Synergistic compositions containing guanidine
Patent Information
- Application Number
- EP2024706927
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-02-23
- Filing Date
- 2024-02-16
- Publication Date
- 2025-12-31
AI Technical Summary
Existing biocide compositions for preserving aqueous technical products, such as paints and detergents, often require high concentrations of individual antimicrobial agents, which can lead to incompatibilities and inefficiencies, particularly with guanidine salts causing coagulation issues in color compositions and polymer dispersions.
A synergistic composition combining guanidine and/or its salts with other antimicrobial agents like 5-chloro-2-methyl-4-isothiazolin-3-one, bronopol, and others, allowing for lower overall concentrations and improved antimicrobial effectiveness when used together.
The synergistic combination enables effective antimicrobial protection at lower concentrations, reducing the risk of incompatibilities and enhancing the durability and hygiene of technical products.
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Abstract
Description
[0001] Synergistic compositions containing guanidine
[0002] The present invention relates to a composition comprising (a) guanidine and / or a salt of the unsubstituted guanidine 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, octylisothiazolinone,
[0003] Bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynylbutylcarbamate, amino-methyl-propanol, amino-ethyl-propanediol, monoethanolamine,
[0004] Ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bisphosphonic acid, sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid, and zinc. The invention further relates to technical products containing components (a) and (b) and to the use of the compositions for the container preservation and the preservation of technical products. The invention also 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 group (b) defined above.
[0005] Technical products, especially aqueous ones, such as paints, varnishes, emulsions, detergents, cleaning agents, and cosmetic products, are typically manufactured using natural or biodegradable raw materials. These raw materials and the water used as a solvent are often contaminated with germs such as bacteria, yeasts, and fungi. If these products are not preservative-free, they can exhibit high bacterial counts just one day after production.
[0006] CONFIRMATION! COPY To ensure that these products and, where applicable, the components used in their manufacture meet the hygiene requirements and to ensure the durability of the technical products, so-called biocides are usually added to the products or even to their components.
[0007] One class of biocides used for the preservation of aqueous technical products, such as paints, plasters, detergents and cleaning agents, or varnishes, or components thereof, is the so-called 3-isothiazolin-3-ones. This class of substances includes highly effective antimicrobial compounds with sometimes differing activity profiles. Synergistic combinations of different 3-isothiazolin-3-ones are often used to reduce the amount of biocide needed. For example, WO 99 / 08530 A1 proposes the combined use of methylisothiazolin-3-one and l,2-benzisothiazolin-3-one.
[0008] EP-B 1 030 558 also discloses a synergistic biocidal composition containing 2-methylisothiazolin-3-one and 3-iodo-2-propynyl-N-butylcarbamate. This synergistic composition is suitable for controlling microorganisms even at low concentrations.
[0009] Another class of biocides are the so-called alkylguanidinium salts and polyguanidinium salts. For example, it is known from the "Directory of Microbicides for the Protection of Materials," Springer 2005, pages 726 to 731, that medium- and long-chain guanidines and biguanidines, such as cocospropylenediamine-1,5-bis-guanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylenebiguanidine) hydrochloride, di(4'-chlorophenyldiguanido)hexane, chlorhexidine digluconate, and chlorhexidine diacetate, exhibit antimicrobial activity.
[0010] Furthermore, the use of such medium- and long-chain guanidine compounds in combination with other antimicrobial and / or fungicidal agents is known. For example, the combination with 3-iodo-2-propynyl butylcarbamate or formaldehyde depot substances is known. For example, EP 0 891 710 A1 teaches the combined use of dodecylguanidine hydrochloride and IPBC. However, the use of dodecylguanidine salts for the preservation of paint compositions and polymer dispersions has proven problematic, with incompatibilities in the form of coagulation observed when these salts were added.
[0011] Based on the state of the art discussed above, there is a need for further compositions whose components interact synergistically and can therefore be used in lower concentrations when used simultaneously, compared to the concentrations required in the case of the individual components.
[0012] The invention achieves this object by a composition, preferably an aqueous composition, containing:
[0013] (a) guanidine and / or a salt of unsubstituted guanidine, and
[0014] (b) at least one further component selected from the group consisting of,
[0015] 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 butyl carbamate (IPBC), amino-methyl-propanol (AMP), amino-ethyl-propanediol (AEPD), monoethanolamine (MEA), ethylhexylglycerol, hexylglycerol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1 ,2-octanediol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol,
[0016] Ethylenediaminetetraacetic acid (EDTA), (l-hydroxyethylidene)bisphosphonic acid (HEDP), sodium pyrithione, zinc pyrithione, o-phenylphenol (oPP), sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid and zinc.
[0017] The composition according to the invention has the advantage that the guanidine or its salt, component (a), which is hitherto unknown as an antimicrobial agent, and the at least one further component from the above-mentioned group, group (b), interact synergistically and can therefore be used in low concentrations when used simultaneously, compared to the low concentrations required for the individual components. "At least one further component" in the context of the present invention means that the composition contains a single component or compound selected from the group or several, i.e., two, three, four, five, or more, components or compounds from the group.
[0018] Within the scope of the present invention, both the amounts of the respective components (a) and (b) and the weight ratios of components (a) and (b) to one another are specified. The amounts refer in each case to the lead structures, the guanidine, or to the lead structure of component (b). Likewise, when determining the specified weight ratios, the content in relation to the guanidine, without taking into account any counterion, and the content of the lead structure of the further component (b), without taking into account any counterion, in the composition are used as a basis.
[0019] For the purposes of the present invention, guanidine and / or a salt of unsubstituted guanidine means that the composition contains, as active component (a), guanidine and / or optionally also one or more salts of unsubstituted guanidine. The guanidine is the compound according to the formula shown below:
[0020] The salts of non-substituted guanidine or guanidine salts within the meaning of the present invention are guanidine or guanidinium salts of the general formula shown below: where n is 1, 2 or 3, and where the counterion X n ' for example chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, formate, acetate or citrate.
[0021] According to a preferred embodiment of the invention, the composition according to the invention contains as component (a) guanidine hydrochloride and / or guanidine carbonate, according to a particularly preferred embodiment of the invention, the composition contains as component (a) guanidine carbonate.
[0022] The amount of component (a), guanidine and / or its salt contained in the preferably aqueous composition according to the invention can vary over wide ranges and is generally in the range from 100 to 10,000 ppm, preferably in an amount in the range from 200 to 7,500 ppm and particularly preferably in an amount in the range from 300 to 5,000 ppm, wherein the proportion relates to the content of guanidine in the total aqueous composition.
[0023] The amount of components (a) and (b) contained in the preferably aqueous composition according to the invention can vary widely. According to one embodiment, the composition is characterized in that it contains the guanidine and / or its salt and the at least one further component in a total amount in the range of 0.01% to 10%, preferably in the range of 0.02% to 5%, and particularly preferably in the range of 0.03% to 3%, based on the total composition.
[0024] The water content in the preferably aqueous composition according to the invention can vary over a wide range. Typically, the composition is characterized by a water content of greater than 1% by weight, preferably greater than 10% by weight, particularly preferably greater than 20% by weight, based on the total composition. The pH of the aqueous composition can vary over a wide range and is generally in a range from pH 4.5 to pH 12, preferably in the range from pH 5.0 to 11.5, particularly preferably in the range from pH 5.5 to pH 11. The pH can be adjusted to the claimed range using measures familiar to the person skilled in the art.
