Synergistic biocidal compounds containing 5-chloro-2-methylisothiazolin-3-one
Patent Information
- Application Number
- AT2017716784T
- Authority / Receiving Office
- AT · AT
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2016-04-05
- Filing Date
- 2017-03-29
- Publication Date
- 2026-07-15
- Estimated Expiration
- 2037-03-29
AI Technical Summary
Existing biocide compositions, particularly those containing 5-chloro-2-methylisothiazolin-3-one, face challenges such as allergenic effects on users and inefficiencies in concentration usage, necessitating the development of synergistic mixtures that can operate effectively in lower concentrations.
A biocide composition combining 5-chloro-2-methylisothiazolin-3-one with at least one additional component from the group of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropan-1,3-diol, and zinc, with methylisothiazolin-3-one present in concentrations up to 2% by weight, to enhance biocidal efficacy while reducing allergenic risks.
The synergistic interaction allows for effective preservation of technical products at lower concentrations of individual components, reducing the risk of allergies and extending product shelf life by maintaining microbial control without the need for high concentrations of 5-chloro-2-methylisothiazolin-3-one in the final product.
Abstract
Description
Containing synergistic biocidal compositions 5-Chloro-2-methylisothiazolin-3-one The present invention relates to a biocidal composition comprising 5-chloro-2-methylisothiazolin-3-one and at least one further component selected from the group consisting of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, and zinc. The biocidal composition according to the invention is characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. The invention further relates to the use of the biocidal compositions according to the invention for the preservation of technical products. Technical products, especially water-based ones such as paints, varnishes, emulsions, and cosmetics, are typically manufactured using natural or biodegradable raw materials. These raw materials and the water used as a solvent are often contaminated with microorganisms such as bacteria, yeasts, and fungi. If these products are not preservatives, they can exhibit high microbial counts as early as one day after production. To ensure that these products meet hygienic requirements and thus guarantee the shelf life of the technical products, so-called biocides are added. One of these biocides is 5-chloro-2-methylisothiazolin-3-α (CMIT). This compound has a broad biocidal effect but several disadvantages in practical handling. For example, it can trigger allergies in people who handle it. To overcome the disadvantages of CMIT, which, although highly effective, also has drawbacks for the end user, the search in the 1990s focused on alternative biocides or biocidal compositions whose active ingredients work synergistically and can be used in lower concentrations when applied together, compared to the concentrations required for the individual components. Thus, since the beginning of the 1990s, the synergistic mixture of the isothiazolinones 2-methylisothiazolin-3-one (MIT) and 1,2-benzisothiazolin- disclosed in EP 1 005 271 Bl has been available. 3-on (BIT) is used as a biocidal composition. This mixture is marketed by Thor GmbH (Speyer, Germany) as Acticide MBS and is free of 5- Chloro-2-methylisothiazolin-3-one and currently represents the standard for container preservation of water-based paints and plasters. Furthermore, for example, European patent application EP 0 676 140 discloses a synergistic biocidal composition containing 2-methylisothiazolin-3-one and 2-n-octylisothiazolin-3-one as a replacement for compositions containing 5-chloro-2-methylisothiazolin-3-one. EP-B 1 030 558 also discloses a synergistic biocidal composition containing 2-methylisothiazolin-3-one and 3-iodo-2-propynyl-N-butylcarbamate. This synergistic composition is suitable for controlling microorganisms even at low concentrations. Based on the state of the art discussed above, there is a need for further biocide compositions whose components work synergistically together and can therefore be used in lower concentrations when used simultaneously, compared to the concentrations required in the case of the individual components. The invention solves this problem by providing a biocide composition containing 5-chloro-2-methylisothiazolin-3-one, and at least one further component selected from the group consisting of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, and zinc. The biocide composition according to the invention is characterized in that it contains methyl- 4-isothiazolin-3-one in the range of 0 to 2 wt%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. The