Aqueous compositions of agricultural chemicals stabilized against microbial infestation

Abstract

The invention relates to aqueous compositions of agricultural chemicals stabilized against microbial infestation, comprising the following components: (a) 1 to 90 wt. % of at least one agricultural chemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete killers, defoliants, desiccants and mixtures thereof, (b) water and (c) 0.1 to 1.5 wt. % guanidine and / or at least one salt of guanidine, wherein the proportion by weight refers to the content of guanidine in the entire composition.

Description

[0001] Thor GmbH August 14, 2025

[0002] THO4 2024PC

[0003] Aqueous compositions of agricultural chemicals stabilized against microbial infestation

[0004] The invention relates to aqueous compositions of agricultural chemicals stabilized against microbial attack, comprising the following components: (a) 1 to 90 wt.% of at least one agricultural chemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete-killing agents, defoliants, desiccants, and mixtures thereof; (b) water; and (c) 0.1 to 1.5 wt.% guanidine and / or at least one salt of guanidine, wherein the wt. percentage refers to the guanidine content in the total composition. The compositions are characterized in that they have a pH value in the range of pH 8 to 11. The present invention further relates to a process for producing aqueous compositions of agricultural chemicals and a process for stabilizing aqueous compositions of agricultural chemicals against microbial attack.

[0005] Aqueous products, such as paints, varnishes, adhesives, and aqueous agrochemicals, are typically manufactured using natural or biodegradable raw materials. These raw materials and the water used as a solvent are often contaminated with microorganisms such as bacteria, yeasts, and fungi. If these products are not preservatives, they can exhibit high microbial counts as early as one day after production.

[0006] To ensure that these products, and where applicable, their manufacturing components, meet hygienic requirements and thus guarantee their shelf life, biocides are usually added to the products or their components. One such biocide used to preserve aqueous compositions of agrochemicals, or components of this class of biocides, is the so-called 3-isothiazolin-3-ones. This class of substances includes highly antimicrobial compounds with sometimes differing activity profiles. Synergistic combinations of different 3-isothiazolin-3-ones are often used to reduce the amount of biocide required. For example, WO 99 / 08530 Al proposes the combined use of methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one.

[0007] Another class of biocides are the so-called alkylguanidinium salts and also 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 biguadinines, such as cocospropylenediamine-1,5-bis-guanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylene biguadinine) hydrochloride, di(4'-chlorophenyldiguanido)hexane, chlorhexidine digluconate, and chlorhexidine diacetate, exhibit antimicrobial activity.

[0008] Furthermore, it is known to use such medium- and long-chain guanidine compounds together with other antimicrobial and / or fungicidal active ingredients. For example, combinations with 3-iodo-2-propynyl butylcarbamate or formaldehyde depot agents are known. EP 0 891 710 Al, for instance, teaches the combined use of dodecylguanidine hydrochloride and IPBC. However, the use of dodecylguanidine salts for preserving coating compositions and polymer dispersions has proven problematic; incompatibilities in the form of coagulation have been observed upon the addition of these salts.

[0009] Sometimes the use of conventional biocides or preservatives is not an option because these are increasingly subject to legal restrictions.

[0010] In this context, it has already been proposed to provide shelf-stable dispersion paints without conventional preservatives by raising their pH value to effectively prevent microbial growth. A pH value of at least 10 is targeted, as microbial growth cannot be reliably prevented at lower pH values. European patent EP 2 942 336 Bl protects an aqueous adhesive composition containing at least 50% water by weight, 0.1 to 4.0% water glass by weight, 0.1 to 7.0% starch and / or starch derivatives by weight, 0 to 15% fillers by weight, and polymer binders. The water glass is intended to raise the pH value of the aqueous composition to such an extent that preservatives can normally be omitted.

[0011] A disadvantage of the aforementioned preservation method, however, is the comparatively high pH values ​​required in the preparations, which necessitates particular care during handling. Furthermore, increased contamination by alkaliphilic germs—microorganisms that can survive and multiply under alkaline conditions—has recently been observed in these preparations.

[0012] Despite the numerous known combinations of active ingredients and the measures already taken, there is a growing demand, particularly due to increasing regulatory restrictions, for aqueous compositions of agricultural chemicals stabilized against microbial infestation, which preferably do without or with a reduced content of classic preservatives or biocides, such as isothiazolinones, bronopol and pyrithione ions.

