WO2025125110A1 - Guanidine- and carbonate-containing compositions - Google Patents

Abstract

The present invention relates to compositions, in particular aqueous compositions, comprising the following components: (a) guanidine and/or at least one salt of unsubstituted guanidine and (b) one or more carbonate compound(s) selected from the group consisting of sodium hydrogencarbonate, sodium carbonate, potassium hydrogencarbonate, potassium carbonate, ammonium hydrogencarbonate and ammonium carbonate. The compositions are characterized in that the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, where the determining of the weight ratio is based in each case on the content relative to the guanidine and carbonate in the overall composition. The invention further relates to industrial products containing the compositions of the invention, and to the use of the compositions for stabilization of aqueous industrial products against microbial contamination.

Description

Compositions containing guanidine and carbonate

The present invention relates to compositions, in particular aqueous compositions, which contain the components: (a) guanidine and/or at least one salt of unsubstituted guanidine and (b) one or more carbonate compounds selected from the group consisting of 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 from 1:14 to 54:1, the content of guanidine and carbonate in the total composition being used as the basis for determining the weight ratio. The invention further relates to technical products which contain the compositions according to the invention, and to the use of the compositions for stabilizing aqueous technical products against microbial attack.

Technical products, especially water-based ones, such as paints, varnishes, glazes, plasters, and emulsions, are typically manufactured using natural or biodegradable raw materials. These raw materials and the water used as a solvent are often contaminated with germs such as bacteria, yeasts, and fungi. If these products are not preserved during production, they can exhibit high bacterial counts just one day after production.

In order to ensure that these products and, where applicable, the components used in their manufacture meet the hygiene requirements and to ensure the durability of the technical products, so-called biocides are usually added to the products or even to their components. One class of biocides used for the preservation of aqueous coatings, such as paints, plasters, varnishes, or glazes, or components thereof, is the so-called 3-isothiazolin-3-ones. This class of substances includes highly antimicrobially effective compounds with sometimes differing activity profiles. Synergistic combinations of different 3-isothiazolin-3-ones are often used to reduce the amount of biocide needed. For example, WO 99/08530 A1 proposes the combined use of methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one.

Another class of biocides are the so-called alkylguanidinium salts and polyguanidinium salts. For example, it is known from the "Directory of Microbicides for the Protection of Materials," Springer 2005, pages 726 to 731, that medium- and long-chain guanidines and biguanidines, such as cocospropylenediamine-1,5-bis-guanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylenebiguanidine) hydrochloride, di(4'-chlorophenyldiguanido)hexane, chlorhexidine digluconate, and chlorhexidine diacetate, exhibit antimicrobial activity.

Furthermore, the use of such medium- and long-chain guanidine compounds in combination with other antimicrobial and/or fungicidal agents is known. For example, the combination with 3-iodo-2-propynyl butylcarbamate or formaldehyde depot substances is known. For example, EP 0 891 710 A1 teaches the combined use of dodecylguanidine hydrochloride and IPBC. However, the use of dodecylguanidine salts for the preservation of paint compositions and polymer dispersions has proven problematic; incompatibilities in the form of coagulation have been observed upon the addition of these salts.

The use of conventional biocides or preservatives is increasingly being considered because they are increasingly subject to legal restrictions.

It has therefore already been proposed to provide storage-stable aqueous coating materials without the content of conventional preservatives by increasing their pH value so that microbial attack is effectively prevented. a pH of at least 10, since microbial contamination cannot be prevented with sufficient reliability at lower pH values. Thus, in the prior art, the pH is increased by adding water glass, for example, according to EP 1 297 079 A1. Alternatively, DE10 2014 013 455 A1 and WO2017/144694A1 disclose the use of siliconates as a pH-increasing additive. However, the disadvantages of the above-described preservation methods are the comparatively high pH values in the coating materials required for preservation, which requires particular care in their handling.

As another preservative-free preservation system, OMYA INTERNATIONAL AG promotes a buffer system called Omyasmart Next Generation (OSNG) technology, which is intended to enable the long-term stability of water-based systems and biocide-free formulations against microbial attack. This buffer system is the subject of International Patent Application WO 2022/223804 AL. This discloses a buffer composition comprising a first and a second buffer component, wherein a) the first buffer component is at least one water-soluble or water-dispersible source of magnesium ions and/or zinc ions, and b) the second buffer component is at least one alkali carbonate and/or at least one alkali bicarbonate.

Despite the numerous known combinations of active ingredients and the measures taken in the meantime, there is an increased demand, particularly due to increasing regulatory restrictions, for compositions or stabilized products that stabilize against microbial infestation, preferably without or with a reduced content of classic preservatives or biocides, such as isothiazolinones, bronopol and pyrithiones.

The invention achieves this object by a composition, preferably an aqueous composition, containing the components:

(a) guanidine and/or at least one salt of the unsubstituted guanidine and (b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate (NaHCCE), sodium carbonate (TS^CCE), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3) and ammonium carbonate ((NFL^CCh), characterized in that the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, wherein the content in relation to the guanidine and carbonate in the entire composition is used as the basis for determining the weight ratio, wherein in the case of the use or presence of guanidine carbonate as component (a), the counterion (the carbonate) is also taken into account.