biocide composition according to the invention has the advantage that the 5-chloro-2-methylisothiazolin-3-οη and the at least one component from the group mentioned above act synergistically together and can therefore be used in low concentrations when used simultaneously, compared to low concentrations in the case of the individual components. The present invention further makes it possible to use the extremely effective 5-Chloro-2-methylisothiazolin-3-one, which is free or nearly free of 2-methylisothiazolin-3- The aim is to preserve products with it and to treat them before placing them on the market so that the 5-chloro-2-methylisothiazolin-3-one is no longer present in the final product, thus significantly reducing the allergy risk posed by these products to the end user. The biocidal composition according to the invention is generally characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. According to a preferred embodiment of the invention, the biocidal composition is characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 1 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. According to a particularly preferred embodiment, the biocidal composition is characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 0.5 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. In the context of the present invention, "at least one" means that the biocide composition contains a single additional component or compound, or several, i.e., two or three components or compounds from the respective group. According to a preferred embodiment, the present invention relates to a biocidal composition containing 5-chloro-2-methylisothiazolin-3-one and at least one further component. The biocidal composition is characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. The biocidal composition is further characterized in that that the weight ratio of 5-chloro-2-methylisothiazolin-3-one to 1,2-benzisothiazolin-3-0 is in the range of 1:2.5 to 1:300, that the weight ratio of 5-chloro-2-methylisothiazolin-3-one to 2-bromo-2-nitropropane-1,3-diol is in the range of 1:2 to 1:40 and that the weight ratio of 5-chloro-2-methylisothiazolin-3-one to zinc is in the range of 1:6 to 1:576. Svnergistic biocidal composition containing 5-chloro-2-methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one (BIT): According to one embodiment, the invention relates to a biocidal composition containing 5-chloro-2-methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one (BIT). The biocidal composition according to the invention is characterized in that it contains methyl- 4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. According to a preferred embodiment, the invention relates to a biocide composition containing 5-chloro-2-methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one, in a weight ratio of 5-chloro-2-methylisothiazolin-3-one to 1,2-benzisothiazolin-3-one generally in the range of 1:2.5 to 1:300, preferably in the range of 1:2.5 to 1:100, and particularly preferably in the range of 1:2.5 to 1:50. The biocide composition according to the invention is characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. Svnergistic biocidal composition containing 5-chloro-2-methylisothiazolin-3-one and 2-bromo-2-nitropropane-1,3-diol (Bronopol): According to one embodiment, the invention relates to a biocidal composition containing 5-chloro-2-methylisothiazolin-3-one and 2-bromo-2-nitropropane-1,3-diol (Bronopol). The biocidal composition according to the invention is characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. According to a preferred embodiment, the invention relates to a biocidal composition containing 5-chloro-2-methylisothiazolin-3-one and 2-bromo-2-nitropropane-1,3-diol in a weight ratio of 5-chloro-2-methylisothiazolin-3-one to 2-bromo-2-nitropropane-1,3-diol, generally in the range of 1:2 to 1:40, preferably in the range of 1:2 to 1:30, and particularly preferably in the range of 1:5 to 1:30. The biocidal composition according to the invention is characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. A supplementary biocidal composition containing 5-chloro-2-methylisothiazolin-3-one and zinc is also described. According to one embodiment, the invention relates to a biocide composition containing 5-chloro-2-methylisothiazolin-3-one and zinc. The biocide composition according to the invention is characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. Within the scope of the invention, it was demonstrated that the effect of 5-chloro-2-methyl-4-isothiazolin-3-one is surprisingly synergistically enhanced in the presence of zinc. In the context of the present invention, the zinc is provided by at least one zinc compound serving as a zinc source. The zinc compound is preferably selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc ascorbate, zinc dehydroacetate, zinc hydroxide, and zinc carboxylate. According to a preferred embodiment of the invention, the zinc compound is selected from the group consisting of zinc oxide, zinc chloride, and zinc carbonate. According to a preferred embodiment, the invention relates to a biocide composition containing 5-chloro-2-methylisothiazolin-3-one and zinc in a weight ratio of 5-chloro-2-methylisothiazolin-3-one to zinc, generally in the range of 1:6 to 1:576, preferably in the range of 1:6 to 1:250, and particularly preferably in the range of 1:6 to 1:125. The zinc compound(s) mentioned above is / are...are present in such a quantity that the ratio between 5-chloro-2-methylisothiazolin-3-one and zinc defined above results in the biocide composition. The biocide composition according to the invention is further characterized in that it contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one. A biocidal composition comprising exclusively 5-chloro-2-methylisothiazolin-3-one with a methyl-4-isothiazolin-3-one content in the range of 0 to 2 wt.%, based on the total content of 5-chloro-2-methyl-4-isothiazolin-3-one, and at least one further component selected from the group consisting of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol and zinc in the respective specified weight ratios, without the presence of any further component, shall be referred to within the scope of the present invention as the “biocidal composition according to the invention”. In addition to 5-chloro-2-methylisothiazolin-3-0α with a methyl-4-isothiazolin-3-one content in the range of 0 to 2 wt%, based on the total content of 5-chloro-2-methyl-4-isothiazolin-3-one, and at least one further component selected from the group consisting of 1,2-benzisothiazolin-3-0α, 2-bromo-2-nitropropane-1,3-diol, and zinc, a "biocidal composition according to the invention" may comprise one or more further components. The further component(s) may have a microbicidal effect, or they may not have a microbicidal effect, i.e., they may be, for example, a solvent, dispersant, or suspending agent. It is advantageous if the biocide composition according to the invention contains 5-chloro-2-methylisothiazolin-3-0α with a methyl-4-isothiazolin-3-one content in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one, and at least one further component selected from the group consisting of 1,2-benzisothiazolin-3-0α, 2-bromo-2-nitropropane-1,3-diol and zinc in a total concentration of 0.5 to 50 wt.%, preferably 1 to 20 wt.%, particularly preferably 2.5 to 10 wt.%, each based on the total biocide composition. In a further embodiment, the biocide composition according to the invention consists predominantly of 5-chloro-2-methylisothiazolin-3-one with a methyl-4-isothiazolin-3-one content in the range of 0 to 2 wt.-%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one, and at least one further component selected from the group consisting of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, and zinc (i.e., the biocidal composition or biocidal mixture according to the invention). This means that the biocidal composition according to the invention contains, as its main component, the biocidal mixture according to the invention, preferably in an amount equal to or greater than 50% by weight, more preferably in an amount equal to or greater than 70% by weight, in particular in an amount equal to or greater than 90% by weight, and in particular in an amount equal to or greater than 95% by weight, based on the total mass of biocidal active ingredient. In addition, at least one further biocide may be present, as well as one or more solvents, dispersants, or suspending agents. According to a further embodiment of the invention, the biocidal composition according to the invention consists essentially of the biocidal mixture according to the invention, i.e., that in addition to the mixture, one or more other biocides may be present, but these are present in such a quantity that the respective biocide, different from the components of the mixture, does not contribute to the overall effect of the resulting mixture. Therefore, if the biocidal effect of a biocidal composition according to the invention, which—in addition to the components of the biocidal mixture according to the invention as an essential component—also contains one or more other biocides in subordinate or lesser concentrations, is unchanged compared to the use of the biocidal mixture according to the invention, the latter is referred to in connection with the present invention as "essentially consisting of".One or more other components without a biocidal effect may be present, such as solvents. In a further embodiment, the biocidal composition according to the invention