Synergistic Compositions Containing Guanidine

Abstract

The present invention relates to (a) salts of guanidine and / or unsubstituted guanidine, and (b) 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, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, and the like. The present invention relates to a composition containing at least one additional component selected from the group consisting of butylcarbamate, aminomethylpropanol, aminoethylpropanediol, monoethanolamine, ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bisphosphonic acid, sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc. The present invention further relates to industrial products containing components (a) and (b), and to uses of the composition for container preservation and industrial product preservation. The present invention also relates to the use of (a) a salt of guanidine and / or unsubstituted guanidine to improve the antibacterial efficacy of one or more compounds selected from group (b) above.

Description

[Technical Field]

[0001] The present invention relates to (a) salts of guanidine and / or unsubstituted guanidine, and (b) 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, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, aminomethylpropanol, aminoethylpropanediol, monoethanolamine, ethylenediamine, ethylenediamine-3-one, ethylenediamine-4-isothiazolin ... The present invention relates to a composition comprising at least one additional component selected from the group consisting of ethylhexylglycerol, hexylglycerol, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bisphosphonic acid, sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc. The present invention further relates to industrial products containing components (a) and (b), as well as the use of the composition for in-can preservation and preservation of industrial products. Similarly, the present invention relates to the use of (a) a salt of guanidine and / or unsubstituted guanidine to improve the antimicrobial efficacy of one or more compounds selected from group (b) defined above. [Background technology]

[0002] Industrial products, especially water-based industrial products such as paints, varnishes, emulsions, washing and cleaning compositions, and cosmetics, are usually produced 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 produced without preservatives, they may have high microbial counts even one day after production.

[0003] To ensure that hygiene requirements are met by these products and, where appropriate, also by the components used in their production, and thus that the shelf life of the industrial product is guaranteed, so-called biocides are usually added to the product or directly to the components.

[0004] One class of biocides used in the preservation of water-based industrial products such as paints, primers, cleaning and washing compositions, glazes, or their components is called 3-isothiazolin-3-ones. This class of substances includes highly antimicrobially active compounds with somewhat different action profiles. To reduce the amount of biocide used, synergistic combinations of different 3-isothiazolin-3-ones are often used. For example, WO 99 / 08530 proposes the use of methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one in combination.

[0005] EP 1030558 similarly discloses a synergistic biocidal composition containing 2-methylisothiazolin-3-one and 3-iodo-2-propynyl N-butylcarbamate, which is suitable for controlling microorganisms even at low concentrations.

[0006] A further class of biocides is the so-called alkylguanidinium salts and also polyguanidinium salts.Thus, for example, from "Directory of microbicides for the protection of materials", Springer 2005, pp. 726-731, it is known that antibacterial effect is possessed by medium- and long-chain guanidines and biguanidines, such as cocopropylenediamine-1,5-bisguanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylenebiguanidine) hydrochloride, di(4'-chlorophenyldiguanido)hexane, chlorhexidine digluconate, chlorhexidine diacetate.

[0007] It is also known to use such medium- and long-chain guanidine compounds in combination with other antibacterial and / or fungicidal active substances. For example, known examples include 3-iodo-2-propynyl butylcarbamate or a combination with formaldehyde-releasing agents. Thus, for example, European Patent Application Publication No. 0891710 teaches the use of dodecylguanidine hydrochloride and IPBC in combination. However, the use of dodecylguanidine salts for preserving coating compositions and polymer dispersions has proven problematic; for example, incompatibility in the form of coagulum can be observed when these salts are added.

[0008] Moving beyond the prior art described above, there is a need for additional compositions in which the components of the composition interact synergistically and therefore can be used in lower concentrations than would be required for the individual components when used simultaneously. Summary of the Invention

[0009] The present invention provides (a) salts of guanidine and / or unsubstituted guanidine, and (b) 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-methyl-4-isothiazolin-3-one (MIT), 1,2-benzisothiazolin-3-one (BIT), N-butyl-1,2-benzisothiazolin-3-one (BBIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT), octylisothiazolinone (OIT), bronopol, dibromonitrilopropionamide (DBNPA), dibromodicyanobutane (DBDCB), iodopropynyl butylcarbamate (IPBC), aminomethylpropanol (AMP), aminoethylpropanediol (AEPD), molybdenum nitrite (MOI), and methylisothiazolinone (MMN). at least one additional component selected from the group consisting of monoethanolamine (MEA), ethylhexylglycerol, hexylglycerol, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid (EDTA), (1-hydroxyethylidene)bisphosphonic acid (HEDP), sodium pyrithione, zinc pyrithione, o-phenylphenol (oPP), sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc. The above objects are achieved by a composition, preferably an aqueous composition, comprising:

[0010] The compositions of the present invention have the advantage that guanidine or a salt thereof, component (a), which has not been known so far as an antibacterial active substance, and at least one further component from the group indicated above, group (b), interact synergistically and therefore, when used simultaneously, can be used in lower concentrations compared to the lower concentrations of the individual components. DETAILED DESCRIPTION OF THE INVENTION

[0011] In the context of the present invention, "at least one further component" means that the composition contains a single component or compound selected from the group, or several components or compounds from the group, i.e., two, three, four, five or more components or two, three, four, five or more compounds.

[0012] In the context of the present invention, both the amount of each of components (a) and (b) and the weight ratio of components (a) and (b) to each other are specified. The amounts relate, respectively, to the lead structure, guanidine, or the lead structure of component (b). The determination of the weight ratio specified is likewise based in each case on the content of guanidine in the composition without taking into account any counterions, and on the content of the lead structure of further component (b) without taking into account any counterions.

[0013] For the purposes of the present invention, what is meant by salts of guanidine and / or unsubstituted guanidine is that the composition contains as active ingredient (a) one or more salts of guanidine and / or therefore optionally also unsubstituted guanidine. Guanidine has the formula shown below: [ka] is a compound of

[0014] In the context of the present invention, salts of unsubstituted guanidine or guanidine salts are those of the general formula shown below: [ka] (wherein n is 1, 2 or 3; and the counter ion X n- is, for example, chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, formate, acetate or citrate) is a guanidine or guanidinium salt of

[0015] In a preferred embodiment of the invention, the composition of the invention contains guanidine hydrochloride and / or guanidine carbonate as component (a), and in a particularly preferred embodiment of the invention, the composition contains guanidine carbonate as component (a).

[0016] The amount of component (a), guanidine and / or salts thereof, present in the preferably aqueous compositions of the present invention can vary within wide limits, generally in the range of 100 to 10,000 ppm, preferably in an amount in the range of 200 to 7,500 ppm, more preferably in an amount in the range of 300 to 5,000 ppm, this proportion relating to the guanidine content in the total aqueous composition.

[0017] The amounts of components (a) and (b) present in the preferably aqueous compositions of the present invention may vary over a wide range. In one embodiment, the composition is characterized in that it contains guanidine and / or a salt thereof and at least one further component in a total amount ranging from 0.01% to 10%, preferably from 0.02% to 5%, more preferably from 0.03% to 3%, based on the total composition.

[0018] The water content in the preferably aqueous compositions of the present invention can vary within wide limits, and typically the compositions are characterized as 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 total composition.

[0019] The pH of the aqueous composition can vary over a wide range, generally in the range of pH 4.5 to pH 12, preferably in the range of pH 5.0 to pH 11.5, and more preferably in the range of pH 5.5 to pH 11. The pH can be adjusted to the ranges set forth in the claims using means well known to those skilled in the art.

[0020] As can be seen from the examples, the preferred weight ratio of components (a) to (b) relative to one another, which allows achieving a surprisingly good antimicrobial effect, can vary individually.

[0021] Synergistic compositions containing guanidine and 5-chloro-2-methylisothiazolin-3-one (CIT): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof, and also 5-chloro-2-methylisothiazolin-3-one.

[0022] In a preferred embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and 5-chloro-2-methylisothiazolin-3-one, in a weight ratio of guanidine and / or a salt thereof to 5-chloro-2-methylisothiazolin-3-one in the range from 62:1 to 9270:1, preferably in the range from 62:1 to 500:1, more preferably in the range from 62:1 to 300:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and 5-chloro-2-methylisothiazolin-3-one without taking into account any counter ions in the composition.

[0023] Synergistic compositions containing guanidine and 2-methylisothiazolin-3-one (MIT): In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and 2-methylisothiazolin-3-one.

[0024] In a preferred embodiment, the present invention relates to a composition containing guanidine and / or a salt thereof and 2-methylisothiazolin-3-one, in a weight ratio of guanidine to 2-methylisothiazolin-3-one generally in the range of 10.3:1 to 773:1, preferably in the range of 10.3:1 to 500:1, more preferably in the range of 10.3:1 to 300:1, wherein the basis for determining the weight ratio is in each case the contents of guanidine and 2-methylisothiazolin-3-one, without taking into account any counter ions in the composition.

[0025] Synergistic compositions containing guanidine and 1,2-benzisothiazolin-3-one (BIT): In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and 1,2-benzisothiazolin-3-one.

[0026] In a preferred embodiment, the present invention relates to a composition containing guanidine and / or a salt thereof and 1,2-benzisothiazolin-3-one, in a weight ratio of guanidine to 1,2-benzisothiazolin-3-one generally in the range of from 1.3:1 to 309:1, preferably in the range of from 1.3:1 to 200:1, more preferably in the range of from 1.3:1 to 100:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and 1,2-benzisothiazolin-3-one, without taking into account any counter ions in the composition.

[0027] Synergistic compositions containing guanidine and N-butyl-1,2-benzisothiazolin-3-one (BBIT): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and N-butyl-1,2-benzisothiazolin-3-one.

[0028] In a preferred embodiment, the present invention relates to a composition containing guanidine and / or a salt thereof and N-butyl-1,2-benzisothiazolin-3-one, in a weight ratio of guanidine to N-butyl-1,2-benzisothiazolin-3-one generally in the range of 0.52:1 to 309:1, preferably in the range of 0.52:1 to 200:1, more preferably in the range of 0.52:1 to 100:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and N-butyl-1,2-benzisothiazolin-3-one, without taking into account any counter ions in the composition.

