Biocidal mixture

Abstract

The present invention relates to certain biocidal mixtures containing IPBC and azoxystrobin, their preparation, coatings containing them, and their use in inhibiting or controlling the growth of filamentous fungi on or in surface coatings.

Description

[Technical field]

[0001] The present invention relates to certain biocide mixtures comprising IPBC and azoxystrobin, their preparation, coating compositions containing them, and their use to inhibit or control the growth of mold on or in surface coatings. [Background technology]

[0002] US Pat. No. 5,399,433 has already disclosed the use of IPBC (3-iodopropynyl N-butylcarbamate) in coating compositions to protect against mold growth, but the use of IPBC on its own still has disadvantages.

[0003] Therefore, it was necessary to search for a more effective solution to improve the antibacterial spectrum of coating composition preparations against mold.For example, in (Patent Document 2), IPBC is combined with DCOIT (4,5-dichloro-2-n-octyl-4-isothiazolin-3-one) as a mixing partner to achieve this purpose (see Table 1 therein).However, DCOIT is now to be avoided in an increasing number of application fields, so alternative mixing partners had to be searched for for improved effectiveness compared to IPBC as an individual active ingredient.

[0004] Other mixtures of IPBC, for example those with certain strobilurins, such as kresoxim-methyl, have already been described in the examples of (US Pat. No. 5,399,633) for wood-rotting fungi, but such mixtures also have disadvantages for other applications, in particular for use in aqueous coating compositions, such as paints, for the purpose of protecting coatings against molds, such as Ascomycetes and Deuteromycetes. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Pat. No. 4,276,211 [Patent Document 2] European Patent Application Publication No. 431752 [Patent Document 3] JP 2003073211 A Summary of the Invention [Problem to be solved by the invention]

[0006] It was therefore an object of the present invention to find improved biocide mixtures suitable for use in aqueous coating compositions, e.g. paints, in particular for the purpose of protecting coatings against molds, e.g. Ascomycetes and Deuteromycetes. [Means for solving the problem]

[0007] Biocide Mixtures What was surprisingly found was that it is a biocide. a) Azoxystrobin (methyl(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate) (or in the following text also abbreviated as AZO), and b) IPBC wherein the weight ratio of components a) to b) is from 6:1 to 1:6, preferably from 1.8:1 to 1:6, in particular from 1.5:1 to 1:6. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In a preferred embodiment, the biocide mixture according to the invention comprises the two components a) and b) in total more than 90% by weight, in particular more than 95% by weight, particularly preferably more than 99% by weight, based on the total of all biocides. Examples of preferred biocides that may also be used are in-can preservatives, such as OIT (2-octyl-2H-isothiazol-3-one) and / or BIT (1,2-benzothiazol-3-one), the total proportion of which is preferably less than 5%, preferably less than 1%, by weight of the biocide mixture, based on the total of the biocides.