[0013] This task is solved by an aqueous composition of agrochemicals containing the following components:

[0014] (a) 1 to 90 wt.%, preferably 2 to 80 wt.% of at least one agrochemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete-killing agents, defoliants, desiccants and mixtures thereof,

[0015] (b) water and

[0016] (c) 0.1 to 1.5 wt.%, preferably 0.2 to 0.7 wt.% guanidine and / or at least one salt of guanidine, wherein the wt.% refers to the guanidine content in the total composition, characterized in that the composition has a pH value in the range of pH 8 to 11, preferably pH 8.5 to 10.5.

[0017] The aqueous compositions of agricultural chemicals stabilized against microbial attack according to the invention require significantly fewer, and in some cases even no, preservatives than those typically used in such compositions. Nevertheless, these compositions are characterized by excellent resistance to microbial attack, particularly during storage, due to the surprisingly effective interaction of guanidine or the guanidine salt and the corresponding pH value in the range of pH 8 to 11.0. This significantly improves the environmental compatibility of the aforementioned aqueous compositions of agricultural chemicals, and they also exhibit all known properties relating to good and safe storage and usability.Furthermore, the compositions according to the invention are particularly protected against infestation by adapted alkaliphilic microorganisms, especially alkaliphilic bacteria and neutrophilic to weakly alkaliphilic bacteria. This allows them to be formulated with a less strongly alkaline composition, which is advantageous with regard to safe handling.

[0018] Within the scope of the present invention, the values ​​"wt.%" refer to the entire aqueous composition.

[0019] According to a preferred embodiment of the invention, the aqueous composition is essentially free, preferably entirely 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, dichlorooctylisothiazolinone, dithiobisbenzmethylamide, formaldehyde and formaldehyde releasers, quaternary or quaternary ammonium compounds, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, thiabendazole, sodium pyrithione, zinc pyrithione, o-phenylphenol and combinations thereof. Essentially free in this context means that the composition contains a total amount of less than 10 ppm, preferably less than 5 ppm, and particularly preferably less than 1 ppm, based on the entire composition.

[0020] The term "agrochemical," as used herein, means a chemical substance, whether naturally or synthetically obtained, applied to a plant, pest, or a gene locus therein, resulting in the expression of the desired biological activity. The term "biological activity," as used herein, means the inducing of a stimulating, inhibiting, regulatory, therapeutic, toxic, or lethal response in a plant or pest, such as a pathogen, parasite, or feeding organism present in or on a plant, or causing the inducing of such a response at a gene locus of a plant, pest, or structure. The term "plant" includes, but is not limited to, all foodstuffs, fibers, feed and forage crops (pre- and post-harvest, seeds and seed treatment), trees, turf, and ornamental plants.Examples of agrochemical substances include chemical pesticides (such as herbicides, algicides, fungicides, antivirals, insecticides, acaricides, miticides, nematocides, and molluscicides commonly used in agriculture), herbicide safeners, plant growth regulators, fertilizers and nutrients, gamete killers, defoliants, desiccants, and mixtures thereof, and the like. Biocides commonly used for container preservation, such as isothiazolinones, pyrithiones, formaldehyde, and formaldehyde releasers, are not covered by the term agrochemical.

[0021] The aqueous composition of agrochemicals according to the invention contains, based on the total composition, 1 to 90 wt.%, preferably 2 to 80 wt.%, at least one agrochemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete-killing agents, defoliants, desiccants, and mixtures thereof. "At least one," as used herein, means that at least one agrochemical or a plurality of agrochemicals from the aforementioned group is / are contained in the composition of agrochemicals according to the invention. The agrochemical, component (a), may be dissolved or dispersed in water.According to a preferred embodiment of the invention, the aqueous composition is characterized in that the component (a) is contained in the composition in the form of particles with a mean particle size in the range of 0.25 to 200 pm, preferably in the range of 0.5 to 100 pm, particularly preferably in the range of 1 to 50 pm.

