the invention are commercially available chemicals, which are known in the art.
  • compositions according to the invention are suitable for the protection of technical materials and products against infestation and destruction by microorganisms.
  • the compositions according to the invention can be used to preserve functional fluids and water-containing technical products which are susceptible to microbial attack.
  • paints, paints, plasters and other coating compositions such as for example, pressure thickeners, slurries of other raw materials such as color pigments (eg iron oxide pigments, carbon black pigments, titanium dioxide pigments) or slurries of fillers and coating pigments such as kaolin, calcium carbonate or talc, construction chemicals such as concrete additives based on molasses, lignosulfonates or polyacrylates, bituminous emulsions or jointing compounds, glues or adhesives
  • polymer dispersions based on, for example, polyacrylate, polystyrene acrylate, styrene butadiene, polyvinyl acetate, etc.
  • biocidal compositions according to the invention are known to the person skilled in the art of biocides and can be selected from them depending on the application of the biocidal composition according to the invention.
  • the use concentrations of the composition to be used according to the invention depend on the nature and occurrence of the microorganisms to be controlled, the initial microbial load and on the composition of the material to be protected. The optimum amount to be used for a particular application can be determined prior to practical use by means of test series in the laboratory. In general, the use concentrations are in the range of 0.01 to 5 wt .-%, preferably from 0.05 to 1.0 wt .-% of the composition according to the invention, based on the material to be protected.
  • biocide compositions according to the invention were prepared and stored at 21 ° C. over a period of 26 weeks.
  • storage-stable dispersions or compositions can be obtained by adding the zinc component.
  • ACTICIDE BW 33 (aqueous dispersion with 33% BIT)

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une composition biocide aqueuse stable au stockage se présentant sous la forme d'une dispersion, contenant les composants suivants : (a) 1 à 20 % en poids de 1,2-benzo-isothiazolin-3-one (BIT) et/ou ses sels de métaux alcalins ; (b) 10 à 70 % en poids de tétraméthylol-acétylène-diurée (TMAD) ; (c) 0,5 à 20 % en poids d'un ou de plusieurs composants de zinc choisis parmi le groupe constitué d'oxyde de zinc (ZnO), d'hydroxyde de zinc (Zn(OH)2), de carbonate de zinc (ZnCO3) et de mélanges de ces derniers et un complément d'eau jusqu'à 100 %. L'invention concerne en outre des procédés de fabrication desdites compositions biocides ainsi que leur utilisation pour protéger des matériaux et produits techniques contre l'infestation et la destruction par des micro-organismes.
PCT/EP2018/000551 2017-12-22 2018-12-11 Formulation de tmad/bit stable au stockage WO2019120602A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP18830381.2A EP3726993A1 (fr) 2017-12-22 2018-12-11 Formulation de tmad/bit stable au stockage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP17002068 2017-12-22
EP17002068.9 2017-12-22

Publications (1)

Publication Number Publication Date
WO2019120602A1 true WO2019120602A1 (fr) 2019-06-27

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EP (1) EP3726993A1 (fr)
WO (1) WO2019120602A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4188376A (en) 1977-09-30 1980-02-12 Imperial Chemical Industries Limited Stable liquid compositions containing salts of 1,2-benzisothiazolin-3-one
EP0060471A1 (fr) 1981-03-13 1982-09-22 Riedel-De Haen Aktiengesellschaft Microbiocide et son usage
EP1249166A1 (fr) 2001-03-16 2002-10-16 Bode Chemie GmbH & Co. Combinaisons synergistiques de principes biocides comprenant tetramethylol acetylendiurée et une isothiazolin-3-one, et leur utilisation comme conservateurs
WO2004040980A1 (fr) * 2002-11-08 2004-05-21 Lanxess Deutschland Gmbh Substances microbicides
WO2006102994A1 (fr) 2005-03-26 2006-10-05 Lanxess Deutschland Gmbh Formulations contenant du bit/tmad a base d'eau
US20070275945A1 (en) * 2006-05-25 2007-11-29 Troy Corporation Immobilized 1,2-benzisothiazolin-3-one
EP2020178A1 (fr) * 2007-08-01 2009-02-04 THOR GmbH Composition biocide comportant le sel de potassium de 1,2-benzisothiazolin-3-one et éthylène glycol
CN103627239A (zh) * 2013-12-12 2014-03-12 李泽国 一种水性涂料抗菌防霉防藻伴侣及其制备方法
WO2017174180A1 (fr) * 2016-04-05 2017-10-12 Thor Gmbh Compositions biocides synergiques contenant de la 5-chloro-2-méthylisothiazolin-3-one

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4188376A (en) 1977-09-30 1980-02-12 Imperial Chemical Industries Limited Stable liquid compositions containing salts of 1,2-benzisothiazolin-3-one
EP0060471A1 (fr) 1981-03-13 1982-09-22 Riedel-De Haen Aktiengesellschaft Microbiocide et son usage
EP1249166A1 (fr) 2001-03-16 2002-10-16 Bode Chemie GmbH & Co. Combinaisons synergistiques de principes biocides comprenant tetramethylol acetylendiurée et une isothiazolin-3-one, et leur utilisation comme conservateurs
WO2004040980A1 (fr) * 2002-11-08 2004-05-21 Lanxess Deutschland Gmbh Substances microbicides
WO2006102994A1 (fr) 2005-03-26 2006-10-05 Lanxess Deutschland Gmbh Formulations contenant du bit/tmad a base d'eau
US20070275945A1 (en) * 2006-05-25 2007-11-29 Troy Corporation Immobilized 1,2-benzisothiazolin-3-one
EP2020178A1 (fr) * 2007-08-01 2009-02-04 THOR GmbH Composition biocide comportant le sel de potassium de 1,2-benzisothiazolin-3-one et éthylène glycol
CN103627239A (zh) * 2013-12-12 2014-03-12 李泽国 一种水性涂料抗菌防霉防藻伴侣及其制备方法
WO2017174180A1 (fr) * 2016-04-05 2017-10-12 Thor Gmbh Compositions biocides synergiques contenant de la 5-chloro-2-méthylisothiazolin-3-one

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