Composition containing guanidine and carbonate

Abstract

This invention relates to compositions, particularly aqueous compositions, comprising: (a) guanidine and / or at least one unsubstituted guanidine salt, and (b) one or more carbonate compounds selected from sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, and ammonium carbonate. The compositions are characterized in that the weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, and in each case, the weight ratio is determined based on the content of guanidine and carbonate ions in the entire composition. The invention further relates to industrial products comprising the compositions of the invention, and the use of the compositions for stabilizing aqueous industrial products against microbial invasion.

Description

[0001] This invention relates to compositions, particularly aqueous compositions, comprising: (a) a guanidine and / or a salt of at least one unsubstituted guanidine, and (b) one or more carbonate compounds selected from sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, and ammonium carbonate. The compositions are characterized in that the weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, and in each case, the weight ratio is determined based on the content of guanidine and carbonate ions in the entire composition. The invention further relates to industrial products comprising the compositions of the invention, and the use of the compositions for stabilizing aqueous industrial products against microbial invasion.

[0002] Industrial products, especially water-based ones such as paints, varnishes, dyes, plasters, and emulsions, are typically produced using natural or biodegradable raw materials. These raw materials and the water used as solvents are frequently contaminated with microorganisms such as bacteria, yeasts, and fungi. If these products are not produced without preservatives, they may exhibit high microbial counts as early as one day after production.

[0003] To ensure that these products, and in relevant cases, the ingredients used in their production, meet hygiene requirements and thus guarantee the shelf life of industrial products, agents known as biocides are typically added to the products and / or even to their ingredients.

[0004] One class of biocides used to preserve water-based coatings, such as paints, plasters, varnishes, or dyes, or their components, are those called 3-isothiazolin-3-ones. This category of materials includes highly reactive compounds with varying activity spectra in some cases. It is also common practice to use synergistic combinations of different 3-isothiazolin-3-ones to reduce the amount of biocid used. For example, WO 99 / 08530 A1 proposes the combined use of methylisothiazolin-3-one and 1,2-benzisisothiazolin-3-one.

[0005] Another class of biocides are so-called alkylguanidinium salts and polyguanidinium salts. Thus, as known for example from "Directory of microbicides for the protection of materials", Springer 2005, pp. 726-731, medium-chain and long-chain guanidines and biguanides, such as cocopropanediamine-1,5-biguanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylene biguanide) hydrochloride, di(4'-chlorophenylbiguanidinyl)hexane, chlorhexidine digluconate, and chlorhexidine diacetate, exhibit antimicrobial activity.

[0006] The use of such medium- and long-chain guanidine compounds in conjunction with other active antimicrobial and / or fungicidal ingredients is also known. For example, combinations with 3-iodo-2-propynyl butylcarbamate or formaldehyde-depot compounds are known. Thus, EP 0 891 710 A1, for example, teaches the combined use of dodecyl guanidine hydrochloride and IPBC. However, the use of dodecyl guanidine salts in the preservation of paint compositions and polymer dispersions has proven problematic, with the addition of these salts leading to observed incompatibility in the form of condensation.

[0007] Due to increasing legal restrictions, the use of conventional biocides / preservatives is becoming increasingly unfeasible.

[0008] Therefore, it has been proposed to provide storage-stable waterborne coatings without conventional preservatives by raising their pH to effectively prevent microbial invasion. The target pH is at least 10, as it is impossible to sufficiently definitively prevent microbial invasion at lower pH values. For example, in the prior art, such as according to EP 1 297 079 A1, the pH is raised by adding water glass. Alternatively, DE 10 2014 013 455 A1 and WO 2017 / 144694 A1 disclose the use of siliconates as additives to raise the pH. However, a drawback of the above preservation methods is the relatively high pH value required for preservation in the coating, which necessitates special care during handling.

[0009] Another preservative-free preservation system promoted by OMYA INTERNATIONAL AG as its so-called Omyasmart Next Generation (OSNG) technology is a buffer system that supposedly achieves long-term stability against microbial invasion in water-based systems and biocidal-free formulations. This buffer system is the subject of International Publication WO 2022 / 223804 A1. It discloses a buffer composition comprising first and second buffer components, wherein a) the first buffer component is at least one water-soluble or water-dispersible magnesium and / or zinc ion source, and b) the second buffer component is at least one alkali metal carbonate and / or at least one alkali metal bicarbonate.

[0010] Despite the many known combinations and measures of active ingredients used simultaneously, there is a growing need, particularly due to increasing regulatory restrictions, for compositions and stabilized products that provide stabilizing effects against microbial invasion, preferably free of or containing reduced amounts of conventional preservatives / biocides such as isothiazolinone, bronopol, and pyrithione.

[0011] This invention achieves this objective through a composition, preferably an aqueous composition, the composition comprising the following components:

[0012] (a) guanidine and / or at least one unsubstituted guanidine salt

[0013] and

[0014] (b) One or more carbonate compounds selected from sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3), and ammonium carbonate ((NH4)2CO3).

[0015] The composition is characterized in that the weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, preferably in the range of 1:8.6 to 21:1, more preferably in the range of 1:8 to 8:1, and very preferably in the range of 1:3.4 to 1.6:1. In each case, the weight ratio is determined based on the content of guanidine and carbonate in the whole composition, wherein when guanidine carbonate is used / present as component (a), the counterion (carbonate) is included in the calculation.