[0009] The biocide mixture according to the invention may optionally further comprise various auxiliaries, such as surface-active substances, defoamers, wetting agents, emulsifiers, dispersants, stabilizers, adhesives, protective colloids, spreading agents, fragrances, colorants, buffer substances, buffer systems, pH regulators, thickeners, dust control agents, flow agents, release agents, in-can preservatives or mixtures thereof. For the auxiliaries described below, in each case independently of one another, it is also possible that they are not present. The amounts are each based on the biocide mixture. Examples of possible auxiliaries are: Surface-active substances, for example surfactants. The surfactants can be, for example, nonionic, cationic and amphoteric surfactants, preferably anionic surfactants. Anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyltaurates, acylisethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, in particular the alkali metal and alkaline earth metal salts, for example sodium, potassium, magnesium, calcium, and also the ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can in each case, for example, have 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units. Suitable are, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate. Based on the biocide mixture, for example, 0.01% to 10% by weight, preferably 0.2% to 8% by weight, particularly preferably 0.3% to 5% by weight, very particularly preferably 0.5% to 3% by weight of surface-active substances may be present. Antifoaming agents. The antifoaming agents used are generally surface-active substances which are sparingly soluble in the surfactant solution. Preferred antifoaming agents are those derived from natural fats and oils, petroleum derivatives or silicone oils. Based on the biocide mixture, for example, 0.01% to 5% by weight, preferably 0.05% to 3% by weight, particularly preferably 0.1% to 1.5% by weight of antifoaming agent may be present. Wetting agents, for example the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkylsulfonates and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexadecanol, heptadecanol and octadecanol or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, naphthalene or naphthalenesulfonic acid with phenols and and formaldehyde condensation products, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenols, octylphenols or nonylphenols, alkylphenol or tributylphenyl polyglycol ethers, tris-sterylphenyl ether ethoxylates, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylenes, lauryl alcohol polyglycol ether acetates, sorbitol esters, lignosulfite waste liquors or methylcellulose. Based on the biocide mixture, 0.01% to 8% by weight, preferably 0.2% to 6% by weight, particularly preferably 0.3% to 5% by weight, very particularly preferably 0.5% to 3% by weight of wetting agents may be present, for example. Emulsifiers, e.g., with chain length C 10 ~C 20 Sodium, potassium and ammonium salts of linear aliphatic carboxylic acids, sodium hydroxyoctadecanesulfonate, chain length C 10 ~C 20 and their sulfated or acetylated products, and also alkyl sulfates, alkyl-(C 10 ~C 20 )-sulfonate, alkyl-(C 10 ~C 20 )-Aryl sulfonate, dimethyldialkyl-(C8-C18 )-Ammonium chloride, acyl oxetylates, alkyl oxetylates, oleyl oxetylates and alkylaryl oxetylates and their sulfated products, chain length C4-C 16 Sulfosuccinic acid ester with aliphatic saturated monohydric alcohol, chain length C 10 ~C 12 sulfosuccinic acid 4-ester (disodium salt) with polyethylene glycol ethers of monohydric aliphatic alcohols of the formula (I), sulfosuccinic acid 4-ester (disodium salt) with polyethylene glycol ethers, alkali metal salts of bis(cyclohexyl)sulfosuccinate (sodium salt), lignosulfonic acid and its calcium, magnesium, sodium and ammonium salts, polyoxyethylene sorbitan monooleate with 20 ethylene oxide groups, resin acids, hydrogenated and dehydrogenated resin acids and their alkali metal salts, sodium dodecylated diphenyl ether disulfonate and copolymers of ethylene oxide and propylene oxide, preferably with a minimum content of ethylene oxide of 10% by weight. Preferably, the emulsifiers used are sodium lauryl sulfate, sodium lauryl ether sulfate, ethoxylated (3 ethylene oxide groups); polyethylene glycol (4-20) ether of oleyl alcohol and polyethene oxide (4-14) ether of nonylphenol. Based on the biocide mixture, 0.01% to 15% by weight, preferably 0.02% to 8% by weight, particularly preferably 0.05% to 6% by weight and very particularly preferably 0.1% to 5% by weight of emulsifier may be present, for example. Dispersants, such as alkylphenol polyglycol ethers, polyacrylates and polymeric carboxylates. Based on the biocide mixture, 0.01% to 15% by weight, preferably 0.02% to 8% by weight, particularly preferably 0.05% to 6% by weight, very particularly preferably 0.1% to 5% by weight of dispersants may be present, for example. Stabilizers, such as cellulose and cellulose derivatives, as well as antioxidants, radical scavengers or UV absorbers. Based on the biocide mixture, for example, 0.01% to 6% by weight, preferably 0.01% to 3% by weight, particularly preferably 0.01% to 2% by weight, very particularly preferably 0.01% to 1% by weight of stabilizers may be present. Adhesives and / or protective colloids, such as, for example, carboxymethylcellulose, polyvinylpyrrolidone and its derivatives, natural and synthetic powdery, granular or latex-like polymers, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as, for example, cephalin and lecithin, and synthetic phospholipids, and paraffin oil. Based on the biocide mixture, 0.01% to 8% by weight, preferably 0.05% to 4% by weight, particularly preferably 0.2% to 3% by weight, very particularly preferably 0.2% to 2% by weight of adhesives and / or protective colloids may be present, for example. Spreading agents, for example isopropyl myristate, polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl phenyl ether. Based on the biocide mixture, 0.01% to 20% by weight, preferably 0.1% to 10% by weight, particularly preferably 0.1% to 5% by weight and very particularly preferably 0.1% to 2% by weight of spreading agent may be present, for example. Fragrances and / or colorants, for example inorganic pigments, such as iron oxide, titanium oxide, Prussian blue, and organic dyes, such as alizarin, azo and metallophthalocyanine dyes, and micronutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. Based on the biocide mixture, in each case 0.001% to 4% by weight, preferably 0.01% to 1% by weight, particularly preferably 0.01% to 0.8% by weight of fragrances and / or colorants may be present, for example. Buffer substances, buffer systems and / or pH regulators. These may be present, for example, in amounts of 0.01% to 10% by weight, preferably 0.1% to 5% by weight, in each case based on the biocide mixture. Thickeners, such as polysaccharides, xanthan gum, sodium or magnesium silicates, heteropolysaccharides, alginates, carboxymethylcellulose, gum arabic or polyacrylic acid, preferably xanthan gum. Based on the biocide mixture, in each case 0.01% to 10% by weight, preferably 0.1% to 5% by weight, of thickeners may be present, for example. The dedusting agents are, for example, polyglycols and polyglycol ethers. Based on the biocide mixture, in each case 0.01% to 2% by weight of dedusting agent, preferably 0.05% to 1% by weight, particularly preferably 0.1% to 0.5% by weight, may be present, for example. As flow agents and / or release agents, for example, natural rock flours such as kaolin, clay, talc, marble, chalk, quartz, bentonite, smectite, attapulgite, montmorillonite or diatomaceous earth, or synthetic inorganic substances such as micronized silica, alumina and silicates, or Mg salts of fatty acids or mixtures thereof can be used. Based on the biocide mixture, in each case 0.01% to 15% by weight of these, preferably 0.05% to 8% by weight, particularly preferably 0.1% to 5% by weight of flow agents and / or release agents can be present. In-can preservatives are, for example, biocides, bactericides and fungicides. In-can preservatives may, for example, be present in amounts of 0.01% to 2% by weight of these, preferably 0.05% to less than 1% by weight, in each case based on the biocide mixture.