[0029] Synergistic compositions containing guanidine and N-methyl-1,2-benzisothiazolin-3-one (MBIT): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and N-methyl-1,2-benzisothiazolin-3-one.

[0030] In a preferred embodiment, the present invention relates to a composition comprising guanidine and N-methyl-1,2-benzisothiazolin-3-one, in a weight ratio of guanidine to N-methyl-1,2-benzisothiazolin-3-one generally in the range of from 7.8:1 to 618:1, preferably in the range of from 7.8:1 to 400:1, more preferably in the range of from 7.8:1 to 300:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and N-methyl-1,2-benzisothiazolin-3-one, without taking into account any counter ions in the composition.

[0031] Synergistic compositions containing guanidine and N-octylisothiazolin-3-one: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and N-octylisothiazolin-3-one.

[0032] In a preferred embodiment, the present invention relates to a composition comprising guanidine and N-octylisothiazolin-3-one in a weight ratio of guanidine to N-octylisothiazolin-3-one generally in the range of from 1.4:1 to 82:1, preferably in the range of from 1.4:1 to 50:1, wherein the basis for determining the weight ratio is the content in terms of guanidine and N-octylisothiazolin-3-one in each case without taking into account any counter ions in the composition.

[0033] Synergistic compositions containing guanidine and bronopol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and bronopol.

[0034] In a preferred embodiment, the present invention relates to a composition containing guanidine and bronopol in a weight ratio of guanidine to bronopol generally in the range of 7.8:1 to 824:1, preferably in the range of 7.8:1 to 200:1, and more preferably in the range of 7.8:1 to 100:1, wherein the basis for determining the weight ratio is in each case the contents in terms of guanidine and bronopol, without taking into account any counter ions in the composition.

[0035] Synergistic compositions containing guanidine and 2,2-dibromo-3-nitrilopropionamide: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and 2,2-dibromo-3-nitrilopropionamide.

[0036] In a preferred embodiment, the present invention relates to a composition comprising guanidine and 2,2-dibromo-3-nitrilopropionamide in a weight ratio of guanidine to 2,2-dibromo-3-nitrilopropionamide generally in the range of from 7.8:1 to 3090:1, preferably in the range of from 7.8:1 to 250:1, more preferably in the range of from 7.8:1 to 100:1, wherein the basis for determining the weight ratio is the content in relation to guanidine and 2,2-dibromo-3-nitrilopropionamide, in each case without taking into account any counter ions in the composition.

[0037] Synergistic compositions containing guanidine and dibromodicyanobutane (DBDCB): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and dibromodicyanobutane.

[0038] In a preferred embodiment, the present invention relates to a composition comprising guanidine and dibromodicyanobutane in a weight ratio of guanidine to dibromodicyanobutane generally in the range of 0.78:1 to 309:1, preferably in the range of 0.8:1 to 200:1, more preferably in the range of 0.8:1 to 100:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and dibromodicyanobutane, without taking into account any counter ions in the composition.

[0039] Synergistic compositions containing guanidine and iodopropynyl butylcarbamate (IPBC): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and iodopropynyl butylcarbamate.

[0040] In a preferred embodiment, the present invention relates to a composition comprising guanidine and iodopropynyl butylcarbamate in a weight ratio of guanidine to iodopropynyl butylcarbamate generally in the range of 0.83:1 to 103:1, preferably in the range of 1:1 to 90:1, more preferably in the range of 1:1 to 80:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and iodopropynyl butylcarbamate, without taking into account any counterions in the composition.

[0041] Synergistic compositions containing guanidine and 2-amino-2-methyl-1-propanol (AMP): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and 2-amino-2-methyl-1-propanol.

[0042] In a preferred embodiment, the present invention relates to a composition comprising guanidine and 2-amino-2-methyl-1-propanol, generally in a weight ratio of guanidine to 2-amino-2-methyl-1-propanol ranging from 0.3:1 to 20:1, preferably from 0.5:1 to 15:1, more preferably from 1:1 to 10:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and 2-amino-2-methyl-1-propanol, without taking into account any counter ions in the composition.

[0043] Synergistic compositions containing guanidine and 2-aminoethylpropane-1,3-diol (AEPD): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and 2-aminoethylpropane-1,3-diol.

[0044] In a preferred embodiment, the present invention relates to a composition comprising guanidine and 2-aminoethylpropane-1,3-diol in a weight ratio of guanidine to 2-aminoethylpropane-1,3-diol generally in the range of 0.2:1 to 15:1, preferably in the range of 0.5:1 to 10:1, more preferably in the range of 1:1 to 10:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and 2-aminoethylpropane-1,3-diol, without taking into account any counterions in the composition.

[0045] Synergistic compositions containing guanidine and monoethanolamine (MEA): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and monoethanolamine.

[0046] In a preferred embodiment, the present invention relates to a composition comprising guanidine and monoethanolamine in a weight ratio of guanidine to monoethanolamine generally in the range of 0.2:1 to 30:1, preferably in the range of 0.5:1 to 20:1, more preferably in the range of 1:1 to 10:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and monoethanolamine, without taking into account any counter ions in the composition.

[0047] Synergistic Compositions Containing Guanidine and Ethylhexylglycerol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and ethylhexylglycerol.

[0048] In a preferred embodiment, the present invention relates to a composition containing guanidine and ethylhexylglycerol, generally in a weight ratio of guanidine to ethylhexylglycerol ranging from 0.5:1 to 15:1, preferably from 0.5:1 to 10:1, wherein the basis for determining the weight ratio is the content in relation to guanidine and monoethanolamine, in each case without taking into account any counterions in the composition.

[0049] Synergistic Compositions Containing Guanidine and Hexylglycerol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and hexylglycerol.

[0050] In a preferred embodiment, the present invention relates to a composition containing guanidine and hexylglycerol in a weight ratio of guanidine to hexylglycerol generally in the range of 0.5:1 to 15:1, preferably in the range of 0.5:1 to 10:1, wherein the basis for determining the weight ratio is the content in relation to guanidine and hexylglycerol, in each case without taking into account any counterions in the composition.

[0051] Synergistic compositions containing guanidine and pentane-1,2-diol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and pentane-1,2-diol.

[0052] In a preferred embodiment, the present invention relates to a composition comprising guanidine and pentane-1,2-diol in a weight ratio of guanidine to pentane-1,2-diol generally in the range of 0.07:1 to 7.5:1, preferably in the range of 0.1:1 to 7.5:1, more preferably in the range of 0.5:1 to 7.5:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and pentane-1,2-diol, without taking into account any counterions in the composition.

[0053] Synergistic compositions containing guanidine and hexane-1,2-diol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and hexane-1,2-diol.

[0054] In a preferred embodiment, the present invention relates to a composition comprising guanidine and hexane-1,2-diol in a weight ratio of guanidine to hexane-1,2-diol generally in the range of 0.06:1 to 15:1, preferably in the range of 0.1:1 to 10:1, more preferably in the range of 0.5:1 to 10:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and hexane-1,2-diol, without taking into account any counterions in the composition.

[0055] Synergistic compositions containing guanidine and heptane-1,2-diol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and heptane-1,2-diol.

[0056] In a preferred embodiment, the present invention relates to a composition comprising guanidine and heptane-1,2-diol in a weight ratio of guanidine to heptane-1,2-diol generally in the range of 0.25:1 to 30:1, preferably in the range of 0.5:1 to 20:1, more preferably in the range of 0.5:1 to 10:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and heptane-1,2-diol, without taking into account any counterions in the composition.

[0057] Synergistic compositions containing guanidine and octane-1,2-diol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and octane-1,2-diol.

[0058] In a preferred embodiment, the present invention relates to a composition containing guanidine and octane-1,2-diol in a weight ratio of guanidine to octane-1,2-diol generally ranging from 0.2:1 to 6:1, preferably ranging from 0.5:1 to 6:1, wherein the basis for determining the weight ratio is the content in relation to guanidine and octane-1,2-diol in each case without taking into account any counterions in the composition.

[0059] Synergistic compositions containing guanidine and phenoxyethanol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and phenoxyethanol.

[0060] In a preferred embodiment, the present invention relates to a composition containing guanidine and phenoxyethanol in a weight ratio of guanidine to phenoxyethanol generally in the range of 0.13:1 to 3.6:1, preferably in the range of 0.3:1 to 3.6:1, more preferably in the range of 0.5:1 to 3.6:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and phenoxyethanol, without taking into account any counter ions in the composition.

[0061] Synergistic compositions containing guanidine and phenethyl alcohol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and phenethyl alcohol.

[0062] In a preferred embodiment, the present invention relates to a composition containing guanidine and phenethyl alcohol in a weight ratio of guanidine to phenethyl alcohol generally in the range of 0.15:1 to 12:1, preferably in the range of 0.3:1 to 12:1, more preferably in the range of 0.5:1 to 12:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and phenoxyethanol, without taking into account any counter ions in the composition.

[0063] Synergistic compositions containing guanidine and phenylpropanol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and phenylpropanol.

[0064] In a preferred embodiment, the present invention relates to a composition containing guanidine and phenylpropanol in a weight ratio of guanidine to phenylpropanol generally ranging from 0.4:1 to 6:1, preferably ranging from 0.5:1 to 6:1, the basis for determining the weight ratio being the content in relation to guanidine and phenoxyethanol in each case without taking into account any counterions in the composition.

[0065] Synergistic compositions containing guanidine and benzyl alcohol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and benzyl alcohol.

[0066] In a preferred embodiment, the present invention relates to a composition containing guanidine and benzyl alcohol in a weight ratio of guanidine to benzyl alcohol generally in the range of 1:1 to 12:1, preferably in the range of 1:1 to 10:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and benzyl alcohol, without taking into account any counter ions in the composition.

[0067] Synergistic compositions containing guanidine and isopropanol: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and isopropanol.

[0068] In a preferred embodiment, the present invention relates to a composition comprising guanidine and isopropanol in a weight ratio of guanidine to isopropanol generally in the range of 0.004:1 to 3:1, preferably 0.01:1 to 3:1, more preferably 0.1 to 3:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and isopropanol, without taking into account any counter ions in the composition.