[0016] According to a preferred embodiment of the invention, the composition is further characterized in that it comprises a component (a) in an amount in the range of 100 to 7500 ppm, preferably in the range of 250 to 5000 ppm, based on the amount of guanidine in the composition, and a component (b) in an amount in the range of 250 to 25000 ppm, preferably in the range of 500 to 10000 ppm, based on the amount of carbonate.

[0017] Based on their composition, the compositions of the present invention require significantly less of the type of preservatives typically used for preservation, and in some cases, none at all. Nevertheless, due to the remarkably effective interaction between guanidine and / or guanidine salts (component (a)) and the at least one carbonate compound (component (b)), these compositions and products containing these compositions are characterized by excellent resistance to microbial invasion.

[0018] According to the invention, the composition is characterized in that the weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, preferably in the range of 1:8.6 to 21:1, more preferably in the range of 1:8 to 8:1, and very preferably in the range of 1:3.4 to 1.6:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the whole composition. It has proven particularly advantageous in the present invention that the weight ratio of (a) to (b) in the composition is within the range specified above, because the synergistic interaction between guanidine and carbonate has been demonstrated within this range.

[0019] The compositions of the present invention comprise guanidine and / or at least one unsubstituted guanidine salt as component (a). "At least one salt" in the context of the present invention means that the composition comprises a single guanidine salt, or multiple guanidine salts, i.e., two, three, four, five or more guanidine salts.

[0020] In the sense of this invention, guanidine and / or unsubstituted guanidine salts refer to a composition comprising guanidine and / or (and therefore optionally also) one or more unsubstituted guanidine salts as component (a). Guanidine is a compound according to the formula shown below:

[0021]

[0022] Unsubstituted guanidine salts or guanidine salts, in the sense of this invention, include guanidine and guanidineonium salts of the following general formulas:

[0023]

[0024] Where n is 1, 2, or 3, and where the counter ion X n-Examples include chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, hydrogencarbonate, guanidinosilicate, formate, acetate, or citrate.

[0025] According to a preferred embodiment of the invention, the composition of the invention comprises guanidine hydrochloride and / or guanidine carbonate and / or guanidine hydrogencarbonate as component (a); according to a particularly preferred embodiment of the invention, the composition comprises guanidine carbonate as component (a).

[0026] As component (b), the compositions of the present invention comprise one or more carbonate compounds selected from sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3), and ammonium carbonate ((NH4)2CO3). "Multiple" herein means that the composition may comprise two, three, four, five, or six specified carbonate compounds.

[0027] According to a preferred embodiment of the invention, the composition comprises sodium carbonate (Na₂CO₃) and / or sodium bicarbonate (NaHCO₃) as component (b). Using this or these carbonate compounds yields a composition with additional improved properties.

[0028] In this invention, not only are the amounts of components (a) and (b) specified, but also their weight ratios relative to each other. Unless otherwise stated, these amounts in each case are based on the dominant structure of component (a), namely guanidine (CN3H5), and the dominant structure of component (b), namely carbonate (CO3). 2- The specified weight ratio is also determined in each case based on the content of guanidine-related components (excluding any counterions) as component (a) and the content of carbonate components (excluding any counterions) as component (b) in the composition.

[0029] The amount of component (a) included in the compositions of the present invention, namely guanidine and / or its salts, can vary over a wide range and is generally in the range of 100 ppm to 10,000 ppm, preferably in the range of 250 ppm to 7,500 ppm, more preferably in the range of 250 ppm to 5,000 ppm, based on the amount of guanidine in the whole composition.

[0030] The amount of component (b) included in the composition of the present invention, namely the one or more carbonate compounds, can vary over a wide range and is generally in the range of 100 ppm to 50,000 ppm, preferably in the range of 500 ppm to 25,000 ppm, and more preferably in the range of 1,000 ppm to 10,000 ppm, based on the amount of carbonate ions.

[0031] Therefore, according to one embodiment, the present invention relates to a composition characterized by comprising the following components:

[0032] (a) Based on the amount of guanidine in the composition, in the range of 100 to 10,000 ppm, preferably in the range of 250 to 7,500 ppm, more preferably in the range of 500 to 5,000 ppm, and

[0033] (b) Based on the amount of carbonate, the amount is in the range of 100 ppm to 50,000 ppm, preferably in the range of 500 ppm to 25,000 ppm, and more preferably in the range of 1,000 ppm to 10,000 ppm.

[0034] The weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, preferably in the range of 1:8.6 to 21:1, more preferably in the range of 1:8 to 8:1, and very preferably in the range of 1:3.4 to 1.6:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the whole composition.

[0035] The pH of the compositions of the present invention can vary over a wide range. According to one embodiment of the invention, the composition is characterized by having a pH in the range of pH 8 to pH 12, preferably in the range of pH 8.5 to pH 11.5, and more preferably in the range of pH 9.0 to pH 11.0. The pH can be adjusted to the claimed range using methods familiar to those skilled in the art.

[0036] The compositions of the present invention are preferably aqueous compositions, and their water content can vary over a wide range. The water content is typically from 10% to 90% by weight, based on the entire composition. According to one embodiment of the invention, the composition is characterized by having a water content of greater than 1% by weight, preferably greater than 10% by weight, and more preferably greater than 20% by weight, based on the entire composition.

