Synergistic compositions containing guanidines

Abstract

The present invention relates to a composition containing (a) a guanidine and / or an unsubstituted guanidine salt, and (b) at least one further component selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1, 2-benzisothiazolin-3-one, N-butyl-1, 2-benzisothiazolin-3-one, N-methyl-1, 2-benzisothiazolin-3-one, N-methyl-1, 2-benzisothiazolin-3-one, N-methyl-1, 2-benzisothiazolin-3-one, N-methyl-1, 2-benzisothiazolin-3-one, N-methyl-1, 2-benzisothiazolin-3-one, N-methyl-1, 2-benzisothiazolin-3-one, N-methyl-1, 2-benzisothiazolin-3-one, N-methyl-1, the cleaning agent is prepared from 2-benzisothiazolin-3-one, octyl isothiazolinone, bronopol, dibromo-nitrilopropionamide, dibromo-dicyanobutane, butyl carbamic acid iodopropynyl ester, aminomethyl propanol, aminoethyl propylene glycol, monoethanolamine, ethylhexylglycerin, hexylglycerin, 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-heptanediol, 1, 2-octylene glycol, phenoxy ethanol and phenethyl alcohol. The cleaning agent is prepared from phenyl propanol, benzyl alcohol, isopropanol, ethylenediamine tetraacetic acid, (1-hydroxyethylidene) diphosphonic acid, 2-mercaptopyridine sodium oxide, 2-mercaptopyridine zinc oxide, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid and zinc. The invention also relates to an industrial product containing components (a) and (b), and to the use of said composition for the preservation of containers and for the preservation of industrial products. The invention also relates to the use of (a) a guanidine and / or an unsubstituted guanidine salt for improving the antimicrobial efficacy of one or more compounds selected from the group (b) described above.

Description

[0001] The present invention relates to a composition comprising: (a) guanidine and / or a salt of unsubstituted guanidine; and (b) at least one other component selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, butyl The present invention also relates to industrial products containing components (a) and (b), and to the use of the composition for can preservation and for the preservation of industrial products. The present invention also relates to the use of (a) guanidine and / or a salt of unsubstituted guanidine to improve the antimicrobial efficacy of one or more compounds selected from group (b) above.

[0002] Industrial products, particularly water-based ones such as paints, varnishes, emulsions, detergents and cleaning compositions, and cosmetics, are often 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 can have high microbial counts even on the first day after production.

[0003] In order to ensure that these products and, if appropriate, all components in production, meet hygiene requirements and thus ensure the shelf life of the industrial products, so-called biocides are usually added to the products or directly to their components.

[0004] One class of biocides used for the corrosion protection of water-based industrial products such as paints, plasters, washing and cleaning compositions, glazes, or their components is the so-called 3-isothiazolin-3-one compounds. This substance class includes compounds with high antimicrobial activity that have somewhat different modes of action. In this context, synergistic combinations of different 3-isothiazolin-3-one compounds are often used to reduce the amount of biocide used. For example, WO 99 / 08530 A1 proposes the combined use of methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one.

[0005] EP-B 1 030 558 also discloses synergistic biocide compositions containing 2-methylisothiazolin-3-one and 3-iodo-2-propynyl N-butylcarbamate. Such synergistic compositions are suitable for controlling microorganisms even at low concentrations.

[0006] Another type of biocide is the so-called alkylguanidinium salts and polyguanidinium salts. For example, it is known from "Directory of microbicides for protection of materials", Springer 2005, pp. 726 to 731 that medium-chain and long-chain guanidines and biguanides have an antimicrobial effect, such as cocoylpropylenediamine-1,5-biguanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylenebiguanide) hydrochloride, bis(4'-chlorophenylbiguanidino)hexane, chlorhexidine gluconate, chlorhexidine diacetate.

[0007] It is also known to use such medium-chain and long-chain guanidine compounds together with other antimicrobial and / or antifungal active substances. For example, known examples are combinations with 3-iodo-2-propynyl butylcarbamate or formaldehyde reservoirs. For example, EP 0 891 710 A1 teaches the combined use of dodecylguanidine hydrochloride and IPBC. However, problems have been found with the use of dodecylguanidine salts for corrosion protection of paint compositions and polymer dispersions; for example, incompatibilities in the form of aggregates have been observed when these salts are added.

[0008] In light of the above prior art, there exists a need for other compositions whose components interact synergistically so that when used together, the concentrations of the components are lower than would be necessary if the individual components were used individually.

[0009] The present invention achieves this object by a composition, preferably an aqueous composition, comprising:

[0010] (a) guanidine and / or a salt of unsubstituted guanidine, and

[0011] (b) at least one other component selected from the group consisting of 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), aminoethylpropylene glycol (AEPD), monoethanolamine (MEA), ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenylethyl alcohol, phenylpropanol, benzyl alcohol, isopropyl alcohol, 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.

[0012] The advantage of the composition of the present invention is that guanidine or a salt thereof as component (a) is hitherto not known to have antimicrobial activity, and said component (a) and at least one further component selected from the above group (b) interact synergistically and can therefore be used simultaneously in lower concentrations than when these components are used individually.

[0013] In the present invention, "at least one other component" means that the composition contains a single component or compound selected from this group, or contains a plurality of components or compounds selected from this group, ie, two, three, four, five or more components or compounds selected from this group.

[0014] The amounts of the respective components (a) and (b) and the weight ratios between the components (a) and (b) are specified herein. These amounts represent the predominant structure of guanidine or the predominant structure of component (b), respectively. The specified weight ratios are also determined in each case based on the guanidine content in the composition without taking into account any counterions and based on the content of the predominant structure of the other component (b) without taking into account any counterions.

[0015] For the purposes of the present invention, guanidine and / or a salt of unsubstituted guanidine means a composition containing guanidine and / or one or more salts of, optionally unsubstituted guanidine as active ingredient (a). Guanidine is a compound represented by the following formula:

[0016] .

[0017] In the present invention, the unsubstituted guanidine salt or guanidinium salt is a guanidine or guanidinium salt represented by the following general formula:

[0018]

[0019] wherein n is 1, 2 or 3, and the counterion X n- Examples are chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, formate, acetate or citrate.

[0020] In a preferred embodiment of the present invention, the composition according to the present invention contains guanidine hydrochloride and / or guanidine carbonate as component (a); in a particularly preferred embodiment of the present invention, the composition according to the present invention contains guanidine carbonate as component (a).

[0021] In the preferred aqueous compositions of the present invention, the amount of guanidine and / or its salts present as component (a) can vary within wide ranges and is 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, wherein the stated ratios relate to the guanidine content in the entire aqueous composition.

[0022] In the preferred aqueous composition of the present invention, the amounts of components (a) and (b) present may vary within wide limits. In one embodiment, the composition is characterized in that it contains guanidine and / or its salt and at least one other component in a total content of 0.01% to 10%, preferably 0.02% to 5%, more preferably 0.03% to 3%, based on the entire composition.

[0023] In the preferred aqueous compositions of the present invention, the water content may vary within a wide range. Typically, the composition is characterized by having a water content greater than 1% by weight, preferably greater than 10% by weight, more preferably greater than 20% by weight, based on the total composition.

[0024] The pH of the aqueous composition may vary within a wide range and is generally in the range of pH 4.5 to pH 12, preferably pH 5.0 to pH 11.5, more preferably pH 5.5 to pH 11. The pH can be adjusted to the specified range by means well known to those skilled in the art.

[0025] The preferred weight ratios between component (a) and component (b) can be varied individually, and it can be seen from the examples that surprisingly good antimicrobial effects can be achieved at these ratios.

[0026] Synergistic combination containing guanidine and 5-chloro-2-methylisothiazolin-3-one (CIT):

[0027] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and comprising 5-chloro-2-methylisothiazolin-3-one.

[0028] In a preferred embodiment, the present invention relates to a composition containing guanidine and / or its salts and 5-chloro-2-methylisothiazolin-3-one, wherein the weight ratio of guanidine and / or its salts to 5-chloro-2-methylisothiazolin-3-one is in the range of 62:1 to 9270:1, preferably 62:1 to 500:1, more preferably 62:1 to 300:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the content of 5-chloro-2-methylisothiazolin-3-one.

[0029] Synergistic composition containing guanidine and 2-methylisothiazolin-3-one (MIT):

[0030] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and 2-methylisothiazolin-3-one.

[0031] In a preferred embodiment, the present invention relates to a composition containing guanidine and / or its salts and 2-methylisothiazolin-3-one, wherein the weight ratio of guanidine to 2-methylisothiazolin-3-one is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the content of 2-methylisothiazolin-3-one.

[0032] Synergistic combination containing guanidine and 1,2-benzisothiazolin-3-one (BIT):

[0033] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and 1,2-benzisothiazolin-3-one.

[0034] In a preferred embodiment, the present invention relates to a composition containing guanidine and / or its salts and 1,2-benzisothiazolin-3-one, wherein the weight ratio of guanidine to 1,2-benzisothiazolin-3-one is generally in the range of 1.3:1 to 309:1, preferably in the range of 1.3:1 to 200:1, more preferably in the range of 1.3:1 to 100:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the content of 1,2-benzisothiazolin-3-one.

[0035] Synergistic combination containing guanidine and N-butyl-1,2-benzisothiazolin-3-one (BBIT):

[0036] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and N-butyl-1,2-benzisothiazolin-3-one.

[0037] In a preferred embodiment, the present invention relates to a composition containing guanidine and / or its salts and N-butyl-1,2-benzisothiazolin-3-one, wherein the weight ratio of guanidine to N-butyl-1,2-benzisothiazolin-3-one is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the content of N-butyl-1,2-benzisothiazolin-3-one.

[0038] Synergistic combination containing guanidine and N-methyl-1,2-benzisothiazolin-3-one (MBIT):

[0039] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and N-methyl-1,2-benzisothiazolin-3-one.

[0040] In a preferred embodiment, the present invention relates to a composition containing guanidine and N-methyl-1,2-benzisothiazolin-3-one, wherein the weight ratio of guanidine to N-methyl-1,2-benzisothiazolin-3-one is generally in the range of 7.8:1 to 618:1, preferably in the range of 7.8:1 to 400:1, more preferably in the range of 7.8:1 to 300:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the content of N-methyl-1,2-benzisothiazolin-3-one.