[0025] The preferred weight ratios of components (a) to (b) to one another, under which a surprisingly good antimicrobial effect can be achieved, can, as can be seen from the examples, vary individually.
[0026] Synergistic composition containing guanidine and 5-chloro-2-methylisothiazolin-3-one (CIT):
[0027] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt, and 5-chloro-2-methylisothiazolin-3-one.
[0028] According to a preferred embodiment, the invention relates to a composition containing guanidine and / or its salt and 5-chloro-2-methylisothiazolin-3-one, in a weight ratio of guanidine and / or its salt to 5-chloro-2-methylisothiazolin-3-one in the range from 62:1 to 9270:1, preferably in the range from 62:1 to 500:1, particularly preferably in the range from 62:1 to 300:1, wherein the content in relation to the guanidine, without taking into account any counterion, and the 5-chloro-2-methylisothiazolin-3-one in the composition is used as the basis for determining the weight ratio.
[0029] Synergistic composition containing guanidine and 2-methylisothiazolin-3-one (MIT):
[0030] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and 2-methylisothiazolin-3-one.
[0031] According to a preferred embodiment, the invention relates to a composition containing guanidine and / or its salt and 2-methylisothiazolin-3-one, in a weight ratio of guanidine to 2-methylisothiazolin-3-one generally in the range from 10.3:1 to 773:1, preferably in the range from 10.3:1 to 500:1, particularly preferably in the range from 10.3:1 to 300:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 2-methylisothiazolin-3-one in the composition.
[0032] Synergistic composition containing guanidine and l,2-benzisothiazolin-3-one (BIT):
[0033] According to one embodiment, the invention relates to a composition comprising guanidine and / or its salt and l,2-benzisothiazolin-3-one.
[0034] According to a preferred embodiment, the invention relates to a composition containing guanidine and / or its salt and l,2-benzisothiazolin-3-one, in a weight ratio of guanidine to l,2-benzisothiazolin-3-one generally in the range from 1.3:1 to 309:1, preferably in the range from 1.3:1 to 200:1, particularly preferably in the range from 1.3:1 to 100:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-benzisothiazolin-3-one in the composition. containing guanidine and N-butyl-1,2-benzisothiazolin-
[0035] 3-on (BBIT):
[0036] According to one embodiment, the invention relates to a composition comprising guanidine and / or its salt and N-butyl-1,2-benzisothiazolin-3-one.
[0037] According to a preferred embodiment, the invention relates to a composition containing guanidine and / or its salt and N-butyl-1,2-benzisothiazolin-3-one, in a weight ratio of guanidine to N-butyl-1,2-benzisothiazolin-3-one generally in the range from 0.52:1 to 309:1, preferably in the range from 0.52:1 to 200:1, particularly preferably in the range from 0.52:1 to 100:1, wherein the weight ratio is determined in each case based on the content in relation to the guanidine, without taking into account any counterion, and the N-butyl-1,2-benzisothiazolin-3-one in the composition.
[0038] Synergistic composition containing guanidine and N-methyl-1,2-
[0039] Benzisothiazolin-3-one (MBIT): According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and N-methyl-1,2-benzisothiazolin-3-one.
[0040] According to a preferred embodiment, the invention relates to a composition containing guanidine and N-methyl-l,2-benzisothiazolin-3-one, in a weight ratio of guanidine to N-methyl-l,2-benzisothiazolin-3-one generally in the range from 7.8:1 to 618:1, preferably in the range from 7.8:1 to 400:1, particularly preferably in the range from 7.8:1 to 300:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the N-methyl-l,2-benzisothiazolin-3-one in the composition.
[0041] Synergistic composition containing guanidine and N-octylisothiazolin-3-one:
[0042] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and N-octylisothiazolin-3-one.
[0043] According to a preferred embodiment, the invention relates to a composition containing guanidine and N-octylisothiazolin-3-one, in a weight ratio of guanidine to N-octylisothiazolin-3-one generally in the range from 1.4:1 to 82:1, preferably in the range from 1.4:1 to 50:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the N-octylisothiazolin-3-one in the composition.
[0044] Synergistic composition containing guanidine and bronopol:
[0045] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and bronopol.
[0046] According to a preferred embodiment, the invention relates to a composition containing guanidine and bronopol, in a weight ratio of guanidine to bronopol generally in the range from 7.8:1 to 824:1, preferably in the range from 7.8:1 to 200:1, particularly preferably in the range from 7.8:1 to 100:1, wherein the weight ratio is determined based on the content in relation to the guanidine, without taking into account any counterion, and the bronopol in the composition. containing guanidine and 2,2-dibromo-3-
[0047] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and 2,2-dibromo-3-nitrilopropionamide.
[0048] According to a preferred embodiment, the invention relates to a composition containing guanidine and 2,2-dibromo-3-nitrilepropionamide, in a weight ratio of guanidine to 2,2-dibromo-3-nitrilepropionamide, generally in the range from 7.8:1 to 3090:1, preferably in the range from 7.8:1 to 250:1, particularly preferably in the range from 7.8:1 to 100:1, wherein the content in relation to the guanidine, without taking into account any counterion, and the 2,2-dibromo-3-nitrilopropionamide in the composition is used as the basis for determining the weight ratio.
[0049] Synergistic composition containing guanidine and dibromodicyanobutane (DBDCB):
[0050] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and dibromodicyanobutane.
[0051] According to a preferred embodiment, the invention relates to a composition containing guanidine and dibromodicyanobutane in a weight ratio of guanidine to dibromodicyanobutane generally in the range from 0.78:1 to 309:1, preferably in the range from 0.8:1 to 200:1, particularly preferably in the range from 0.8:1 to 100:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the N-dibromodicyanobutane in the composition.
[0052] Synergistic composition containing guanidine and iodopropynyl butylcarbamate (IPBC):
[0053] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and iodopropynyl butylcarbamate.
[0054] According to a preferred embodiment, the invention relates to a composition containing guanidine and iodopropynyl butylcarbamate in a weight ratio of guanidine to iodopropynyl butylcarbamate generally in the range from 0.83:1 to 103:1, preferably in the range from 1:1 to 90:1, particularly preferably in the range from 1:1 to 80:1, wherein the weight ratio is determined based on the content in relation to the guanidine, without taking into account any counterion, and the iodopropynyl butylcarbamate in the composition.
[0055] Synergistic composition containing guanidine and 2-amino-2-methyl-l-propanol (AMP):
[0056] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and 2-amino-2-methyl-l-propanol.
[0057] According to a preferred embodiment, the invention relates to a composition containing guanidine and 2-amino-2-methyl-1-propanol, in a weight ratio of guanidine to 2-amino-2-methyl-1-propanol generally in the range from 0.3:1 to 20:1, preferably in the range from 0.5:1 to 15:1, particularly preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 2-amino-2-methyl-1-propanol in the composition.
[0058] Synergistic composition containing guanidine and 2-amino-l,3-ethylpropanediol (AEPD):
[0059] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and 2-amino-1,3-ethylpropanediol.