[0022] The aqueous composition of agricultural chemicals according to the invention contains, as component (c), guanidine and / or at least one salt of guanidine, in an amount in the range of 0.1 to 1.5 wt.%, preferably in an amount in the range of 0.1 to 1.0 wt.%, and particularly preferably in an amount in the range of 0.2 to 0.7 wt.%, wherein the specified weight percentage refers to the guanidine content in the entire composition, thus providing stabilization against microbial attack, especially during storage. The amount of component (c) required for stabilization is determined by a person skilled in the art depending on the specific composition using methods familiar to them.

[0023] In the context of the invention, "at least one salt of guanidine" means that the composition contains one or two, three, four, five or six, i.e., also a mixture of salts of guanidine.

[0024] The aqueous compositions of agricultural chemicals stabilized against microbial attack exhibit improved stability against microbial attack compared to non-stabilized aqueous compositions, i.e., compositions that contain no guanidine or no salt of guanidine, or contain insufficient amounts of guanidine or its salt, and are therefore less prone to microbial contamination. Within the scope of the invention, it was found that guanidine amounts of up to 1.5 wt%, preferably up to 1.0 wt%, and particularly preferably up to 0.7 wt%, are sufficient to ensure stabilization of the composition against microbial attack. Higher amounts than, for example, 1.5 wt% guanidine are not desirable from a practical standpoint with regard to stabilization, and especially from an economic point of view.The aqueous composition according to the invention is characterized in that the component (c) is contained in the composition in an amount in the range of 0.1 to 1.5 wt.%, preferably in an amount in the range of 0.1 to 1.0 wt.%, preferably in an amount in the range of 0.2 to 0.7 wt.%, wherein the specified weight fraction refers to the content of unsubstituted guanidine according to the formula shown below: in the entire aqueous composition. Therefore, when determining the guanidine content, in the case of guanidine salts, only the guanidine content is considered, without taking any counterion into account.

[0025] The guanidine salt that may be present in the aqueous composition is preferably at least one guanidine salt selected from the group consisting of guanidine hydrochloride, guanidine carbonate, guanidine nitrate, guanidine sulfate, guanidine thiocyanate, guanidine phosphate, guanidine hydrogen carbonate, guanidine formate, guanidine acetate, guanidine silicate, and / or guanidine citrate. "At least one guanidine salt" means that one, two, three, four, five, or even more guanidine salts may be present.

[0026] The salts of guanidine according to the present invention are unsubstituted guanidine or guanidinium salts of the general formula shown below: where n is equal to 1, 2 or 3, and where the counterion X 11 'for example chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, formate, acetate or citrate.

[0027] According to a preferred embodiment of the invention, the aqueous composition contains, as component (c), guanidine hydrochloride and / or guanidine carbonate as a guanidine compound; according to a particularly preferred embodiment of the invention, the aqueous composition contains, as component (c), guanidine carbonate.

[0028] The pH value of the aqueous composition of agricultural chemicals generally lies in the range of pH 8 to 11. According to a preferred embodiment of the invention, the aqueous composition is characterized in that it has a pH value in the range of 8.5 to 10.5. By adjusting the pH value to a value in the range of 8 to 11, more skin-friendly compositions are obtained. In particular, less stringent requirements apply to the handling of the compositions according to the invention.

[0029] Adjusting the pH value to the required range can be achieved using methods familiar to those skilled in the art. This can be done, for example, by using guanidine carbonate as a guanidine salt. Similarly, the pH value can be adjusted to the required range by adding alkaline substances, also known as alkali adjusters. Such pH-adjusting compounds are known to those skilled in the art; the required amount can vary widely and can be determined using familiar methods. Examples of alkali adjusters include:

[0030] • Guanidine carbonate,

[0031] • Alkali metal hydroxides, such as lithium, sodium and / or potassium hydroxide,

[0032] • Alkaline earth metal hydroxides, such as magnesium, calcium, and / or barium hydroxide, ammonium hydroxide, xonotlite and / or ettringite (Ca6[Al(OH)e]2(SO4 x 26 H2O)),

[0033] • Water glass, such as sodium, lithium and potassium water glass, or mixtures thereof,

[0034] • Siliconates, such as alkali metal alkyl siliconates or alkaline earth alkyl siliconates, in particular compounds according to the general formula R-Si(OH)2OM A or [R-Si(OH)2O]2M E designated, wherein M A for an alkali metal such as lithium, sodium, potassium, M E where R represents an alkaline earth metal, such as magnesium or calcium, and R represents an alkyl group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or i-butyl.