[0069] Synergistic compositions containing guanidine and ethylenediaminetetraacetic acid (EDTA): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and ethylenediaminetetraacetic acid and / or a salt(s) thereof.

[0070] In a preferred embodiment, the present invention relates to a composition comprising guanidine and ethylenediaminetetraacetic acid in a weight ratio of guanidine to ethylenediaminetetraacetic acid generally in the range of 0.6:1 to 37:1, preferably 0.6:1 to 20:1, more preferably 0.6:1 to 15:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and ethylenediaminetetraacetic acid, without taking into account any counterions in the composition.

[0071] Synergistic compositions containing guanidine and (1-hydroxyethylidene)bisphosphonic acid (HEDP): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and (1-hydroxyethylidene)bisphosphonic acid and / or a salt(s) thereof.

[0072] In a preferred embodiment, the present invention relates to a composition containing guanidine and (1-hydroxyethylidene)bisphosphonic acid in a weight ratio of guanidine to (1-hydroxyethylidene)bisphosphonic acid generally in the range of 0.6:1 to 1.5:1, preferably in the range of 0.6:1 to 1:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and (1-hydroxyethylidene)bisphosphonic acid, without taking into account any counterions in the composition.

[0073] Synergistic compositions containing guanidine and sodium pyrithione: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and sodium pyrithione.

[0074] In a preferred embodiment, the present invention relates to a composition containing guanidine and sodium pyrithione in a weight ratio of guanidine to sodium pyrithione generally in the range of 3.6:1 to 180:1, preferably 3.6:1 to 100:1, more preferably 3.6:1 to 50:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and sodium pyrithione, without taking into account any counter ions in the composition.

[0075] Synergistic compositions containing guanidine and zinc pyrithione: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and zinc pyrithione.

[0076] In a preferred embodiment, the present invention relates to a composition containing guanidine and zinc pyrithione in a weight ratio of guanidine to zinc pyrithione generally in the range of 3.6:1 to 180:1, preferably 3.6:1 to 100:1, more preferably 3.6:1 to 50:1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine and zinc pyrithione, without taking into account any counter ions in the composition.

[0077] Synergistic compositions containing guanidine and o-phenylphenol (oPP): In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and o-phenylphenol.

[0078] In a preferred embodiment, the present invention relates to a composition comprising guanidine and o-phenylphenol in a weight ratio of guanidine to o-phenylphenol generally in the range of 0.62:1 to 49:1, preferably 0.62:1 to 40:1, more preferably 0.62:1 to 30:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and o-phenylphenol, without taking into account any counterions in the composition.

[0079] Synergistic compositions containing guanidine and sorbic acid: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof, and also sorbic acid and / or a salt(s) thereof.

[0080] In a preferred embodiment, the present invention relates to a composition comprising guanidine and sorbic acid in a weight ratio of guanidine to sorbic acid generally in the range of from 0.1:1 to 50:1, preferably from 0.25:1 to 40:1, more preferably from 0.25:1 to 30:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and sorbic acid, without taking into account any counterions in the composition.

[0081] Synergistic compositions containing guanidine and benzoic acid: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and benzoic acid and / or a salt(s) thereof.

[0082] In a preferred embodiment, the present invention relates to a composition comprising guanidine and benzoic acid in a weight ratio of guanidine to benzoic acid generally in the range of 0.25:1 to 88:1, preferably 0.25:1 to 50:1, more preferably 0.25:1 to 30:1, wherein the basis for determining the weight ratio is in each case the contents in relation to guanidine and benzoic acid, without taking into account any counterions in the composition.

[0083] Synergistic compositions containing guanidine and salicylic acid: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and salicylic acid and / or a salt(s) thereof.

[0084] In a preferred embodiment, the present invention relates to a composition containing guanidine and salicylic acid in a weight ratio of guanidine to salicylic acid generally in the range of 0.24:1 to 43:1, preferably in the range of 0.24:1 to 30:1, wherein the basis for determining the weight ratio is the content in terms of guanidine and salicylic acid in each case without taking into account any counterions in the composition.

[0085] Synergistic compositions containing guanidine and lactic acid: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and lactic acid and / or a salt(s) thereof.

[0086] In a preferred embodiment, the present invention relates to a composition containing guanidine and lactic acid in a weight ratio of guanidine to lactic acid generally in the range of 0.03:1 to 23:1, preferably in the range of 0.03:1 to 10:1, wherein the basis for determining the weight ratio is the content in relation to guanidine and lactic acid in each case without taking into account any counter ions in the composition.

[0087] Synergistic compositions containing guanidine and citric acid: In one embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof and citric acid and / or a salt(s) thereof.

[0088] In a preferred embodiment, the present invention relates to a composition comprising guanidine and citric acid in a weight ratio of guanidine to citric acid ranging from 1:0.014 to 12:1, wherein the basis for determining the weight ratio is the content in relation to guanidine and citric acid in each case without taking into account any counter ions in the composition.

[0089] Synergistic compositions containing guanidine and zinc: In one embodiment, the present invention relates to a composition containing guanidine and / or a salt thereof and zinc. In the context of the present invention, zinc is provided by at least one zinc compound that functions as a zinc source. The zinc compound is preferably selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc ascorbate, zinc dehydroacetate, zinc hydroxide, and zinc carboxylate. In a preferred embodiment of the present invention, the zinc compound is selected from the group consisting of zinc oxide, zinc chloride, and zinc carbonate. Zinc is most preferably provided or introduced into the composition by zinc oxide.

[0090] In a preferred embodiment, the present invention relates to a composition containing guanidine and zinc in a weight ratio of guanidine to zinc ranging from 0.77:1 to 12:1, preferably from 1:1 to 12:1, wherein the basis for determining the weight ratio is the content in terms of guanidine and in terms of zinc ions, in each case without taking into account any counter ions.

[0091] In a preferred embodiment of the present invention, the composition of the present invention comprises: a weight ratio of guanidine and / or a salt thereof to 5-chloro-2-methylisothiazolin-3-one in the range of 62:1 to 9270:1; a weight ratio of guanidine and / or a salt thereof to 2-methyl-4-isothiazolin-3-one in the range of 10.3:1 to 773:1; a weight ratio of guanidine and / or a salt thereof to 1,2-benzisothiazolin-3-one in the range of 1.3:1 to 309:1; a weight ratio of guanidine and / or a salt thereof to N-butyl-1,2-benzisothiazolin-3-one in the range of 0.52:1 to 309:1; a weight ratio of guanidine and / or a salt thereof to N-methyl-1,2-benzisothiazolin-3-one in the range of 7.8:1 to 618:1; a weight ratio of guanidine and / or a salt thereof to N-octylisothiazolin-3-one in the range of 1.4:1 to 82:1; the weight ratio of guanidine and / or a salt thereof to bronopol is in the range of 7.8:1 to 824:1; the weight ratio of guanidine and / or a salt thereof to 2,2-dibromo-3-nitrilopropionamide is in the range of 7.8:1 to 3090:1; The weight ratio of guanidine and / or its salt to dibromodicyanobutane is in the range of 0.78:1 to 309:1. the weight ratio of guanidine and / or a salt thereof to iodopropynyl butylcarbamate is in the range of 0.83:1 to 103:1; the weight ratio of guanidine and / or a salt thereof to 2-amino-2-methyl-1-propanol is in the range of 0.3:1 to 20:1; the weight ratio of guanidine and / or a salt thereof to 2-aminoethylpropane-1,3-diol is in the range of 0.2:1 to 15:1; the weight ratio of guanidine and / or a salt thereof to monoethanolamine is in the range of 0.2:1 to 30:1; the weight ratio of guanidine and / or a salt thereof to ethylhexylglycerol is in the range of 0.5:1 to 15:1; the weight ratio of guanidine and / or a salt thereof to hexylglycerol is in the range of 0.5:1 to 15:1, preferably in the range of 0.5:1 to 10:1; the weight ratio of guanidine and / or a salt thereof to pentane-1,2-diol is in the range of 0.07:1 to 7.5:1; the weight ratio of guanidine and / or a salt thereof to hexane-1,2-diol is in the range of 0.06:1 to 15:1; the weight ratio of guanidine and / or a salt thereof to heptane-1,2-diol is in the range of 0.25:1 to 30:1; the weight ratio of guanidine and / or a salt thereof to octane-1,2-diol is in the range of 0.2:1 to 6:1; the weight ratio of guanidine and / or a salt thereof to phenoxyethanol is in the range of 0.13:1 to 3.6:1; the weight ratio of guanidine and / or a salt thereof to phenethyl alcohol is in the range of 0.15:1 to 12:1; the weight ratio of guanidine and / or a salt thereof to phenylpropanol is in the range of 0.4:1 to 6:1; the weight ratio of guanidine and / or a salt thereof to benzyl alcohol is in the range of 1:1 to 12:1; the weight ratio of guanidine and / or a salt thereof to isopropanol is in the range of 0.004:1 to 3:1; the weight ratio of guanidine and / or a salt thereof to ethylenediaminetetraacetic acid is in the range of 0.6:1 to 37:1; the weight ratio of guanidine and / or a salt thereof to (1-hydroxyethylidene)bisphosphonic acid is in the range of 0.6:1 to 1.5:1; the weight ratio of guanidine and / or a salt thereof to sodium pyrithione is in the range of 3.6:1 to 180:1; the weight ratio of guanidine and / or a salt thereof to zinc pyrithione is in the range of 3.6:1 to 180:1; the weight ratio of guanidine and / or a salt thereof to o-phenylphenol is in the range of 0.62:1 to 49:1; the weight ratio of guanidine and / or a salt thereof to sorbic acid and / or a salt thereof is in the range of 0.1:1 to 50:1; the weight ratio of guanidine and / or a salt thereof to benzoic acid and / or a salt thereof is in the range of 0.25:1 to 88:1; the weight ratio of guanidine and / or a salt thereof to salicylic acid and / or a salt thereof is in the range of 0.24:1 to 43:1; the weight ratio of guanidine and / or a salt thereof to lactic acid and / or a salt thereof is in the range of 0.03:1 to 23:1; the weight ratio of guanidine and / or a salt thereof to citric acid and / or a salt thereof is in the range of 0.014:1 to 12:1; the weight ratio of guanidine and / or a salt thereof to zinc is in the range of 0.77:1 to 12:1; The basis for determining the weight ratio is in each case the content in terms of guanidine without taking into account any counter ions in the composition. It is characterized by:

[0092] In one embodiment of the present invention, the aqueous composition is characterized in that it is an industrial product selected from the group consisting of lignosulfonate and starch formulations in paints, pigments, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, chalk slurries, ore slurries, ceramic compounds, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and pigment dispersions, inks, lithography fluids, thickeners, cosmetics, toiletries, water cycle fluids, wood processing fluids, oil production fluids, paper processing fluids, leather manufacturing fluids, textile manufacturing fluids, drilling and cutting oils, hydraulic oils, cooling lubricants and biocidal products.