[0060] According to a preferred embodiment, the invention relates to a composition containing guanidine and 2-amino-l,3-ethylpropanediol, in a weight ratio of guanidine to 2-amino-l,3-ethylpropanediol generally in the range from 0.2:1 to 15:1, preferably in the range from 0.5:1 to 10:1, particularly preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 2-amino-l,3-ethylpropanediol in the composition.
[0061] Synergistic composition containing guanidine and monoethanolamine (MEA): According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and monoethanolamine.
[0062] According to a preferred embodiment, the invention relates to a composition containing guanidine and monoethanolamine, in a weight ratio of guanidine to monoethanolamine generally in the range from 0.2:1 to 30:1, preferably in the range from 0.5:1 to 20:1, particularly preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined in each case based on the content in relation to the guanidine, without taking into account any counterion, and the monoethanolamine in the composition.
[0063] Synergistic composition containing guanidine and ethylhexylglycerin:
[0064] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and ethylhexylglycerin.
[0065] According to a preferred embodiment, the invention relates to a composition containing guanidine and ethylhexylglycerol, in a weight ratio of guanidine to ethylhexylglycerol generally in the range from 0.5:1 to 15:1, preferably in the range from 0.5:1 to 10:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the monoethanolamine in the composition.
[0066] Synergistic composition containing guanidine and hexylglycerin:
[0067] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and hexylglycerol.
[0068] According to a preferred embodiment, the invention relates to a composition containing guanidine and hexylglycerol, in a weight ratio of guanidine to hexylglycerol generally in the range from 0.5:1 to 15:1, preferably in the range from 0.5:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the hexylglycerol in the composition.
[0069] Synergistic composition containing guanidine and 1,2-pentanediol: According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and 1,2-pentanediol.
[0070] According to a preferred embodiment, the invention relates to a composition containing guanidine and 1,2-pentanediol, in a weight ratio of guanidine to 1,2-pentanediol generally in the range from 0.07:1 to 7.5:1, preferably in the range from 0.1:1 to 7.5:1, particularly preferably in the range from 0.5:1 to 7.5:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-pentanediol in the composition.
[0071] Synergistic composition containing guanidine and 1,2-hexanediol:
[0072] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and 1,2-hexanediol.
[0073] According to a preferred embodiment, the invention relates to a composition containing guanidine and 1,2-hexanediol, in a weight ratio of guanidine to 1,2-hexanediol generally in the range from 0.06:1 to 15:1, preferably in the range from 0.1:1 to 10:1, particularly preferably in the range from 0.5:1 to 10:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-hexanediol in the composition.
[0074] Synergistic composition containing guanidine and 1,2-heptanediol:
[0075] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and 1,2-heptanediol.
[0076] According to a preferred embodiment, the invention relates to a composition containing guanidine and 1,2-heptanediol, in a weight ratio of guanidine to 1,2-heptanediol generally in the range of 0.25:1 to 30:1, preferably in the range of 0.5:1 to 20:1, particularly preferably in the range of 0.5:1 to 10:1, wherein the weight ratio is determined based on the content of guanidine, without taking into account any counterion, and the 1,2-heptanediol in the composition. Synergistic composition containing guanidine and 1,2-octanediol:
[0077] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and 1,2-octanediol.
[0078] According to a preferred embodiment, the invention relates to a composition containing guanidine and 1,2-octanediol, in a weight ratio of guanidine to 1,2-octanediol generally in the range from 0.2:1 to 6:1, preferably in the range from 0.5:1 to 6:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-octanediol in the composition.
[0079] Synergistic composition containing guanidine and phenoxyethanol:
[0080] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and phenoxyethanol.
[0081] According to a preferred embodiment, the invention relates to a composition containing guanidine and phenoxyethanol in a weight ratio of guanidine to phenoxyethanol generally in the range from 0.13:1 to 3.6:1, preferably in the range from 0.3:1 to 3.6:1, particularly preferably in the range from 0.5:1 to 3.6:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the phenoxyethanol in the composition.
[0082] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and phenethyl alcohol.
[0083] According to a preferred embodiment, the invention relates to a composition containing guanidine and phenethyl alcohol, in a weight ratio of guanidine to phenethyl alcohol generally in the range from 0.15:1 to 12:1, preferably in the range from 0.3:1 to 12:1, particularly preferably in the range from 0.5:1 to 12:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the phenoxyethanol in the composition.
[0084] Synergistic composition containing guanidine and phenylpropanol:
[0085] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and phenylpropanol.
[0086] According to a preferred embodiment, the invention relates to a composition containing guanidine and phenylpropanol in a weight ratio of guanidine to phenylpropanol generally in the range from 0.4:1 to 6:1, preferably in the range from 0.5:1 to 6:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the phenoxyethanol in the composition.
[0087] Synergistic composition containing guanidine and benzyl alcohol:
[0088] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and benzyl alcohol.
[0089] According to a preferred embodiment, the invention relates to a composition containing guanidine and benzyl alcohol in a weight ratio of guanidine to benzyl alcohol generally in the range from 1:1 to 12:1, preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the benzyl alcohol in the composition.
[0090] Synergistic composition containing guanidine and isopropanol:
[0091] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and isopropanol.
[0092] According to a preferred embodiment, the invention relates to a composition containing guanidine and isopropanol, in a weight ratio of guanidine to isopropanol generally in the range from 0.004:1 to 3:1, preferably in the range from 0.01:1 to 3:1, particularly preferably 0.1 to 3:1, wherein in the determination of the
[0093] The weight ratio is based on the content in relation to the guanidine, without taking into account any counterion, and the isopropanol in the composition.
[0094] Synergistic composition containing guanidine and ethylenediaminetetraacetic acid (EDTA):
[0095] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and ethylenediaminetetraacetic acid and / or its salt(s).
[0096] According to a preferred embodiment, the invention relates to a composition containing guanidine and ethylenediaminetetraacetic acid, in a weight ratio of guanidine to ethylenediaminetetraacetic acid generally in the range from 0.6:1 to 37:1, preferably in the range from 0.6:1 to 20:1, particularly preferably 0.6:1 to 15:1, wherein the weight ratio is determined in each case based on the content in relation to the guanidine, without taking into account any counterion, and the ethylenediaminetetraacetic acid in the composition.
[0097] Synergistic composition containing guanidine and (1-hydroxyethylidenebisphosphonic acid (HEPP):
[0098] According to one embodiment, the invention relates to a composition comprising guanidine and / or its salt and (l-hydroxyethylidene)bisphosphonic acid and / or its salt(s).
[0099] According to a preferred embodiment, the invention relates to a composition containing guanidine and (l-hydroxyethylidene)bisphosphonic acid, in a weight ratio of guanidine to (l-hydroxyethylidene)bisphosphonic acid generally in the range from 0.6:1 to 1.5:1, preferably in the range from 0.6:1 to 1:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the (1-hydroxyethylidene)bisphosphonic acid in the composition.
[0100] Synergistic composition containing guanidine and sodium pyrithione: According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and sodium pyrithione.
[0101] According to a preferred embodiment, the invention relates to a composition containing guanidine and sodium pyrithione, in a weight ratio of guanidine to sodium pyrithione generally in the range from 3.6:1 to 180:1, preferably in the range from 3.6:1 to 100:1, particularly preferably 3.6:1 to 50:1, wherein the weight ratio is determined in each case based on the content in relation to the guanidine, without taking into account any counterion, and the sodium pyrithione in the composition.