[0010] The total content of auxiliaries, in particular those mentioned above, based on the biocide mixture is preferably 0.001% by weight to 20% by weight, more preferably 0.1% by weight to 15% by weight, particularly preferably 0.1% by weight to 10% by weight.

[0011] The biocide mixtures according to the invention can be present in various forms, for example as solid formulations, for example powder mixtures, or as granules, preferably water-dispersible granules, which, in addition to the active ingredients of components a) and b), can also contain solid auxiliaries, for example the above-mentioned flow agents and / or exfoliants, for example natural rock flours, for example kaolin, clay, talc, marble, chalk, quartz, bentonite, smectite, attapulgite, montmorillonite or diatomaceous earth, or synthetic inorganic substances, for example micronized silica, alumina and silicates, or mixtures thereof.

[0012] The solid formulations may be obtained in a manner known per se, for example by intimate mixing of components a) and b), preferably in a specific weight ratio with a solid auxiliary, and preferably followed by common grinding.Furthermore, the solid formulations may be obtained by drying, for example spray drying, the liquid formulations.

[0013] A preferred solid formulation comprises components a) and b) in a particular weight ratio, for example 10% to 100% by weight, preferably 15% to 98% by weight.

[0014] The biocide mixtures according to the invention can also be in the form of liquid formulations, for example in the form of suspensions, dispersions, gels or pastes.

[0015] Preferred liquid formulations are aqueous dispersions. Liquid, in particular aqueous, formulations of the biocide mixture according to the invention generally comprise from 2% to 95% by weight, preferably from 5% to 75% by weight, particularly preferably from 5% to 50% by weight, very particularly preferably from 5% to 35% by weight of components a) and b). Furthermore, they preferably comprise further auxiliaries, in particular those mentioned above, in an amount of from 0.001% to 20% by weight, preferably from 0.1% to 15% by weight, particularly preferably from 0.1% to 10% by weight, as well as preferably water as the remainder.

[0016] Preferred liquid biocide mixtures according to the invention are those which: a total of 2% to 95% by weight, preferably 5% to 75% by weight, in particular 5% to 50% by weight and very particularly preferably 5% to 35% by weight of components a) and b), - 0.001% to 20% by weight, preferably 0.1% to 15% by weight, particularly preferably 0.1% to 10% by weight of at least one auxiliary agent, preferably one or more of the above-mentioned auxiliary agents, - Characterized in that it contains water as the balance.