[0093] The content (use concentration) of components (a) and (b) of the above-defined technical products can vary within wide limits depending on the intended use and is usually determined by a person skilled in the art of biocides. The concentration ranges specified below provide the skilled person with a guide to the amounts to be used in each case.

[0094] The amount of component (a), guanidine and / or its salts, present in the industrial product can vary over a wide range, generally in the range of 100 to 10,000 ppm, preferably in the range of 200 to 7,500 ppm, more preferably in the range of 300 to 5,000 ppm, this percentage relating to the guanidine content of the entire industrial product.

[0095] The amount of component (b) present in the technical product may likewise vary within wide limits: When 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) is present as component (b) in an aqueous composition or industrial product, it is generally present in an amount ranging from 0.5 to 200 ppm, preferably from 5 to 100 ppm, more preferably from 10 to 50 ppm, and especially preferably from 15 to 30 ppm.

[0096] When 2-methyl-4-isothiazolin-3-one (MIT) is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 0.5 to 200 ppm, preferably from 1 to 150 ppm, more preferably from 5 to 125 ppm, and especially preferably from 10 to 100 ppm.

[0097] When 1,2-benzisothiazolin-3-one (BIT) is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 500 ppm, preferably from 5 to 500 ppm, and more preferably from 10 to 500 ppm.

[0098] N-butyl-1,2-benzisothiazolin-3-one (BBIT), when present in the aqueous composition or industrial product as component (b), is generally present in an amount ranging from 5 to 2500 ppm, preferably from 10 to 2000 ppm, and more preferably from 10 to 1500 ppm.

[0099] N-methyl-1,2-benzisothiazolin-3-one (MBIT), when present in the aqueous composition or industrial product as component (b), is generally present in an amount ranging from 1 to 500 ppm, preferably from 5 to 500 ppm, and more preferably from 10 to 1000 ppm.

[0100] Octylisothiazolinone (OIT), when present in the aqueous composition or industrial product as component (b), is generally present in an amount ranging from 1 to 2500 ppm, preferably from 5 to 2000 ppm, and more preferably from 10 to 1500 ppm.

[0101] When bronopol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 1000 ppm, preferably from 5 to 750 ppm, more preferably from 10 to 500 ppm.

[0102] When dibromonitrilopropionamide (DBNPA) is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 1000 ppm, preferably from 5 to 750 ppm, and more preferably from 10 to 500 ppm.

[0103] Dibromodicyanobutane (DBDCB), when present as an additional ingredient in products stored with the compositions of the present invention, is generally in an amount ranging from 1 to 1000 ppm, preferably in an amount from 5 to 750 ppm, more preferably in an amount from 10 to 500 ppm.

[0104] When iodopropynyl butylcarbamate (IPBC) is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 5000 ppm, preferably from 25 to 4500 ppm, and more preferably from 50 to 4000 ppm.

[0105] When aminomethylpropanol (AMP) is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 25 to 7,500 ppm, and more preferably from 50 to 5,000 ppm.

[0106] When aminoethylpropanediol (AEPD) is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 25 to 7,500 ppm, and more preferably from 50 to 5,000 ppm.

[0107] When monoethanolamine (MEA) is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 25 to 7,500 ppm, and more preferably from 50 to 5,000 ppm.

[0108] When ethylhexylglycerol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, and more preferably from 100 to 5,000 ppm.

[0109] When hexylglycerol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, more preferably from 100 to 5,000 ppm.

[0110] When pentane-1,2-diol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, and more preferably from 100 to 5,000 ppm.

[0111] When hexane-1,2-diol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, and more preferably from 100 to 5,000 ppm.

[0112] When heptane-1,2-diol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, and more preferably from 100 to 5,000 ppm.

[0113] When octane-1,2-diol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, and more preferably from 100 to 5,000 ppm.

[0114] When phenoxyethanol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, more preferably from 100 to 5,000 ppm.

[0115] When phenethyl alcohol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, more preferably from 100 to 5,000 ppm.

[0116] When phenylpropanol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, more preferably from 100 to 5,000 ppm.

[0117] When benzyl alcohol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, more preferably from 100 to 5,000 ppm.

[0118] When isopropanol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 30,000 ppm, preferably from 50 to 20,000 ppm, more preferably from 100 to 15,000 ppm.

[0119] Ethylenediaminetetraacetic acid (EDTA), when present in the aqueous composition or industrial preservation product as component (b), is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, and more preferably from 100 to 5,000 ppm.

[0120] When (1-hydroxyethylidene)bisphosphonic acid (HEDP) is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, and more preferably from 100 to 5,000 ppm.

[0121] When sodium pyrithione is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 2500 ppm, preferably from 5 to 1500 ppm, more preferably from 10 to 1000 ppm.

[0122] When zinc pyrithione is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 2500 ppm, preferably from 5 to 1500 ppm, more preferably from 10 to 1000 ppm.

[0123] When o-phenylphenol is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 10,000 ppm, preferably from 10 to 5,000 ppm, more preferably from 25 to 2,500 ppm, and especially preferably from 50 to 1,500 ppm.

[0124] When sorbic acid is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 10,000 ppm, preferably from 5 to 7,500 ppm, more preferably from 10 to 5,000 ppm.

[0125] When benzoic acid is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 10,000 ppm, preferably from 5 to 7,500 ppm, more preferably from 10 to 5,000 ppm.

[0126] When salicylic acid is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 10,000 ppm, preferably from 5 to 7,500 ppm, more preferably from 10 to 5,000 ppm.

[0127] When lactic acid is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 50,000 ppm, preferably from 5 to 25,000 ppm, more preferably from 10 to 15,000 ppm.

[0128] When citric acid is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 1 to 100,000 ppm, preferably from 5 to 50,000 ppm, more preferably from 10 to 25,000 ppm.

[0129] When zinc is present in the aqueous composition or industrial product as component (b), it is generally present in an amount ranging from 10 to 5000 ppm, preferably from 25 to 2500 ppm, preferably from 50 to 1000 ppm, and particularly preferably from 100 to 500 ppm.

[0130] The present invention further relates to the use of a composition, preferably aqueous, as defined above, for the in-can preservation or preservation of industrial products selected from the group consisting of lignosulfonate and starch formulations in paints, colors, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, chalk slurries, ore slurries, ceramic compounds, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and pigment dispersions, inks, lithography fluids, thickeners, cosmetics, toiletries, water cycles, wood working fluids, oil production fluids, paper working fluids, leather manufacturing fluids, textile manufacturing fluids, drilling and cutting oils, hydraulic oils and cooling lubricants.

[0131] In a further embodiment, the present invention provides (b) 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, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, aminomethylpropanol, aminoethylpropanediol, monoethanolamine, ethylhexylglycerol, hexylglycerol The present invention relates to the use of (a) a salt of guanidine and / or unsubstituted guanidine for improving the antibacterial efficacy of one or more compounds selected from the group consisting of ethanol, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bisphosphonic acid, sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc.

[0132] As can be seen from the examples presented below, the use of guanidine or its salts, which was not previously known as an antibacterial active substance, leads to a surprising synergistic increase in the effect of at least one further ingredient from group (b) shown above.

[0133] Due to this surprising increase in effectiveness, at least one biocidally active ingredient from group (b) can be used in significantly lower concentrations in the presence of guanidine. The amounts of components (a) and (b) used can vary over a wide range, for example in the range of 0.01% to 10%, preferably in the range of 0.02% to 5%, more preferably in the range of 0.03% to 3%, based on the total composition in which they are present.