[0102] Synergistic composition containing guanidine and zinc pyrithione:
[0103] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and zinc pyrithione.
[0104] According to a preferred embodiment, the invention relates to a composition containing guanidine and zinc pyrithione, in a weight ratio of guanidine to zinc pyrithione generally in the range from 3.6:1 to 180:1, preferably in the range from 3.6:1 to 100:1, particularly preferably 3.6:1 to 50:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the zinc pyrithione in the composition.
[0105] Synergistic composition containing guanidine and o-phenylphenol (oPP):
[0106] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and o-phenylphenol.
[0107] According to a preferred embodiment, the invention relates to a composition containing guanidine and o-phenylphenol, in a weight ratio of guanidine to o-phenylphenol generally in the range of 0.62:1 to 49:1, preferably in the range of 0.62:1 to 40:1, particularly preferably 0.62:1 to 30:1, wherein the weight ratio is determined based on the content of guanidine, without taking into account any counterion, and the o-phenylphenol in the composition. Synergistic composition containing guanidine and sorbic acid:
[0108] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and sorbic acid and / or its salt(s).
[0109] According to a preferred embodiment, the invention relates to a composition containing guanidine and sorbic acid, in a weight ratio of guanidine to sorbic acid generally in the range from 0.1:1 to 50:1, preferably in the range from 0.25:1 to 40:1, particularly preferably 0.25:1 to 30:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the sorbic acid in the composition.
[0110] Synergistic composition containing guanidine and benzoic acid:
[0111] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and benzoic acid and / or its salt(s).
[0112] According to a preferred embodiment, the invention relates to a composition containing guanidine and benzoic acid in a weight ratio of guanidine to benzoic acid generally in the range from 0.25:1 to 88:1, preferably in the range from 0.25:1 to 50:1, particularly preferably 0.25:1 to 30:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the benzoic acid in the composition.
[0113] Synergistic composition containing guanidine and salicylic acid:
[0114] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and salicylic acid and / or its salt(s).
[0115] According to a preferred embodiment, the invention relates to a composition containing guanidine and salicylic acid in a weight ratio of guanidine to salicylic acid generally in the range from 0.24:1 to 43:1, preferably in the range from 0.24:1 to 30:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the salicylic acid in the composition.
[0116] Synergistic composition containing guanidine and lactic acid:
[0117] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and lactic acid and / or its salt(s).
[0118] According to a preferred embodiment, the invention relates to a composition containing guanidine and lactic acid, in a weight ratio of guanidine to lactic acid generally in the range from 0.03:1 to 23:1, preferably in the range from 0.03:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the lactic acid in the composition.
[0119] Synergistic composition containing guanidine and citric acid:
[0120] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and citric acid and / or its salt(s).
[0121] According to a preferred embodiment, the invention relates to a composition containing guanidine and citric acid in a weight ratio of guanidine to citric acid in the range from 1:0.014 to 12:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the citric acid in the composition.
[0122] Synergistic composition containing guanidine and zinc:
[0123] According to one embodiment, the invention relates to a composition containing guanidine and / or its salt and zinc. Within the scope of the present invention, the zinc is provided by at least one zinc compound serving as a zinc source. The zinc compound is preferably selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc ascorbate, zinc dehydroacetate, zinc hydroxide, and zinc carboxylate. According to a preferred embodiment of the 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 incorporated into the composition.
[0124] According to a preferred embodiment, the invention relates to a composition containing guanidine and zinc in a weight ratio of guanidine to zinc in the range from 0.77:1 to 12:1, preferably 1:1 to 12:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and in relation to the zinc ion.
[0125] According to a preferred embodiment of the invention, the composition according to the invention is characterized in that the weight ratio of guanidine and / or its salt to 5-chloro-2-methylisothiazolin-3-one is in the range from 62:1 to 9270:1, that the weight ratio of guanidine and / or its salt to 2-methyl-4-isothiazolin-3-one is in the range from 10.3:1 to 773:1, that the weight ratio of guanidine and / or its salt to 1,2-benzisothiazolin-3-one is in the range from 1.3:1 to 309:1, that the weight ratio of guanidine and / or its salt to N-butyl-1,2-benzisothiazolin-3-one is in the range from 0.52:1 to 309:1, that 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, that 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,that the weight ratio of guanidine and / or its salt to bronopol is in the range from 7.8:1 to 824:1, that the weight ratio of guanidine and / or its salt to 2,2-dibromo-3-nitrilopropionamide is in the range from 7.8:1 to 3090:1, that the weight ratio of guanidine and / or its salt to dibromodicyanobutane is in the range from 0.78:1 to 309:1, that the weight ratio of guanidine and / or its salt to iodopropynyl butylcarbamate is in the range from 0.83:1 to 103:1, that the weight ratio of guanidine and / or its salt to 2-amino-2-methyl-l-propanol is in the range from 0.3:1 to 20:1, that the weight ratio of guanidine and / or its salt to 2-Amino-l,3-ethylpropanediol is in the range of 0.2:1 to 15:1, that the weight ratio of guanidine and / or its salt to monoethanolamine is in the range of 0.2:1 to 30:1, that the weight ratio of guanidine and / or its salt to ethylhexylglycerol is in the range of 0.5:1 to 15:1, that 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, that 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, that the weight ratio of guanidine and / or its salt to 1,2-hexanediol is in the range of 0.06:1 to 15:1, that the weight ratio of guanidine and / or its salt to 1,2-heptanediol is in the range of 0.25:1 to 30:1, that the weight ratio of guanidine and / or its salt to 1,2-octanediol is in the range of 0.2:1 to 6:1, that the 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 phenethyl alcohol 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, that the weight ratio of guanidine and / or its salt to benzyl alcohol is in the range of 1:1 to 12:1, that the weight ratio of guanidine and / or its salt to isopropanol is in the range of 0.004:1 to 3:1, that the weight ratio of guanidine and / or its salt to ethylenediaminetetraacetic acid is in the range of 0.6:1 to 37:1, that the weight ratio of guanidine and / or its salt to (1-hydroxyethylidene)bisphosphonic acid is in the range of 0.6:1 to 1.5:1, that the weight ratio of guanidine and / or its salt to sodium pyrithione is in the range of 3.6:1 to 180:1, that the weight ratio of guanidine and / or its salt to zinc pyrithione is in the range of 3.6:1 to 180:1 that the weight ratio of guanidine and / or its salt to o-phenylphenol is in the range of 0.62: 1 to 49: 1, that 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, that the weight ratio of guanidine and / or its salt to benzoic acid and / or its salt is in the range from 0.25:1 to 88:1, that the weight ratio of guanidine and / or its salt to salicylic acid and / or its salt is in the range from 0.24:1 to 43:1, that the weight ratio of guanidine and / or its salt to lactic acid and / or its salt is in the range from 0.03:1 to 23:1, that the weight ratio of guanidine and / or its salt to citric acid and / or its salt is in the range from 0.014:1 to 12:1, that the weight ratio of guanidine and / or its salt to zinc is in the range from 0.77:1 to 12:1, wherein in determining the weight ratio the content in relation to the guanidine, without taking into account any Counterion in the composition is taken as a basis.,
[0126] According to one embodiment of the present invention, the aqueous composition is characterized in that it is a technical product selected from the group consisting of: lignosulfonates and starch preparations in coatings, paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, chalk slurries, mineral slurries, ceramic masses, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning agents, pigment pastes and pigment dispersions, inks, lithographic fluids, thickeners, cosmetic products, toiletries, water circuits, fluids in wood processing, fluids in petroleum production, fluids in paper processing, fluids in leather production, fluids in textile production, drilling and cutting oils, hydraulic fluids,Cooling lubricants and biocidal products.,
[0127] The content of components (a) and (b) in the technical products defined above (the application concentration) can vary widely depending on the intended use and is usually determined by the person skilled in the art of biocides. The concentration ranges given below provide the person skilled in the art with an indication of the amounts to be used:
[0128] The amount of component (a), guanidine and / or its salt contained in the technical products can vary over wide ranges and is generally in the range from 100 to 10,000 ppm, preferably in an amount in the range from 200 to 7,500 ppm and particularly preferably in an amount in the range from 300 to 5,000 ppm, wherein the proportion relates to the content of guanidine in the entire technical product.