can consist of the components of the biocidal mixture according to the invention as the sole biocidal active ingredients, i.e., an active ingredient content of 100% 5-chloro-2-methylisothiazolin-3-one with a content of methyl-4-isothiazolin-3-one in the range of 0 to 2 wt%, based on the total content of 5-chloro-2-methyl-4-isothiazolin-3-one, and at least one further component selected from the group consisting of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, and zinc. In such a case, it is only possible that one or more further components without a biocidal effect are present, such as solvents or stabilizing agents. According to one embodiment of the invention, the biocidal composition according to the invention is available as a concentrate, which is added to the substances or products to be preserved. The concentrate advantageously contains 5-chloro-2-methylisothiazolin-3-one in an amount of 0.5 to 50 wt.%, preferably in an amount of 0.5 to 20 wt.%, and particularly preferably in an amount of 0.7 to 10 wt.%, based on the total mass of the concentrate. The amount of at least one further compound selected from the group consisting of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, and zinc in the concentrate is generally 0.5 to 50 wt.%, preferably 1 to 20 wt.%, and particularly preferably 1 to 5 wt.%, based on the total mass of the concentrate. In an advantageous embodiment, the biocidal composition is in the form of a liquid preparation, for example as a solution, suspension, or dispersion in a liquid medium. Of course, the biocidal composition according to the invention can also be mixed directly into a product to be preserved. This is done by adding the individual microbicidal active components to the product to be preserved. It is advantageous if the biocide composition according to the invention is available for use in combination with a polar or non-polar liquid medium. Preferred polar liquid media are water, aliphatic alcohols with 1 to 4 carbon atoms, for example ethanol and isopropanol, a glycol, for example ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol and tripropylene glycol, a glycol ether, such as butyl glycol and butyldiglycol, a glycol ester, such as butyl glycol acetate or 2,2,4-trimethylpentanediol monoisobutyrate, a polyethylene glycol, a propylene glycol, N,N-dimethylformamide or a mixture of two or more such media. The polar liquid medium is, in particular, water and / or glycol. Nonpolar liquid media such as aromatics, preferably xylene and toluene, can be used; these can also be used alone or as mixtures of two or more such media. The biocide composition according to the invention can also be combined simultaneously with a polar or a non-polar liquid medium. In general, it is possible to adapt the biocidal composition according to the invention to specific areas of application by adding further active ingredients, for example, to increase its efficacy or improve its compatibility with the substances that protect against microorganisms. These further substances are known to those skilled in the art in the field of biocides and can be selected by them depending on the application of the biocidal composition according to the invention. The biocidal composition according to the invention can be used for preservation in a wide variety of fields. The preparation according to the invention is preferably used for container preservation, particularly for the preservation of coatings such as paints, varnishes, and plasters, polymer dispersions, emulsions, slurries, pigment preparations, detergents and cleaning agents, and adhesives. The invention also relates to products containing the biocidal composition according to the invention.These products are generally selected from lignosulfonates and starch preparations in coatings, paints, varnishes, stains and plasters, emulsions, latices, polymer dispersions, chalk impregnations, mineral slurries, ceramic masses, adhesives, perfumes, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, pigment pastes and pigment dispersions, inks, lithographic fluids, thickeners, cosmetic products, toiletries, water cycles, fluids used in wood processing, fluids used in petroleum production, fluids used in paper processing, fluids used in leather production, fluids used in textile production, drilling and cutting oils, hydraulic fluids and cooling lubricants. In practical application, the biocidal composition can be introduced into the product to be preserved either as a ready-made mixture or by separately adding the individual components. The concentration of the components in the preservation application (the application concentration) can vary widely depending on the intended use and is usually determined by a person skilled in the art in biocides. The