[0035] • Buffer systems, for example based on at least one phosphate or polyphosphate salt, preferably K3PO4 or NasPCU, and at least one alkali hydroxide, preferably lithium, sodium and / or potassium hydroxide,

[0036] • Alkali and / or alkaline earth carbonates and / or hydrogen carbonates,

[0037] • Ammonia and ammonium compounds,

[0038] • Amines, amino compounds and amino alcohols.

[0039] According to a preferred embodiment of the invention, the pH value is adjusted to the claimed range using guanidine carbonate and / or sodium carbonate.

[0040] According to one embodiment of the invention, the aqueous composition is characterized in that it further comprises as component (d) one or more carbonate compound(s) selected from the group consisting of sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, ammonium hydrogen carbonate and ammonium carbonate.

[0041] As component (d), the composition according to this embodiment of the invention comprises one or more carbonate compounds selected from the group consisting of sodium hydrogen carbonate (NaHCCE), sodium carbonate (Na2COs), potassium hydrogen carbonate (KHCO3), potassium carbonate (K2CO3),

[0042] Ammonium hydrogen carbonate (NH4HCO3) and ammonium carbonate (NH^CCh). "Several" here means that the composition can contain two, three, four, five, or six of the mentioned carbonate compounds.

[0043] According to a preferred embodiment of the invention, the composition contains as component(s) (d) sodium carbonate (Na₂CC>3) and / or sodium bicarbonate (NaHCCE). In the case of using these carbonate compound(s), compositions with additionally improved antimicrobial properties are obtained.

[0044] Within the scope of the present invention, both the quantities of components (c) and (d) and the weight ratios of components (c) and (d) to each other are specified. Unless otherwise stated, the quantities refer to the lead structures, guanidine (CN3H5) as component (c) and carbonate (CO3), respectively. 2). Likewise, when determining the specified weight ratios, the content of guanidine, without consideration of any counterion, as component (c), and the content of carbonate, without consideration of any counterion, as component (d), in the composition are taken as a basis.

[0045] The amount of component (d) containing one or more carbonate compounds in the composition according to the invention 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 particularly preferably in the range of 1,000 ppm to 10,000 ppm, based on the amount of carbonate in the composition.

[0046] The weight ratio of component (c) to component (d) is generally in the range of 1 :14 to 54 : 1, preferably in the range of 1 :8.6 to 21 : 1, particularly preferably in the range of 1 :8 to 8 : 1 and most 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 entire composition.

[0047] In the context of the present invention, an aqueous composition or aqueous composition of agrochemicals means that the composition contains water, which makes it somewhat susceptible to microbial contamination. The composition generally has a water content of at least 1 wt.%, preferably at least 5 wt.%, and particularly preferably at least 10 wt.%, wherein the components forming the composition always add up to 100.0 wt.%. As already described in the introduction, such aqueous compositions are usually produced using natural or biodegradable raw materials. These raw materials and the water used as a solvent are frequently contaminated with microorganisms such as bacteria, yeasts, and fungi.The water content of the aqueous composition can vary over a wide range and is generally in the range of 1 to 97.5 wt%, preferably in the range of 5 to 95 wt%, with the components forming the composition always adding up to 100.0 wt%. This invention further relates to a process for producing the aqueous compositions of agricultural chemicals according to the invention, comprising mixing the components defined above.

[0048] The present invention further relates to a method for stabilizing an aqueous composition of agricultural chemicals against microbial infestation, which comprises the following process steps:

[0049] (i) Providing an aqueous composition containing:

[0050] (a) 1 to 90 wt.%, preferably 2 to 80 wt.% of at least one agrochemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete-killing agents, defoliants, desiccants and mixtures thereof and

[0051] (b) water,

[0052] (ii) Mixing at least one salt of guanidine with the aqueous composition and

[0053] (iii) optionally adjusting the pH value, characterized in that the stabilized aqueous composition has a pH value in the range of pH 8 to 11.0, preferably pH 8.5 to 10.5, and further characterized in that the amount of the guanidine salt or guanidine salts is in the range of 0.1 to 1.5 wt.%, wherein the wt. fraction refers to the guanidine content in the total aqueous composition.