[0041] Synergistic combination containing guanidine and N-octylisothiazolin-3-one:

[0042] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and N-octylisothiazolin-3-one.

[0043] In a preferred embodiment, the present invention relates to a composition containing guanidine and N-octylisothiazolin-3-one, wherein the weight ratio of guanidine to N-octylisothiazolin-3-one is generally in the range from 1.4:1 to 82:1, preferably in the range from 1.4:1 to 50:1, the basis for determining the weight ratio in each case being the guanidine content in the composition without taking into account any counterions, and the content of N-octylisothiazolin-3-one.

[0044] Synergistic combination containing guanidine and bronopol:

[0045] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and bronopol.

[0046] In a preferred embodiment, the present invention relates to a composition comprising guanidine and bronopol, wherein the weight ratio of guanidine to bronopol is generally in the range of 7.8:1 to 824:1, preferably in the range of 7.8:1 to 200:1, more preferably in the range of 7.8:1 to 100:1, wherein the weight ratio is determined in each case based on the guanidine content in the composition without taking into account any counterions, and the bronopol content.

[0047] Synergistic combination containing guanidine and 2,2-dibromo-3-nitrilopropionamide:

[0048] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and 2,2-dibromo-3-nitrilopropionamide.

[0049] In a preferred embodiment, the present invention relates to a composition containing guanidine and 2,2-dibromo-3-nitrilopropionamide, wherein the weight ratio of guanidine to 2,2-dibromo-3-nitrilopropionamide is generally in the range of 7.8:1 to 3090:1, preferably in the range of 7.8:1 to 250:1, more preferably in the range of 7.8:1 to 100:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the content of 2,2-dibromo-3-nitrilopropionamide.

[0050] Synergistic compositions containing guanidine and dibromodicyanobutane (DBDCB):

[0051] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and dibromodicyanobutane.

[0052] In a preferred embodiment, the present invention relates to a composition containing guanidine and dibromodicyanobutane, wherein the weight ratio of guanidine to dibromodicyanobutane is generally in the range from 0.78:1 to 309:1, preferably in the range from 0.8:1 to 200:1, more preferably in the range from 0.8:1 to 100:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the dibromodicyanobutane content.

[0053] Synergistic composition containing guanidine and iodopropynyl butylcarbamate (IPBC):

[0054] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and iodopropynyl butylcarbamate.

[0055] In a preferred embodiment, the present invention relates to a composition containing guanidine and iodopropynyl butylcarbamate, wherein the weight ratio of guanidine to iodopropynyl butylcarbamate is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the content of iodopropynyl butylcarbamate.

[0056] Synergistic combination containing guanidine and 2-amino-2-methyl-1-propanol (AMP):

[0057] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and 2-amino-2-methyl-1-propanol.

[0058] In a preferred embodiment, the present invention relates to a composition containing guanidine and 2-amino-2-methyl-1-propanol, wherein the weight ratio of guanidine to 2-amino-2-methyl-1-propanol is generally in the range of 0.3:1 to 20:1, preferably in the range of 0.5:1 to 15:1, more preferably in the range of 1:1 to 10:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the content of 2-amino-2-methyl-1-propanol.

[0059] Synergistic composition containing guanidine and 2-aminoethyl-1,3-propanediol (AEPD):

[0060] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and 2-aminoethyl-1,3-propanediol.

[0061] In a preferred embodiment, the present invention relates to a composition containing guanidine and 2-aminoethyl-1,3-propanediol, wherein the weight ratio of guanidine to 2-aminoethyl-1,3-propanediol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the content of 2-aminoethyl-1,3-propanediol.

[0062] Synergistic composition containing guanidine and monoethanolamine (MEA):

[0063] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and monoethanolamine.

[0064] In a preferred embodiment, the present invention relates to a composition comprising guanidine and monoethanolamine, wherein the weight ratio of guanidine to monoethanolamine is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the monoethanolamine content.

[0065] Contains a synergistic combination of guanidine and ethylhexylglycerin:

[0066] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and ethylhexylglycerin.

[0067] In a preferred embodiment, the present invention relates to a composition comprising guanidine and ethylhexylglycerol, wherein the weight ratio of guanidine to ethylhexylglycerol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the content of monoethanolamine.

[0068] Contains a synergistic combination of guanidine and hexylglycerin:

[0069] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and hexylglycerol.

[0070] In a preferred embodiment, the present invention relates to a composition comprising guanidine and hexylglycerol, wherein the weight ratio of guanidine to hexylglycerol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the hexylglycerol content.

[0071] Synergistic combination containing guanidine and 1,2-pentanediol:

[0072] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and 1,2-pentanediol.

[0073] In a preferred embodiment, the present invention relates to a composition containing guanidine and 1,2-pentanediol, wherein the weight ratio of guanidine to 1,2-pentanediol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the 1,2-pentanediol content.

[0074] Synergistic composition containing guanidine and 1,2-hexanediol:

[0075] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and 1,2-hexanediol.

[0076] In a preferred embodiment, the present invention relates to a composition containing guanidine and 1,2-hexanediol, wherein the weight ratio of guanidine to 1,2-hexanediol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the 1,2-hexanediol content.

[0077] Synergistic combination containing guanidine and 1,2-heptanediol:

[0078] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and 1,2-heptanediol.

[0079] In a preferred embodiment, the present invention relates to a composition containing guanidine and 1,2-heptanediol, wherein the weight ratio of guanidine to 1,2-heptanediol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the 1,2-heptanediol content.

[0080] Contains a synergistic combination of guanidine and 1,2-octanediol:

[0081] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and 1,2-octanediol.

[0082] In a preferred embodiment, the present invention relates to a composition containing guanidine and 1,2-octanediol, wherein the weight ratio of guanidine to 1,2-octanediol is generally in the range from 0.2:1 to 6:1, preferably in the range from 0.5:1 to 6:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the 1,2-octanediol content.

[0083] Contains a synergistic combination of guanidine and phenoxyethanol:

[0084] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and phenoxyethanol.

[0085] In a preferred embodiment, the present invention relates to a composition comprising guanidine and phenoxyethanol, wherein the weight ratio of guanidine to phenoxyethanol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the phenoxyethanol content.

[0086] Synergistic combination containing guanidine and phenylethanol:

[0087] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and phenylethanol.

[0088] In a preferred embodiment, the present invention relates to a composition comprising guanidine and phenethyl alcohol, wherein the weight ratio of guanidine to phenethyl alcohol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the phenoxyethanol content.

[0089] Synergistic combination containing guanidine and phenylpropanol:

[0090] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and phenylpropanol.

[0091] In a preferred embodiment, the present invention relates to a composition comprising guanidine and phenylpropanol, wherein the weight ratio of guanidine to phenylpropanol is generally in the range of 0.4:1 to 6:1, preferably in the range of 0.5:1 to 6:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the content of phenoxyethanol.

[0092] Synergistic combination containing guanidine and benzyl alcohol:

[0093] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and benzyl alcohol.

[0094] In a preferred embodiment, the present invention relates to a composition containing guanidine and benzyl alcohol, wherein the weight ratio of guanidine to benzyl alcohol is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the benzyl alcohol content.

[0095] Synergistic composition containing guanidine and isopropyl alcohol:

[0096] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and isopropyl alcohol.

[0097] In a preferred embodiment, the present invention relates to a composition comprising guanidine and isopropanol, wherein the weight ratio of guanidine to isopropanol is generally in the range of 0.004:1 to 3:1, preferably in the range of 0.01:1 to 3:1, more preferably 0.1 to 3:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the isopropanol content.

[0098] Synergistic composition containing guanidine and ethylenediaminetetraacetic acid (EDTA):

[0099] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and ethylenediaminetetraacetic acid and / or its salts.

[0100] In a preferred embodiment, the present invention relates to a composition comprising guanidine and ethylenediaminetetraacetic acid, wherein the weight ratio of guanidine to ethylenediaminetetraacetic acid is generally in the range of 0.6:1 to 37:1, preferably in the range of 0.6:1 to 20:1, more preferably 0.6:1 to 15:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the content of ethylenediaminetetraacetic acid.

[0101] Synergistic compositions containing guanidine and (1-hydroxyethylidene)bisphosphonic acid (HEDP):

[0102] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and (1-hydroxyethylene)bisphosphonic acid and / or its salts.

[0103] In a preferred embodiment, the present invention relates to a composition comprising guanidine and (1-hydroxyethylene)bisphosphonic acid, wherein the weight ratio of guanidine to (1-hydroxyethylene)bisphosphonic acid is generally in the range from 0.6:1 to 1.5:1, preferably in the range from 0.6:1 to 1:1, the weight ratio being determined in each case based on the guanidine content in the composition without taking into account any counterions, and the content of (1-hydroxyethylene)bisphosphonic acid.

[0104] Synergistic composition containing guanidine and sodium 2-pyrithione:

[0105] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and sodium pyrithione.

[0106] In a preferred embodiment, the present invention relates to a composition comprising guanidine and sodium pyrithione, wherein the weight ratio of guanidine to sodium pyrithione is generally in the range of 3.6:1 to 180:1, preferably in the range of 3.6:1 to 100:1, more preferably 3.6:1 to 50:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the sodium pyrithione content.

[0107] Synergistic combination containing guanidine and zinc pyrithione:

[0108] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and zinc pyrithione.

[0109] In a preferred embodiment, the present invention relates to a composition comprising guanidine and zinc pyrithione, wherein the weight ratio of guanidine to zinc pyrithione is generally in the range of 3.6:1 to 180:1, preferably in the range of 3.6:1 to 100:1, more preferably 3.6:1 to 50:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the zinc pyrithione content.

[0110] Synergistic compositions containing guanidine and o-phenylphenol (oPP):

[0111] In one embodiment, the present invention is directed to a composition comprising guanidine and / or its salts and o-phenylphenol.

[0112] In a preferred embodiment, the present invention relates to a composition containing guanidine and o-phenylphenol, wherein the weight ratio of guanidine to o-phenylphenol is generally in the range of 0.62:1 to 49:1, preferably in the range of 0.62:1 to 40:1, more preferably 0.62:1 to 30:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the o-phenylphenol content.

[0113] Synergistic combination containing guanidine and sorbic acid:

[0114] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and comprising sorbic acid and / or its salts.