[0017] Preferably, the biocide mixtures according to the invention in the form of their liquid formulations comprise at least 90% by volume of all solid particles with a particle size of less than 150 μm, preferably less than 100 μm, particularly preferably less than 50 μm and very particularly preferably less than 20 μm.

[0018] method The present invention also relates to a method for preparing a biocide mixture according to the invention, said method comprising the steps of: i) The biocides of components a) and b) are preferably mixed in water; ii) optionally adding one or more auxiliary agents which may also be used; iii) homogenization, optionally milling, preferably with the aid of shear forces, in particular until at least 90% by volume of the solid particles are present with a particle size of less than 150 μm, preferably less than 100 μm, particularly preferably less than 50 μm and very particularly preferably less than 20 μm, iv) and optionally also adding one or more further auxiliaries, in particular thickeners and / or in-can preservatives, v) The resulting dispersion is optionally dried. It is characterized in that

[0019] In the preferred procedure, liquid, preferably aqueous dispersion medium, is introduced first, and then components a) and b) are added, as well as dispersant and any further auxiliaries, such as wetting agent, antifoaming agent and / or in-can preservative.Then, this mixture is preferably homogenized using a high-speed stirrer.Suitable as such are, for example, dissolvers or rotor-stator systems, such as Ultraturrax, Dispermix, Dispermat, high-pressure dispersers, nozzle assemblies with axial flow, or similar systems known to those skilled in the art.

[0020] The resulting dispersion is then preferably processed in a mill, in particular a ball mill or basket mill, so that preferably at least 90% by volume of the solid particles are present with a particle size of less than 150 μm, preferably less than 100 μm, particularly preferably less than 50 μm, very particularly preferably less than 20 μm. A thickener is preferably added before, during or after grinding to set the desired viscosity.

[0021] If the solids used already have a suitable particle size, grinding can also be omitted.

[0022] In a preferred embodiment, steps i) to iv) of the process according to the invention are carried out at a temperature in the range of 5°C to 40°C, in particular at a temperature of 10°C to 30°C, particularly preferably at a temperature below 30°C.

[0023] Liquid formulations, such as, in particular, aqueous dispersions, can be prepared in a manner known per se, for example by grinding components a) and b) together with further auxiliaries present in the liquid formulation, or by intimately mixing the particulate components a) and b) and further substances present in the liquid formulation with one another by means of a dissolver or stirrer.

[0024] Coating Composition The present invention also provides a biocide mixture according to the invention or Components a) and b) of the biocide mixture according to the invention (the weight ratio of components a) to b) is from 6:1 to 1:6, preferably from 1.8:1 to 1:6, in particular from 1.5:1 to 1:6) at least one binder, Optionally pigments and / or paints, and ·water The present invention relates to a coating composition comprising:

[0025] Preferably, the coating composition according to the present invention comprises: 0.1% to 5% by weight, in particular 0.3% to 3% by weight, preferably 0.3% to 2% by weight, of the biocide mixture according to the invention, or 0.02% to 5.0% by weight, preferably 0.1% to 1.5% by weight and particularly preferably 0.2% to 0.8% by weight of components a) and b) of the biocide mixture according to the invention, the weight ratio of components a) to b) being 6:1 to 1:6, preferably 1.8:1 to 1:6 and in particular 1.5:1 to 1:6.

[0026] The proportion of binder in the coating composition according to the invention is preferably from 5% to 80% by weight, in particular from 10% to 60% by weight.

[0027] Preferred binders used are preferably film-forming binders, in particular acrylate, alkyd, urethane, styrene or vinyl acetate based binders and hybrid systems thereof. The amount of binder is preferably 10% to 60% by weight, based on the coating composition.

[0028] Also preferably, the coating composition according to the invention may comprise a solvent and / or dispersant, optionally a filler, optionally a wetting agent, and optionally other additives, such as an antifoaming agent.

[0029] Furthermore, the coating composition according to the invention may also comprise solvents, such as glycols and glycol ethers, in-can preservatives, and optionally further additives, such as antifoaming agents, thickening agents, wetting agents, anti-settling agents and dispersing agents. Examples of such auxiliaries are those mentioned above.