According to a preferred embodiment of the invention, the composition is further characterized in that it contains component (a) in an amount in the range of 100 to 7,500 ppm, preferably in the range of 250 to 5,000 ppm, based on the amount of guanidine in the composition and component (b) in an amount in the range of 250 to 25,000 ppm, preferably in the range of 500 to 10,000 ppm, based on the amount of carbonate.

Due to their composition, the compositions according to the invention require significantly fewer, and in some cases even no, preservatives, as are conventionally included for preservation. Nevertheless, these compositions, or the products containing these compositions, are characterized by excellent resistance to microbial attack due to the surprisingly effective interaction of the guanidine or guanidine salt, component (a), and the at least one carbonate compound, component (b).

According to the invention, the compositions are characterized in that the weight ratio of components (a) to (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, wherein in determining the weight ratio, the content in relation to the guanidine and carbonate in the It has proven particularly advantageous within the scope of the invention if the weight ratio of (a) to (b) in the compositions according to the invention lies within the ranges specified above, since a synergistic interaction of the guanidine and the carbonate has been demonstrated within this range.

The composition according to the invention contains, as component (a), guanidine and/or at least one salt of unsubstituted guanidine. "At least one salt" in the context of the present invention means that the composition contains a single salt of guanidine or several, i.e., two, three, four, five, or more, salts of guanidine.

For the purposes of the present invention, guanidine and/or a salt of unsubstituted guanidine means that the composition contains, as component (a), guanidine and/or optionally also one or more salts of unsubstituted guanidine. The guanidine is the compound according to the following formula:

wobei n gleich 1, 2 oder 3 ist, und wobei das Gegenion X¹¹' beispielsweise Chlorid, Carbonat, Nitrat, Sulfat, Thiocyanat, Phosphat, Hydrogencarbonat, Guanidinsilikate, Formiat, Acetat oder Citrat ist. The salts of unsubstituted guanidine or guanidine salts within the meaning of the present invention are guanidine or guanidinium salts of the general formula shown below:

where n is 1, 2 or 3, and where the counterion X ¹¹ ' is, for example, chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, guanidine silicates, formate, acetate or citrate.

According to a preferred embodiment of the invention, the composition according to the invention contains as component (a) guanidine hydrochloride and/or guanidine carbonate and/or guanidine hydrogen carbonate, according to a particularly preferred embodiment of the invention, the composition contains as component (a) guanidine carbonate.

As component (b), the composition according to the invention contains one or more carbonate compounds selected from the group consisting of sodium hydrogen carbonate (NaHCCL), sodium carbonate (TSfeCCL),

Potassium hydrogen carbonate (KHCO3), potassium carbonate (K2CO3),

Ammonium bicarbonate (NH4HCO3) and ammonium carbonate ((NH^CCh). Multiple means that the composition can contain two, three, four, five or six of the carbonate compounds mentioned.

According to a preferred embodiment of the invention, the composition contains sodium carbonate (Na2CO3) and/or sodium bicarbonate (NaHCCE) as component (b). When using these carbonate compounds, compositions with additionally improved properties are obtained.

Within the scope of the present invention, both the amounts of components (a) and (b) and the weight ratios of components (a) and (b) to one another are stated. Unless otherwise stated, the amounts relate in each case to the lead structures, guanidine (CN3H5) as component (a), or to the lead structure of component (b), carbonate ( ^CO32 ). Likewise, when determining the stated weight ratios, the content in relation to guanidine, without taking into account any counterion, as component (a), and the content of carbonate, without taking into account any counterion, as component (b), in the composition are used as the basis. The amount of component (a), guanidine and/or its salt contained in the composition according to the invention can vary over wide ranges and is generally in the range from 100 ppm to 10,000 ppm, preferably in the range from 250 ppm to 7,500 ppm and particularly preferably in the range from 250 ppm to 5,000 ppm, based on the amount of guanidine in the total composition.

The amount of component (b), the one or more carbonate compound(s), contained in the composition according to the invention can vary over wide ranges and is generally in the range from 100 ppm to 50,000 ppm, preferably in the range from 500 ppm to 25,000 ppm, particularly preferably in the range from 1,000 ppm to 10,000 ppm, based on the amount of carbonate.

The invention therefore relates, according to one embodiment, to a composition which is characterized in that it comprises the components:

(a) in an amount in the range of 100 to 10,000 ppm, preferably in the range of 250 to 7,500 ppm, particularly preferably in the range of 500 to 5,000 ppm, based on the amount of guanidine in the composition and

(b) in an amount in the range from 100 ppm to 50,000 ppm, preferably in the range from 500 to 25,000 ppm, particularly preferably in the range from 1,000 to 10,000 ppm, based on the amount of carbonate, wherein the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, wherein the content in relation to the guanidine and carbonate in the entire composition is used as the basis for determining the weight ratio.