[0115] In a preferred embodiment, the present invention relates to a composition comprising guanidine and sorbic acid, wherein the weight ratio of guanidine to sorbic acid is generally in the range from 0.1:1 to 50:1, preferably in the range from 0.25:1 to 40:1, more preferably from 0.25:1 to 30:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the sorbic acid content.

[0116] Synergistic combination containing guanidine and benzoic acid:

[0117] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and comprising benzoic acid and / or its salts.

[0118] In a preferred embodiment, the present invention relates to a composition comprising guanidine and benzoic acid, wherein the weight ratio of guanidine to benzoic acid is generally in the range of 0.25:1 to 88:1, preferably in the range of 0.25:1 to 50:1, more preferably in the range of 0.25:1 to 30:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the benzoic acid content.

[0119] Contains a synergistic combination of guanidine and salicylic acid:

[0120] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and comprising salicylic acid and / or its salts.

[0121] In a preferred embodiment, the present invention relates to a composition comprising guanidine and salicylic acid, wherein the weight ratio of guanidine to salicylic acid is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the salicylic acid content.

[0122] Synergistic combination containing guanidine and lactic acid:

[0123] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and comprising lactic acid and / or its salts.

[0124] In a preferred embodiment, the present invention relates to a composition comprising guanidine and lactic acid, wherein the weight ratio of guanidine to lactic acid is 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 in each case is the guanidine content in the composition without taking into account any counterions, and the lactic acid content.

[0125] Synergistic combination containing guanidine and citric acid:

[0126] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and comprising citric acid and / or its salts.

[0127] In a preferred embodiment, the present invention relates to a composition containing guanidine and citric acid, wherein the weight ratio of guanidine to citric acid is in the range from 1:0.014 to 12:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the citric acid content.

[0128] Synergistic combination containing guanidine and zinc:

[0129] In one embodiment, the present invention relates to a composition comprising guanidine and / or its salts and zinc. In the present invention, the zinc is provided by at least one zinc compound, which serves 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 carboxylates. 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. Most preferably, the zinc is provided by zinc oxide or introduced into the composition.

[0130] In a preferred embodiment, the present invention relates to a composition containing guanidine and zinc, wherein the weight ratio of guanidine to zinc is in the range from 0.77:1 to 12:1, preferably from 1:1 to 12:1, wherein the basis for determining the weight ratio in each case is the guanidine content in the composition without taking into account any counterions, and the content of zinc ions.

[0131] In a preferred embodiment of the present invention, the composition according to the invention is characterized in that:

[0132] The weight ratio of guanidine and / or its salt to 5-chloro-2-methylisothiazolin-3-one is in the range of 62:1 to 9270:1,

[0133] The weight ratio of guanidine and / or its salt to 2-methyl-4-isothiazolin-3-one is in the range of 10.3:1 to 773:1,

[0134] The weight ratio of guanidine and / or its salt to 1,2-benzisothiazolin-3-one is in the range of 1.3:1 to 309:1,

[0135] The weight ratio of guanidine and / or its salt to N-butyl-1,2-benzisothiazolin-3-one is in the range of 0.52:1 to 309:1,

[0136] The weight ratio of guanidine and / or its salt to N-methyl-1,2-benzisothiazolin-3-one is in the range of 7.8:1 to 618:1,

[0137] The weight ratio of guanidine and / or its salt to N-octylisothiazolin-3-one is in the range of 1.4:1 to 82:1,

[0138] The weight ratio of guanidine and / or its salt to bronopol is in the range of 7.8:1 to 824:1,

[0139] The weight ratio of guanidine and / or its salt to 2,2-dibromo-3-nitrilopropionamide is in the range of 7.8:1 to 3090:1,

[0140] The weight ratio of guanidine and / or its salt to dibromodicyanobutane is in the range of 0.78:1 to 309:1,

[0141] The weight ratio of guanidine and / or its salt to iodopropynyl butylcarbamate is in the range of 0.83:1 to 103:1,

[0142] The weight ratio of guanidine and / or its salt to 2-amino-2-methyl-1-propanol is in the range of 0.3:1 to 20:1,

[0143] The weight ratio of guanidine and / or its salt to 2-aminoethyl-1,3-propanediol is in the range of 0.2:1 to 15:1,

[0144] The weight ratio of guanidine and / or its salt to monoethanolamine is in the range of 0.2:1 to 30:1,

[0145] The weight ratio of guanidine and / or its salt to ethylhexylglycerin is in the range of 0.5:1 to 15:1,

[0146] The weight ratio of guanidine and / or its salt to hexylglycerol is in the range of 0.5:1 to 15:1, preferably in the range of 0.5:1 to 10:1,

[0147] The weight ratio of guanidine and / or its salt to 1,2-pentanediol is in the range of 0.07:1 to 7.5:1,

[0148] The weight ratio of guanidine and / or its salt to 1,2-hexanediol is in the range of 0.06:1 to 15:1,

[0149] The weight ratio of guanidine and / or its salt to 1,2-heptanediol is in the range of 0.25:1 to 30:1,

[0150] The weight ratio of guanidine and / or its salt to 1,2-octanediol is in the range of 0.2:1 to 6:1,

[0151] The weight ratio of guanidine and / or its salt to phenoxyethanol is in the range of 0.13:1 to 3.6:1,

[0152] The weight ratio of guanidine and / or its salt to phenylethanol is in the range of 0.15:1 to 12:1,

[0153] The weight ratio of guanidine and / or its salt to phenylpropanol is in the range of 0.4:1 to 6:1,

[0154] The weight ratio of guanidine and / or its salt to benzyl alcohol is in the range of 1:1 to 12:1,

[0155] The weight ratio of guanidine and / or its salt to isopropyl alcohol is in the range of 0.004:1 to 3:1,

[0156] The weight ratio of guanidine and / or its salt to ethylenediaminetetraacetic acid is in the range of 0.6:1 to 37:1,

[0157] The weight ratio of guanidine and / or its salt to (1-hydroxyethylene)bisphosphonic acid is in the range of 0.6:1 to 1.5:1,

[0158] The weight ratio of guanidine and / or its salt to sodium 2-pyrithione is in the range of 3.6:1 to 180:1,

[0159] The weight ratio of guanidine and / or its salt to zinc pyrithione is in the range of 3.6:1 to 180:1,

[0160] The weight ratio of guanidine and / or its salt to o-phenylphenol is in the range of 0.62:1 to 49:1,

[0161] The weight ratio of guanidine and / or its salt to sorbic acid and / or its salt is in the range of 0.1:1 to 50:1,

[0162] The weight ratio of guanidine and / or its salt to benzoic acid and / or its salt is in the range of 0.25:1 to 88:1,

[0163] The weight ratio of guanidine and / or its salt to salicylic acid and / or its salt is in the range of 0.24:1 to 43:1,

[0164] The weight ratio of guanidine and / or its salt to lactic acid and / or its salt is in the range of 0.03:1 to 23:1,

[0165] The weight ratio of guanidine and / or its salt to citric acid and / or its salt is in the range of 0.014:1 to 12:1,

[0166] The weight ratio of guanidine and / or its salt to zinc is in the range of 0.77:1 to 12:1,

[0167] The basis for determining the weight ratios in each case is the guanidine content in the composition without taking into account any counterions.

[0168] In one embodiment of the invention, the aqueous composition is characterized in that it is an industrial product selected from the group consisting of lignin sulfonate and starch preparations in paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, chalk slurries, mineral slurries, ceramic composites, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and pigment dispersions, inks, lithographic fluids, thickeners, cosmetics, sanitary products, water circuits, woodworking fluids, oil production fluids, paper processing fluids, leather production fluids, textile production fluids, drilling and cutting oils, hydraulic fluids, cooling lubricants and biocidal products.

[0169] The content (use concentration) of components (a) and (b) in the above-mentioned industrial products can vary within wide limits depending on the intended use and is generally determined by a person skilled in the art of biocides. The concentration ranges specified below provide the person skilled in the art with an indication of the amount to be used in each case:

[0170] The amount of guanidine and / or its salts present as component (a) in the technical product can vary within wide ranges and is generally in the range from 100 to 10,000 ppm, preferably in the range from 200 to 7,500 ppm, more preferably in the range from 300 to 5,000 ppm, wherein the stated ratios relate to the guanidine content in the overall technical product.

[0171] Similarly, the amount of component (b) present in the industrial product may vary within wide limits:

[0172] When 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) is present as component (b) in an aqueous composition or industrial product, the amount of the substance present is generally in the range of 0.5 to 200 ppm, preferably 5 to 100 ppm, more preferably 10 to 50 ppm, and especially preferably 15 to 30 ppm.

[0173] When 2-methyl-4-isothiazolin-3-one (MIT) is present as component (b) in an aqueous composition or industrial product, the amount of the substance present is generally in the range of 0.5 to 200 ppm, preferably 1 to 150 ppm, more preferably 5 to 125 ppm, and particularly preferably 10 to 100 ppm.

[0174] When 1,2-benzisothiazolin-3-one (BIT) is present as component (b) in an aqueous composition or industrial product, the substance is generally present in an amount ranging from 1 to 500 ppm, preferably from 5 to 500 ppm, more preferably from 10 to 500 ppm.

[0175] When N-butyl-1,2-benzisothiazolin-3-one (BBIT) is present as component (b) in an aqueous composition or industrial product, the amount of the substance present is generally in the range of 5 to 2500 ppm, preferably 10 to 2000 ppm, more preferably 10 to 1500 ppm.

[0176] When N-methyl-1,2-benzisothiazolin-3-one (MBIT) is present as component (b) in an aqueous composition or industrial product, the amount of the substance present is generally in the range of 1 to 500 ppm, preferably 5 to 500 ppm, more preferably 10 to 1000 ppm.

[0177] When octylisothiazolinone (OIT) is present as component (b) in the aqueous composition or industrial product, the amount of the substance present is generally in the range of 1 to 2500 ppm, preferably 5 to 2000 ppm, more preferably 10 to 1500 ppm.

[0178] When bronopol is present as component (b) in an aqueous composition or industrial product, the substance 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.

[0179] When dibromonitrilopropionamide (DBNPA) is present as component (b) in an aqueous composition or industrial product, the substance 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.

[0180] When dibromodicyanobutane (DBDCB) is present as an additional component in products preserved with the compositions of the present invention, 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.