[0030] Methods for inhibiting or controlling mold growth The present invention also relates to a non-therapeutic method for inhibiting or controlling the growth of molds found on or in a surface coating, characterized in that a coating is formed by applying a coating composition to the surface, the coating composition being a coating composition according to the invention or comprising a biocide mixture according to the invention.

[0031] The moulds against which the method according to the invention provides particularly effective protection are preferably those of the classes Ascomycetes and Deuteromycetes, in particular Aspergillus niger, Aspergillus versicolor, Cladosporium cladosporioides, Stachybotrys chartarum and Trichoderma virens.

[0032] The coatings which are protected using the method according to the invention are preferably obtained by applying and drying the coating composition on the surface, preferably as a continuous solid film which adheres to the surface. EXAMPLES

[0033] Example 1: Preparation of Azoxystrobin / IPBC Dispersion: The dispersions were prepared in a manner known to those skilled in the art.

[0034] Preparation of Azoxystrobin / IPBC Dispersion Using the Example of a 1:1 Mixture: 327.6 g of water are initially introduced. 5 g of an emulsifier based on EO / PO block copolymer (Pluronic® F127 Prill, BASF), 7.5 g of a protective colloid based on polyvinylpyrrolidone (Sokalan® VA64, BASF) and 5 g of a dispersant based on polyacrylate (Dispex® AA4144, BASF) are added in succession and homogenized.

[0035] Under high shear (dissolver), 75g of Azoxystrobin and 75g of IPBC are added successively and homogenized. During homogenization, 1.63g of silicone-based antifoam agent (Xiameter Antifoam 1530) is added.

[0036] The resulting dispersion is finely ground using a bead mill (DynoMill Multilab) until a particle size (d90) of less than 20 μm is achieved.

[0037] Subsequently, 0.2% of an in-can preservative (Preventol BIT20D, 20% aqueous dispersion) is added and 0.45% of xanthan gum is used to thicken the mixture. A biocide mixture with a content of 15% by weight of each of the active ingredients azoxystrobin and IPBC is obtained.

[0038] All other mixtures with other mixing ratios were similarly prepared according to this method.

[0039] Example 2: Comparative effectiveness against mold The kresoxim-methyl mixtures from JP2003073211 were directly compared with the corresponding AZO / IPBC mixtures according to the invention with regard to their effectiveness against mold (see Table 1).

[0040] For this purpose, mycelial masses were punched out from appropriate mold colonies and incubated on nutrient agar containing malt extract at 26°C. Here, mycelial growth with and without the active ingredient was compared. The concentration that completely inhibited radial mycelial growth was expressed as the minimum inhibitory concentration (MIC).

[0041] [Table 1]

[0042] The considerably increased effectiveness of the biocide mixture according to the invention compared with the kresoxim-methyl / IPBC mixture from JP 2003073211 is evident from the comparison according to Table 1.

[0043] Example 3: Synergy Study Mycelial masses were punched out from appropriate mold colonies and incubated on nutrient agar containing malt extract at 26°C, where mycelial growth with and without the active ingredient was compared. The concentration that completely inhibited radial mycelial growth was expressed as the minimum inhibitory concentration (MIC).

[0044] Synergy was determined by the method described by Kull et al. (FC Kull, PC Eismann, HD Sylvestrowicz, RL Mayer, Applied Microbiology 1961, 9, 538-541). The following relationships apply:

number

[0045] 3.1 Combination of AZO and IPBC against the molds Aspergillus niger and Aspergillus versicolor

[0046] [Table 2]

[0047] The synergistic effect of the biocide mixtures according to the invention in comparison with the individual active ingredients in the case of various moulds is evident from the test series according to Table 2.

[0048] 3.2 Combination of AZO and IPBC against the fungus Trichoderma virens

[0049] [Table 3]

[0050] The synergistic effect of the biocide mixtures according to the invention in comparison with the individual active ingredients in the case of various moulds is evident from the series of tests according to Table 3.

[0051] 3.3 Combination of AZO and IPBC against the fungus Cladosporium cladosporioides

[0052] [Table 4]

[0053] The synergistic effect of the biocide mixtures according to the invention in comparison with the individual active ingredients in the case of various moulds is evident from the series of tests according to Table 4.