The pH of the composition according to the invention can vary over a wide range. According to one embodiment of the invention, the composition is characterized in that it has a pH in the range of pH 8 to pH 12, preferably a pH in the range of pH 8.5 to 11.5, particularly preferably a pH in the Range of pH 9.0 to 11.0. The pH value can be adjusted to the claimed range using methods familiar to the person skilled in the art.

The composition according to the invention is preferably an aqueous composition whose water content can vary widely. This is generally between 10 and 90% by weight, based on the total 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, particularly preferably greater than 20% by weight, based on the total composition.

The composition, in particular the aqueous composition, according to the present invention is generally a technical, in particular an aqueous technical product, selected from the group consisting of: paints, varnishes, glazes and plasters, fillers and fillers, primers, emulsions, latices, polymer dispersions, chalk slurries, mineral slurries, titanium dioxide slurries, ceramic masses, modeling clays, adhesives, glues, case-containing products, starch- and cellulose-containing products, concrete admixtures, lignin sulfonates, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning agents, pigment pastes and pigment dispersions, wax emulsions, silicone emulsions, impregnating agents, release agents and lubricants, inks, lithographic fluids, thickeners and thickener preparations, rheology aids, cosmetic products, fragrances, toiletries, cooling water, water in circuits, water for humidification and irrigation, Production, rinsing and recycling water, liquids in wood processing, liquids in petroleum production, liquids in paper processing, liquids in leather production, liquids in textile production, liquids in glass processing, drilling and cutting oils, hydraulic fluids, cooling lubricants, fertilizers and pesticides, and biocidal products. According to a preferred embodiment of the present invention, the composition according to the invention is an aqueous technical product selected from the group consisting of paints, varnishes, glazes, plasters, fillers and putties, pigment pastes and pigment dispersions, starch- and cellulose-containing products, thickeners and thickener preparations, mineral slurries, titanium dioxide slurries, ceramic masses, detergents and cleaning agents.

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

(a) guanidine and/or at least one salt of guanidine,

(b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate (NaHCCL), sodium carbonate (TS^CCh), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3) and ammonium carbonate ((NEL^CCL), and

(c) one or more zinc compounds selected from the group consisting of 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, wherein the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, wherein the content in relation to the guanidine and carbonate in the entire composition is used as the basis for determining the weight ratio.

Component (c) is generally selected from the group consisting of 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 the group consisting of zinc oxide and zinc carbonate; according to a particularly preferred embodiment, component (c) is zinc oxide. The composition according to the invention according to this embodiment, which further contains component (c), has the advantage that the at least one zinc compound, component (c), interacts synergistically with components (a) and (b), whereby the content of components (a), (b) and (c) in the composition can be further reduced while maintaining the stabilizing activity against microorganisms.

The weight ratio of components (a) to (c) can vary widely. According to a preferred embodiment, the composition according to the invention is characterized in that the weight ratio of (a) to (c) is in the range from 0.77:1 to 12:1, preferably in the range from 1:1 to 10:1, wherein the content of guanidine and zinc is used as the basis for determining the weight ratio.

The amount of component (c), the at least one zinc compound, contained in the composition according to the invention can vary over wide ranges and is in the range from 10 to 5,000 ppm, preferably in the range from 25 to 2,500 ppm, particularly preferably in the range from 50 to 1,000 ppm, in each case based on the content of zinc in the composition.

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

(a) guanidine and/or at least one salt of guanidine,

(b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate (NaHCCE), sodium carbonate (TS^CCh), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3) and ammonium carbonate ((NEL^CCh), and optionally:

(c) one or more zinc compounds selected from the group consisting of 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, and if applicable:

(d) one or more compounds selected from the group consisting of 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,

Contains dichlorooctylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol, dibromodicyanobutane and quaternary ammonium compounds, wherein the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, wherein the content in relation to the guanidine and carbonate in the entire composition is used as the basis for determining the weight ratio.

The inventive composition according to this embodiment, which further comprises component (d), has the advantage that the at least one compound selected from the group consisting of 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, interacts synergistically with component (a), whereby the content of components (a), (b), optionally (c) and (d), while maintaining the antimicrobial Effectiveness, in the composition can be reduced even further.

According to this embodiment, the invention therefore relates to a particularly aqueous composition containing:

(a) guanidine and/or at least one salt of unsubstituted guanidine,

(b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate (NaHCCE), sodium carbonate (TS^CCh), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3) and ammonium carbonate ((NEL^CCh), characterized in that the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, wherein the content in relation to the guanidine and carbonate in the entire composition is used as the basis for determining the weight ratio, and optionally:

(c) one or more zinc compounds selected from the group consisting of 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, and optionally:

(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, l,2-benzisothiazolin-3-one, N-methyl-l,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol, dibromodicyanobutane and quaternary ammonium compounds.