[0181] When iodopropynyl butylcarbamate (IPBC) is present as component (b) in an aqueous composition or industrial product, the substance is generally present in an amount ranging from 10 to 5000 ppm, preferably from 25 to 4500 ppm, more preferably from 50 to 4000 ppm.

[0182] When aminomethylpropanol (AMP) is present as component (b) in the aqueous composition or industrial product, the amount of the substance present is generally in the range of 10 to 10,000 ppm, preferably 25 to 7,500 ppm, more preferably 50 to 5,000 ppm.

[0183] When aminoethylpropylene glycol (AEPD) is present as component (b) in the aqueous composition or industrial product, the amount of this material present is generally in the range of 10 to 10,000 ppm, preferably 25 to 7,500 ppm, more preferably 50 to 5,000 ppm.

[0184] When monoethanolamine (MEA) is present as component (b) in the aqueous composition or industrial product, the amount of this substance present is generally in the range of 10 to 10,000 ppm, preferably 25 to 7,500 ppm, more preferably 50 to 5,000 ppm.

[0185] When ethylhexylglycerin is present as component (b) in an aqueous composition or industrial product, 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.

[0186] When hexylglycerol is present as component (b) in an aqueous composition or industrial product, 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.

[0187] When 1,2-pentanediol is present as component (b) in an aqueous composition or industrial product, the substance 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.

[0188] When 1,2-hexanediol is present as component (b) in an aqueous composition or industrial product, the substance 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.

[0189] When 1,2-heptanediol is present as component (b) in the aqueous composition or industrial product, the substance 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.

[0190] When 1,2-octanediol is present as component (b) in an aqueous composition or industrial product, the substance 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.

[0191] When phenoxyethanol is present as component (b) in an aqueous composition or industrial product, the amount of this material present is generally in the range of 10 to 10,000 ppm, preferably 50 to 7,500 ppm, more preferably 100 to 5,000 ppm.

[0192] When phenylethanol is present as component (b) in an aqueous composition or industrial product, the substance 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.

[0193] When phenylpropanol is present as component (b) in the aqueous composition or industrial product, the substance 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.

[0194] When benzyl alcohol is present as component (b) in an aqueous composition or industrial product, the substance 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.

[0195] When isopropyl alcohol is present as component (b) in the aqueous composition or industrial product, the amount of this substance present is generally in the range of 10 to 30,000 ppm, preferably 50 to 20,000 ppm, more preferably 100 to 15,000 ppm.

[0196] When ethylenediaminetetraacetic acid (EDTA) is present as component (b) in aqueous compositions or industrial products, or preserved products, the amount of the substance present is generally in the range of 10 to 10,000 ppm, preferably 50 to 7,500 ppm, more preferably 100 to 5,000 ppm.

[0197] When (1-hydroxyethylene)bisphosphonic acid (HEDP) is present as component (b) in the aqueous composition or industrial product, the amount of this substance present is generally in the range of 10 to 10,000 ppm, preferably 50 to 7,500 ppm, more preferably 100 to 5,000 ppm.

[0198] When sodium pyrithione is present as component (b) in an aqueous composition or industrial product, the substance 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.

[0199] When zinc pyrithione is present as component (b) in an aqueous composition or industrial product, the material 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.

[0200] When o-phenylphenol is present as component (b) in an aqueous composition or industrial product, the substance 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 particularly preferably from 50 to 1,500 ppm.

[0201] When sorbic acid is present as component (b) in the aqueous composition or industrial product, the substance 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.

[0202] When benzoic acid is present as component (b) in the aqueous composition or industrial product, the substance 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.

[0203] When salicylic acid is present as component (b) in the aqueous composition or industrial product, the substance 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.

[0204] When lactic acid is present as component (b) in the aqueous composition or industrial product, the amount of the substance present is generally in the range of 1 to 50,000 ppm, preferably 5 to 25,000 ppm, more preferably 10 to 15,000 ppm.

[0205] When citric acid is present as component (b) in the aqueous composition or industrial product, the substance 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.

[0206] When zinc is present as component (b) in the aqueous composition or industrial product, 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.

[0207] The invention also relates to the use of the preferably aqueous composition defined above for the preservation of cans or for the preservation of industrial products selected from the group consisting of lignin sulfonates and starch preparations in paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, chalk slurries, mineral slurries, ceramic composites, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and pigment dispersions, inks, lithographic fluids, thickeners, cosmetics, sanitary products, water circuits, woodworking fluids, oil production fluids, paper processing fluids, leather production fluids, textile production fluids, drilling and cutting oils, hydraulic fluids and cooling lubricants.

[0208] In other embodiments, the present invention relates to the use of (a) guanidine and / or a salt of unsubstituted guanidine for improving the antimicrobial efficacy of one or more compounds selected from the following group (b):

[0209] (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, octylisothiazolin-3-one, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, aminomethylpropanol, aminoethyl Propylene glycol, monoethanolamine, ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenylethyl alcohol, phenylpropanol, benzyl alcohol, isopropyl alcohol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bisphosphonic acid, sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc.

[0210] As can be seen from the following examples, the use of guanidine or its salts, which has hitherto not been used as an antimicrobial active substance, surprisingly synergistically enhances the effect of at least one other component selected from the above-mentioned group (b).

[0211] Due to this surprising effect-enhancing effect, at least one biocidally active component selected from group (b) can be used in the presence of guanidine at significantly lower concentrations. The amount of components (a) and (b) used can vary within 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 containing the components.

[0212] Particularly advantageous improvements in antimicrobial efficacy can be achieved when the weight ratio of guanidine and / or its salt to 5-chloro-2-methylisothiazolin-3-one is in the range of 62:1 to 9270:1, and / or the weight ratio of guanidine and / or its salt to 2-methyl-4-isothiazolin-3-one is in the range of 10.3:1 to 773:1, and / or the weight ratio of guanidine and / or its salt to 1,2-benzisothiazolin-3-one is in the range of 1.3:1 to 309:1, and / or the weight ratio of guanidine and / or its salt to N-butyl-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 salt to N-methyl ... The weight ratio of guanidine and / or its salt to 2-benzisothiazolin-3-one is in the range of 7.8:1 to 618:1, and / or the weight ratio of guanidine and / or its salt 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 salt to bronopol is in the range of 7.8:1 to 824:1, and / or the weight ratio of guanidine and / or its salt 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 its salt to dibromodicyanobutane is in the range of 0.78:1 to 309:1, and / or the weight ratio of guanidine and / or its salt to iodopropynyl butylcarbamate is in the range of 0.83:1 to 1 The weight ratio of guanidine and / or its salt 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 its salt to 2-aminoethyl-1,3-propanediol is in the range of 0.2:1 to 15:1, and / or the weight ratio of guanidine and / or its salt to monoethanolamine is in the range of 0.2:1 to 30:1, and / or the weight ratio of guanidine and / or its salt to ethylhexylglycerol is in the range of 0.5:1 to 15:1, and / or the weight ratio of guanidine and / or its salt to hexylglycerol is in the range of 0.5:1 to 15:1, preferably 0.5:1 to 10:1, and / or the weight ratio of guanidine and / or its salt to 1,2-pentanediol is in the range of 0.2:1 to 15:1, and / or the weight ratio of guanidine and / or its salt to 2-aminoethyl-1,3-propanediol is in the range of 0.2:1 to 15:1, and / or the weight ratio of guanidine and / or its salt to monoethanolamine is in the range of 0.2:1 to 30:1, and / or the weight ratio of guanidine and / or its salt to ethylhexylglycerol is in the range of 0.5:1 to 15:1, preferably 0.5:1 to 10:1, and / or the weight ratio of guanidine and / or its salt to 1,2-pentanediol is in the range of 0.2:1 to 15:1, and / or the weight ratio of guanidine and / or its salt to 2-aminoethyl-1,3-propanediol is in the range of 0.2:1 to 15:1, and / or the weight ratio of The weight ratio of guanidine and / or its salt to 1,2-hexanediol is in the range of 0.07:1 to 7.5:1, and / or the weight ratio of guanidine and / or its salt to 1,2-heptanediol is in the range of 0.25:1 to 30:1, and / or the weight ratio of guanidine and / or its salt to 1,2-octanediol is in the range of 0.2:1 to 6:1, and / or the weight ratio of guanidine and / or its salt to phenoxyethanol is in the range of 0.13:1 to 3.6:1, and / or the weight ratio of guanidine and / or its salt to phenylethanol is in the range of 0.15:1 to 12:1, and / or the weight ratio of guanidine and / or its salt to phenylpropanol is in the range of 0.The weight ratio of guanidine and / or its salt to benzyl alcohol is in the range of 1:1 to 12:1, and / or the weight ratio of guanidine and / or its salt to isopropyl alcohol is in the range of 0.004:1 to 3:1, and / or the weight ratio of guanidine and / or its salt to ethylenediaminetetraacetic acid is in the range of 0.6:1 to 37:1, and / or the weight ratio of guanidine and / or its salt to (1-hydroxyethylene)bisphosphonic acid is in the range of 0.6:1 to 1.5:1, and / or the weight ratio of guanidine and / or its salt to sodium 2-pyrithione is in the range of 3.6:1 to 180:1, and / or the weight ratio of guanidine and / or its salt to zinc 2-pyrithione is in the range of 3.6:1 to 180:1, and / or the weight ratio of guanidine and / or its salt to o-phenylphenol is in the range of 0.62:1 to 1. and / or the weight ratio of guanidine and / or its salts to sorbic acid and / or its salts is in the range of 0.1:1 to 50:1, and / or the weight ratio of guanidine and / or its salts to benzoic acid and / or its salts is in the range of 0.25:1 to 88:1, and / or the weight ratio of guanidine and / or its salts to salicylic acid and / or its salts is in the range of 0.24:1 to 43:1, and / or the weight ratio of guanidine and / or its salts to lactic acid and / or its salts is in the range of 0.03:1 to 23:1, and / or the weight ratio of guanidine and / or its salts to citric acid and / or its salts is in the range of 0.014:1 to 12:1, and / or the weight ratio of guanidine and / or its salts to zinc is in the range of 0.77:1 to 12:1, wherein the weight ratios are in each case determined based on the total content of guanidine and acid in the composition.