[0037] The compositions according to the invention, especially aqueous compositions, are generally selected from the following industrial products (especially aqueous industrial products): paints, varnishes, stains and renders, fillers and filling compounds, primers, emulsions, latexes, polymer dispersions, chalk suspensions, mineral slurries, titanium dioxide slurries, ceramic compounds, kneading compounds, adhesives, sizes, casein-containing products, starch- and cellulose-containing products, concrete admixtures, lignosulfonates, bitumen emulsions, and surfactant solutions. Solutions, fuels, laundry detergents, cleaning products, pigment pastes and pigment dispersions, wax emulsions, silicone emulsions, impregnating materials, release agents, lubricants, inks, lithographic fluids, thickeners and thickener preparations, rheological assistants, cosmetics, fragrances, toiletries, cooling water, water in circuits, water for humidification and irrigation.Products include wetting and irrigation water, production water, rinsing water and recycling water, wood processing liquids, petroleum recovery liquids, paper processing liquids, leather production liquids, textile production liquids, glassworking liquids, drilling and cutting oils, hydraulic fluids, cooling lubricants, fertilizers and crop protection materials, and biocides.

[0038] According to a preferred embodiment of the present invention, the composition of the present invention is an aqueous industrial product selected from paints, varnishes, dyes, plasters, fillers and filler blends, pigment pastes and pigment dispersions, products containing starch and cellulose, thickeners and thickener formulations, mineral slurries, titanium dioxide slurries, ceramic blends, laundry detergents and cleaning products.

[0039] According to an advantageous embodiment of the invention, the composition is characterized in that it comprises:

[0040] (a) guanidine and / or at least one guanidine salt,

[0041] (b) One or more carbonate compounds selected from sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3), and ammonium carbonate ((NH4)2CO3), and

[0042] (c) One or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2·[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydracetate, and zinc carboxylate.

[0043] The weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, preferably in the range of 1:8.6 to 21:1, more preferably in the range of 1:8 to 8:1, and very preferably in the range of 1:3.4 to 1.6:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the whole composition.

[0044] Component (c) is typically selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2·[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate. According to a preferred embodiment of the invention, component (c) is selected from zinc oxide and zinc carbonate; according to a particularly preferred embodiment, component (c) is zinc oxide.

[0045] The composition of the present invention according to this embodiment, which further includes component (c), has the advantage that the at least one zinc compound, i.e., component (c), interacts synergistically with components (a) and (b) in each case, thereby enabling a further reduction in the content of components (a), (b) and (c) in the composition while maintaining the stabilizing activity against microorganisms.

[0046] The weight ratio of components (a) to (c) can vary over a wide range. According to a preferred embodiment, the composition of the present invention is characterized in that the weight ratio of (a) to (c) is in the range of 0.77:1 to 12:1, preferably in the range of 1:1 to 10:1, wherein said weight ratio is determined based on the content of guanidine and zinc in each case.

[0047] The amount of component (c) (the at least one zinc compound) contained in the compositions of the present invention can vary over a wide range, and is in the range of 10 to 5000 ppm, preferably in the range of 25 to 2500 ppm, more preferably in the range of 50 to 1000 ppm, in each case based on the zinc content in the composition.

[0048] According to an advantageous embodiment of the invention, the composition is characterized in that it comprises:

[0049] (a) guanidine and / or at least one guanidine salt,

[0050] (b) One or more carbonate compounds selected from sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3), and ammonium carbonate ((NH4)2CO3).

[0051] And optional:

[0052] (c) One or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2·[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate.

[0053] And optional:

[0054] (d) One or more compounds selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol, dibromodicyanobutane, and quaternary ammonium compounds.

[0055] The weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, preferably in the range of 1:8.6 to 21:1, more preferably in the range of 1:8 to 8:1, and very preferably in the range of 1:3.4 to 1.6:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the whole composition.

[0056] The composition of the present invention according to this embodiment, which further includes component (d), has the advantage that at least one compound selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, bromonitrobenzinol, dibromodiazinopropionamide, iodopropynyl butyl carbamate, phenoxyethanol, dibromodicyanobutane, and quaternary ammonium compounds interact synergistically with component (a), thereby enabling a further reduction in the content of components (a), (b), optionally (c), and (d) in the composition while maintaining antimicrobial activity.

[0057] Therefore, according to this embodiment, the present invention relates to a composition, and more particularly to an aqueous composition, comprising:

[0058] (a) guanidine and / or at least one unsubstituted guanidine salt,

[0059] (b) One or more carbonate compounds selected from sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3), and ammonium carbonate ((NH4)2CO3).

[0060] The composition is characterized by a weight ratio of component (a) to component (b) ranging from 1:14 to 54:1, preferably from 1:8.6 to 21:1, more preferably from 1:8 to 8:1, and very preferably from 1:3.4 to 1.6:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the entire composition.

[0061] And optional:

[0062] (c) One or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2·[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate.

[0063] And optional:

[0064] (d) One or more compounds selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, bromonitrile glycol, dibromo-nitropropionamide, iodopropynyl carbamate, phenoxyethanol, dibromodicyanobutane, and quaternary ammonium compounds.

[0065] The amount of component (d) contained in the composition of the present invention can vary over a wide range. According to a preferred embodiment of the present invention, the composition is characterized in that it contains the following as component (d):

[0066] (d1) Amounts in the range of 100 to 10,000 ppm, preferably in the range of 250 to 7,500 ppm, more preferably in the range of 500 to 5,000 ppm, of phenoxyethanol, and / or

[0067] (d2) A total amount in the range of 1 to 2000 ppm, preferably in the range of 1 to 1000 ppm, more preferably in the range of 1 to 750 ppm, selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, bromonitrobenzinol, dibromonitropropionamide, iodopropynyl butyl carbamate, dibromodicyanobutane, and one or more quaternary ammonium compounds.