[0054] The inventive process is advantageously characterized by the fact that it enables the production of aqueous agrochemical compositions stabilized against microbial attack. Due to their composition, these compositions require significantly fewer, and in some cases even no, preservatives than those typically found in such compositions. Nevertheless, the aqueous compositions exhibit excellent resistance to microbial attack, particularly during storage, due to the surprisingly effective interaction of at least one guanidine salt or the resulting guanidine and the corresponding pH value in the range of pH 8 to 11.0. This significantly improves the compositions' environmental compatibility.

[0055] In step (i) of the inventive process, the aqueous composition to be stabilized against microbial attack is provided. Stabilizing against microbial attack, within the scope of the present invention, means that the composition, in its unstabilized state, particularly during storage, is prone to microbial attack and thus spoils.

[0056] The aqueous composition provided in step (i) is mixed with at least one guanidine salt in process step (ii). The amount of guanidine salt required for stabilization is determined by a person skilled in the art, depending on the specific product, using methods familiar to them. The aqueous compositions stabilized against microbial attack exhibit improved stability against microbial attack compared to non-stabilized aqueous compositions, i.e., compositions that contain no guanidine salt or guanidine, or contain the guanidine salt or guanidine in insufficient quantities, and are therefore less prone to microbial contamination.

[0057] The amount of guanidine salt(s) used in process step (ii) can vary over a range depending on the composition provided and is generally in the range of 0.1 to 1.5 wt.%, preferably in the range of 0.1 to 1.0 wt.%, particularly preferably in the range of 0.2 to 0.7 wt.%, wherein the weight fraction refers to the guanidine content, without taking into account any counterion, in the total aqueous composition.

[0058] According to a preferred embodiment of the invention, guanidine hydrochloride and / or guanidine carbonate are used in process step (ii), and according to a particularly preferred embodiment of the invention, guanidine carbonate is used.

[0059] In process step (iii) of the process for stabilizing the aqueous composition, the pH is optionally adjusted so that the composition has a pH in the range of pH 8 to 11.0, preferably in the range of pH 8.5 to 10.5. "Optionally" here means that the pH is already in the range of pH 8 to 11.0, preferably in the range of pH 8.5 to 10.5, due to the composition of the aqueous composition or the guanidine salt used in process step (ii), so that adjustment is not necessary.

[0060] The present invention further relates to a process for producing an aqueous composition of agricultural chemicals which comprises the process steps:

[0061] (i) Providing an aqueous composition containing:

[0062] (a) 1 to 90 wt.%, preferably 2 to 80 wt.% of at least one agrochemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete-killing agents, defoliants, desiccants and mixtures thereof and

[0063] (b) water,

[0064] (ii) Mixing at least one salt of guanidine with the aqueous composition such that the amount of the guanidine salt, based on the content of guanidine in the total aqueous composition, is in the range of 0.1 to 1.5 wt.%, and

[0065] (iii) optionally adjusting the pH value, characterized in that the aqueous composition produced has a pH value in the range of pH 8 to 11.0.

[0066] The manufacturing process according to the invention is advantageously characterized by the fact that it enables the production of aqueous compositions of agricultural chemicals stabilized against microbial attack, which, due to their composition, require significantly fewer, and in some cases even no, preservatives such as those typically included in these compositions for preservation. Nevertheless, the aqueous compositions of agricultural chemicals are characterized by excellent resistance to microbial attack, particularly during storage, due to the surprisingly effective interaction of the at least one guanidine salt and the corresponding pH value in the range of pH 8 to 11.0. In step (i) of the manufacturing process according to the invention, the aqueous composition to be stabilized against microbial attack is prepared.Stabilizing against microbial attack, within the scope of the present invention, means that in an unstabilized state, it tends to be susceptible to microbial attack, particularly during storage, and thus spoils.

[0067] The aqueous composition provided in step (i), which contains at least one agricultural chemical, is then mixed with at least one guanidine salt in process step (ii). The amount of guanidine salt required for stabilization is determined by a person skilled in the art, depending on the specific composition provided, using methods familiar to them. The aqueous composition stabilized against microbial attack exhibits improved stability against microbial attack compared to non-stabilized compositions, i.e., compositions that do not contain a salt of unsubstituted guanidine or that contain an insufficient amount of the guanidine salt, and is therefore less prone to microbial contamination.