[0134] Particularly advantageous improvements in antibacterial efficacy are achieved when the weight ratio of guanidine and / or salts thereof to 5-chloro-2-methylisothiazolin-3-one is in the range of from 62:1 to 9270:1, and / or the weight ratio of guanidine and / or salts thereof to 2-methyl-4-isothiazolin-3-one is in the range of from 10.3:1 to 773:1, and / or the weight ratio of guanidine and / or salts thereof to 1,2-benzisothiazolin-3-one is in the range of from 1.3:1 to 309:1, and / or the weight ratio of guanidine and / or salts thereof to N-butyl-1,2 - the weight ratio of guanidine and / or its salts to N-methyl-1,2-benzisothiazolin-3-one is in the range of 0.52:1 to 309:1, and / or the weight ratio of guanidine and / or its salts to N-octylisothiazolin-3-one is in the range of 1.4:1 to 82:1, and / or the weight ratio of guanidine and / or its salts to bronopol is in the range of 7.8:1 to 824:1, and / or and / or the weight ratio of guanidine and / or a salt thereof to 2,2-dibromo-3-nitrilopropionamide is in the range of 7.8:1 to 3090:1, and / or the weight ratio of guanidine and / or a salt thereof to dibromodicyanobutane is in the range of 0.78:1 to 309:1, and / or the weight ratio of guanidine and / or a salt thereof to iodopropynyl butylcarbamate is in the range of 0.83:1 to 103:1, and / or the weight ratio of guanidine and / or a salt thereof to 2-amino-2-methyl-1-propanol is in the range of 0.3:1 to 20:1. and / or the weight ratio of guanidine and / or a salt thereof to 2-aminoethylpropane-1,3-diol is in the range of 0.2:1 to 15:1, and / or the weight ratio of guanidine and / or a salt thereof to monoethanolamine is in the range of 0.2:1 to 30:1, and / or the weight ratio of guanidine and / or a salt thereof to ethylhexylglycerol is in the range of 0.5:1 to 15:1, and / or the weight ratio of guanidine and / or a salt thereof to hexylglycerol is in the range of 0.5:1 to 15:1, preferably 0.and / or the weight ratio of guanidine and / or a salt thereof to pentane-1,2-diol is in the range of 0.07:1 to 7.5:1, and / or the weight ratio of guanidine and / or a salt thereof to hexane-1,2-diol is in the range of 0.06:1 to 15:1, and / or the weight ratio of guanidine and / or a salt thereof to heptane-1,2-diol is in the range of 0.25:1 to 30:1, and / or the weight ratio of guanidine and / or a salt thereof to octane-1,2-diol is in the range of 0.2:1 to 6:1. and / or the weight ratio of guanidine and / or a salt thereof to phenoxyethanol is in the range of 0.13:1 to 3.6:1, and / or the weight ratio of guanidine and / or a salt thereof to phenethyl alcohol is in the range of 0.15:1 to 12:1, and / or the weight ratio of guanidine and / or a salt thereof to phenylpropanol is in the range of 0.4:1 to 6:1, and / or the weight ratio of guanidine and / or a salt thereof to benzyl alcohol is in the range of 1:1 to 12:1, and / or the weight ratio of guanidine and / or a salt thereof to isopropanol is in the range of 0.004:1 to 3:1, and / or the weight ratio of guanidine and / or a salt thereof to ethylenediaminetetraacetic acid is in the range of 0.6:1 to 37:1, and / or the weight ratio of guanidine and / or a salt thereof to (1-hydroxyethylidene)bisphosphonic acid is in the range of 0.6:1 to 1.5:1, and / or the weight ratio of guanidine and / or a salt thereof to sodium pyrithione is in the range of 3.6:1 to 180:1, and / or the weight ratio of guanidine and / or a salt thereof to zinc pyrithione. and / or the weight ratio of guanidine and / or a salt thereof to o-phenylphenol is in the range of 3.6:1 to 180:1, and / or the weight ratio of guanidine and / or a salt thereof to sorbic acid and / or a salt thereof is in the range of 0.62:1 to 49:1, and / or the weight ratio of guanidine and / or a salt thereof to sorbic acid and / or a salt thereof is in the range of 0.1:1 to 50:1, and / or the weight ratio of guanidine and / or a salt thereof to benzoic acid and / or a salt thereof is in the range of 0.25:1 to 88:1, and / or the weight ratio of guanidine and / or a salt thereof to salicylic acid and / or a salt thereof is 0.This can be achieved when the weight ratio of guanidine and / or salts thereof to lactic acid and / or salts thereof is in the range of 24:1 to 43:1, and / or the weight ratio of guanidine and / or salts thereof to citric acid and / or salts thereof is in the range of 0.03:1 to 23:1, and / or the weight ratio of guanidine and / or salts thereof to citric acid and / or salts thereof is in the range of 0.014:1 to 12:1, and / or the weight ratio of guanidine and / or salts thereof to zinc is in the range of 0.77:1 to 12:1, the basis for determining the weight ratio in each case being the total content of guanidine and acid in the composition. [Example]

[0135] The following examples serve to further illustrate the present invention:

[0136] Study of synergistic interactions Guanidine (added in the form of guanidine hydrochloride) and 5-chloro-2-methyl-4-isothiazolin-3-one (CIT), 2-methyl-4-isothiazolin-3-one (MIT), 1,2-benzisothiazolin-3-one (BIT), N-butyl-1,2-benzisothiazolin-3-one (BBIT), N-methyl-1,2-benzisothiazolin-3-one (MBIT), octylisothiazolinone (OIT), bronopol, dibromonitrilopropionamide (DBNPA), dibromodicyanobutane (DBDCB), iodopropynyl butylcarbamate (IPBC), aminomethylpropanol (AMP), aminoethylpropanol (AM), The synergistic effects of combinations with biocides or substances selected from the group consisting of benzophenone-1,2-diol (AEPD), monoethanolamine (MEA), ethylhexylglycerol, hexylglycerol, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, phenoxyethanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid (EDTA), (1-hydroxyethylidene)bisphosphonic acid (HEDP), pyrithione, o-phenylphenol (oPP), sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc oxide (ZnO) were examined for synergistic interactions.

[0137] The test organisms used were Gram-negative bacterial species from the Pseudomonad group, Pseudomonas putida DSM 115323 and Pseudomonas spec. DSM 115322. For this purpose, mixtures with different concentrations of each active substance were prepared and their effect on Pseudomonads was tested. The test was carried out at 10 per ml. 6 Microbial cell density was measured in Mueller-Hinton broth (MHB). When organic acids were used as combination partners with guanidine, MHB was adjusted to pH 5.5.

[0138] Incubation was carried out in microplates at 30°C for 48 hours. After 48 hours, the batches were evaluated for turbidity resulting from growth and the optical density was determined photometrically. In this way, the minimum inhibitory concentrations (MICs) of the two active substances were determined individually and in combination.

[0139] The resulting synergistic effect was quantified by calculating the synergy index (SI). The calculation was performed according to the standard method of F.C. Kull et al., Applied Microbiology, vol. 9 (1961), p. 538.

[0140] This involves calculating the synergy index (SI) according to the following formula:

number

[0141] If the synergy index is greater than 1, this means that there is antagonism. If the synergy index assumes a value of 1, this means that the effects of the two biocides / compounds are additive. If the synergy index assumes a value less than 1, this means that there is a synergistic effect between the two biocides / compounds.

[0142] Example 1: Study of the synergistic interaction of guanidine and 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) Calculation of synergy index of guanidine and CIT for Pseudomonas putida DSM 115323 at 30 °C and 48 h incubation time.

[0143] [Table 1]

[0144] Table 1 shows that the optimal synergistic effect of the guanidine and CIT composition, i.e., the lowest synergy index (0.75), is obtained at a ratio of 1545 ppm guanidine to 1.5 ppm CIT. Synergistic effect can be demonstrated when the weight ratio of guanidine to CIT ranges from 62:1 to 9270:1.

[0145] Example 2: Study of the synergistic interaction of guanidine and 2-methyl-4-isothiazolin-3-one (MIT) Calculation of synergy index of guanidine and MIT for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0146] [Table 2]

[0147] Table 2 shows that the optimal synergistic effect of the guanidine and MIT composition, i.e., the lowest synergy index (0.73), is obtained at a ratio of 3090 ppm guanidine to 30 ppm MIT. Synergistic effect can be demonstrated when the weight ratio of guanidine to MIT ranges from 10.3:1 to 773:1.

[0148] Example 3: Study of the synergistic interaction of guanidine and 1,2-benzisothiazolin-3-one (BIT) Calculation of synergy index of guanidine and BIT for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0149] [Table 3]

[0150] Table 3 shows that the optimal synergistic effect of the guanidine and BIT composition, i.e., the lowest synergy index (0.67), is obtained at a ratio of 3090 ppm guanidine to 100 ppm BIT. Synergistic effect can be demonstrated when the weight ratio of guanidine to BIT ranges from 1.3:1 to 309:1.

[0151] Example 4: Study of the synergistic interaction of guanidine and N-butyl-1,2-benzisothiazolin-3-one (BBIT) Calculation of synergy index of guanidine and BBIT for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0152] [Table 4]

[0153] Table 4 shows that the optimal synergistic effect of the guanidine and BBIT composition, i.e., the lowest synergy index (0.67), is obtained at a ratio of 1545 ppm guanidine to 200 ppm BBIT. Synergistic effect can be demonstrated when the weight ratio of guanidine to BBIT ranges from 0.52:1 to 309:1.

[0154] Example 5: Study of the synergistic interaction of guanidine and N-methyl-1,2-benzisothiazolin-3-one (MBIT) Calculation of synergy index of guanidine and MBIT for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0155] [Table 5]

[0156] Table 5 shows that the optimal synergistic effect of the guanidine and MBIT composition, i.e., the lowest synergy index (0.75), is obtained at a ratio of 3090 ppm guanidine to 125 ppm MBIT. Synergistic effect can be demonstrated when the weight ratio of guanidine to MBIT ranges from 7.8:1 to 618:1. Example 6: Study of the synergistic interaction of guanidine and octylisothiazolinone (OIT) Calculation of synergy index for guanidine and OIT for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0157] [Table 6]

[0158] Table 6 shows that the optimal synergistic effect of the guanidine and OIT composition, i.e., the lowest synergy index (0.87), is obtained at a ratio of 618-1590 ppm guanidine to 200-175 ppm OIT. Synergistic effect can be demonstrated when the weight ratio of guanidine to OIT is in the range of 1.4:1 to 82:1.

[0159] Example 7: Study of the synergistic interaction of guanidine and bronopol Calculation of synergy index of guanidine and bronopol for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0160] [Table 7]

[0161] Table 7 shows that the optimal synergy of the guanidine and bronopol composition, i.e., the lowest synergy index (0.77), is obtained at a ratio of 1545 ppm guanidine to 15 ppm bronopol. Synergy can be demonstrated when the weight ratio of guanidine to bronopol is in the range of 7.8:1 to 824:1.

[0162] Example 8: Study of the synergistic interaction of guanidine and dibromonitrilopropionamide (DBNPA) Calculation of synergy index of guanidine and DBNPA for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0163] [Table 8]

[0164] Table 8 shows that the optimal synergistic effect of the guanidine and DBNPA composition, i.e., the lowest synergy index (0.82), is obtained at a ratio of 155 ppm guanidine to 20 ppm DBNPA. Synergistic effect can be demonstrated when the weight ratio of guanidine to DBNPA ranges from 7.8:1 to 3090:1.

[0165] Example 9: Study of the synergistic interaction of guanidine and dibromodicyanobutane (DBDCB) Calculation of synergy index of guanidine and DBDCB for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0166] [Table 9]

[0167] Table 9 shows that the optimal synergy of the guanidine and DBDCB composition, i.e., the lowest synergy index (0.77), is obtained at a ratio of 1590 ppm guanidine to 150 ppm DBDCB. Synergy can be demonstrated when the weight ratio of guanidine to DBDCB ranges from 0.78:1 to 309:1.