[0213] The following examples are used to further illustrate the present invention:

[0214] Study of synergistic interactions:

[0215] The synergistic interaction of guanidine (added in the form of guanidine hydrochloride) in combination with biocides / substances selected from the group consisting of 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), dibromo Dicyanobutane (DBDCB), iodopropynyl butylcarbamate (IPBC), aminomethylpropanol (AMP), aminoethylpropylene glycol (AEPD), monoethanolamine (MEA), ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, benzyl alcohol, isopropyl alcohol, ethylenediaminetetraacetic acid (EDTA), (1-hydroxyethylidene)bisphosphonic acid (HEDP), 2-pyrithione, o-phenylphenol (oPP), sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc oxide (ZnO).

[0216] The test organisms used were the Gram-negative bacteria Pseudomonas putida DSM 115323 and Pseudomonas spec. DSM 115322 from the genus Pseudomonas. For this purpose, mixtures with different concentrations of the individual active substances were prepared and their effect on Pseudomonas was tested. The assay was performed in MHB broth at a cell density of 10 6 When an organic acid is used as a combination partner with guanidine, MHB is adjusted to pH 5.5.

[0217] Incubate in microtiter plates at 30° C. for 48 hours. After 48 hours, the batches are evaluated for signs of turbidity due to growth and the optical density is also determined photometrically. In this way, the minimum inhibitory concentration (MIC) of the two active substances is determined individually and in combination.

[0218] The synergistic effect was numerically expressed by calculating the synergy index (SI), which was calculated according to the standard method described by FC Kull et al. in "Applied Microbiology", Vol. 9 (1961), p. 538.

[0219] This involves calculating the Synergy Index (SI) according to the following formula:

[0220] Synergy Index SI = Q a / Q A + Q b / Q B

[0221] Q a = the concentration of component A in the A+B mixture,

[0222] Q A = concentration of component A as the sole biocide,

[0223] Q b = the concentration of component B in the A+B mixture,

[0224] Q B = Concentration of Component B as the sole biocide.

[0225] If the value of the synergy index is greater than 1, it means that there is antagonism. If the synergy index is 1, it means that there is an additive effect of the two biocides / compounds. If the value of the synergy index is less than 1, it means that there is a synergistic effect between the two biocides / compounds.

[0226] Example 1: Study on the Synergistic Interaction between Guanidine and 5-Chloro-2-methyl-4-isothiazolin-3-one (CIT)

[0227] The synergy index between guanidine and CIT against Pseudomonas putida DSM 115323 was calculated when incubated at 30°C for 48 hours.

[0228] Table 1

[0229]

[0230] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0231] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0232] Qb: concentration of CIT in the mixture showing the endpoint,

[0233] QB: Concentration of CIT as the only reagent showing the endpoint.

[0234] Table 1 shows that the best synergy, i.e., the lowest synergy index (0.75) for the combination of guanidine and CIT is at a ratio of 1545 ppm guanidine to 1.5 ppm CIT. Synergy can be demonstrated when the weight ratio of guanidine to CIT is in the range of 62:1 to 9270:1.

[0235] Example 2: Study on the synergistic interaction between guanidine and 2-methyl-4-isothiazolin-3-one (MIT)

[0236] The synergy index between guanidine and MIT for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0237] Table 2

[0238]

[0239] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0240] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0241] Qb: concentration of MIT in the mixture showing the endpoint,

[0242] QB: Concentration of MIT as the only reagent showing the endpoint.

[0243] Table 2 shows that the best synergy, i.e., the lowest synergy index (0.73) for the combination of guanidine and MIT, is at a ratio of 3090 ppm guanidine to 30 ppm MIT. Synergy can be demonstrated when the weight ratio of guanidine to MIT is in the range of 10.3:1 to 773:1.

[0244] Example 3: Study on the synergistic interaction between guanidine and 1,2-benzisothiazolin-3-one (BIT)

[0245] The synergy index between guanidine and BIT for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0246] Table 3

[0247]

[0248] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0249] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0250] Qb: concentration of BIT in the mixture at the end point,

[0251] QB: Concentration of BIT as the only reagent showing the endpoint.

[0252] Table 3 shows that the best synergy, i.e., the lowest synergy index (0.67) for the combination of guanidine and BIT is at a ratio of 3090 ppm guanidine to 100 ppm BIT. Synergy can be demonstrated when the weight ratio of guanidine to BIT is in the range of 1.3:1 to 309:1.

[0253] Example 4: Study on the synergistic interaction between guanidine and N-butyl-1,2-benzisothiazolin-3-one (BBIT)

[0254] The synergy index between guanidine and BBIT for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0255] Table 4

[0256]

[0257] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0258] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0259] Qb: Concentration of BBIT in the mixture at the indicated endpoint,

[0260] QB: Concentration of BBIT as the sole reagent showing the endpoint.

[0261] Table 4 shows that the best synergy, i.e., the lowest synergy index (0.67) for the combination of guanidine and BBIT, is at a ratio of 1545 ppm guanidine to 200 ppm BBIT. Synergy can be demonstrated when the weight ratio of guanidine to BBIT is in the range of 0.52:1 to 309:1.

[0262] Example 5: Study on the synergistic interaction between guanidine and N-methyl-1,2-benzisothiazolin-3-one (MBIT)

[0263] The synergy index between guanidine and MBIT for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0264] Table 5

[0265]

[0266] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0267] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0268] Qb: Concentration of MBIT in the mixture showing the endpoint,

[0269] QB: Concentration of MBIT as the sole reagent showing the endpoint.

[0270] Table 5 shows that the best synergy, i.e., the lowest synergy index (0.75) for the combination of guanidine and MBIT is at a ratio of 3090 ppm guanidine to 125 ppm MBIT. Synergy can be demonstrated when the weight ratio of guanidine to MBIT is in the range of 7.8:1 to 618:1.

[0271] Example 6: Study on the synergistic interaction between guanidine and octylisothiazolinone (OIT)

[0272] The synergy index between guanidine and OIT for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0273] Table 6

[0274]

[0275] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0276] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0277] Qb: Concentration of OIT in the mixture showing the endpoint,

[0278] QB: Concentration of OIT as the only reagent showing the endpoint.

[0279] Table 6 shows that the best synergy, i.e., the lowest synergy index (0.87) for the combination of guanidine and OIT, is at a ratio of 618 to 1590 ppm guanidine to 200 to 175 ppm OIT. Synergy can be demonstrated when the weight ratio of guanidine to OIT is in the range of 1.4:1 to 82:1.

[0280] Example 7: Study on the synergistic interaction between guanidine and bronopol

[0281] The synergy index of guanidine and bronopol against Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0282] Table 7

[0283]

[0284] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0285] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0286] Qb: concentration of bronopol in the mixture at the indicated endpoint,

[0287] QB: Concentration of bronopol as the sole reagent that indicates the endpoint.

[0288] Table 7 shows that the best synergy, i.e., the lowest synergy index (0.77) for the combination of guanidine and bronopol, is 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.

[0289] Example 8: Study on the Synergistic Interaction between Guanidine and Dibromonitrilopropionamide (DBNPA)

[0290] The synergy index between guanidine and DBNPA for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0291] Table 8

[0292]

[0293] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0294] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0295] Qb: Concentration of DBNPA in the mixture at the indicated endpoint,

[0296] QB: Concentration of DBNPA as the sole reagent showing the endpoint.

[0297] Table 8 shows that the best synergy, i.e., the lowest synergy index (0.82) for the combination of guanidine and DBNPA, is at a ratio of 155 ppm guanidine to 20 ppm DBNPA. Synergy can be demonstrated when the weight ratio of guanidine to DBNPA is in the range of 7.8:1 to 3090:1.

[0298] Example 9: Study on the Synergistic Interaction between Guanidine and Dibromodicyanobutane (DBDCB)

[0299] The synergy index between guanidine and DBDCB was calculated for Pseudomonas sp. DSM 115322 when incubated at 30°C for 48 hours.

[0300] Table 9

[0301]

[0302] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0303] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0304] Qb: Concentration of DBDCB in the mixture at the indicated endpoint,

[0305] QB: Concentration of DBDCB as the sole reagent showing the endpoint.

[0306] Table 9 shows that the best synergy, i.e., the lowest synergy index (0.77) for the combination of guanidine and DBDCB is at a ratio of 1590 ppm guanidine to 150 ppm DBDCB. Synergy can be demonstrated when the weight ratio of guanidine to DBDCB is in the range of 0.78:1 to 309:1.

[0307] Example 10: Study on the Synergistic Interaction between Guanidine and Iodopropynyl Butylcarbamate (IPBC)

[0308] The synergy index between guanidine and IPBC was calculated for Pseudomonas sp. DSM 115322 when incubated at 30°C for 48 hours.

[0309] Table 10

[0310]

[0311] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0312] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0313] Qb: shows the concentration of IPBC in the mixture at the endpoint,

[0314] QB: Concentration of IPBC as the only reagent showing the endpoint.

[0315] Table 10 shows that the best synergy, i.e., the lowest synergy index (0.83) for the combination of guanidine and IPBC is at a ratio of 4635 ppm guanidine to 300 ppm IPBC. Synergy can be demonstrated when the weight ratio of guanidine to IPBC is in the range of 0.83:1 to 103:1.

[0316] Example 11: Study on the synergistic interaction between guanidine and 2-amino-2-methyl-1-propanol (AMP)

[0317] The synergy index between guanidine and AMP for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0318] Table 11

[0319]

[0320] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0321] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0322] Qb: shows the concentration of AMP in the mixture at the end point,

[0323] QB: The concentration of AMP as the only reagent showing the endpoint.

[0324] Table 11 shows that the best synergy, i.e., the lowest synergy index (0.73) for the combination of guanidine and AMP is at a ratio of 3090 ppm guanidine to 1000 ppm AMP. Synergy can be demonstrated when the weight ratio of guanidine to AMP is in the range of 0.3:1 to 20:1.

[0325] Example 12: Study on the synergistic interaction between guanidine and 2-aminoethyl-1,3-propanediol (AEPD)

[0326] The synergy index between guanidine and AEPD for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0327] Table 12

[0328]

[0329] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0330] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0331] Qb: concentration of AEPD in the mixture showing the endpoint,

[0332] QB: Concentration of AEPD as the sole reagent showing the endpoint.

[0333] Table 12 shows that the best synergy, i.e., the lowest synergy index (0.73) for the combination of guanidine and AEPD, is at a ratio of 3090 ppm guanidine to 2000 ppm AEPD. Synergy can be demonstrated when the weight ratio of guanidine to AEPD is in the range of 0.2:1 to 15:1.