[0129] The amount of component (b) contained in the technical products can also vary over a wide range:
[0130] When 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 0.5 to 200 ppm, preferably from 5 to 100 ppm, particularly preferably from 10 to 50 ppm, and especially preferably from 15 to 30 ppm. When 2-methyl-4-isothiazolin-3-one (MIT) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 0.5 to 200 ppm, preferably from 1 to 150 ppm, particularly preferably from 5 to 125 ppm, and especially preferably from 10 to 100 ppm.
[0131] When l,2-benzisothiazolin-3-one (BIT) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 500 ppm, preferably in an amount from 5 to 500 ppm, particularly preferably in an amount from 10 to 500 ppm.
[0132] In the presence of N-butyl-1,2-benzisothiazolin-3-one (BBIT) as component (b), this is generally contained in the aqueous composition or the technical product in an amount in the range from 5 to 2,500 ppm, preferably in an amount from 10 to 2,000 ppm, particularly preferably in an amount from 10 to 1,500 ppm.
[0133] When N-methyl-1,2-benzisothiazolin-3-one (MBIT) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 500 ppm, preferably in an amount from 5 to 500 ppm, particularly preferably in an amount from 10 to 1,000 ppm.
[0134] When octylisothiazolinone (OIT) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 2,500 ppm, preferably in an amount from 5 to 2,000 ppm, particularly preferably in an amount from 10 to 1,500 ppm.
[0135] When Bronopol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 1 to 1,000 ppm, preferably from 5 to 750 ppm, particularly preferably from 10 to 500 ppm. When dibromonitrilopropionamide (DBNPA) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 1 to 1,000 ppm, preferably from 5 to 750 ppm, particularly preferably from 10 to 500 ppm.
[0136] In the presence of dibromodicyanobutane (DBDCB) as a further component, this is generally contained in the product preserved with the composition according to the invention in an amount in the range of 1 to 1,000 ppm, preferably in an amount of 5 to 750 ppm, particularly preferably in an amount of 10 to 500 ppm.
[0137] When iodopropynyl butylcarbamate (IPBC) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 5,000 ppm, preferably in an amount from 25 to 4,500 ppm, particularly preferably in an amount from 50 to 4,000 ppm.
[0138] When aminomethylpropanol (AMP) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 25 to 7,500 ppm, particularly preferably in an amount from 50 to 5,000 ppm.
[0139] When aminoethylpropanediol (AEPD) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 25 to 7,500 ppm, particularly preferably in an amount from 50 to 5,000 ppm.
[0140] When monoethanolamine (MEA) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 10 to 10,000 ppm, preferably from 25 to 7,500 ppm, particularly preferably from 50 to 5,000 ppm. When ethylhexylglycerol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, particularly preferably from 100 to 5,000 ppm.
[0141] When hexylglycerol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount of from 50 to 7,500 ppm, particularly preferably in an amount of from 100 to 5,000 ppm.
[0142] When 1,2-pentanediol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
[0143] When 1,2-hexanediol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
[0144] When 1,2-heptanediol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
[0145] When 1,2-octanediol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, particularly preferably from 100 to 5,000 ppm. When phenoxyethanol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 10 to 10,000 ppm, preferably from 50 to 7,500 ppm, particularly preferably from 100 to 5,000 ppm.
[0146] When phenethyl alcohol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
[0147] When phenylpropanol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
[0148] When benzyl alcohol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
[0149] When isopropanol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 30,000 ppm, preferably in an amount from 50 to 20,000 ppm, particularly preferably in an amount from 100 to 15,000 ppm.
[0150] When ethylenediaminetetraacetic acid (EDTA) is present as component (b), it is generally present in the aqueous composition or the technical product preserved in an amount ranging from 10 to 10,000 ppm, preferably in an amount ranging from 50 to 7,500 ppm, particularly preferably in an amount ranging from 100 to 5,000 ppm. TI
[0151] When (l-hydroxyethylidene)bisphosphonic acid (HEDP) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
[0152] When sodium pyrithione is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 2,500 ppm, preferably in an amount of 5 to 1,500 ppm, particularly preferably in an amount of 10 to 1,000 ppm.
[0153] When zinc pyrithione is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 2,500 ppm, preferably in an amount of 5 to 1,500 ppm, particularly preferably in an amount of 10 to 1,000 ppm.
[0154] When o-phenylphenol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 10,000 ppm, preferably in an amount from 10 to 5,000 ppm, particularly preferably in an amount from 25 to 2,500 ppm, especially preferably in an amount from 50 to 1,500 ppm.
[0155] When sorbic acid is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 10,000 ppm, preferably in an amount of 5 to 7,500 ppm, particularly preferably in an amount of 10 to 5,000 ppm.
[0156] When benzoic acid is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 1 to 10,000 ppm, preferably from 5 to 7,500 ppm, particularly preferably from 10 to 5,000 ppm. When salicylic acid is present as component (b), it is generally present in the aqueous composition or the technical product in an amount ranging from 1 to 10,000 ppm, preferably from 5 to 7,500 ppm, particularly preferably from 10 to 5,000 ppm.
[0157] When lactic acid is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 50,000 ppm, preferably in an amount of 5 to 25,000 ppm, particularly preferably in an amount of 10 to 15,000 ppm.
[0158] When citric acid is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 100,000 ppm, preferably in an amount of 5 to 50,000 ppm, particularly preferably in an amount of 10 to 25,000 ppm.
[0159] When zinc is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 5,000 ppm, preferably in an amount from 25 to 2,500 ppm, preferably in an amount from 50 to 1,000 ppm, particularly preferably in an amount from 100 to 500 ppm.
[0160] The present invention further relates to the use of the above-defined, preferably aqueous compositions for the preservation of containers, or the use for the preservation of technical products selected from the group consisting of lignin sulfonates and starch preparations in coatings, paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, chalk slurries, mineral slurries, ceramic masses, adhesives, fragrances, case-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning agents, pigment pastes and pigment dispersions, inks, lithographic liquids, thickeners, cosmetic products, toiletries, water cycles, liquids in wood processing, liquids in petroleum production, liquids in paper processing, liquids in leather production, liquids in textile production,Drilling and cutting oils, hydraulic fluids and cooling lubricants.