The amount of component (d) contained in the composition according to the invention can vary widely. According to a preferred embodiment of the invention, the composition is characterized in that it contains, as component (d):

(dl) phenoxyethanol in an amount in the range of 100 to 10,000 ppm, preferably in an amount in the range of 250 to 7,500 ppm, particularly preferably in an amount in the range of 500 to 5,000 ppm and/or

(d2) 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, l,2-benzisothiazolin-3-one, N-butyl-l,2-benzisothiazolin-3-one, octylisothiazolinone, dichlorooctylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, dibromodicyanobutane and quaternary ammonium compounds in a total amount in the range of 1 to 2000 ppm, preferably in a total amount in the range of 1 to 1000 ppm and particularly preferably in a total amount in the range of 1 to 750 ppm.

The present invention further provides a process for preparing the preferably aqueous compositions according to the invention, comprising mixing the above-defined components (a), (b), optionally (c) and optionally (d).

According to one embodiment, the present invention relates to a concentrate containing components (a) and (b). This concentrate is suitable for stabilizing technical products against microbial attack by incorporating a certain amount of the concentrate into the technical product to be stabilized against microbial attack.

The concentrate according to the invention is the composition defined above, which is characterized in that it contains components (a) and (b) in an amount in the range from 1 to 100% by weight, preferably in the range from 10 to 60% by weight, particularly preferably in the range from 20 to 40% by weight.

Specifically, this embodiment relates to a concentrate for stabilizing technical compositions against microbial attack, containing:

(a) guanidine and/or at least one salt of the unsubstituted guanidine and

(b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate (NaHCCE), sodium carbonate (TS^CCE), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3) and ammonium carbonate ((NH^CCE), characterized in that the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, wherein in determining the weight ratio the content in Reference to the guanidine and carbonate in the entire composition, further characterized in that the concentrate contains components (a) and (b) in an amount in the range of 1 to 100 wt.%, preferably in the range of 10 to 60 wt.%, particularly preferably in the range of 20 to 40 wt.%.

The concentrate can be in the form of a powder mixture or as a liquid concentrate, for example as an aqueous concentrate.

According to a preferred embodiment, the concentrate according to the invention comprises the following components:

(a) 5 to 40 wt.%, preferably 10 to 30 wt.% guanidine carbonate and

(b) 2.5 to 15 wt.%, preferably 5 to 10 wt.% sodium carbonate.

The following aqueous concentrates (A) to (D) have proven to be particularly advantageous, having the following composition:

(A) 20 wt% guanidine carbonate + 10 wt% sodium carbonate + 70 wt% water

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

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

(D) 10 wt% guanidine carbonate + 10 wt% sodium carbonate + 80 wt% water

According to a preferred embodiment, the concentrate according to the invention comprises the following components:

(a) 10 to 20 wt.% guanidine carbonate,

(b) 5 to 10 wt.% sodium carbonate and

Ad 100 wt% water. According to a further preferred embodiment, the concentrate according to the invention comprises the following components or consists of:

(a) 18 to 22 wt.%, preferably 20 wt.% guanidine carbonate,

(b) 1.85 to 2.45%, preferably 2.05% by weight of sodium bicarbonate and

Ad 100 wt% water.

According to a particularly preferred embodiment, the concentrate according to the invention consists of the following components: 20.00 wt.% guanidinium carbonate, 2.05 wt.% sodium hydrogen carbonate and 100% water.

According to one embodiment of the present invention, the composition is an aqueous technical product stabilized against microbial attack, which is selected from a paint, a plaster and a filler, comprising:

(a) guanidine and/or at least one salt of guanidine,

(b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate (NaHCCh), sodium carbonate (TS^CCh), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3) and ammonium carbonate ((NFL^CCh), characterized in that the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, wherein the content in relation to the guanidine and carbonate in the entire composition is used as the basis for determining the weight ratio,

(c) optionally one or more zinc compounds selected from the group consisting of 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, 2-methyl-4-isothiazolin-3-one, l,2-benzisothiazolin-3-one, N-methyl-l,2-benzisothiazolin-3- on, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynylbutylcarbamate, phenoxyethanol, dibromodicyanobutane and quaternary ammonium compounds,

(e) 1.0 to 85% by weight of pigment and/or filler,

(f) 1 to 35 wt.% polymer dispersion calculated as solids content and

(g) 100% supplemented water content.

The composition defined above optionally contains components (c) and (d). This means that components (c) and/or (d) may be present in the composition, but the composition may also be free of components (c) and (d), and therefore neither component (c) nor component (d) is present.

The aqueous technical product stabilized against microbial attack according to the invention, which is a paint, plaster, or filler, requires significantly less, in some cases even none, of the preservatives typically contained in such products for in-container preservation due to its composition. Nevertheless, due to the surprisingly effective interaction of the guanidine or the guanidine salt and the carbonate compound(s), these products are characterized by excellent resistance to microbial attack, particularly during storage. As a result, the aforementioned technical products are significantly improved in terms of their environmental compatibility and furthermore exhibit all known properties related to good and safe processing characteristics.