[0334] Example 13: Study on the synergistic interaction between guanidine and monoethanolamine (MEA)

[0335] The synergy index between guanidine and MEA for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0336] Table 13

[0337]

[0338] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0339] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0340] Qb: Concentration of MEA in the mixture at the end point,

[0341] QB: Concentration of MEA as the only reagent showing the endpoint.

[0342] Table 13 shows that the best synergy, i.e., the lowest synergy index (0.79) for the combination of guanidine and MEA is 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.

[0343] Example 14: Study on the synergistic interaction between guanidine and ethylhexylglycerol (EHG)

[0344] The synergy index between guanidine and EHG for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0345] Table 14

[0346]

[0347] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0348] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0349] Qb: concentration of EHG in the mixture at the indicated endpoint,

[0350] QB: Concentration of EHG as the sole reagent showing the endpoint.

[0351] Table 14 shows that the best synergy, i.e., the lowest synergy index (0.69) for the combination of guanidine and EHG is at a ratio of 618 ppm guanidine to 1250 ppm EHG. Synergy can be demonstrated when the weight ratio of guanidine to EHG is in the range of 0.5:1 to 15:1.

[0352] Example 15: Study on the synergistic interaction between guanidine and hexylglycerol

[0353] The synergy index of guanidine and hexylglycerol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30° C. for 48 hours.

[0354] Table 15

[0355]

[0356] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0357] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0358] Qb: concentration of hexylglycerol in the mixture at the indicated endpoint,

[0359] QB: Concentration of hexylglycerol as the sole reagent showing the endpoint.

[0360] Table 15 shows that the best synergy, i.e., the lowest synergy index (0.69) for the combination of guanidine and hexylglycerol, is at a ratio of 618 ppm guanidine to 1250 ppm hexylglycerol. Synergy can be demonstrated when the weight ratio of guanidine to hexylglycerol is in the range of 0.5:1 to 15:1.

[0361] Example 16: Study on the synergistic interaction between guanidine and 1,2-pentanediol

[0362] The synergy index of guanidine and 1,2-pentanediol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30° C. for 48 hours.

[0363] Table 16

[0364]

[0365] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0366] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0367] Qb: concentration of 1,2-pentanediol in the mixture at the indicated endpoint,

[0368] QB: Concentration of 1,2-pentanediol as the sole reagent showing the endpoint.

[0369] Table 16 shows that the best synergy, i.e., the lowest synergy index (0.87) for the combination of guanidine and 1,2-pentanediol, is at a ratio of 6180 ppm guanidine to 2000 ppm 1,2-pentanediol. Synergy can be demonstrated when the weight ratio of guanidine to 1,2-pentanediol is in the range of 0.07:1 to 7.5:1.

[0370] Example 17: Study on the synergistic interaction between guanidine and 1,2-hexanediol

[0371] The synergy index of guanidine and 1,2-hexanediol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30° C. for 48 hours.

[0372] Table 17

[0373]

[0374] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0375] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0376] Qb: shows the concentration of 1,2-hexanediol in the mixture at the endpoint,

[0377] QB: Concentration of 1,2-hexanediol as the only reagent showing the endpoint.

[0378] Table 17 shows that the best synergy, i.e., the lowest synergy index (0.67) for the combination of guanidine and 1,2-hexanediol, is at a ratio of 1545 to 3090 ppm of guanidine to 3750 to 2500 ppm of 1,2-hexanediol. Synergy is demonstrated when the weight ratio of guanidine to 1,2-hexanediol is in the range of 0.06:1 to 15:1.

[0379] Example 18: Study on the synergistic interaction between guanidine and 1,2-heptanediol

[0380] The synergy index of guanidine and 1,2-heptanediol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30° C. for 48 hours.

[0381] Table 18

[0382]

[0383] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0384] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0385] Qb: concentration of 1,2-heptanediol in the mixture at the indicated endpoint,

[0386] QB: Concentration of 1,2-heptanediol as the sole reagent showing the endpoint.

[0387] Table 18 shows that the best synergy, i.e., the lowest synergy index (0.70) for the combination of guanidine and 1,2-heptanediol, is at a ratio of 1545 ppm guanidine to 2000 ppm 1,2-heptanediol. Synergy can be demonstrated when the weight ratio of guanidine to 1,2-heptanediol is in the range of 0.25:1 to 30:1.

[0388] Example 19: Study on the synergistic interaction between guanidine and 1,2-octanediol

[0389] The synergy index of guanidine and 1,2-octanediol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30° C. for 48 hours.

[0390] Table 19

[0391]

[0392] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0393] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0394] Qb: Concentration of 1,2-octanediol in the mixture at the end point,

[0395] QB: Concentration of 1,2-octanediol as the sole reagent showing the endpoint.

[0396] Table 19 shows that the best synergy, i.e., the lowest synergy index (0.88) for the combination of guanidine and 1,2-octanediol, is at a ratio of 4635 ppm guanidine to 750 ppm 1,2-octanediol. Synergy can be demonstrated when the weight ratio of guanidine to 1,2-octanediol is in the range of 0.2:1 to 6:1.

[0397] Example 20: Study on the synergistic interaction between guanidine and phenoxyethanol

[0398] The synergy index of guanidine and phenoxyethanol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0399] Table 20

[0400]

[0401] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0402] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0403] Qb: concentration of phenoxyethanol in the mixture at the indicated endpoint,

[0404] QB: Concentration of phenoxyethanol alcohol as the sole reagent that indicated the endpoint.

[0405] Table 20 shows that the best synergy, i.e., the lowest synergy index (0.83) for the combination of guanidine and phenoxyethanol, is 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.

[0406] Example 21: Study on the synergistic interaction between guanidine and phenylethanol

[0407] The synergy index of guanidine and phenylethanol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0408] Table 21

[0409]

[0410] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0411] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0412] Qb: concentration of phenylethanol in the mixture at the end point,

[0413] QB: Concentration of phenylethanol as the sole reagent showing the endpoint.

[0414] Table 21 shows that the best synergy, i.e., the lowest synergy index (0.83) for the combination of guanidine and phenylethanol, is at a ratio of 309 to 3090 ppm guanidine to 1250 to 2000 ppm phenylethanol. Synergy can be demonstrated when the weight ratio of guanidine to phenylethanol is in the range of 0.15:1 to 12:1.

[0415] Example 22: Study on the synergistic interaction between guanidine and phenylpropanol

[0416] The synergy index of guanidine and phenylpropanol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0417] Table 22

[0418]

[0419] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0420] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0421] Qb: indicates the concentration of phenylpropanol in the mixture at the endpoint,

[0422] QB: Concentration of phenylpropanol as the sole reagent showing the endpoint.

[0423] Table 22 shows that the best synergy, i.e., the lowest synergy index (0.79) for the combination of guanidine and phenylpropanol, is 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.

[0424] Example 23: Study on the synergistic interaction between guanidine and benzyl alcohol

[0425] The synergy index of guanidine and benzyl alcohol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0426] Table 23

[0427]

[0428] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0429] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0430] Qb: concentration of benzyl alcohol in the mixture showing the endpoint,

[0431] QB: Concentration of benzyl alcohol as the sole reagent showing the endpoint.

[0432] Table 23 shows that the best synergy, i.e., the lowest synergy index (0.71) for the combination of guanidine and benzyl alcohol, is 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.

[0433] Example 24: Study on the synergistic interaction between guanidine and isopropanol

[0434] The synergy index of guanidine and isopropanol for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0435] Table 24

[0436]

[0437] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0438] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0439] Qb: indicates the concentration of isopropanol in the mixture at the endpoint,

[0440] QB: Concentration of isopropanol as the sole reagent showing the endpoint.

[0441] Table 24 shows that the best synergy, i.e., the lowest synergy index (0.53) for the combination of guanidine and isopropyl alcohol, is at a ratio of 309 ppm guanidine to 30,000 ppm isopropyl alcohol. Synergy can be demonstrated when the weight ratio of guanidine to isopropyl alcohol is in the range of 0.004:1 to 3:1.

[0442] Example 25: Study on the synergistic interaction between guanidine and ethylenediaminetetraacetic acid (EDTA)

[0443] The synergy index of guanidine and EDTA for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0444] Table 25

[0445]

[0446] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0447] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0448] Qb: EDTA concentration in the mixture showing the endpoint,

[0449] QB: The concentration of EDTA as the only reagent that indicates the endpoint.

[0450] Table 25 shows that the best synergy, i.e., the lowest synergy index (0.83) for the combination of guanidine and EDTA, is at a ratio of 1545 ppm guanidine to 200 ppm EDTA. Synergy can be demonstrated when the weight ratio of guanidine to EDTA is in the range of 0.6:1 to 37:1.

[0451] Example 26: Study on the Synergistic Interaction between Guanidine and (1-Hydroxyethylidene) Diphosphonic Acid (HEDP)

[0452] The synergy index between guanidine and HEDP for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0453] Table 26

[0454]

[0455] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0456] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0457] Qb: Concentration of HEDP in the mixture at the indicated endpoint,

[0458] QB: Concentration of HEDP as the only reagent showing the endpoint.

[0459] Table 26 shows that the best synergy, i.e., the lowest synergy index (0.73) for the combination of guanidine and HEDP, is 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.

[0460] Example 27: Study on the synergistic interaction between guanidine and 2-pyrithione (added in the form of sodium 2-pyrithione)

[0461] The synergy index of guanidine and 2-pyrithione against Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0462] Table 27

[0463]

[0464] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0465] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0466] Qb: The concentration of 2-pyrithione in the mixture showing the endpoint,

[0467] QB: Concentration of 2-pyrithione as the sole reagent that indicates the endpoint.

[0468] Table 27 shows that the best synergy, i.e., the lowest synergy index (0.70) for the combination of guanidine and pyrithione is at a ratio of 309 ppm guanidine to 85 ppm pyrithione. Synergy can be demonstrated when the weight ratio of guanidine to pyrithione is in the range of 3.6:1 to 180:1.

[0469] Example 28: Study on the synergistic interaction between guanidine and o-phenylphenol (oPP)

[0470] The synergy index between guanidine and oPP for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0471] Table 28

[0472]

[0473] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0474] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0475] Qb: concentration of oPP in the mixture at the indicated endpoint,

[0476] QB: Concentration of oPP as the only reagent showing the endpoint.