[0068] A further subject of the invention is a method for producing the preferred aqueous composition of the invention, comprising mixing components (a), (b), optionally (c), and optionally (d) as defined above.

[0069] According to one embodiment, the present invention relates to a concentrate comprising components (a) and (b). Such a concentrate is suitable for stabilizing industrial products against microbial invasion by introducing a certain amount of the concentrate into the industrial product to be stabilized against microbial invasion.

[0070] The concentrate of the present invention comprises the composition as defined above, characterized in that it comprises components (a) and (b) in amounts ranging from 1% to 100% by weight, preferably from 10% to 60% by weight, and more preferably from 20% to 40% by weight.

[0071] Specifically, this embodiment relates to a concentrate for stabilizing industrial compositions against microbial invasion, comprising:

[0072] (a) guanidine and / or at least one unsubstituted guanidine salt, and

[0073] (b) One or more carbonate compounds selected from sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3), and ammonium carbonate ((NH4)2CO3).

[0074] The product is characterized in that the weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, preferably in the range of 1:8.6 to 21:1, more preferably in the range of 1:8 to 8:1, and very preferably in the range of 1:3.4 to 1.6:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the whole composition in each case, and is further characterized in that the concentrate contains components (a) and (b) in amounts ranging from 1% to 100% by weight, preferably from 10% to 60% by weight, and more preferably from 20% to 40% by weight.

[0075] The concentrate may be in the form of a powder mixture or a liquid concentrate, such as an aqueous concentrate.

[0076] According to a preferred embodiment, the concentrate of the present invention comprises the following components:

[0077] (a) 5% to 40% by weight, preferably 10% to 30% by weight, of guanidine carbonate, and

[0078] (b) 2.5% to 15% by weight, preferably 5% to 10% by weight of sodium carbonate.

[0079] The following aqueous concentrates (A) to (D) having the following compositions have been found to be particularly advantageous:

[0080] (A) 20% guanidine carbonate + 10% sodium carbonate + 70% water

[0081] (B) 15% wt% guanidine carbonate + 5% wt% sodium carbonate + 80% wt% water

[0082] (C) 15% wt% guanidine carbonate + 10% wt% sodium carbonate + 75% wt% water

[0083] (D) 10 wt% guanidine carbonate + 10 wt% sodium carbonate + 80 wt% water.

[0084] According to a preferred embodiment, the concentrate of the present invention comprises the following components:

[0085] (a) 10% to 20% by weight of guanidine carbonate,

[0086] (b) 5% to 10% by weight of sodium carbonate, and

[0087] Add water up to 100% by weight.

[0088] According to a further preferred embodiment, the concentrate of the present invention comprises or is composed of the following components:

[0089] (a) 18% to 22% by weight, preferably 20% by weight, of guanidine carbonate.

[0090] (b) 1.85% to 2.45% by weight, preferably 2.05% by weight, of sodium bicarbonate.

[0091] Add water up to 100% by weight.

[0092] According to a particularly preferred embodiment, the concentrate of the present invention comprises the following components: 20.00% by weight of guanidinium carbonate, 2.05% by weight of sodium bicarbonate, and water to 100%.

[0093] According to one embodiment of the present invention, the composition is an aqueous industrial product stabilized against microbial invasion and selected from paints, plasters, and filler blends, comprising:

[0094] (a) guanidine and / or at least one guanidine salt,

[0095] (b) One or more carbonate compounds selected from sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3), and ammonium carbonate ((NH4)2CO3).

[0096] The composition is characterized by a weight ratio of component (a) to component (b) ranging from 1:14 to 54:1, preferably from 1:8.6 to 21:1, more preferably from 1:8 to 8:1, and very preferably from 1:3.4 to 1.6:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the entire composition.

[0097] (c) Optionally, one or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2·[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate.

[0098] (d) Optionally, one or more compounds selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bromonitrobenzyl glycol, dibromo-nitropropionamide, iodopropynyl butyl carbamate, phenoxyethanol, dibromodicyanobutane, and quaternary ammonium compounds.

[0099] (e) 1.0% to 85% by weight of pigments and / or fillers,

[0100] (f) Polymer dispersions, calculated as solids fractions, from 1 wt% to 35 wt%, and

[0101] (g) Add water to a total of 100% by weight.

[0102] The composition defined above optionally includes components (c) and (d). This means that components (c) and / or (d) may be included in the composition, but it may also be without components (c) and (d), and therefore contain neither component (c) nor component (d).

[0103] Based on their composition, the aqueous industrial products of this invention, which stabilize against microbial invasion and are used as paints, plasters, or filler blends, require significantly less of the preservatives typically included in such products for in-can preservation, and in some cases, none at all. Nevertheless, these products are characterized by excellent resistance to microbial invasion, particularly during storage, due to the remarkably effective interaction between guanidine or guanidine salts and carbonate compounds. Therefore, the aforementioned industrial products exhibit significant improvements in their ecocompatibility and also possess all known qualities associated with good and reliable processing properties.

[0104] According to a preferred embodiment, the water-based industrial product, as a paint, plaster, or filler compound, is characterized in that it contains components (a) and (b) in a total amount based on the entire industrial product, ranging from 0.05% to 10% by weight, preferably from 0.1% to 5% by weight, and more preferably from 0.2% to 2.5% by weight.