[0054] 3.4 Combination of AZO and IPBC against the mold Stachybotrys chartarum

[0055] [Table 5]

[0056] The synergistic effect of the biocide mixtures according to the invention in comparison with the individual active ingredients in the case of various moulds is evident from the series of tests according to Table 5.

[0057] Example 4: Protection of acrylic paint coatings against mildew A water-based white acrylic paint of the following composition (see Table 6):

[0058] [Table 6]

[0059] was treated with 0.67% of a combination of biocide mixtures according to the invention (corresponding to 0.1% AZO and 0.1% IPBC based on the paint) from example 1 compared to the corresponding untreated paint and tested according to the British Standard BS3900-Part G6 (Testing of paints - Assessment of resistance to fungal growth) test method.

[0060] The paint was applied onto the pine wood and the coated wood specimens were then conditioned for 7 days at 23° C. After subsequent artificial exposure (QUV exposure device from Q-Panel Lab Products), the wood specimens were incubated with a mold mixture and incubated in a humidity chamber for 12 weeks. The following molds were used: Aspergillus versicolor Aureobasidium pullulans Cladosporium cladosporioides Penicillium purpurogenum Chaetomium globosum Alternaria alternata Phoma herbarum Ulocladium atrum Stachybotrys chartarum

[0061] Test results after 12 weeks: All paint coupons that were not treated with fungicide showed very high levels of mold infestation (>70% infestation of the total coated area).

[0062] The test specimens coated with the acrylic paint treated with the biocide mixture according to the invention (AZO / IPBC 1:1) showed either a complete absence of mold growth or only very slight traces of mold growth (growing less than 0.5% of the total coated area).

Claims

1. It is a biocide a) Azoxystrobin (methyl(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate) and b) IPBC (3-iodopropynyl N-butylcarbamate) A biocide mixture for inhibiting or controlling mold growth comprising: A biocide mixture wherein the weight ratio of components a) to b) is from 6:1 to 1:

6.

2. 2. The biocide mixture of claim 1, comprising more than 90% by weight of the two components a) and b), based on the sum of all biocides.

3. 3. Biocide mixture according to claim 1 or 2, characterized in that it is in the form of a liquid formulation comprising a total of 2% to 95% by weight of components a) and b).

4. A biocide mixture according to at least one of claims 1 to 3, characterized in that it contains auxiliaries selected from surface-active substances, antifoaming agents, wetting agents, emulsifiers, dispersants, stabilizers, adhesives, protective colloids, spreading agents, fragrances, colorants, buffer substances, buffer systems, pH regulators, thickeners, dust control agents, flow agents, stripping agents, in-can preservatives and mixtures thereof.

5. - 2% to 95% by weight in total of components a) and b), - 0.001% to 20% by weight of at least one auxiliary agent, and - Water as the balance 5. The biocide mixture according to claim 1, wherein the biocide mixture comprises

6. - 5% to 50% by weight in total of components a) and b), - 0.001% to 20% by weight of at least one auxiliary agent, and - Water as the balance 6. The biocide mixture according to claim 1, wherein the biocide mixture comprises

7. 2. A method for preparing a biocide mixture for inhibiting or controlling mold growth according to claim 1, characterized in that i) the biocides of components a) and b) are mixed in water.

8. - a biocide mixture for inhibiting or controlling the growth of mold according to at least one of claims 1 to 6, or said components a) and b) of the biocide mixture according to at least one of claims 1 to 6 (the weight ratio of components a) to b) is between 6:1 and 1:6); at least one binder, - optionally pigments and / or paints, and -water 1. A coating composition comprising:

9. - 0.1% to 5% by weight of a biocide mixture according to at least one of claims 1 to 6, or - 0.02% to 5.0% by weight of components a) and b) a) Azoxystrobin (methyl(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate) and b) IPBC (3-iodopropargyl N-butylcarbamate), 9. The coating composition of claim 8, wherein the weight ratio of components a) to b) is from 6:1 to 1:

6.

10. 10. A non-therapeutic method for inhibiting or controlling the growth of mold on or in a surface coating, characterized in that the coating is formed by applying a coating composition to a surface, the coating composition being a coating composition according to claim 8 or 9 or comprising a biocide mixture according to at least one of claims 1 to 6.

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