According to a preferred embodiment, the aqueous technical product, which is a paint, a plaster or a filler, is characterized in that it contains the components (a) and (b) in a total amount in the range from 0.05 wt.% to 10 wt.%, preferably in the range from 0.1 wt.% to 5 wt.%, particularly preferably in the range from 0.2 wt.% to 2.5 wt.%, based on the total technical product.

According to a preferred embodiment, the aqueous technical product, which is a paint, a plaster or a filler, contains as component (a) guanidine hydrochloride and/or guanidine carbonate. According to a preferred embodiment, the aqueous technical product, which is a paint, a plaster or a filler, contains sodium carbonate and/or sodium bicarbonate as component (b).

The aqueous technical product, which is a paint, plaster, or filler, generally contains, as component (e), 1.0 to 85% by weight of pigment and/or filler. According to a preferred embodiment of the invention, the coating composition contains 1 to 25% by weight of pigments and/or 5 to 50% by weight of fillers.

The pigments used can be the usual pigment admixtures of emulsion paints, such as titanium dioxide, iron oxide, chromium oxide, cobalt blue, phthalocyanine pigments, spinel pigments, as well as nickel and chromium titanates. Silicates, carbonates, fluorspar, sulfates, and oxides are preferred fillers in the composition.

As component (f), the aqueous technical product, which is a paint, plaster, or filler, generally contains 1 to 35% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 12% by weight of polymer dispersion, calculated in each case as the solids content of the polymer dispersion. The polymer dispersions contained in the coating composition can be any polymer dispersions known per se from the prior art in the field of coating or paint systems. The properties of the dispersion, as well as of the finished products produced from it, are predominantly determined by the respective polymer. The polymer is composed of various building blocks, the so-called monomers, which can also be combined with one another depending on the desired property profile. Suitable monomers are, for example, vinyl carboxylates having 3 to 20 carbon atoms, N-vinylpyrrolidone, vinyl aromatics, vinyl halides, ethylenically unsaturated carboxylic acids, their esters, their amides or their anhydrides, nanohybrid dispersions, water glass, silicone resin emulsions, aqueous polyurethane dispersions, styrene acrylates, a-olefins and/or 1,3-dienes in the form of aqueous polymer dispersions or water-redispersible polymer powders. The use of ethylenically unsaturated carboxylic acids is particularly preferred, in particular Acrylic and methacrylic acid, furthermore ethylenically unsaturated carboxylic acid esters, especially acrylic and methacrylic acid esters with 1 to 12 carbon atoms in the alcohol moiety. The alcohol moiety of the esters can consist of linear or branched alkyl chains, cycloaliphatics, or aromatics, which can additionally be modified with hydroxyl groups, halogen atoms, or epoxy groups. The use of styrene and styrene derivatives is also particularly preferred.

Furthermore, the aqueous technical product, which is a paint, plaster or filler, may contain additional additives such as dispersants, thickeners, stabilizers, defoamers and/or hydrophobic agents.

As component (g), the aqueous technical product, which is a paint, plaster, or filler, contains 100% water. The water content can generally vary over a wide range and is at least 10% by weight, preferably at least 15% by weight, particularly preferably at least 20% by weight.

According to a preferred embodiment of the invention, the aqueous technical product, which is a paint, a plaster or a filler, is substantially free, preferably completely free, of preservatives selected from the group consisting of 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, Diehl oroctylisothiazolinone,

Dithiobisbenzmethylamide, formaldehyde and formaldehyde releasers, quaternary ammonium compounds, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, thiabendazole, sodium pyrithione, zinc pyrithione, o-phenylphenol and combinations thereof.

According to a further embodiment, the present invention also relates to the use of the compositions defined above, comprising the components:

(a) guanidine and/or at least one salt of the unsubstituted guanidine and

(b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate and ammonium carbonate, characterized in that the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, preferably in the range from 1:8.6 to 21:1, particularly preferably in the range from 1:8 to 8:1 and very particularly preferably in the range from 1:3.4 to 1.6:1, the content in relation to the guanidine and carbonate in the entire composition being used as the basis for determining the weight ratio, for stabilizing aqueous technical products against microbial attack.

Within the scope of the invention, it was surprisingly discovered that aqueous products, i.e., water-based products, require significantly less, and in some cases even none, of the preservatives typically contained in these products for preservation due to their content of guanidine, component (a), and carbonate, component (b). Nevertheless, these products are characterized by excellent resistance to microbial attack, especially during storage.

The amounts of components (a) and (b) used during use can vary widely. According to one embodiment of the invention, components (a) and (b) are used or added to the total aqueous technical product in a total amount in the range from 0.05 wt.% to 10 wt.%, preferably in the range from 0.1 wt.% to 5 wt.%, particularly preferably in the range from 0.2 wt.% to 2.5 wt.%.