[0105] According to a preferred embodiment, the aqueous industrial product, as a paint, plaster, or filler compound, contains guanidine hydrochloride and / or guanidine carbonate as components (a).

[0106] According to a preferred embodiment, the aqueous industrial product, as a paint, plaster, or filler compound, contains sodium carbonate and / or sodium bicarbonate as components (b).

[0107] Waterborne industrial products used as paints, plasters, or filler blends typically contain 1.0% to 85% by weight of pigments and / or fillers as component (e). According to a preferred embodiment of the invention, the coating contains 1% to 25% by weight of pigments and / or 5% to 50% by weight of fillers.

[0108] The pigments used in this case can be conventional pigment admixtures for latex paints, such as titanium dioxide, iron oxide, chromium oxide, cobalt blue, phthalocyanine pigments, spinel pigments, and nickel and chromium titanates. The fillers included in the composition are preferably silicates, carbonates, fluorite, sulfates, and oxides.

[0109] As component (f), aqueous industrial products used as paints, plasters, or filler blends typically contain 1% to 35% by weight, preferably 2% to 20% by weight, more preferably 3% to 12% by weight, of a polymer dispersion, calculated in each case as a solids fraction of the polymer dispersion. In the case of polymer dispersions included in coatings, any polymer dispersion known to date in the art of coatings or paint systems can be used. The property pattern of the dispersion and the property pattern of the finished product made from it are primarily influenced by the specific polymer. This polymer consists of different structural units called monomers, which can also be combined with each other according to the desired property conditions. Examples of suitable monomers are vinyl carboxylate esters having 3 to 20 carbon atoms, N-vinylpyrrolidone, vinyl aromatic compounds, vinyl halides, olefinic unsaturated carboxylic acids, their esters, their amides or their anhydrides, nano-hybrid dispersions, water glass, silicone resin emulsions, aqueous polyurethane dispersions, styrene acrylates, aqueous polymer dispersions, or α-olefins and / or 1,3-dienes in the form of water-redispersible polymer powders. Particularly preferred are olefinically unsaturated carboxylic acids, especially acrylic acid and methacrylic acid, and olefinically unsaturated carboxylic acid esters, particularly acrylates and methacrylates having 1 to 12 carbon atoms in the alcohol residue. The alcohol residue of the ester may consist of linear or branched alkyl chains, alicyclic compounds, or aromatic compounds, which may be further modified by hydroxyl, halogen, or epoxy groups. Styrene and styrene derivatives are also particularly preferred.

[0110] In addition, water-based industrial products used as paints, plasters or filler mixtures may contain additional additives such as dispersants, thickeners, stabilizers, defoamers and / or hydrophobic agents.

[0111] As a component (g), the water-based industrial product, as a paint, plaster, or filler compound, comprises a water content to a total of 100%. The water content can typically vary over a wide range and is at least 10% by weight, preferably at least 15% by weight, more preferably at least 20% by weight.

[0112] According to a preferred embodiment of the invention, the aqueous industrial product, as a paint, plaster, or filler compound, is substantially free of, and preferably completely free of, preservatives selected from 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, dithiobisbenzmethylamide, formaldehyde and formaldehyde donors, quaternary ammonium compounds, bromonitrobenzyl glycol, dibromodiazoxypropionamide, dibromodicyanobutane, iodopropynyl butyl carbamate, thiabendazole, sodium pyrithione, zinc pyrithione, o-phenylphenol, and combinations thereof.

[0113] According to another embodiment, the present invention also relates to the use of the composition defined above for stabilizing aqueous industrial products against microbial invasion, said composition comprising the following components:

[0114] (a) guanidine and / or at least one unsubstituted guanidine salt, and

[0115] (b) One or more carbonate compounds selected from sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, and ammonium carbonate.

[0116] The composition is characterized in that the weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, preferably in the range of 1:8.6 to 21:1, more preferably in the range of 1:8 to 8:1, and very preferably in the range of 1:3.4 to 1.6:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the whole composition.

[0117] In the context of this invention, it has been surprisingly found that, due to the content of guanidine (component (a)) and carbonate (component (b)), aqueous products (i.e., water-based products) require significantly less of the type of preservatives typically included in these products for preservation, and in some cases, none at all. Nevertheless, these products are characterized by excellent resistance to microbial contamination, especially during storage.

[0118] The amounts of components (a) and (b) used in this application can vary over a wide range. According to one embodiment of the invention, components (a) and (b) are used in / added to the product in a total amount ranging from 0.05 wt% to 10 wt%, preferably from 0.1 wt% to 5 wt%, and more preferably from 0.2 wt% to 2.5 wt%, based on the entire water-based industrial product.

[0119] The following examples are used to further illustrate the present invention:

[0120] 1. Research on the cooperating effects of guanidine hydrochloride

[0121] The study investigated the synergistic interactions between guanidine (added in the form of guanidine hydrochloride) and combinations of sodium carbonate (Na2CO3) or sodium bicarbonate (NaHCO3).

[0122] The experimental organisms used were from Pseudomonas. Pseudomonas spec. Gram-negative bacterial species of DSM 115322. For this study, mixtures of guanidine and sodium carbonate or sodium bicarbonate at different concentrations were prepared and their effects on *Pseudomonas* spec. DSM 115322 were tested. The titration was performed using a microtiter plate method in Müller-Hinton broth (MHB) at a concentration of 10... 6 The experiment was conducted at a cell density of one microorganism per ml.