[0477] Table 28 shows that the best synergy, i.e., the lowest synergy index (0.50) for the combination of guanidine and oPP, is at a ratio of 1545 ppm guanidine to 250 ppm oPP. Synergy can be demonstrated when the weight ratio of guanidine to oPP is in the range of 0.62:1 to 49:1.

[0478] Example 29: Study on the synergistic interaction between guanidine and sorbic acid (added as potassium sorbate)

[0479] The synergy index of guanidine and sorbic acid for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0480] Table 29

[0481]

[0482] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0483] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0484] Qb: concentration of sorbic acid in the mixture at the indicated endpoint,

[0485] QB: Concentration of sorbic acid as the sole reagent showing the endpoint.

[0486] Table 29 shows that the best synergy, i.e., the lowest synergy index (0.55) for the combination of guanidine and sorbic acid is 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 is in the range of 0.1:1 to 50:1.

[0487] Example 30:Study on the synergistic interaction between guanidine and benzoic acid (added as sodium benzoate)

[0488] The synergy index of guanidine and benzoic acid for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0489] Table 30

[0490]

[0491] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0492] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0493] Qb: concentration of benzoic acid in the mixture at the indicated endpoint,

[0494] QB: Concentration of benzoic acid as the sole reagent showing the endpoint.

[0495] Table 30 shows that the best synergy, i.e., the lowest synergy index (0.63) for the combination of guanidine and benzoic acid, is at a ratio of 1545 to 4635 ppm guanidine to 840 to 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.

[0496] Example 31: Study on the synergistic interaction between guanidine and salicylic acid (added as sodium salicylate)

[0497] The synergy index of guanidine and salicylic acid against Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0498] Table 31

[0499]

[0500] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0501] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0502] Qb: concentration of salicylic acid in the mixture at the indicated endpoint,

[0503] QB: Concentration of salicylic acid as the sole reagent that indicates the endpoint.

[0504] Table 31 shows that the best synergy, i.e., the lowest synergy index (0.63) for the combination of guanidine and salicylic acid, is at a ratio of 1545 to 4635 ppm guanidine to 856 to 428 ppm salicylic acid. Synergy can be demonstrated when the weight ratio of guanidine to salicylic acid is in the range of 0.24:1 to 43:1.

[0505] Example 32: Study on the synergistic interaction between guanidine and lactic acid (added as sodium L-lactate)

[0506] The synergy index of guanidine and lactic acid for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0507] Table 32

[0508]

[0509] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0510] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0511] Qb: shows the concentration of lactic acid in the mixture at the end point,

[0512] QB: Concentration of lactic acid as the only reagent showing the endpoint.

[0513] Table 32 shows that the best synergy, i.e., the lowest synergy index (0.63) for the combination of guanidine and lactic acid, is at a ratio of 4635 to 6180 ppm guanidine to 3974 to 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.

[0514] Example 33: Study on the synergistic interaction between guanidine and citric acid (added as trisodium citrate)

[0515] The synergy index of guanidine and citric acid for Pseudomonas sp. DSM 115322 was calculated when incubated at 30°C for 48 hours.

[0516] Table 33

[0517]

[0518] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0519] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0520] Qb: concentration of citric acid in the mixture at the indicated endpoint,

[0521] QB: Concentration of citric acid as the sole reagent showing the endpoint.

[0522] Table 33 shows that the best synergy, i.e., the lowest synergy index (0.45) for the combination of guanidine and citric acid, is at a ratio of 309 ppm guanidine to 21983 ppm citric acid. Synergy can be demonstrated when the weight ratio of guanidine to citric acid is in the range of 0.014:1 to 12:1.

[0523] Example 34: Study on the synergistic interaction between guanidine and zinc (added in the form of zinc oxide)

[0524] In Example 34, the synergistic interaction between guanidine and a zinc compound (zinc oxide) against microbial infections was tested by adding specific amounts of guanidine in the form of guanidine hydrochloride and zinc compound in the form of zinc oxide to an emulsion paint, and the stability against microbial infections was tested. The paint tested was an emulsion paint for interior applications based on a styrene-acrylate binder (PVK 77%, pH 8.8), which was prepared in the laboratory without the addition of conventional preservatives.

[0525] These samples were inoculated with a bacterial cell suspension (2% v / w) having the following composition in duplicate for a total of three times.

[0526] Bacterial mixture A:

[0527] Alcaligenes faecalis NCIMB 13145,

[0528] Escherichia coli DSM 13631,

[0529] Burkholderia cepacia DSM 9241,

[0530] Staphylococcus aureus DSM 799,

[0531] Pseudomonas aeruginosa DSM 50071,

[0532] Pseudomonas putida DSM 13624.

[0533] The cell suspension of bacterial mixture A was prepared by growing each bacterium in liquid medium at 30°C on a shaker for 24 hours. The growth medium used for the bacteria was Liquid culture medium. After growth, each liquid culture was centrifuged and the cells were resuspended in physiological saline solution. In order to adjust the mixture to 10 9 The total cell count per ml was determined by diluting the respective bacterial suspension accordingly before combining with the saline solution if necessary. The cell count of the inoculum was determined in each case by counting plates.

[0534] After each inoculation and after 7 days of incubation at 30° C., the microbial infection in the samples was evaluated by counting viable bacteria per gram of paint (colony forming units, CFU / g). The CFU / g was determined each time by extracting an aliquot (1 g) from the previously homogenized sample and performing a serial ten-fold dilution series in physiological saline solution (0.9% NaCl) by streaking on tryptone soya agar, followed by incubation of the agar plates at 30° C. for 48 hours.

[0535] Example 34 / Table 34: Inoculation with bacterial mixture A, cell count 10 9 / ml

[0536]

[0537] Using the outcome endpoint after 3 inoculations to reach a maximum of 1000 CFU / g, a synergistic effect between guanidine and zinc was demonstrated.

[0538] Example 34 / Table 35

[0539]

[0540] Qa: the concentration of guanidine in the mixture that indicates the endpoint,

[0541] QA: Concentration of guanidine as the only reagent to indicate endpoint,

[0542] Qb: indicates the concentration of zinc in the mixture at the end point,

[0543] QB: Concentration of zinc as the sole reagent showing the endpoint.

[0544] Table 35 shows that the best synergy, i.e., the lowest synergy index (0.40) for the combination of guanidine and zinc is at a ratio of 618 ppm guanidine to 402 ppm zinc. Synergy can be demonstrated when the weight ratio of guanidine to zinc is in the range of 0.77:1 to 12:1.

[0545] In the following Examples 35 to 38, the synergistic interaction between guanidine and antimicrobial substances against microbial infection was studied using emulsified paints and laundry detergents or cleaning compositions by adding specific amounts of guanidine salts and isothiazolinones and testing their stability against microbial infection:

[0546] The paint tested was an emulsion paint for interior applications based on a styrene-acrylate binder (PVK 77%, pH 8.8), which was prepared in the laboratory without the addition of conventional preservatives.

[0547] 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 of which was also prepared in the laboratory without the addition of conventional preservatives.

[0548] Process:

[0549] To each paint, specific concentrations of the following substances were added, either alone or in combination: guanidinium hydrochloride, benzisothiazolinone (BIT), and a mixture of chloromethylisothiazolinone (CIT) and methylisothiazolinone (MIT). Laundry detergents and cleaning compositions were mixed with specific concentrations of guanidinium hydrochloride and benzisothiazolinone (BIT).

[0550] The paint batches thus prepared were inoculated with a mixture of different bacterial species (bacterial mixture B); the laundry detergent and cleaning composition batches thus prepared were inoculated with a yeast mixture.

[0551] Bacterial mixture B:

[0552] Pseudomonas spp. (Pseudomonas oleovorans group) DSM 33933,

[0553] Pseudomonas aeruginosa DSM 33935,

[0554] Pseudomonas oleovorans DSM 33936,

[0555] Pseudomonas species (Pseudomonas spec. DSM 33937),

[0556] Pseudomonas aeruginosa DSM 33938.

[0557] Yeast mixture:

[0558] Pichia manshurica DSM 12249,

[0559] Rhodotorula mucilaginosa DSM 12248,

[0560] Candida boidinii DSM 13622,

[0561] Candida albicans DSM 1386.

[0562] In each inoculation, the inoculum was added to each sample at 2% (v / w) as a fresh cell suspension in physiological saline solution (0.9% NaCl). The cell count of the added inoculum was 10 9 / ml, for yeast mixture is 10 8 / ml, constituting equal parts of each bacterial or yeast strain.

[0563] A cell suspension of the bacterial mixture was prepared by growing each bacterium in liquid medium at 30°C on a shaker for 24 hours. The growth medium used for the bacteria was Liquid culture medium. After growth, each liquid culture was centrifuged and the cells were resuspended in physiological saline solution. In order to adjust the mixture to 10 9 The total cell count per ml was determined by diluting the respective bacterial suspension accordingly before combining with the saline solution if necessary. The cell count of the inoculum was determined in each case by counting plates.

[0564] A cell suspension of the yeast mixture was prepared by growing the yeast strains on Sabouraud dextrose agar at 25°C for 48 hours and washing the plates with physiological saline solution (0.9% NaCl). The 10 μg / ml suspension for determination of the inoculum suspension was prepared in a similar manner to the bacterial suspension. 8 Additional steps for cell counting / ml.

[0565] In Examples 35 to 38, these samples were inoculated once with the corresponding cell suspension (2% v / w) and, after propagation of bacteria (bacterial mixture B) or yeast, subjected to a semi-quantitative evaluation method. In each case, the inoculated samples were evaluated for microbial infestation on the 1st and 6th day after incubation at 30°C for a further 5 days (emulsion paint), or on the 3rd day after incubation at 30°C for a further 2 days (laundry detergent, cleaning composition). For this purpose, an aliquot was taken from each sample after homogenization using a sterile plastic inoculating loop (10µl) and evenly streaked onto an agar plate (tryptone soy agar in the case of bacteria, Sabouraud dextrose agar in the case of 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, the bacterial or yeast colonies grown on the agar plates were visually evaluated and quantified according to the following scale:

[0566]

[0567] Tables 36 to 39 show the results of Examples 35 to 38:

[0568] Example 35 / Table 36 :

[0569] Inoculate with 2% (w / v) bacterial mixture B and count 10 cells. 9 / ml

[0570]

[0571] From the results shown in Table 36, it can be seen that the synergistic interaction between BIT and guanidine that has been demonstrated under the above laboratory conditions can also be demonstrated in practical applications in emulsion paints.