The following examples serve to further illustrate the present invention:

1. Investigation of the synergistic interaction using guanidine hydrochloride:

A combination of guanidine (added in the form of guanidine hydrochloride) with sodium carbonate (Na2CO3) or sodium bicarbonate (NaHCCh) was investigated for their synergistic interaction.

A Gram-negative bacterial species from the Pseudomonad group, Pseudomonas spec. DSM 115322, was used as the test organism. Mixtures with varying concentrations of guanidine and sodium carbonate or sodium bicarbonate were prepared and tested for their effect on Pseudomonas spec. DSM 115322. The test was performed using a microtiter plate method in Müller-Hinton Broth (MHB) at a cell density of 10 ⁶ bacteria 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. This allowed the minimum inhibitory concentrations (MICs) of the two substances to be determined individually and in combination.

The resulting synergism was numerically expressed by calculating the synergy index (SI). The calculation was carried out according to the standard method of F.C. Kull et al., Applied Microbiology, Vol. 9 (1961), p. 538.

There, the synergy index (SI) is calculated using the following formula:

Synergy index SI = Q _a /Q \ + Qb/Qß

Q _a = concentration of component A in the mixture A + B

QA = Concentration of component A as sole agent

Qb = Concentration of component B in the mixture A + B

QB = Concentration of component B as sole agent If the synergy index is above 1, this means that antagonism exists. If the synergy index is above 1, this means that the effects of the two compounds are additive. If the synergy index is below 1, this means that the two compounds are synergistic.

Example 1: Investigation of the synergistic interaction between guanidine and sodium carbonate (IS^CCh). Calculation of the synergistic index of guanidine and sodium carbonate with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.

Table 1

Qa: Concentration of guanidine in the mixture showing an endpoint QA: Concentration of guanidine as the sole agent showing an endpoint

Qb: Concentration of sodium carbonate in the mixture showing an endpoint

QB: Concentration of sodium carbonate as the sole agent showing an endpoint Table 1 shows that the optimal synergism, i.e., the lowest synergy index (0.57) of a composition of guanidine and sodium carbonate, is at a ratio of 1545 ppm guanidine to 2000 ppm sodium carbonate. Synergism can be demonstrated when the weight ratio of guanidine to sodium carbonate is in the range of 1:25 to 30:1, or, converted to the lead structures, the weight ratio of guanidine to carbonate is in the range of 1:14 to 54:1.

Example 2: Investigation of the synergistic interaction between guanidine and sodium bicarbonate (NaHCCE)

Calculation of the synergy index of guanidine and sodium bicarbonate with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.

Table 2

Qa: Concentration of guanidine in the mixture showing an endpoint

QA: Concentration of guanidine as the sole agent showing an endpoint

Qb: Concentration of sodium bicarbonate in the mixture showing an endpoint QB: Concentration of sodium bicarbonate as the sole agent showing an endpoint

Table 2 shows that the optimal synergism, i.e., the lowest synergy index (0.82) of a composition of guanidine and sodium bicarbonate, is at a ratio of 618 ppm guanidine to 7500 ppm sodium bicarbonate. Synergism can be demonstrated when the weight ratio of guanidine to sodium bicarbonate is in the range of 1:12 to 15:1, or, converted to the lead structures, the weight ratio of guanidine to carbonate is in the range of 1:8.6 to 21:1.

In Examples 3 and 4, the synergistic interaction between guanidine and sodium carbonate against microbial attack in an emulsion paint was tested by adding specific amounts of guanidine in the form of guanidine hydrochloride and sodium carbonate to the paint, and examining its stability against microbial attack. The paint tested was a emulsion paint based on a vinyl acetate-ethylene binder (PVK 77%, pH 8.0) for interior use, produced in the laboratory without the addition of the usual preservatives.

Procedure:

The paint was mixed with various concentrations of sodium carbonate or guanidine hydrochloride and homogenized. The resulting batches of the prepared paint were inoculated with various bacterial mixtures. Bacterial mixture 1 consisted of standard bacteria used for microbial load tests on technical products (ag) and contamination-relevant wild-type bacterial strains isolated from commercial, microbially contaminated emulsion paints containing conventional preservatives (h-1). Bacterial mixture 2 consisted of alkaliphilic bacteria isolated from commercial, so-called preservative-free alkaline emulsion paints that were microbially contaminated in practice. Bacteria mixture 1 :

(a) Alcaligenes faecalis NCIMB 13145

(b) Aeromonas hydrophila DSM 6173

(c) Escherichia coli DSM 13631

(d) Burkholderia cepacia DSM 9241

(e) Staphylococcus aureus DSM 799

(f) Pseudomonas aeruginosa DSM 50071

(g) Pseudomonas putida DSM 13624

(h) Pseudomonas spp. (Pseudomonas oleovorans group) DSM 33933

(i) Pseudomonas aeruginosa DSM 33935

(j) Pseudomonas oleovorans DSM 33936

(k) Pseudomonas spec. DSM 33937

(l) Pseudomonas aeruginosa DSM 33938

Bacteria mixture 2:

(a) Nesterenkonia sp. DSM 108520

(b) Nesterenkonia sp. DSM 108521

(c) Alkalibacterium pelagium DSM 108522

(d) Nesterenkonia massiliensis DSM 110679

(e) Nesterenkonia sp. DSM 108519

The cell suspensions of the bacterial mixtures were prepared by culturing the individual bacteria for 24 hours at 30°C in liquid culture on a shaker. A Müller-Hinton liquid medium served as the medium for the cultivation of bacteria from bacterial mixture 1. Bacteria from bacterial mixture 2 were cultivated in a Müller-Hinton liquid medium, which had previously been adjusted to pH 9.5-9.7 with an alkaline buffer solution. After cultivation, the individual liquid cultures were centrifuged, and the cells resuspended in physiological saline. To adjust the mixture to a total cell count of 10 ⁹ /ml, the individual bacterial suspensions were, if necessary, mixed with saline before combining. diluted. The cell count of the vaccine suspension was determined using the chamber counting method.

In Examples 3 and 4, a so-called repetitive challenge test was conducted by repeatedly inoculating the samples at specific intervals with a bacterial suspension containing a cell count of 10 ⁹ /ml (2% v/w), and monitoring the development of the bacteria 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 the bacterial contamination was semi-quantitatively assessed after these periods. For this purpose, an aliquot was taken from each sample after homogenization using a sterile plastic loop (10 μl) and spread evenly on agar plates (bacterial mixture 1 on tryptone soy agar, bacterial mixture 2 on alkaline nutrient agar DSMZ 31). The plated agar plates were then incubated for 48 hours at 30 °C (bacterial mixture 1) or 5 to 7 days (bacterial mixture 2). After incubation, the bacterial colonies grown on the agar plates were visually assessed and quantified according to the following scheme:

A total of 3 vaccination cycles were performed for each repetitive stress test. Example 3 / Table 3:

Beispiel 4 / Tabelle 4: Inoculation 2% (w/v) with bacterial mixture 1, cell count 10 ⁹ /ml

Example 4 / Table 4:

Inoculation 2% (w/v) with bacterial mixture 2, cell count 10 ⁹ /ml

As can be seen from the results presented in Tables 3 and 4, the synergistic interaction between guanidine and sodium carbonate, which was already demonstrated under laboratory conditions, can also be demonstrated in a practical application, in an emulsion paint. 2, Investigation of synergistic interaction using guanidine carbonate:

A combination of guanidine (added in the form of guanidine carbonate) with sodium carbonate (Na2CO3) or sodium bicarbonate (NaHCCh) was investigated for their synergistic interaction.

A Gram-negative bacterial species from the Pseudomonad group, Pseudomonas spec. DSM 115322, was used as the test organism. Mixtures with varying concentrations of guanidine and sodium carbonate or sodium bicarbonate were prepared and tested for their effect on Pseudomonas spec. DSM 115322. The test was performed using a microtiter plate method in Müller-Hinton Broth (MHB) at a cell density of 10 ⁶ bacteria 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. This allowed the minimum inhibitory concentrations (MICs) of the two substances to be determined individually and in combination.

The resulting synergism was numerically represented by calculating the synergy index (SI). The calculation was also carried out in the following examples according to the standard method of F.C. Kull et al., Applied Microbiology, Vol. 9 (1961), p. 538.

If the synergy index is above 1, this means that antagonism exists. If the synergy index is above 1, this means that the effects of the two compounds are additive. If the synergy index is below 1, this means that the two compounds are synergistic. Example 5: Investigation of the synergistic interaction between guanidine and sodium carbonate (Na ₂ CO3)

Calculation of the synergy index of guanidine and sodium carbonate with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.

Table 5

Qa: Concentration of guanidine in the mixture showing an endpoint QA: Concentration of guanidine as the sole agent showing an endpoint

Qb: Concentration of sodium carbonate in the mixture showing an endpoint

QB: Concentration of sodium carbonate as the sole agent showing an endpoint

Table 5 shows that the optimal synergism, i.e., the lowest synergy index (0.78) of a composition of guanidine and sodium carbonate, is at a ratio of 1155 ppm guanidine to 1000 ppm sodium carbonate. Synergism can be demonstrated when the weight ratio of guanidine to sodium carbonate is in the range of 1:20 to 13:1, or, converted to the lead structures, the weight ratio of guanidine to carbonate is in the range of 1:12 to 1.8:1. Example 6: Investigation of the synergistic interaction between guanidine and sodium bicarbonate (NaHCCE)

Calculation of the synergy index of guanidine and sodium bicarbonate with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.

Table 6

Qa: Concentration of guanidine in the mixture showing an endpoint

QA: Concentration of guanidine as the sole agent showing an endpoint

Qb: Concentration of sodium bicarbonate in the mixture showing an endpoint

QB: Concentration of sodium bicarbonate as the sole agent showing an endpoint

Table 6 shows that the optimal synergism, i.e., the lowest synergy index (0.85) of a composition of guanidine and sodium bicarbonate, is at a ratio of 990 ppm guanidine to 3500 ppm sodium bicarbonate. Synergism can be demonstrated when the weight ratio of guanidine to sodium bicarbonate is in the range of 1:4 to 1.6:1, or, converted to the lead structures, the weight ratio of guanidine to carbonate is in the range of 1:3.4 to 1.6:1.