[0123] Microtiter plates were incubated at 30°C for 48 hours. After 48 hours, the growth-induced turbidity of the batch was assessed, and the optical density was also determined photometrically. In this way, the minimum inhibitory concentration (MIC) of the two substances was determined individually and in combination.

[0124] Synergy is expressed numerically by calculating the synergy index (SI). The calculation is performed according to the standard method of FCKull et al., Applied Microbiology, Vol. 9 (1961), p. 538.

[0125] The Synergy Index (SI) is calculated using the following formula:

[0126] Synergy Index SI = Q a / Q A + Q b / Q B

[0127] Q a = Concentration of component A in mixture A + B

[0128] Q A = Concentration of component A as the sole reagent

[0129] Q b = Concentration of component B in mixture A + B

[0130] Q B = Concentration of component B as the sole reagent

[0131] If the synergy index is greater than 1, it indicates an antagonistic effect. If the synergy index is 1, it indicates that the effects of the two compounds are additive. If the synergy index is less than 1, it indicates a synergistic effect between the two compounds.

[0132] Example 1: Study on the synergistic interaction between guanidine and sodium carbonate (Na2CO3)

[0133] Under a culture time of 48 hours at 30°C, the effects of guanidine and sodium carbonate on... Pseudomonas spec. Calculation of the synergy index of DSM115322.

[0134] Table 1

[0135]

[0136] Qa: Shows the concentration of guanidine in the mixture at the endpoint.

[0137] QA: The concentration of guanidine as the sole reagent indicating the endpoint.

[0138] Qb: Shows the concentration of sodium carbonate in the mixture at the endpoint.

[0139] QB: The concentration of sodium carbonate as the sole reagent indicating the endpoint.

[0140] As is evident from Table 1, the optimal synergistic effect of the guanidine and sodium carbonate composition, i.e., the lowest synergistic index (0.57), is at a ratio of 1545 ppm guanidine / 2000 ppm sodium carbonate. A synergistic effect can be observed if the weight ratio of guanidine to sodium carbonate is in the range of 1:25 to 30:1, or, after conversion based on the dominant structure, the weight ratio of guanidine to carbonate is in the range of 1:14 to 54:1.

[0141] Example 2: Study on the synergistic interaction between guanidine and sodium bicarbonate (NaHCO3)

[0142] At 30°C for 48 hours, the effects of guanidine and sodium bicarbonate on... Pseudomonas spec. Calculation of the synergy index of DSM 115322.

[0143] Table 2

[0144]

[0145] Qa: Shows the concentration of guanidine in the mixture at the endpoint.

[0146] QA: The concentration of guanidine as the sole reagent indicating the endpoint.

[0147] Qb: Shows the concentration of sodium bicarbonate in the mixture at the endpoint.

[0148] QB: The concentration of sodium bicarbonate as the sole reagent indicating the endpoint.

[0149] As is evident from Table 2, the optimal synergistic effect of the guanidine and sodium bicarbonate composition, i.e., the lowest synergistic index (0.82), is at a ratio of 618 ppm guanidine / 7500 ppm sodium bicarbonate. A synergistic effect can be observed if the weight ratio of guanidine to sodium bicarbonate is in the range of 1:12 to 15:1, or, after conversion based on the dominant structure, the weight ratio of guanidine to carbonate is in the range of 1:8.6 to 21:1.

[0150] In Examples 3 and 4, the synergistic interaction between guanidine and sodium carbonate against microbial invasion was tested in an emulsion paint containing a limited amount of guanidine hydrochloride and sodium carbonate. The paint tested was an interior emulsion paint (PVC 77%, pH 8.0) based on vinyl acetate-ethylene binder, manufactured in a laboratory without the addition of conventional preservatives.

[0151] program:

[0152] The paint was mixed with sodium carbonate or guanidine hydrochloride of various concentrations and homogenized. The resulting batches of paint were then inoculated with different bacterial mixtures. Bacterial mixture 1 consisted of standard bacteria (ag) used for microbial load testing of industrial products and contamination-related wild-type bacterial strains (hl) isolated from commercial latex paints containing conventional preservatives that were microbially contaminated. Bacterial mixture 2 consisted of alkaliphilic bacteria isolated from commercial, so-called preservative-free alkaline latex paints that were actually microbially contaminated.

[0153] Bacterial mixture 1:

[0154] (a) Alcaligenes faecalis NCIMB 13145

[0155] (b) Aeromonas hydrophila DSM 6173

[0156] (c) Escherichia coli DSM 13631

[0157] (d) Burkholderia cepacia DSM 9241

[0158] (e) Staphylococcus aureus DSM 799

[0159] (f) Pseudomonas aeruginosa DSM 50071

[0160] (g) Pseudomonas putida DSM 13624

[0161] (h) Pseudomonas spp. (Pseudomonas soleovorans group) DSM 33933

[0162] (i) Pseudomonas aeruginosa DSM 33935

[0163] (j) Pseudomonas oleovorans DSM 33936

[0164] (k) Pseudomonas spec. DSM 33937

[0165] (l) Pseudomonas aeruginosa DSM 33938

[0166] Bacterial mixture 2:

[0167] (a) Nesterenkonia sp. DSM 108520

[0168] (b) Nesterenkonia sp. DSM 108521

[0169] (c) Alkalibacterium pelagium DSM 108522

[0170] (d) Nesterenkonia massiliensis DSM 110679

[0171] (e) Nesterenkonia sp. DSM 108519

[0172] Cell suspensions of bacterial mixtures were prepared by culturing each bacterium in liquid culture on a shaker at 30°C for 24 hours. The culture medium used for bacteria from bacterial mixture 1 was Müller-Hinton liquid medium. Bacteria from bacterial mixture 2 were cultured in Müller-Hinton liquid medium pre-adjusted to pH 9.5–9.7 with an alkaline buffer. After culturing, each liquid culture was centrifuged, and the cells were resuspended in physiological saline solution. To adjust the mixture to pH 10... 9 The total cell count was [value] / ml, and individual bacterial suspensions were diluted with saline solution accordingly before pooling, if appropriate. Cell counts in the inoculated suspensions were determined by chamber counting in each case.

[0173] In Examples 3 and 4, by using a cell count of 10 9 A so-called repeated loading test was performed by repeatedly inoculating samples with a bacterial suspension of 2% v / w / ml at defined time intervals and monitoring bacterial development using a semi-quantitative assessment method. After each inoculation, the samples were incubated at 30°C for 6 days (bacterial mixture 1) or 7 and 14 days (bacterial mixture 2), and bacterial invasion was semi-quantitatively assessed at each of these time points. For this assessment, after homogenization, an aliquot (10 µl) of each sample was extracted using a sterile plastic inoculation loop and evenly spread onto agar plates (bacterial mixture 1 on tryptone-soy agar, and bacterial mixture 2 on alkaline nutrient agar DSMZ 31). After spreading, the agar plates were incubated at 30°C for 48 hours (bacterial mixture 1) or 5 to 7 days (bacterial mixture 2). After incubation, the bacterial colonies growing on the agar plates were visually assessed and quantified according to the following protocol:

[0174]

[0175] A total of 3 vaccination cycles were performed for each repetitive load test.

[0176] Example 3 / Table 3:

[0177] Inoculate with bacterial mixture 1 at 2% (w / v) concentration, cell count 10-1 9 / ml

[0178]

[0179] Example 4 / Table 4:

[0180] Inoculate with bacterial mixture 2% (w / v) and count cells at 10-10. 9 / ml

[0181]

[0182] The results shown in Tables 3 and 4 demonstrate that the synergistic interaction between guanidine and sodium carbonate, which has been confirmed under laboratory conditions, can also be confirmed in practical applications of latex paint.

[0183] 2. Studies using guanidine carbonate to investigate synergistic interactions:

[0184] The study investigated the synergistic interactions between guanidine (added in the form of guanidine carbonate) and combinations of sodium carbonate (Na2CO3) or sodium bicarbonate (NaHCO3).

[0185] The experimental organisms used were from Pseudomonas. Pseudomonas spec. Gram-negative bacterial species of DSM 115322. For this study, mixtures of guanidine and sodium carbonate or sodium bicarbonate at different concentrations were prepared and their effects on *Pseudomonas* spec. DSM 115322 were tested. The titration was performed using a microtiter plate method in Müller-Hinton broth (MHB) at a concentration of 10... 6 The experiment was conducted at a cell density of one microorganism per ml.

[0186] The microtiter plates were incubated at 30°C for 48 hours. After 48 hours, the turbidity of the batch due to growth was assessed, and the optical density was also determined by spectrophotometry. In this manner, the minimum inhibitory concentration (MIC) of the two substances was determined individually and in combination.

[0187] The synergistic effect is expressed numerically by calculating the Synergy Index (SI). For the following examples, the calculation is also performed according to the standard method of FC Kull et al., Applied Microbiology, Vol. 9 (1961), p. 538.

[0188] If the synergy index is greater than 1, it indicates an antagonistic effect. If the synergy index is 1, it indicates that the effects of the two compounds are additive. If the synergy index is less than 1, it indicates a synergistic effect between the two compounds.

[0189] Example 5: Study on the synergistic interaction between guanidine and sodium carbonate (Na2CO3)

[0190] Under a culture time of 48 hours at 30°C, the effects of guanidine and sodium carbonate on... Pseudomonas spec. Calculation of the synergy index of DSM115322.

[0191] Table 5

[0192]

[0193] Qa: Shows the concentration of guanidine in the mixture at the endpoint.

[0194] QA: The concentration of guanidine as the sole reagent indicating the endpoint.

[0195] Qb: Shows the concentration of sodium carbonate in the mixture at the endpoint.

[0196] QB: The concentration of sodium carbonate as the sole reagent indicating the endpoint.

[0197] As is evident from Table 5, the optimal synergistic effect of the guanidine and sodium carbonate composition, i.e., the lowest synergistic index (0.78), is at a ratio of 1155 ppm guanidine / 1000 ppm sodium carbonate. A synergistic effect can be observed if the weight ratio of guanidine to sodium carbonate is in the range of 1:20 to 13:1, or, after conversion based on the dominant structure, the weight ratio of guanidine to carbonate is in the range of 1:12 to 1.8:1.

[0198] Example 6: Study on the synergistic interaction between guanidine and sodium bicarbonate (NaHCO3)

[0199] At 30°C for 48 hours, the effects of guanidine and sodium bicarbonate on... Pseudomonas spec. Calculation of the synergy index of DSM 115322.

[0200] Table 6

[0201]

[0202] Qa: Shows the concentration of guanidine in the mixture at the endpoint.