[0161] According to a further embodiment, the present invention relates to the use of:
[0162] (a) Guanidine and / or a salt of unsubstituted guanidine to improve the antimicrobial efficacy of one or more compounds selected from the group (b) consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, l,2-benzisothiazolin-3-one, N-butyl-l,2-benzisothiazolin-3-one, N-methyl-l,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, aminomethylpropanol, aminoethylpropanediol, monoethanolamine, ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1 ,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (1-hydroxyethylidene)bis-phosphonic acid,
[0163] Sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid and zinc.
[0164] As can be seen from the examples given below, the use of guanidine or its salt, which is not known to date as an antimicrobial active ingredient, leads to a surprising synergistic increase in the effect of at least one further component from the group (b) given above.
[0165] Due to this surprising increase in activity, the at least one biocidal active component from group (b) can be used in significantly lower concentrations in the presence of guanidine. The amounts of components (a) and (b) used can vary widely and are, for example, in the range from 0.01% to 10%, preferably in the range from 0.02% to 5%, and particularly preferably in the range from 0.03% to 3%, based on the total composition containing the components. 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 l,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-1,2-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 103:1 and / or the weight ratio of guanidine and / or its salt to 2-amino-2-methyl-l-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-amino-l,3-ethylpropanediol 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 in the range of 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 0.07:1 to 7.5:1 and / or the weight ratio of guanidine and / or its salt to 1,2-hexanediol is in the range of 0.06:1 to 15:1 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 phenethyl alcohol 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 0.4:1 to 6:1 and / or 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 isopropanol 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-hydroxyethylidene)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 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 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 49:1 and / or 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 and / or 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 and / or 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 and / or 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 and / or 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, and / or the weight ratio of guanidine and / or its salt to zinc is in the range of 0.77:1 to 12:1, whereby the total content of guanidine and acid in the composition is used as the basis for determining the weight ratio.
[0166] The following examples serve to further illustrate the present invention:
[0167] Investigation of the synergistic interaction
[0168] The synergism of a combination of guanidine (added in the form of guanidine hydrochloride) with one biocide or one fungicide was investigated.a substance selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one (CIT), 2-methyl-4-isothiazolin-3-one (MIT), l,2-benzisothiazolin-3-one (BIT), N-butyl-1,2-benzisothiazolin-3-one (BBIT), N-methyl-l,2-benzisothiazolin-3-one (MBIT), octylisothiazolinone (OIT), bronopol, dibromonitrilopropionamide (DBNPA), dibromodicyanobutane (DBDCB), iodopropynyl butylcarbamate (IPBC), amino-methyl-propanol (AMP), amino-ethyl-propanediol (AEPD), monoethanolamine (MEA), ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1 ,2-Heptanediol, 1,2-Octanediol, Phenoxyethanol, Benzyl alcohol, Isopropanol, ethylenediaminetetraacetic acid (EDTA), (1-Hydroxyethylidene)bisphosphonic acid (HEDP), Pyrithione, o-Phenylphenol (oPP), Sorbic acid, Benzoic acid, Salicylic acid, Lactic acid, Citric acid and Zinc oxide (ZnO) were investigated for a synergistic interaction.
[0169] Gram-negative bacterial species from the Pseudomonad group, Pseudomonas putida DSM 115323 and Pseudomonas spec. DSM 115322, were used as test organisms. Mixtures with different concentrations of the respective active ingredients were prepared and tested for their effect on the Pseudomonads. The tests were carried out in Müller-Hinton Broth (MHB) at a cell density of 10 6 Germs per ml. When using organic acids as combination partners to the guanidine, MHB was adjusted to pH 5.5.
[0170] Incubation took place in microtiter plates for 48 hours at 30 °C. After 48 hours, the samples were evaluated for turbidity due to growth, and the optical density was also determined photometrically. This allowed the minimum inhibitory concentrations (MICs) of the two active substances to be determined individually and in combination.
[0171] The resulting synergism was numerically expressed by calculating the synergy index (SI). The calculation was carried out according to the standard method of FC Kull et al., Applied Microbiology, Vol. 9 (1961), p. 538. There, the synergy index (SI) is calculated using the following formula:
[0172] Synergy Index SI = Q S / QA + Qb / Qß
[0173] Q a = Concentration of component A in the mixture A + B
[0174] QA = Concentration of component A as the sole biocide
[0175] Qb = Concentration of component B in the mixture A + B
[0176] QB = Concentration of component B as sole biocide
[0177] If the synergy index is above 1, this means that antagonism exists. If the synergy index is above 1, this means that the effects of the two biocides / compounds are additive. If the synergy index is below 1, this means that the two biocides / compounds are synergistic.
[0178] Example 1: Investigation of the synergistic interaction between guanidine and 5-chloro-2-methyl-4-isothiazolin-3-one (CIT)
[0179] Calculation of the synergy index of guanidine and CIT with respect to Pseudomonas putida DSM 115323 during an incubation time of 48 hours at 30 °C.
[0180] Table 1
[0181] Qa: Concentration of guanidine in the mixture showing an endpoint
[0182] QA: Concentration of guanidine as the sole agent showing an endpoint
[0183] Qb: Concentration of CIT in the mixture showing an endpoint
[0184] QB: Concentration of CIT as the sole agent showing an endpoint
[0185] Table 1 shows that the optimal synergism, i.e., the lowest synergy index (0.75) of a composition of guanidine and CIT, is at a ratio of 1545 ppm guanidine to 1.5 ppm CIT. Synergism can be demonstrated when the weight ratio of guanidine to CIT is in the range of 62:1 to 9270:1.
[0186] Example 2: Investigation of the synergistic interaction between guanidine and 2-methyl-4-isothiazolin-3-one (MIT)
[0187] Calculation of the synergy index of guanidine and MIT with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0188] Table 2
[0189] Qa: Concentration of guanidine in the mixture showing an endpoint
[0190] QA: Concentration of guanidine as the sole agent showing an endpoint
[0191] Qb: Concentration of MIT in the mixture showing an endpoint
[0192] QB: Concentration of MIT as the sole agent showing an endpoint
[0193] Table 2 shows that the optimal synergism, i.e., the lowest synergy index (0.73) of a guanidine / MIT composition, is at a ratio of 3090 ppm guanidine to 30 ppm MIT. Synergism can be demonstrated when the weight ratio of guanidine to MIT is in the range of 10.3:1 to 773:1.
[0194] Example 3: Investigation of the synergistic interaction between guanidine and l,2-benzisothiazolin-3-one (BIT)
[0195] Calculation of the synergy index of guanidine and BIT with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0196] Table 3
[0197] Qa: Concentration of guanidine in the mixture showing an endpoint QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of BIT in the mixture showing an endpoint QB: Concentration of BIT as the sole agent showing an endpoint
[0198] Table 3 shows that the optimal synergism, i.e., the lowest synergy index (0.67) of a guanidine / BIT composition, is at a ratio of 3090 ppm guanidine to 100 ppm BIT. Synergism can be demonstrated when the weight ratio of guanidine to BIT is in the range of 1.3:1 to 309:1.