[0168] Example 10: Study of the synergistic interaction of guanidine and iodide propynyl butylcarbamate (IPBC) Calculation of synergy index of guanidine and IPBC for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0169] [Table 10]

[0170] Table 10 shows that the optimal synergy of the guanidine and IPBC composition, i.e., the lowest synergy index (0.83), is obtained at a ratio of 4635 ppm guanidine to 300 ppm IPBC. Synergy can be demonstrated when the weight ratio of guanidine to IPBC ranges from 0.83:1 to 103:1.

[0171] Example 11: Study of the synergistic interaction of guanidine and 2-amino-2-methyl-1-propanol (AMP) Calculation of synergy index of guanidine and AMP for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0172] [Table 11]

[0173] Table 11 shows that the optimal synergistic effect of the guanidine and AMP composition, i.e., the lowest synergy index (0.73), is obtained at a ratio of 3090 ppm guanidine to 1000 ppm AMP. Synergistic effect can be demonstrated when the weight ratio of guanidine to AMP ranges from 0.3:1 to 20:1.

[0174] Example 12: Study of the synergistic interaction of guanidine and 2-aminoethylpropane-1,3-diol (AEPD) Calculation of synergy index of guanidine and AEPD for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0175] [Table 12]

[0176] Table 12 shows that the optimal synergy of the guanidine and AEPD composition, i.e., the lowest synergy index (0.73), is obtained at a ratio of 3090 ppm guanidine to 2000 ppm AEPD. Synergy can be demonstrated when the weight ratio of guanidine to AEPD ranges from 0.2:1 to 15:1.

[0177] Example 13: Study of the synergistic interaction of guanidine and monoethanolamine (MEA) Calculation of synergy index for guanidine and MEA on Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0178] [Table 13]

[0179] Table 13 shows that the optimal synergy of the guanidine and MEA composition, i.e., the lowest synergy index (0.79), is obtained at a ratio of 1545 ppm guanidine to 1250 ppm MEA. Synergy can be demonstrated when the weight ratio of guanidine to MEA is in the range of 0.2:1 to 30:1.

[0180] Example 14: Study of the synergistic interaction of guanidine and ethylhexylglycerol (EHG) Calculation of synergy index of guanidine and EHG for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0181] [Table 14]

[0182] Table 14 shows that the optimal synergy of the guanidine and EHG composition, i.e., the lowest synergy index (0.69), is obtained at a ratio of 618 ppm guanidine to 1250 ppm EHG. Synergy can be demonstrated when the weight ratio of guanidine to EHG ranges from 0.5:1 to 15:1.

[0183] Example 15: Study of the synergistic interaction of guanidine and hexylglycerol Calculation of synergy index of guanidine and hexylglycerol for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0184] [Table 15]

[0185] Table 15 shows that the optimal synergy of the guanidine and hexylglycerol composition, i.e., the lowest synergy index (0.69), is obtained at a ratio of 618 ppm guanidine to 1250 ppm hexylglycerol. Synergy can be demonstrated when the weight ratio of guanidine to hexylglycerol ranges from 0.5:1 to 15:1.

[0186] Example 16: Study of the synergistic interaction of guanidine and pentane-1,2-diol Calculation of synergy index of guanidine and pentane-1,2-diol for Pseudomonas sp. DSM 115322 at 30° C. and 48 h incubation time.

[0187] [Table 16]

[0188] Table 16 shows that the optimum synergy of the guanidine and pentane-1,2-diol composition, i.e., the lowest synergy index (0.87), is obtained at a ratio of 6180 ppm guanidine to 2000 ppm pentane-1,2-diol. Synergy can be demonstrated when the weight ratio of guanidine to pentane-1,2-diol ranges from 0.07:1 to 7.5:1.

[0189] Example 17: Study of the synergistic interaction of guanidine and hexane-1,2-diol Calculation of synergy index of guanidine and hexane-1,2-diol for Pseudomonas sp. DSM 115322 at 30° C. and 48 h incubation time.

[0190] [Table 17]

[0191] Table 17 shows that the optimum synergy of the guanidine and hexane-1,2-diol composition, i.e., the lowest synergy index (0.67), is obtained at a ratio of 1545-3090 ppm guanidine to 3750-2500 ppm hexane-1,2-diol. Synergy can be demonstrated when the weight ratio of guanidine to hexane-1,2-diol is in the range of 0.06:1 to 15:1.

[0192] Example 18: Study of the synergistic interaction of guanidine and heptane-1,2-diol Calculation of synergy index of guanidine and heptane-1,2-diol for Pseudomonas sp. DSM 115322 at 30° C. and 48 h incubation time.

[0193] [Table 18]

[0194] Table 18 shows that the optimum synergy of the guanidine and heptane-1,2-diol composition, i.e., the lowest synergy index (0.70), is obtained at a ratio of 1545 ppm guanidine to 2000 ppm heptane-1,2-diol. Synergy can be demonstrated when the weight ratio of guanidine to heptane-1,2-diol ranges from 0.25:1 to 30:1.

[0195] Example 19: Study of the synergistic interaction of guanidine and octane-1,2-diol Calculation of synergy index of guanidine and octane-1,2-diol for Pseudomonas sp. DSM 115322 at 30° C. and 48 h incubation time.

[0196] [Table 19]

[0197] Table 19 shows that the optimum synergy of the guanidine and octane-1,2-diol composition, i.e., the lowest synergy index (0.88), is obtained at a ratio of 4635 ppm guanidine to 750 ppm octane-1,2-diol. Synergy can be demonstrated when the weight ratio of guanidine to octane-1,2-diol is in the range of 0.2:1 to 6:1.

[0198] Example 20: Study of the synergistic interaction of guanidine and phenoxyethanol Calculation of synergy index of guanidine and phenoxyethanol for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0199] [Table 20]

[0200] Table 20 shows that the optimum synergy of the guanidine and phenoxyethanol composition, i.e., the lowest synergy index (0.83), is obtained at a ratio of 1545 ppm guanidine to 2000 ppm phenoxyethanol. Synergy can be demonstrated when the weight ratio of guanidine to phenoxyethanol is in the range of 0.13:1 to 3.6:1.

[0201] Example 21: Study of the synergistic interaction of guanidine and phenethyl alcohol Calculation of synergy index of guanidine and phenethyl alcohol for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0202] [Table 21]

[0203] Table 21 shows that the optimum synergistic effect of the guanidine and phenethyl alcohol composition, i.e., the lowest synergy index (0.83), is obtained at a ratio of 309-3090 ppm guanidine to 1250-2000 ppm phenethyl alcohol. Synergistic effect can be demonstrated when the weight ratio of guanidine to phenethyl alcohol is in the range of 0.15:1 to 12:1.

[0204] Example 22: Study of the synergistic interaction of guanidine and phenylpropanol Calculation of synergy index of guanidine and phenylpropanol for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0205] [Table 22]

[0206] Table 22 shows that the optimal synergy of the guanidine and phenylpropanol composition, i.e., the lowest synergy index (0.79), is obtained at a ratio of 1545 ppm guanidine to 1250 ppm phenylpropanol. Synergy can be demonstrated when the weight ratio of guanidine to phenylpropanol is in the range of 0.4:1 to 6:1.

[0207] Example 23: Study of the synergistic interaction of guanidine and benzyl alcohol Calculation of synergy index of guanidine and benzyl alcohol for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0208] [Table 23]

[0209] Table 23 shows that the optimal synergy of the guanidine and benzyl alcohol composition, i.e., the lowest synergy index (0.71), is obtained at a ratio of 3090 ppm guanidine to 750 ppm benzyl alcohol. Synergy can be demonstrated when the weight ratio of guanidine to benzyl alcohol is in the range of 1:1 to 12:1.

[0210] Example 24: Study of the synergistic interaction of guanidine and isopropanol Calculation of synergy index for guanidine and isopropanol for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0211] [Table 24]

[0212] Table 24 shows that the optimal synergy of the guanidine and isopropanol composition, i.e., the lowest synergy index (0.53), is obtained at a ratio of 309 ppm guanidine to 30,000 ppm isopropanol. Synergy can be demonstrated when the weight ratio of guanidine to isopropanol is in the range of 0.004:1 to 3:1.

[0213] Example 25: Study of the synergistic interaction of guanidine and ethylenediaminetetraacetic acid (EDTA) Calculation of synergy index of guanidine and EDTA for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0214] [Table 25]

[0215] Table 25 shows that the optimal synergy of the guanidine and EDTA composition, i.e., the lowest synergy index (0.83), is obtained at a ratio of 1545 ppm guanidine to 200 ppm EDTA. Synergy can be demonstrated when the weight ratio of guanidine to EDTA ranges from 0.6:1 to 37:1.

[0216] Example 26: Study of the synergistic interaction of guanidine and (1-hydroxyethylidene)bisphosphonic acid (HEDP) Calculation of synergy index of guanidine and HEDP for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0217] [Table 26]

[0218] Table 26 shows that the optimal synergy of the guanidine and HEDP composition, i.e., the lowest synergy index (0.73), is obtained at a ratio of 618 ppm guanidine to 1000 ppm HEDP. Synergy can be demonstrated when the weight ratio of guanidine to HEDP is in the range of 0.6:1 to 1.5:1.

[0219] Example 27: Study of the synergistic interaction of guanidine and pyrithione (added in the form of sodium pyrithione) Calculation of synergy index of guanidine and pyrithione for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0220] [Table 27]

[0221] Table 27 shows that the optimum synergy of the guanidine and pyrithione composition, i.e., the lowest synergy index (0.70), is obtained at a ratio of 309 ppm guanidine to 85 ppm pyrithione. Synergy can be demonstrated when the weight ratio of guanidine to pyrithione ranges from 3.6:1 to 180:1.

[0222] Example 28: Study of the synergistic interaction of guanidine and o-phenylphenol (oPP) Calculation of synergy index of guanidine and oPP for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0223] [Table 28]

[0224] Table 28 shows that the optimal synergy of the guanidine and oPP composition, i.e., the lowest synergy index (0.50), is obtained at a ratio of 1545 ppm guanidine to 250 ppm oPP. Synergy can be demonstrated when the weight ratio of guanidine to oPP ranges from 0.62:1 to 49:1.