[0203] QA: The concentration of guanidine as the sole reagent indicating the endpoint.

[0204] Qb: Shows the concentration of sodium bicarbonate in the mixture at the endpoint.

[0205] QB: The concentration of sodium bicarbonate as the sole reagent indicating the endpoint.

[0206] As is evident from Table 6, the optimal synergistic effect of the guanidine and sodium bicarbonate composition, i.e., the lowest synergistic index (0.85), is at a ratio of 990 ppm guanidine / 3500 ppm sodium bicarbonate. A synergistic effect can be observed if the weight ratio of guanidine to sodium bicarbonate is in the range of 1:4 to 1.6:1, or, after conversion based on the dominant structure, the weight ratio of guanidine to carbonate is in the range of 1:3.4 to 1.6:1.

Claims

1. A composition comprising the following components: (a) guanidine and / or at least one unsubstituted guanidine salt, and (b) One or more carbonate compounds selected from sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, and ammonium carbonate. Its features The weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, and in each case the weight ratio is determined based on the content of guanidine and carbonate in the whole composition.

2. The composition according to claim 1, characterized in that... It contains guanidine hydrochloride and / or guanidine carbonate as components (a).

3. The composition according to claim 1 or 2, characterized in that... It contains sodium carbonate and / or sodium bicarbonate as components (b).

4. The composition according to any one of claims 1 to 3, further comprising the following components: (c) One or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2·[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate and zinc carboxylate.

5. The composition according to any one of claims 1 to 4, further comprising the following components: (d) One or more biocidal compounds selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, bromonitrobenzinol, dibromodiazoxypropionamide, iodopropynyl butyl carbamate, phenoxyethanol, dibromodicyanobutane, and quaternary ammonium compounds.

6. The composition according to any one of claims 1 to 5, characterized in that It has a pH range of 8 to 12.

7. The composition according to any one of claims 1 to 6, characterized in that... The weight ratio of (a) to (b) is in the range of 1:8 to 8:1, and in each case the weight ratio is determined based on the content associated with guanidine and carbonate.

8. The composition according to any one of claims 4 to 7, characterized in that The weight ratio of (a) to (c) is in the range of 0.77:1 to 12:1, and in each case the weight ratio is determined based on the content associated with guanidine and zinc.

9. The composition according to any one of claims 1 to 6, characterized in that... It contains the following components: (a) Based on the amount of guanidine in the composition, in the range of 100 to 10,000 ppm, preferably in the range of 100 to 7,500 ppm, and (b) The amount based on carbonate content, in the range of 100 ppm to 50,000 ppm, preferably in the range of 250 ppm to 25,000 ppm.

10. The composition according to any one of claims 4 to 6, characterized in that It contains a component (c) in an amount ranging from 10 to 5000 ppm based on the amount of zinc in the composition.

11. The composition according to any one of claims 1 to 10, characterized in that The composition contains water as a solvent in an amount ranging from 10% to 90% by weight based on the whole composition.

12. The compositions according to the invention, especially aqueous compositions, are generally selected from industrial products, particularly aqueous industrial products: paints, varnishes, dyes and plasters, fillers and filler blends, primers, emulsions, latexes, polymer dispersions, chalk suspensions, mineral slurries, titanium dioxide slurries, ceramic blends, kneading blends, adhesives, sizing agents, casein-containing products, starch- and cellulose-containing products, concrete admixtures, lignin sulfonates, asphalt emulsions, surfactant solutions, fuels, laundry detergents, cleaning agents, etc. Products, pigment pastes and pigment dispersions, wax emulsions, silicone emulsions, impregnation materials, release agents, lubricants, inks, offset printing fluids, thickeners and thickener formulations, rheology modifiers, cosmetics, fragrances, toiletries, cooling water, circulating water, humidifying and irrigation water, production water, rinsing and circulating water, wood processing fluids, oil recovery fluids, paper processing fluids, leather production fluids, textile production fluids, glass processing fluids, drilling and cutting oils, hydraulic fluids, cooling lubricants, fertilizers and crop protection materials, and biocidal products.

13. The composition according to any one of claims 1 to 8, characterized in that It comprises components (a) and (b) in amounts ranging from 1 wt% to 100 wt%, preferably from 10 wt% to 60 wt%, and more preferably from 20 wt% to 40 wt%.

14. The composition according to any one of claims 1 to 12, characterized in that The composition is an aqueous industrial product stabilized against microbial invasion and selected from paints, plasters, and filler blends, comprising: (a) guanidine and / or at least one guanidine salt, (b) One or more carbonate compounds selected from sodium bicarbonate (NaHCO3), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3), and ammonium carbonate ((NH4)2CO3). The characteristic feature is that the weight ratio of component (a) to component (b) is in the range of 1:14 to 54:1, and in each case, the weight ratio is determined based on the content of guanidine and carbonate in the whole composition. (c) Optionally, one or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2·[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate. (d) Optionally, one or more compounds selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, bromonitrobenzinol, dibromonitropropionamide, iodopropynyl butyl carbamate, phenoxyethanol, dibromodicyanobutane, and quaternary ammonium compounds. (e) 1.0% to 85% by weight of pigments and / or fillers, (f) Polymer dispersions, calculated as solids fractions, from 1 wt% to 35 wt%, and (g) Add water to a total of 100% by weight.

15. Use of the composition according to any one of claims 1 to 11 for stabilizing aqueous industrial products against microbial invasion.

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