[0068] The amount of guanidine salt(s) used in process step (ii) can vary widely depending on the composition provided and is generally in the range of 0.1 to 1.5 wt.%, preferably in the range of 0.1 to 1.0 wt.%, particularly preferably in the range of 0.2 to 0.7 wt.%, wherein the weight fraction refers to the content of guanidine, without taking into account any counterions, in the total aqueous composition.

[0069] According to a preferred embodiment of the invention, in process step (ii) guanidine hydrochloride and / or guanidine carbonate, according to a particularly preferred embodiment of the invention, guanidine carbonate, is used.

[0070] In process step (iii) of the process for producing the aqueous composition of agricultural chemicals, the pH is optionally adjusted so that the produced composition has a pH in the range of pH 8 to 11.0, preferably in the range of pH 8.5 to 10.5. "Optionally" here means that the pH is already in the range of pH 8 to 11.0, preferably in the range of pH 8.5 to 10.5, due to the composition of the aqueous composition or the guanidine salt used in process step (ii), so that adjustment is not necessary.

[0071] The invention further relates to the use of guanidine and / or at least one salt of guanidine in an aqueous composition of agricultural chemicals having a pH value in the range of pH 8 to 11.0, preferably in the range of pH 8.5 to 10.5, in an amount in the range of 0.1 to 1.5 wt.%, preferably in the range of 0.1 to 1.0 wt.%, particularly preferably in the range of 0.2 to 0.7 wt.%, wherein the weight fraction refers to the content of guanidine, without taking into account any counterion, in the entire aqueous composition, for stabilizing the aqueous composition of agricultural chemicals against microbial attack.

[0072] Advantageously, the use of guanidine or at least one guanidine salt in the aqueous composition defined above, as described in the invention, eliminates the need for conventional preservatives typically used in such compositions. This significantly improves the environmental compatibility of aqueous compositions of agricultural chemicals and provides particular protection against infestation by adapted alkaliphilic microorganisms as well as neutrophilic to weakly alkaliphilic microorganisms.

[0073] The following examples serve to further illustrate the present invention:

[0074] To demonstrate the stabilization of the aqueous agrochemical against microbial infestation, an aqueous fungicide suspension concentrate, Lucento Fungicide™ from FMC Corporation, USA (pH 5.3, density 1.186 g / mL, active ingredients 26.5% w / w triazole + 15.5% pyrazolecarboxamide, 5-10% glycerol, 1-5%

[0075] Acetic acid ethenyl ester / polymer with oxirane) were treated with different amounts of guanidine and tested for microbiological stability at different pH values.

[0076] Procedure:

[0077] The aqueous suspension was treated with various concentrations of guanidinium carbonate and homogenized. Samples without guanidinium salt (blanks) were adjusted to the appropriate pH values ​​using sodium hydroxide solution and served as controls.

[0078] The resulting samples of the prepared suspensions were each inoculated with a mixture of different bacterial strains as an inoculum. The bacterial mixture consisted of bacteria commonly used as a standard in tests for the microbial stability of technical, aqueous products.

[0079] Bacterial mixture:

[0080] Alcaligenes faecalis ATCC 8748

[0081] Escherichia coli DSM 1363ATCC 9723

[0082] Burkholderia cepacia ATCC 25416 Staphylococcus aureus ATCC 6538 Pseudomonas aeruginosa ATCC 10145 Pseudomonas putida ATCC 12633

[0083] The bacterial mixture was added as an inoculum to the respective sample at each inoculation with a concentration of 2% (v / w) fresh cell suspension in physiological saline (0.9% NaCl). The cell count of the added inoculum was 10 9 / ml, each consisting of equal parts of the individual bacterial strains. The bacterial cell suspensions were prepared by culturing the individual bacteria for 24–48 h at 30 °C in liquid culture on a shaker. Müller-Hinton liquid medium was used as the culture medium. After cultivation, the individual liquid cultures were centrifuged, and the cells were resuspended in physiological saline. To adjust the mixture to the desired cell count, the individual bacterial suspensions were diluted accordingly, if necessary, before being combined with saline. The cell count of the inoculation suspension was determined using chamber counting.