[0225] Example 29: Study of the synergistic interaction of guanidine and sorbic acid (added in the form of potassium sorbate) Calculation of synergy index of guanidine and sorbic acid for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0226] [Table 29]

[0227] Table 29 shows that the optimum synergy of the guanidine and sorbic acid composition, i.e., the lowest synergy index (0.55), is obtained at a ratio of 3090 ppm guanidine to 555 ppm sorbic acid. Synergy can be demonstrated when the weight ratio of guanidine to sorbic acid ranges from 0.1:1 to 50:1.

[0228] Example 30: Study of the synergistic interaction of guanidine and benzoic acid (added in the form of sodium benzoate) Calculation of synergy index of guanidine and benzoic acid for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0229] [Table 30]

[0230] Table 30 shows that the optimum synergy of the guanidine and benzoic acid composition, i.e., the lowest synergy index (0.63), is obtained at a ratio of 1545-4635 ppm guanidine to 840-400 ppm benzoic acid. Synergy can be demonstrated when the weight ratio of guanidine to benzoic acid is in the range of 0.25:1 to 88:1.

[0231] Example 31: Study of the synergistic interaction of guanidine and salicylic acid (added in the form of sodium salicylate) Calculation of synergy index of guanidine and salicylic acid for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0232] [Table 31]

[0233] Table 31 shows that the optimum synergistic effect of the guanidine and salicylic acid composition, i.e., the lowest synergy index (0.63), is obtained at a ratio of 1545-4635 ppm guanidine to 856-428 ppm salicylic acid. Synergistic effect can be demonstrated when the weight ratio of guanidine to salicylic acid is in the range of 0.24:1 to 43:1.

[0234] Example 32: Study of the synergistic interaction of guanidine and lactic acid (added in the form of sodium L-lactate) Calculation of synergy index of guanidine and lactic acid for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0235] [Table 32]

[0236] Table 32 shows that the optimal synergy of the guanidine and lactic acid composition, i.e., the lowest synergy index (0.63), is obtained at a ratio of 4635-6180 ppm guanidine to 3974-1987 ppm lactic acid. Synergy can be demonstrated when the weight ratio of guanidine to lactic acid is in the range of 0.03:1 to 23:1.

[0237] Example 33: Study of the synergistic interaction of guanidine and citric acid (added in the form of trisodium citrate) Calculation of synergy index of guanidine and citric acid for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0238] [Table 33]

[0239] Table 33 shows that the optimal synergy of the guanidine and citric acid composition, i.e., the lowest synergy index (0.45), is obtained at a ratio of 309 ppm guanidine to 21,983 ppm citric acid. Synergy can be demonstrated when the weight ratio of guanidine to citric acid ranges from 0.014:1 to 12:1.

[0240] Example 34: Study of the synergistic interaction of guanidine and zinc (added in the form of zinc oxide) In Example 34, the synergistic interaction of guanidine and a zinc compound (zinc oxide) with respect to microbial infestation was investigated in emulsion paints by adding specific amounts of guanidine in the form of guanidine hydrochloride and a zinc compound in the form of zinc oxide, and testing the stability against microbial infestation. The paints tested were emulsion paints based on a styrene acrylate binder (PVK 77%, pH 8.8) for indoor use, manufactured in the laboratory without the addition of conventional preservatives.

[0241] The samples were inoculated three times with a bacterial cell suspension (2% v / w) of the following composition:

[0242] Bacterial mixture A: Alcaligenes faecalis NCIMB 13145 Escherichia coli DSM 13631 Burkholderia cepacia DSM 9241 Staphylococcus aureus DSM 799 Pseudomonas aeruginosa DSM 50071 Pseudomonas putida DSM 13624

[0243] Cell suspensions of bacterial mixture A were produced by growing individual bacteria in liquid culture on a shaker at 30°C for 24 h. The growth medium used for the bacteria was Mueller-Hinton liquid medium. After growth, the individual liquid cultures were centrifuged and the cells were resuspended in saline. The mixture was then diluted to 100 ml. 9 To adjust the total cell count to 100 / ml, the individual bacterial suspensions were diluted accordingly, if necessary, before being combined with saline. The cell number of the inoculum was determined each time by chamber counting.

[0244] After each inoculation and after 7 days of incubation at 30°C, the microbial prevalence of the samples was assessed by determining the number of viable bacteria per gram of paint (colony-forming units, CFU / g). CFU / g was determined each time by taking an aliquot (1 g) from the previously homogenized sample, performing serial 10-fold dilutions in saline solution (0.9% NaCl), streaking on tryptone soy agar, and subsequently incubating the agar plates at 30°C for 48 hours.

[0245] [Table 34]

[0246] The synergistic effect of guanidine and zinc was demonstrated using outcome endpoints after 3 inoculations up to 1000 CFU / g.

[0247] [Table 35]

[0248] Table 35 shows that the optimum synergy of the guanidine and zinc composition, i.e., the lowest synergy index (0.40), is obtained at a ratio of 618 ppm guanidine to 402 ppm zinc. Synergy can be demonstrated when the weight ratio of guanidine to zinc ranges from 0.77:1 to 12:1.

[0249] In the following Examples 35-38, the synergistic interaction of guanidine and antimicrobial substances with respect to microbial infestation was studied using emulsion paints and laundry detergents or cleaning compositions by adding specific amounts of guanidine salts and isothiazolinones and examining their stability against microbial infestation:

[0250] The paint tested was an emulsion paint based on a styrene acrylate binder (PVK 77%, pH 8.8) for interior use, manufactured in the laboratory without the addition of conventional preservatives.

[0251] The laundry detergent was a preservative-free heavy-duty laundry detergent (pH 8.1) and the cleaning composition was a preservative-free all-purpose detergent (pH 7.6), each similarly prepared in the laboratory without the addition of additional conventional preservatives. procedure: To each paint, specific concentrations of guanidinium hydrochloride, benzisothiazolinone (BIT), and a mixture of chloromethylisothiazolinone (CIT) and methylisothiazolinone (MIT) were added—individually and in combination. Laundry detergents and cleaning compositions were mixed with specific concentrations of guanidinium hydrochloride and benzisothiazolinone (BIT).

[0252] The resulting batches of paint thus prepared were inoculated with a mixture of different bacterial species (bacterial mixture B); batches of laundry detergent and cleaning compositions thus prepared were inoculated with a yeast mixture.

[0253] Bacterial mixture B: Pseudomonas spp. (Pseudomonas oleovorans group) DSM 33933 Pseudomonas aeruginosa DSM 33935 Pseudomonas oleovorans DSM 33936 Pseudomonas spec. DSM 33937 Pseudomonas aeruginosa DSM 33938

[0254] Yeast mixture: Pichia manshurica DSM 12249 Rhodotorula mucilaginosa DSM 12248 Candida boidinii DSM 13622 Candida albicans DSM 1386

[0255] The inoculum was added to each sample as a fresh cell suspension in saline (0.9% NaCl) at 2% (v / w) for each inoculum. The cell count of the added inoculum was 10 for bacterial mixture A and 10 for bacterial mixture B. 9 / ml, yeast mixture 10 8 / ml and consisted of equal parts of individual bacterial or yeast strains.

[0256] Cell suspensions of the bacterial mixture were produced by growing individual bacteria in liquid culture on a shaker at 30°C for 24 hours. The growth medium used for the bacteria was Mueller-Hinton liquid medium. After growth, the individual liquid cultures were centrifuged and the cells were resuspended in saline. The mixture was then diluted to 100 ml. 9 To adjust the total cell count to 100 / ml, the individual bacterial suspensions were diluted accordingly, if necessary, before being combined with saline. The cell number of the inoculum was determined each time by chamber counting.

[0257] A cell suspension of the yeast mixture was produced by growing the yeast strains on Sabouraud dextrose agar for 48 hours at 25°C and washing off the cell lawn with saline solution (0.9% NaCl). 8 Further steps for determining cell counts / ml were performed similar to the production of bacterial suspensions.

[0258] In Examples 35-38, samples were inoculated once with the respective cell suspension (2% v / w), and bacterial (bacterial mixture B) or yeast growth was then followed by a semiquantitative evaluation method. The inoculated samples were evaluated for microbial spread on day 1 immediately after inoculation and on day 6 after an additional 5 days of incubation at 30°C (emulsion paints), or on day 3 after an additional 2 days of incubation at 30°C (laundry detergents, cleaning compositions). For this purpose, aliquots were taken from each sample after homogenization using a sterile plastic inoculation loop (10 μl) and uniformly streaked onto agar plates (tryptone soy agar for bacteria, Sabouraud dextrose agar for yeast). The streaked agar plates were then incubated at 30°C for 48 hours (bacteria) or at 25°C for 72 hours (yeast). After incubation, bacterial or yeast colonies grown on the agar plates were visually evaluated and quantified according to the following scheme:

[0259] TIFF2026505251000039.tif80149

[0260] The results of Examples 35-38 are shown in Tables 36-39:

[0261] Example 35 / Table 36: [Table 36]

[0262] As can be inferred from the results shown in Table 36, the synergistic interaction of BIT and guanidine already demonstrated under the above laboratory conditions can also be demonstrated in practical applications in emulsion paints.

[0263] Example 36 / Table 37: [Table 37]

[0264] As can be inferred from the results shown in Table 37, the synergistic interaction of MIT and guanidine already demonstrated under the above laboratory conditions can also be demonstrated in practical applications in emulsion paints.

[0265] Example 37 / Table 38: [Table 38]

[0266] As can be inferred from the results shown in Table 38, the synergistic interaction of BIT and guanidine already demonstrated under the above laboratory conditions can also be demonstrated in practical applications in heavy-duty laundry detergents.

[0267] Example 38 / Table 39: [Table 39]

[0268] As can be inferred from the results shown in Table 39, the synergistic interaction of BIT and guanidine already demonstrated under the above laboratory conditions can also be demonstrated in practical applications in heavy-duty laundry detergents.