Claims

Patent claims 1. Composition containing the components: (a) guanidine and/or at least one salt of the unsubstituted guanidine, and (b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate and ammonium carbonate, characterized in that the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, wherein the weight ratio is determined on the basis of the content of guanidine and carbonate in the total composition. 2. Composition according to claim 1, characterized in that it contains as component (a) guanidine hydrochloride and/or guanidine carbonate. 3. Composition according to claim 1 or 2, characterized in that it contains sodium carbonate and/or sodium bicarbonate as component (b). 4. Composition according to any one of claims 1 to 3, further comprising the component: (c) one or more zinc compounds selected from the group consisting of 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. Composition according to any one of claims 1 to 4, further comprising the component: (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, bronopol, dibromonitrilopropionamide, iodopropynylbutylcarbamate, phenoxyethanol dibromodicyanobutane and quaternary ammonium compounds. 6. Composition according to one of claims 1 to 5, characterized in that it has a pH in the range of pH 8 to pH 12. 7. Composition according to one of claims 1 to 6, characterized in that the weight ratio of (a) to (b) is in the range from 1:8 to 8:1, the content in relation to the guanidine and carbonate being used as the basis for determining the weight ratio. 8. Composition according to one of claims 4 to 7, characterized in that the weight ratio of (a) to (c) is in the range from 0.77: 1 to 12: 1, the content in relation to the guanidine and zinc being used as the basis for determining the weight ratio. 9. Composition according to one of claims 1 to 6, characterized in that it comprises the components: (a) in an amount in the range of 100 to 10,000 ppm, preferably in the range of 100 to 7,500 ppm, based on the amount of guanidine in the composition and (b) in an amount in the range of 100 ppm to 50,000 ppm, preferably in the range of 250 to 25,000 ppm, based on the amount of carbonate. 10. Composition according to one of claims 4 to 6, characterized in that it contains component (c) in an amount in the range of 10 to 5,000 ppm, based on the amount of zinc in the composition. 11. Composition according to one of claims 1 to 10, characterized in that the composition contains water as solvent in an amount in the range of 10 to 90% by weight, based on the total composition. 12. The composition, in particular the aqueous composition, according to the present invention is generally a technical, in particular an aqueous technical product, selected from the group consisting of: paints, varnishes, glazes and plasters, putties and fillers, primers, emulsions, latices, polymer dispersions, chalk slurries, mineral slurries, titanium dioxide slurries, ceramic masses, modeling clays, adhesives, glues, casein-containing products, starch- and cellulose-containing products, Concrete admixtures, lignin sulfonates, bitumen emulsions, surfactant solutions, Fuels, detergents, cleaning agents, pigment pastes and pigment dispersions, wax emulsions, silicone emulsions, impregnating agents, release agents and lubricants, inks, lithographic fluids, thickeners and thickener preparations, rheology aids, cosmetic products, fragrances, toiletries, cooling water, water in circuits, water for humidification and irrigation, production, rinsing and recycling water, fluids in wood processing, fluids in petroleum production, fluids in paper processing, fluids in leather production, fluids in textile production, fluids in glass processing, drilling and cutting oils, hydraulic fluids, cooling lubricants, fertilizers and pesticides, and biocide products. 13. Composition according to one of claims 1 to 8, characterized in that it contains components (a) and (b) in an amount in the range from 1 to 100% by weight, preferably in the range from 10 to 60% by weight, particularly preferably in the range from 20 to 40% by weight. 14. Composition according to one of claims 1 to 12, characterized in that the composition is an aqueous technical product stabilized against microbial attack, which is selected from a paint, a plaster and a filler, containing: (a) guanidine and/or at least one salt of guanidine, (b) one or more carbonate compounds selected from the group consisting of sodium bicarbonate (NaHCCE), sodium carbonate (Na2CO3), potassium bicarbonate (KHCO3), potassium carbonate (K2CO3), ammonium bicarbonate (NH4HCO3) and ammonium carbonate ₍ ( _NH4 ) _2CO3 ), characterized in that the weight ratio of component (a) to component (b) is in the range from 1:14 to 54:1, wherein the weight ratio is determined based on the content of guanidine and carbonate in the entire composition, (c) optionally one or more zinc compounds selected from the group consisting of 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, Diehl oroctylisothiazolinone, Bronopol, Dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol, dibromodicyanobutane and quaternary ammonium compounds, (e) 1.0 to 85% by weight of pigment and/or filler, (f) 1 to 35 wt.% polymer dispersion calculated as solids content and (g) 100% supplemented water content. 15. Use of a composition according to any one of claims 1 to 11 for stabilizing aqueous technical products against microbial attack.