[0084] The samples were inoculated three times at weekly intervals with the respective cell suspensions (2% v / w). After the first two inoculations, microbial colonization was assessed after 2 and 5 days of incubation at 30 °C. After the third inoculation, microbial colonization was assessed after 2, 5, and 12 days of incubation at 30 °C.

[0085] To assess microbial growth, an aliquot was taken from each sample after homogenization using a sterile plastic inoculation loop (10 pl) and streaked evenly onto agar plates (tryptone-soy agar). The streaked agar plates were then incubated for 48 hours. After incubation, the bacterial colonies grown on the agar plates were visually assessed and quantified according to the following scheme: The results are shown in Table 1:

[0086] Table 1: Inoculation 2% (w / v) with bacterial mixture, cell count 109 / ml

[0087] *pH adjusted with NaOH

[0088] As can be seen from the test results shown in Table 1, concentrations of 0.2 wt% guanidine carbonate in the fungicide suspension already lead to improved stabilization against microbial infestation at a pH value of 7.9 or higher.

Claims

Thor GmbH August 14, 2025 THO3 2024PC Patent claims 1. Aqueous composition containing the following components: (a) 1 to 90% by weight of at least one agrochemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete-killing agents, defoliants, desiccants and mixtures thereof, (b) water and (c) 0.1 to 1.5 wt% guanidine and / or at least one salt of guanidine, wherein the wt% refers to the guanidine content in the total composition, characterized in that the composition has a pH value in the range of pH 8 to 11.

2. Composition according to claim 1, characterized in that the component (c) is contained in the composition in the range of 0.1 to 1.0 wt.%, wherein the wt.% refers to the guanidine content in the entire composition.

3. Composition according to claim 1 or 2, characterized in that the component (a) is contained in the composition in the form of particles with an average particle size in the range of 0.25 to 200 pm.

4. Composition according to one of claims 1 to 3, characterized in that the component (c) is at least one guanidine salt, guanidine hydrochloride and / or guanidine carbonate.

5. Composition according to one of claims 1 to 4, characterized in that it has a water content in the range of 1 to 97.5 wt.%.

6. Composition according to any one of claims 1 to 5, characterized in that it further comprises as component (d) one or more Carbonate compound(s), selected from the group consisting of Contains sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate and ammonium carbonate.

7. Composition according to any one of claims 1 to 6, characterized in that it comprises one or more preservative(s) 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's octylisothiazolinone, Dithiobisbenzmethylamide, formaldehyde and formaldehyde-releasing compounds, quaternary ammonium compounds, bronopol, dibromonitrilopropionamide, Contains dibromodicyanobutane, iodine propynyl butylcarbamate, thiabendazole, sodium pyrithione, zinc pyrithione and o-phenylphenol in a total amount of less than 10 ppm, based on the composition.

8. Method for stabilizing an aqueous composition against microbial infestation, comprising the following process steps: (i) Providing an aqueous composition containing: (a) 1 to 90 wt.%, preferably 2 to 80 wt.% of at least one agrochemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete-killing agents, defoliants, desiccants and mixtures thereof and (b) water, (ii) Mixing at least one salt of guanidine with the aqueous composition and (iii) optionally adjusting the pH value, characterized in that the stabilized aqueous composition has a pH value in the range of pH 8 to 11.0, and further characterized in that the amount of the guanidine salt(s) is in the range of 0.1 to 1.5 wt.%, wherein the wt. fraction is based on refers to the guanidine content in the entire aqueous composition.

9. Method according to claim 8, characterized in that the at least one is a guanidine salt, guanidine hydrochloride and / or guanidine carbonate.

10. Method for producing an aqueous composition which comprises the following process steps: (i) Providing an aqueous composition containing: (a) 1 to 90 wt.%, preferably 2 to 80 wt.% of at least one agrochemical selected from the group consisting of chemical pesticides, herbicides, plant growth regulators, fertilizers and nutrients, gamete-killing agents, defoliants, desiccants and mixtures thereof and (b) water, (ii) Mixing at least one salt of guanidine with the aqueous composition such that the amount of the guanidine salt, based on the content of guanidine in the total aqueous composition, is in the range of 0.1 to 1.5 wt.%, and (iii) optionally adjusting the pH value, characterized in that the aqueous composition produced has a pH value in the range of pH 8 to 11.0.

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