Claims

1. (a) a salt of guanidine and / or unsubstituted guanidine, and (b) 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, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, aminomethylpropanol, aminoethylpropanediol, monoethanolamine, ethylhexylglycerol at least one further ingredient selected from the group consisting of ethanol, hexylglycerol, pentane-1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bisphosphonic acid, sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc. A composition comprising:

2. a weight ratio of guanidine and / or a salt thereof to 5-chloro-2-methylisothiazolin-3-one in the range of 62:1 to 9270:1; a weight ratio of guanidine and / or a salt thereof to 2-methyl-4-isothiazolin-3-one in the range of 10.3:1 to 773:1; a weight ratio of guanidine and / or a salt thereof to 1,2-benzisothiazolin-3-one in the range of 1.3:1 to 309:1; a weight ratio of guanidine and / or a salt thereof to N-butyl-1,2-benzisothiazolin-3-one in the range of 0.52:1 to 309:1; a weight ratio of guanidine and / or a salt thereof to N-methyl-1,2-benzisothiazolin-3-one in the range of 7.8:1 to 618:1; a weight ratio of guanidine and / or a salt thereof to N-octylisothiazolin-3-one in the range of 1.4:1 to 82:1; the weight ratio of guanidine and / or a salt thereof to bronopol is in the range of 7.8:1 to 824:1; a weight ratio of guanidine and / or a salt thereof to 2,2-dibromo-3-nitrilopropionamide in the range of 7.8:1 to 3090:1; a weight ratio of guanidine and / or a salt thereof to dibromodicyanobutane in the range of 0.78:1 to 309:1; a weight ratio of guanidine and / or a salt thereof to iodopropynyl butylcarbamate in the range of 0.83:1 to 103:1; a weight ratio of guanidine and / or a salt thereof to 2-amino-2-methyl-1-propanol in the range of 0.3:1 to 20:1; a weight ratio of guanidine and / or a salt thereof to 2-aminoethylpropane-1,3-diol in the range of 0.2:1 to 15:1; a weight ratio of guanidine and / or a salt thereof to monoethanolamine in the range of 0.2:1 to 30:1; a weight ratio of guanidine and / or a salt thereof to ethylhexylglycerol in the range of 0.5:1 to 15:1; a weight ratio of guanidine and / or a salt thereof to hexylglycerol in the range of 0.5:1 to 15:1; a weight ratio of guanidine and / or a salt thereof to pentane-1,2-diol in the range of 0.07:1 to 7.5:1; a weight ratio of guanidine and / or a salt thereof to hexane-1,2-diol in the range of 0.06:1 to 15:1; a weight ratio of guanidine and / or a salt thereof to heptane-1,2-diol in the range of 0.25:1 to 30:1; a weight ratio of guanidine and / or a salt thereof to octane-1,2-diol in the range of 0.2:1 to 6:1; a weight ratio of guanidine and / or a salt thereof to phenoxyethanol in the range of 0.13:1 to 3.6:1; a weight ratio of guanidine and / or a salt thereof to phenethyl alcohol in the range of 0.15:1 to 12:1; a weight ratio of guanidine and / or a salt thereof to phenylpropanol in the range of 0.4:1 to 6:1; the weight ratio of guanidine and / or a salt thereof to benzyl alcohol is in the range of 1:1 to 12:1; a weight ratio of guanidine and / or a salt thereof to isopropanol in the range of 0.004:1 to 3:1; the weight ratio of guanidine and / or a salt thereof to ethylenediaminetetraacetic acid is in the range of 0.6:1 to 37:1; the weight ratio of guanidine and / or its salt to (1-hydroxyethylidene)bisphosphonic acid is in the range of 0.6:1 to 1.5:1; the weight ratio of guanidine and / or its salt to sodium pyrithione is in the range of 3.6:1 to 180:1; the weight ratio of guanidine and / or its salt to zinc pyrithione is in the range of 3.6:1 to 180:1; the weight ratio of guanidine and / or a salt thereof to o-phenylphenol is in the range of 0.62:1 to 49:1; a weight ratio of guanidine and / or salts thereof to sorbic acid and / or salts thereof in the range of 0.1:1 to 50:1; a weight ratio of guanidine and / or salts thereof to benzoic acid and / or salts thereof in the range of 0.25:1 to 88:1; a weight ratio of guanidine and / or salts thereof to salicylic acid and / or salts thereof in the range of 0.24:1 to 43:1; a weight ratio of guanidine and / or salts thereof to lactic acid and / or salts thereof in the range of 0.03:1 to 23:1; a weight ratio of guanidine and / or salts thereof to citric acid and / or salts thereof in the range of 0.014:1 to 12:1; characterized in that the weight ratio of guanidine and / or its salt to zinc is in the range of 0.77:1 to 12:1; 2. The composition according to claim 1, wherein the basis for determining the weight ratio is in each case the content in relation to guanidine or further components without taking into account any counterions in the composition.

3. 3. The composition according to claim 1 or 2, characterized in that it contains guanidine and / or a salt thereof and at least one further component in a total amount ranging from 0.01% to 10%, preferably from 0.02% to 5%, more preferably from 0.03% to 3%, based on the total composition.

4. 4. The composition according to claim 1, characterized in that it contains guanidine and / or its salts in an amount ranging from 100 to 10,000 ppm, preferably in an amount ranging from 200 to 7,500 ppm, more preferably in an amount ranging from 300 to 5,000 ppm, the percentages relating to the guanidine content in the total composition.

5. When 5-chloro-2-methyl-4-isothiazolin-3-one is present as a further component, it contains it in an amount ranging from 0.5 to 200 ppm, When 2-methyl-4-isothiazolin-3-one is present as a further component, it contains it in an amount ranging from 0.5 to 200 ppm, When 1,2-benzisothiazolin-3-one is present as a further component, it contains it in an amount ranging from 1 to 500 ppm, When N-butyl-1,2-benzisothiazolin-3-one is present as a further component, it contains it in an amount ranging from 5 to 2500 ppm, When N-methyl-1,2-benzisothiazolin-3-one is present as a further component, it contains it in an amount ranging from 1 to 500 ppm, When octylisothiazolinone is present as a further component, it contains it in an amount ranging from 1 to 2500 ppm; When bronopol is present as a further component, it is contained in an amount ranging from 1 to 1000 ppm, When dibromonitrilopropionamide is present as a further component, it contains it in an amount ranging from 1 to 1000 ppm; When dibromodicyanobutane is present as a further component, it contains it in an amount ranging from 1 to 1000 ppm; When iodopropynyl butylcarbamate is present as a further component, it contains it in an amount ranging from 10 to 5000 ppm; When aminomethylpropanol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When aminoethylpropanediol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When monoethanolamine is present as a further component, it contains it in an amount of 25 to 7500 ppm, When ethylhexylglycerol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm; When hexylglycerol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm; When pentane-1,2-diol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When hexane-1,2-diol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When heptane-1,2-diol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When octane-1,2-diol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When phenoxyethanol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm; When phenethyl alcohol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm; When phenylpropanol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When benzyl alcohol is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When isopropanol is present as a further component, it contains it in an amount ranging from 10 to 30,000 ppm, When ethylenediaminetetraacetic acid is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm; When (1-hydroxyethylidene)bisphosphonic acid is present as a further component, it contains it in an amount ranging from 10 to 10,000 ppm, When sodium pyrithione is present as a further component, it is contained in an amount ranging from 1 to 2500 ppm; When zinc pyrithione is present as a further component, it is contained in an amount ranging from 1 to 2500 ppm; When o-phenylphenol is present as a further component, it contains it in an amount ranging from 1 to 10,000 ppm, When sorbic acid is present as a further component, it contains it in an amount ranging from 1 to 10,000 ppm, When benzoic acid is present as a further component, it contains it in an amount ranging from 1 to 10,000 ppm, When salicylic acid is present as a further component, it contains it in an amount ranging from 1 to 10,000 ppm, When lactic acid is present as a further component, it contains it in an amount ranging from 1 to 50,000 ppm, When citric acid is present as a further component, it contains it in an amount ranging from 1 to 100,000 ppm, When zinc is present as a further component, it is contained in an amount ranging from 10 to 5000 ppm. The composition according to any one of claims 1 to 4, characterized in that

6. Composition according to any one of claims 1 to 5, characterized in that it has a water content of more than 1% by weight.

7. A composition according to any one of claims 1 to 6, characterized in that it has a pH ranging from pH 3.5 to pH 12.

8. The composition according to any one of claims 1 to 7, characterized in that it contains guanidine hydrochloride and / or guanidine carbonate as the guanidine salt.

9. 10. The composition according to any one of claims 1 to 9, characterized in that it is an industrial product selected from the group consisting of lignosulfonate and starch formulations in paints, pigments, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, chalk slurries, ore slurries, ceramic compounds, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and pigment dispersions, inks, lithography fluids, thickeners, cosmetics, toiletries, water cycles, wood processing fluids, petroleum production fluids, paper processing fluids, leather manufacturing fluids, textile manufacturing fluids, drilling and cutting oils, hydraulic oils, cooling lubricants and biocidal products.

10. Use of a composition according to any one of claims 1 to 8 for in-can storage.

11. 9. Use of a composition according to any one of claims 1 to 8 for the preservation of industrial products selected from the group consisting of lignosulfonate and starch formulations in paints, pigments, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, chalk slurries, ore slurries, ceramic compounds, adhesives, fragrances, casein containing products, starch containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and pigment dispersions, inks, lithography fluids, thickeners, cosmetics, toiletries, water cycles, wood working fluids, petroleum production fluids, paper working fluids, leather manufacturing fluids, textile manufacturing fluids, drilling and cutting oils, hydraulic oils and cooling lubricants.

12. (b) 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, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, aminomethylpropanol, aminoethylpropanediol, monoethanolamine, ethylhexylglycerol, hexylglycerol, pentane- 1. (a) Use of a salt of guanidine and / or unsubstituted guanidine to improve the antibacterial efficacy of one or more compounds selected from the group consisting of 1,2-diol, hexane-1,2-diol, heptane-1,2-diol, octane-1,2-diol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bisphosphonic acid, sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc.

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