[0572] Example 36 / Table 37 :

[0573] Inoculate with 2% (w / v) bacterial mixture B and count 10 cells. 9 / ml

[0574]

[0575] From the results shown in Table 37, it can be seen that the synergistic interaction between MIT and guanidine that has been demonstrated under the above laboratory conditions can also be demonstrated in emulsion paints in practical applications.

[0576] Example 37 / Table 38 :

[0577] The yeast mixture was inoculated with 2% (w / v) and the cell count was 10 8 / ml

[0578]

[0579] From the results shown in Table 38, it can be seen that the synergistic interaction between BIT and guanidine that has been demonstrated under the above laboratory conditions can also be demonstrated in practical applications in heavy-duty laundry detergents.

[0580] Example 38 / Table 39:

[0581] The yeast mixture was inoculated with 2% (w / v) and the cell count was 10 8 / ml

[0582]

[0583] From the results shown in Table 39, it can be seen that the synergistic interaction between BIT and guanidine that has been demonstrated under the above laboratory conditions can also be demonstrated in practical applications in heavy-duty laundry detergents.

Claims

1. A composition comprising: (a) guanidine and / or a salt of unsubstituted guanidine, and (b) at least one other component selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, amino Methylpropanol, aminoethylpropylene glycol, monoethanolamine, ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenylethyl alcohol, phenylpropanol, benzyl alcohol, isopropyl alcohol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bisphosphonic acid, sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc.

2. The composition of claim 1, wherein The weight ratio of guanidine and / or its salt to 5-chloro-2-methylisothiazolin-3-one is in the range of 62:1 to 9270:1, The weight ratio of guanidine and / or its salt to 2-methyl-4-isothiazolin-3-one is in the range of 10.3:1 to 773:1, The weight ratio of guanidine and / or its salt to 1,2-benzisothiazolin-3-one is in the range of 1.3:1 to 309:1, The weight ratio of guanidine and / or its salt to N-butyl-1,2-benzisothiazolin-3-one is in the range of 0.52:1 to 309:1, The weight ratio of guanidine and / or its salt to N-methyl-1,2-benzisothiazolin-3-one is in the range of 7.8:1 to 618:1, The weight ratio of guanidine and / or its salt to N-octylisothiazolin-3-one is in the range of 1.4:1 to 82:1, The weight ratio of guanidine and / or its salt to bronopol is in the range of 7.8:1 to 824:1, The weight ratio of guanidine and / or its salt 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 its salt to iodopropynyl butylcarbamate is in the range of 0.83:1 to 103:1, The weight ratio of guanidine and / or its salt 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 its salt to 2-aminoethyl-1,3-propanediol is in the range of 0.2:1 to 15:1, The weight ratio of guanidine and / or its salt to monoethanolamine is in the range of 0.2:1 to 30:1, The weight ratio of guanidine and / or its salt to ethylhexylglycerin is in the range of 0.5:1 to 15:1, The weight ratio of guanidine and / or its salt to hexylglycerol is in the range of 0.5:1 to 15:1, The weight ratio of guanidine and / or its salt to 1,2-pentanediol is in the range of 0.07:1 to 7.5:1, The weight ratio of guanidine and / or its salt to 1,2-hexanediol is in the range of 0.06:1 to 15:1, The weight ratio of guanidine and / or its salt to 1,2-heptanediol is in the range of 0.25:1 to 30:1, The weight ratio of guanidine and / or its salt to 1,2-octanediol is in the range of 0.2:1 to 6:1, The weight ratio of guanidine and / or its salt to phenoxyethanol is in the range of 0.13:1 to 3.6:1, The weight ratio of guanidine and / or its salt to phenylethanol is in the range of 0.15:1 to 12:1, The weight ratio of guanidine and / or its salt to phenylpropanol is in the range of 0.4:1 to 6:1, The weight ratio of guanidine and / or its salt to benzyl alcohol is in the range of 1:1 to 12:1, The weight ratio of guanidine and / or its salt to isopropyl alcohol is in the range of 0.004:1 to 3:1, The weight ratio of guanidine and / or its salt 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-hydroxyethylene)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 2-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 its salt to o-phenylphenol is in the range of 0.62:1 to 49:1, The weight ratio of guanidine and / or its salt to sorbic acid and / or its salt is in the range of 0.1:1 to 50:1, The weight ratio of guanidine and / or its salt to benzoic acid and / or its salt is in the range of 0.25:1 to 88:1, The weight ratio of guanidine and / or its salt to salicylic acid and / or its salt is in the range of 0.24:1 to 43:1, The weight ratio of guanidine and / or its salt to lactic acid and / or its salt is in the range of 0.03:1 to 23:1, The weight ratio of guanidine and / or its salt to citric acid and / or its salt is in the range of 0.014:1 to 12:1, The weight ratio of guanidine and / or its salt to zinc is in the range of 0.77:1 to 12:1, The weight ratios are determined in each case based on the content of guanidine or other components in the composition and without taking into account any counterions.

3. The composition according to claim 1 or 2, wherein The composition contains guanidine and / or its salt and at least one other component in a total amount of 0.01% to 10%, preferably 0.02% to 5%, more preferably 0.03% to 3%, based on the entire composition.

4. The composition according to any one of claims 1 to 3, characterized in that The composition contains 100 to 10,000 ppm, preferably 200 to 7,500 ppm, more preferably 300 to 5,000 ppm of guanidine and / or its salts, wherein the ratios stated relate to the guanidine content in the overall composition.

5. The composition according to any one of claims 1 to 4, characterized in that The composition: - when 5-chloro-2-methyl-4-isothiazolin-3-one is present as another component, the content of the substance is within the range of 0.5 to 200 ppm, - when containing 2-methyl-4-isothiazolin-3-one as another component, the content of the substance is within the range of 0.5 to 200 ppm, - when containing 1,2-benzisothiazolin-3-one as another component, the content of the substance is within the range of 1 to 500 ppm, - when containing N-butyl-1,2-benzisothiazolin-3-one as another component, the content of the substance is within the range of 5 to 2500 ppm, - when containing N-methyl-1,2-benzisothiazolin-3-one as another component, the content of the substance is within the range of 1 to 500 ppm, - when octylisothiazolinone is present as another component, the content of the substance is within the range of 1 to 2500 ppm, - when bronopol is present as another component, the content of the substance is within the range of 1 to 1000 ppm, - when containing dibromonitrilopropionamide as another component, the content of the substance is within the range of 1 to 1000 ppm, - when containing dibromodicyanobutane as another component, the content of the substance is within the range of 1 to 1000 ppm, - when iodopropynyl butylcarbamate is present as another component, the content of the substance is within the range of 10 to 5000 ppm, - when aminomethylpropanol is present as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when aminoethylpropylene glycol is present as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when monoethanolamine is present as another component, the content of the substance is within the range of 25 to 7500 ppm, - when ethylhexylglycerin is present as another component, the content of this substance is within the range of 10 to 10,000 ppm, - when containing hexylglycerin as another component, the content of this substance is within the range of 10 to 10,000 ppm, - when containing 1,2-pentanediol as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when containing 1,2-hexanediol as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when containing 1,2-heptanediol as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when containing 1,2-octanediol as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when phenoxyethanol is present as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when containing phenylethyl alcohol as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when phenylpropanol is present as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when containing benzyl alcohol as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when containing isopropyl alcohol as another component, the content of this substance is within the range of 10 to 30,000 ppm, - when containing ethylenediaminetetraacetic acid as another component, the content of this substance is within the range of 10 to 10,000 ppm, - when (1-hydroxyethylene)bisphosphonic acid is present as another component, the content of the substance is within the range of 10 to 10,000 ppm, - when sodium 2-pyrithione is present as another component, the content of this substance is within the range of 1 to 2500 ppm, - when zinc pyrithione is present as another component, the content of the substance is within the range of 1 to 2500 ppm, - when o-phenylphenol is present as another component, the content of the substance is within the range of 1 to 10,000 ppm, - when containing sorbic acid as another component, the content of the substance is within the range of 1 to 10,000 ppm, - when containing benzoic acid as another component, the content of the substance is within the range of 1 to 10,000 ppm, - when salicylic acid is present as another component, the content of the substance is within the range of 1 to 10,000 ppm, - when lactic acid is present as another component, the content of the substance is within the range of 1 to 50,000 ppm, - when containing citric acid as another component, the content of the substance is within the range of 1 to 100,000 ppm, and - When zinc is present as another component, the content of the substance is within the range of 10 to 5000 ppm.

6. The composition according to any one of claims 1 to 5, characterized in that The composition has a water content of greater than 1% by weight.

7. The composition according to any one of claims 1 to 6, characterized in that The composition has a pH value in the range of pH 3.5 to pH 12.

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

9. The composition according to any one of claims 1 to 9, characterized in that The composition is an industrial product selected from the group consisting of: Lignosulfonate and starch preparations in paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, chalk slurries, mineral slurries, ceramic composites, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and dispersions, inks, lithographic fluids, thickeners, cosmetics, sanitary products, water circuits, woodworking fluids, oil production fluids, paper processing fluids, leather production fluids, textile production fluids, drilling and cutting oils, hydraulic fluids, cooling lubricants and biocidal products.

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

11. Use of the composition according to any one of claims 1 to 8 for the corrosion protection of industrial products selected from the group consisting of lignin sulfonate and starch preparations in paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, chalk slurries, mineral slurries, ceramic composites, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and dispersions, inks, lithographic fluids, thickeners, cosmetics, sanitary products, water circuits, woodworking fluids, oil production fluids, paper processing fluids, leather production fluids, textile production fluids, drilling and cutting oils, hydraulic fluids and cooling lubricants.

12. (a) Use of guanidine and / or unsubstituted guanidine salts for improving the antimicrobial efficacy of one or more compounds selected from the following group (b): (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, octylisothiazolin-3-one, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, aminomethylpropanol, aminoethyl Propylene glycol, monoethanolamine, ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenylethyl alcohol, phenylpropanol, benzyl alcohol, isopropyl alcohol, 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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