concentration ranges given below provide a guideline for the concentrations to be used. In the product preserved with the composition according to the invention, at least one component is selected from the group consisting of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, and zinc. The concentration of the components in the preservative application (the application concentration) can vary over a wide range depending on the intended use and is usually determined by a person skilled in the art in the field of biocides. The concentration ranges given below provide a guideline for the concentrations to be used. In the product preserved with the biocide composition according to the invention, the chlor-2-methylisothiazolin-3-one is generally present in an amount in the range of 1 to 500 ppm, preferably in an amount of 5 to 200 ppm, preferably in an amount of 10 to 100 ppm, and particularly preferably in an amount of 10 to 30 ppm. The product preserved with the composition according to the invention contains at least one further component selected from the group consisting of 1,2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, and zinc. In the presence of 1,2-benzisothiazolin-3-one as a further component, it is generally contained in the product preserved with the composition according to the invention in an amount in the range of 1 to 1,000 ppm, preferably in an amount of 5 to 750 ppm, more preferably in an amount of 10 to 500 ppm, and particularly preferably in an amount of 25 to 250 ppm. In the presence of 2-bromo-2-nitropropane-1,3-diol as a further component, this is generally present in the product preserved with the composition according to the invention in an amount in the range of 1 to 2,000 ppm, preferably in an amount of 5 to 1,000 ppm. ppm, preferably in an amount of 10 to 500 ppm, particularly preferably in an amount of 20 to 250 ppm. In the presence of zinc as a further component, it is generally contained in the product preserved with the composition according to the invention in an amount in the range of 10 to 5,000 ppm, preferably in an amount of 25 to 2,500 ppm, preferably in an amount of 50 to 1,000 ppm, and particularly preferably in an amount of 100 to 500 ppm. The following examples serve to further illustrate the present invention. Investigation of the synergistic effect The synergistic interaction of a combination of 5-chloro-2-methylisothiazolin-3-one, containing 0.003 wt% of the total 5-chloro-2-methyl-4-isothiazolin-3-one, with a biocide / substance selected from the group consisting of 1,2-benzisothiazolin-3-one (BIT), 2-bromo-2-nitropropane-1,3-diol (Bronopol), and zinc was investigated. The Gram-negative bacterium Pseudomonas putida (DSM 25068) was used as the test organism. Mixtures with varying concentrations of the respective active ingredients were prepared and tested for their efficacy against Pseudomonas putida. The tests were performed in Müller-Hinton broth (MHB, pH 7.0) with a cell density of 10 6 Germs per ml. The microtiter plates were incubated for 48 hours at 30 °C. After 48 hours, the samples were evaluated for turbidity due to growth, and the optical density was also determined photometrically. In this way, the minimum inhibitory concentrations (MICs) of the two active ingredients were determined individually and in combination. The resulting synergism was numerically represented by calculating the synergy index (SI). The calculation was performed according to the established method of FC Kuli et al., Applied Microbiology, Vol. 9 (1961), p. 538. There, the SI is calculated using the following formula: Synergy index SI = Q a / Q A + Qb / Qß Q a = Concentration of component A in the mixture A + B Q A = Concentration of component A as the sole biocide Q b = Concentration of component B in the mixture A + B QB = Concentration of component B as the sole biocide If the synergy index is greater than 1, this indicates antagonism. If the synergy index is 1, this indicates that the effects of the two biocides / compounds are additive. If the synergy index is less than 1, this indicates synergism between the two biocides. If the synergy index has a value above 1, this means that an antagonism exists. Example 1: Investigation of the synergistic interaction between chlor-2-methyl-4-isothiazolin-3-one (CMIT) and 1,2-benzisothiazolin-3-one (BIT). Calculation of the synergy index of chlor-2-methyl-4-isothiazolin-3-one (CMIT) and 1,2-benzisothiazolin-3-one (BIT) with respect to Pseudomonas putida at an incubation time of 48 hours at 30 °C. Table 1 Qa: Concentration of CIT in the mixture that shows an endpoint QA: Concentration of CIT as the sole agent that shows an endpoint. Qb: Concentration of BIT in the mixture that shows an endpoint. QB: Concentration of BIT as the sole agent, showing