[0199] Example 4: Investigation of the synergistic interaction between guanidine and N-butyl-l,2-benzisothiazolin-3-one (BBIT)
[0200] Calculation of the synergy index of guanidine and BBIT with respect to Pseudomonas spec.
[0201] DSM 115322 with an incubation time of 48 hours at 30 °C.
[0202] Table 4
[0203] Qa: Concentration of guanidine in the mixture showing an endpoint
[0204] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of BBIT in the mixture showing an endpoint QB: Concentration of BBIT as the sole agent showing an endpoint
[0205] Table 4 shows that the optimal synergism, i.e., the lowest synergy index (0.67) of a guanidine / BBIT composition, is at a ratio of 1545 ppm guanidine to 200 ppm BBIT. Synergism can be demonstrated when the weight ratio of guanidine to BBIT is in the range of 0.52:1 to 309:1.
[0206] Example 5: Investigation of the synergistic interaction between guanidine and N-methyl-1,2-benzisothiazolin-3-one (MBIT)
[0207] Calculation of the synergy index of guanidine and MBIT with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0208] Table 5
[0209] Qa: Concentration of guanidine in the mixture showing an endpoint QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of MBIT in the mixture showing an endpoint QB: Concentration of MBIT as the sole agent showing an endpoint
[0210] Table 5 shows that the optimal synergism, i.e., the lowest synergy index (0.75) of a guanidine / MBIT composition, is at a ratio of 3090 ppm guanidine to 125 ppm MBIT. Synergism can be demonstrated when the weight ratio of guanidine to MBIT is in the range of 7.8:1 to 618:1.
[0211] Example 6: Investigation of the synergistic interaction between guanidine and octylisothiazolinone (OIT)
[0212] Calculation of the synergy index of guanidine and OIT with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0213] Table 6
[0214] Qa: Concentration of guanidine in the mixture showing an endpoint
[0215] QA: Concentration of guanidine as the sole agent showing an endpoint
[0216] Qb: Concentration of OIT in the mixture showing an endpoint
[0217] QB: Concentration of OIT as the sole agent showing an endpoint
[0218] Table 6 shows that the optimal synergism, i.e., the lowest synergy index (0.87) of a guanidine / OIT composition, is at a ratio of 618 to 1590 ppm guanidine to 200 to 175 ppm OIT. Synergism can be demonstrated when the weight ratio of guanidine to OIT is in the range of 1.4:1 to 82:1.
[0219] Example 7: Investigation of the synergistic interaction between guanidine and bronopol
[0220] Calculation of the synergy index of guanidine and bronopol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0221] Table 7
[0222] Qa: Concentration of guanidine in the mixture showing an endpoint
[0223] QA: Concentration of guanidine as the sole agent showing an endpoint
[0224] Qb: Concentration of Bronopol in the mixture showing an endpoint
[0225] QB: Concentration of Bronopol as the sole agent showing an endpoint
[0226] Table 7 shows that the optimal synergism, i.e., the lowest synergy index (0.77) of a guanidine / bronopol composition, is at a ratio of 1545 ppm guanidine to 15 ppm bronopol. Synergism can be demonstrated when the weight ratio of guanidine to bronopol is in the range of 7.8:1 to 824:1.
[0227] Example 8: Investigation of the synergistic interaction between guanidine and dibromonitrilopropionamide (DBNPA)
[0228] Calculation of the synergy index of guanidine and DBNPA with respect to Pseudomonas spec.
[0229] DSM 115322 with an incubation time of 48 hours at 30 °C.
[0230] Table 8
[0231] Qa: Concentration of guanidine in the mixture showing an endpoint
[0232] QA: Concentration of guanidine as the sole agent showing an endpoint
[0233] Qb: Concentration of DBNPA in the mixture showing an endpoint
[0234] QB: Concentration of DBNPA as the sole agent showing an endpoint
[0235] Table 8 shows that the optimal synergism, i.e., the lowest synergy index (0.82) of a guanidine / DBNPA composition, is at a ratio of 155 ppm guanidine to 20 ppm DBNPA. Synergism can be demonstrated when the weight ratio of guanidine to DBNPA is in the range of 7.8:1 to 3090:1.
[0236] Example 9: Investigation of the synergistic interaction between guanidine and dibromodicyanobutane (DBDCB)
[0237] Calculation of the synergy index of guanidine and DBDCB with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0238] Table 9
[0239] Qa: Concentration of guanidine in the mixture showing an endpoint
[0240] QA: Concentration of guanidine as the sole agent showing an endpoint
[0241] Qb: Concentration of DBDCB in the mixture showing an endpoint
[0242] QB: Concentration of DBDCB as the sole agent showing an endpoint
[0243] Table 9 shows that the optimal synergism, i.e., the lowest synergy index (0.77) of a guanidine / DBDCB composition, is at a ratio of 1590 ppm guanidine to 150 ppm DBDCB. Synergism can be demonstrated when the weight ratio of guanidine to DBDCB is in the range of 0.78:1 to 309:1.
[0244] Example 10: Investigation of the synergistic interaction between guanidine and iodopropynyl butylcarbamate (IPBC)
[0245] Calculation of the synergy index of guanidine and IPBC with respect to Pseudomonas spec.
[0246] DSM 115322 with an incubation time of 48 hours at 30 °C.
[0247] Table 10
[0248] Qa: Concentration of guanidine in the mixture showing an endpoint
[0249] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of IPBC in the mixture showing an endpoint QB: Concentration of IPBC as the sole agent showing an endpoint
[0250] Table 10 shows that the optimal synergism, i.e., the lowest synergy index (0.83) of a guanidine / IPBC composition, is at a ratio of 4635 ppm guanidine to 300 ppm IPBC. Synergism can be demonstrated when the weight ratio of guanidine to IPBC is in the range of 0.83:1 to 103:1.
[0251] Example 11 : Investigation of the synergistic interaction between guanidine and 2-amino-2-methyl- 1 -propanol (AMP)
[0252] Calculation of the synergy index of guanidine and AMP with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0253] Table 11
[0254] Qa: Concentration of guanidine in the mixture showing an endpoint
[0255] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of AMP in the mixture showing an endpoint QB: Concentration of AMP as the sole agent showing an endpoint
[0256] Table 11 shows that the optimal synergism, i.e., the lowest synergy index (0.73) of a guanidine-AMP composition, is at a ratio of 3090 ppm guanidine to 1000 ppm AMP. Synergism can be demonstrated when the weight ratio of guanidine to AMP is in the range of 0.3:1 to 20:1.
[0257] Example 12: Investigation of the synergistic interaction between guanidine and 2-amino-1,3-ethylpropanediol (AEPD)
[0258] Calculation of the synergy index of guanidine and AEPD with respect to Pseudomonas spec.
[0259] DSM 115322 with an incubation time of 48 hours at 30 °C.
[0260] Table 12
[0261] Qa: Concentration of guanidine in the mixture showing an endpoint
[0262] QA: Concentration of guanidine as the sole agent showing an endpoint
[0263] Qb: Concentration of AEPD in the mixture showing an endpoint
[0264] QB: Concentration of AEPD as the sole agent showing an endpoint
[0265] Table 12 shows that the optimal synergism, i.e., the lowest synergy index (0.73) of a guanidine / AEPD composition, is at a ratio of 3090 ppm guanidine to 2000 ppm AEPD. Synergism can be demonstrated when the weight ratio of guanidine to AEPD is in the range of 0.2:1 to 15:1.