an endpoint. Table 2 shows that the optimal synergism, i.e., the lowest synergy index (0.69) of a biocidal composition of CMIT and BIT, occurs at a ratio of 1 ppm CMIT to 2.5 ppm BIT. Synergism can be demonstrated when the weight ratio of the biocides CMIT and BIT is in the range of 1:2.5 to 1:300. Example 2: Investigation of the synergistic interaction between chlor-2-methyl-4-isothiazolin-3-one (CMIT) and 2-bromo-2-nitropropane-1,3-diol (Bronopol) Calculation of the synergy index of chloro-2-methyl-4-isothiazolin-3-one (CMIT) and 2-bromo-2-nitropropane-1,3-diol (Bronopol) with respect to Pseudomonas putida after an incubation period of 48 hours at 0 °C. Table 2 Qa: Concentration of CIT in the mixture that shows an endpoint QA: Concentration of CIT as the sole agent that shows an endpoint Qb: Concentration of bronopol in the mixture that shows an endpoint QB: Concentration of bronopol as the sole agent, showing an endpoint Table 2 shows that the optimal synergism, i.e., the lowest synergy index (0.50), of a biocidal composition of CMIT and Bronopol is achieved at a The ratio is 0.25 ppm CMIT to 5 ppm Bronopol. Synergism can be demonstrated if the weight ratio of the biocides CMIT and Bronopol is in the range of 1:2 to 1:40. Example 3: Investigation of the synergistic interaction between chlor-2-methyl-4-isothiazolin-3-one (CMIT) and zinc Calculation of the synergy index of chlor-2-methyl-4-isothiazolin-3-one (CMIT) and zinc (added as zinc chloride, ZnCl2) with respect to Pseudomonas putida at an incubation time of 48 hours at 30 °C. Table 3 Qa: Concentration of CIT in the mixture that shows an endpoint QA: Concentration of CIT as the sole agent that shows an endpoint Qb: Concentration of Zn in the mixture that shows an endpoint QB: Concentration of Zn as the sole agent that shows an endpoint Table 3 shows that the optimal synergism, i.e., the lowest synergy index (0.63), of a biocidal composition of CMIT and ZnCl2 occurs at a ratio of 0.5 ppm CMIT to 72 ppm Zn. Synergism can be demonstrated when the weight ratio of the components CMIT and Zn is in the range of 1:6 to 1:576.
Claims
Patent claims 1. Biocidal composition containing 5-chloro-2-methylisothiazolin-3-one and at least one further component selected from Group 1, 2-benzisothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol and zinc, characterized in that the composition contains methyl-4-isothiazolin-3-one in the range of 0 to 2 wt.%, based on the total proportion of 5-chloro-2-methyl-4-isothiazolin-3-one.
2. Biocidal composition according to claim 1, characterized in that the weight ratio of 5-chloro-2-methylisothiazolin-3-one to 1,2-benzisothiazolin-3-one is in the range of 1:2.5 to 1:300, that the weight ratio of 5-chloro-2-methylisothiazolin-3-one to 2-bromo-2-nitropropane-1,3-diol is in the range of 1:2 to 1:40 and that the weight ratio of 5-chloro-2-methylisothiazolin-3-one to zinc is in the range of 1:6 to 1:
576.
3. Biocidal composition according to claim 1 or 2, characterized in that it contains the 5-chloro-2-methylisothiazolin-3-one and the at least one further biocide in a total concentration of 0.5 to 50 wt.%, based on the total biocidal composition.
4. Biocidal composition according to one of claims 1 to 3, characterized in that it comprises a polar and / or nonpolar medium.
5. Biocidal composition according to claim 4, characterized in that it comprises as a polar liquid medium water, an aliphatic alcohol with 1 to 4 carbon atoms, a glycol, a glycol ether, a glycol ester, a polyethylene glycol, a propylene glycol, N,N-dimethylformamide, 2,2,4-trimethylpentanediol monoisobutyrate or a mixture of such.
6. Biocidal composition according to one of claims 1 to 5, characterized in that it is in the form of a liquid preparation.
7. Use of the biocide composition according to any one of claims 1 to 6 for container preservation.
8. Use of the biocide composition according to claim 7 for the container preservation of coatings such as paints, varnishes and plasters, polymer dispersions, emulsions, latices and adhesives.
9. Preserved product containing a biocide composition as described in any one of claims 1 to 7.
10. Preserved product according to claim 9, selected from lignosulfonates and starch preparations in coatings, paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, chalk slurries, mineral slurries, ceramic masses, adhesives, perfumes, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, pigment pastes and pigment dispersions, inks, lithographic fluids, thickeners, cosmetic products, toiletries, water cycles, fluids used in wood processing, fluids used in petroleum production, fluids used in paper processing, fluids used in leather production, fluids used in textile production, drilling and cutting oils, hydraulic fluids and cooling lubricants.