[0266] Example 13: Investigation of the synergistic interaction between guanidine and monoethanolamine (MEA)
[0267] Calculation of the synergy index of guanidine and MEA with respect to Pseudomonas spec.
[0268] DSM 115322 with an incubation time of 48 hours at 30 °C.
[0269] Table 13
[0270] Qa: Concentration of guanidine in the mixture showing an endpoint
[0271] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of MEA in the mixture showing an endpoint QB: Concentration of MEA as the sole agent showing an endpoint
[0272] Table 13 shows that the optimal synergism, i.e., the lowest synergy index (0.79) of a guanidine / MEA composition, is at a ratio of 1545 ppm guanidine to 1250 ppm MEA. Synergism can be demonstrated when the weight ratio of guanidine to MEA is in the range of 0.2:1 to 30:1.
[0273] Example 14: Investigation of the synergistic interaction between guanidine and ethylhexylglycerin (EHG)
[0274] Calculation of the synergy index of guanidine and EHG with respect to Pseudomonas spec.
[0275] DSM 115322 with an incubation time of 48 hours at 30 °C.
[0276] Table 14
[0277] Qa: Concentration of guanidine in the mixture showing an endpoint
[0278] QA: Concentration of guanidine as the sole agent showing an endpoint
[0279] Qb: Concentration of EHG in the mixture showing an endpoint QB: Concentration of EHG as the sole agent showing an endpoint
[0280] Table 14 shows that the optimal synergism, i.e., the lowest synergy index (0.69) of a guanidine / EHG composition, is at a ratio of 618 ppm guanidine to 1250 ppm EHG. Synergism can be demonstrated when the weight ratio of guanidine to EHG is in the range of 0.5:1 to 15:1.
[0281] Example 15: Investigation of the synergistic interaction between guanidine and hexylglycerol
[0282] Calculation of the synergy index of guanidine and hexylglycerol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0283] Table 15
[0284] Qa: Concentration of guanidine in the mixture showing an endpoint
[0285] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of hexylglycerol in the mixture showing an endpoint QB: Concentration of hexylglycerol as the sole agent showing an endpoint
[0286] Table 15 shows that the optimal synergism, i.e., the lowest synergy index (0.69) of a guanidine / hexylglycerol composition, is at a ratio of 618 ppm guanidine to 1250 ppm hexylglycerol. Synergism can be demonstrated when the weight ratio of guanidine to hexylglycerol is in the range of 0.5:1 to 15:1.
[0287] Example 16: Investigation of the synergistic interaction between guanidine and 1,2-pentanediol
[0288] Calculation of the synergy index of guanidine and 1,2-pentanediol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0289] Table 16
[0290] Qa: Concentration of guanidine in the mixture showing an endpoint
[0291] QA: Concentration of guanidine as the sole agent showing an endpoint
[0292] Qb: Concentration of 1,2-pentanediol in the mixture showing an endpoint
[0293] QB: Concentration of 1,2-pentanediol as the sole agent showing an endpoint
[0294] Table 16 shows that the optimal synergism, i.e., the lowest synergy index (0.87) of a composition of guanidine and 1,2-pentanediol, is at a ratio of 6180 ppm guanidine to 2000 ppm 1,2-pentanediol. Synergism 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.
[0295] Example 17: Investigation of the synergistic interaction between guanidine and 1,2-hexanediol
[0296] Calculation of the synergy index of guanidine and 1,2-hexanediol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0297] Table 17
[0298] Qa: Concentration of guanidine in the mixture showing an endpoint
[0299] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of 1,2-hexanediol in the mixture showing an endpoint QB: Concentration of 1,2-hexanediol as the sole agent showing an endpoint
[0300] Table 17 shows that the optimal synergism, i.e., the lowest synergy index (0.67) of a composition of guanidine and 1,2-hexanediol, is at a ratio of 1545 to 3090 ppm guanidine to 3750 to 2500 ppm 1,2-hexanediol. Synergism can be demonstrated when the weight ratio of guanidine to 1,2-hexanediol is in the range of 0.06:1 to 15:1.
[0301] Example 18: Investigation of the synergistic interaction between guanidine and 1,2-heptanediol
[0302] Calculation of the synergy index of guanidine and 1,2-heptanediol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0303] Table 18
[0304] Qa: Concentration of guanidine in the mixture showing an endpoint
[0305] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of 1,2-heptanediol in the mixture showing an endpoint QB: Concentration of 1,2-heptanediol as the sole agent showing an endpoint
[0306] Table 18 shows that the optimal synergism, i.e., the lowest synergy index (0.70) of a composition of guanidine and 1,2-heptanediol, is at a ratio of 1545 ppm guanidine to 2000 ppm 1,2-heptanediol. Synergism can be demonstrated when the weight ratio of guanidine to 1,2-heptanediol is in the range of 0.25:1 to 30:1.
[0307] Example 19: Investigation of the synergistic interaction between guanidine and 1,2-octanediol
[0308] Calculation of the synergy index of guanidine and 1,2-octanediol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0309] Table 19
[0310] Qa: Concentration of guanidine in the mixture showing an endpoint
[0311] QA: Concentration of guanidine as the sole agent showing an endpoint
[0312] Qb: Concentration of 1,2-octanediol in the mixture showing an endpoint
[0313] QB: Concentration of 1,2-octanediol as the sole agent showing an endpoint
[0314] Table 19 shows that the optimal synergism, i.e., the lowest synergy index (0.88) of a composition of guanidine and 1,2-octanediol, is at a ratio of 4635 ppm guanidine to 750 ppm 1,2-octanediol. Synergism can be demonstrated when the weight ratio of guanidine to 1,2-octanediol is in the range of 0.2:1 to 6:1.
[0315] Example 20: Investigation of the synergistic interaction between guanidine and phenoxyethanol
[0316] Calculation of the synergy index of guanidine and phenoxyethanol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0317] Table 20
[0318] Qa: Concentration of guanidine in the mixture showing an endpoint
[0319] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of phenoxyethanol in the mixture showing an endpoint QB: Concentration of phenoxyethanol as the sole agent showing an endpoint
[0320] Table 20 shows that the optimal synergism, i.e., the lowest synergy index (0.83) of a guanidine / phenoxyethanol composition, is at a ratio of 1545 ppm guanidine to 2000 ppm phenoxyethanol. Synergism can be demonstrated when the weight ratio of guanidine to phenoxyethanol is in the range of 0.13:1 to 3.6:1.
[0321] Example 21: Investigation of the synergistic interaction between guanidine and phenethyl alcohol
[0322] Calculation of the synergy index of guanidine and phenethyl alcohol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0323] Table 21
[0324] Qa: Concentration of guanidine in the mixture showing an endpoint
[0325] QA: Concentration of guanidine as the sole agent showing an endpoint
[0326] Qb: Concentration of phenethyl alcohol in the mixture showing an endpoint
[0327] QB: Concentration of phenethyl alcohol as the sole agent showing an endpoint
[0328] Table 21 shows that the optimal synergism, i.e., the lowest synergy index (0.83) of a composition of guanidine and phenethyl alcohol, is at a ratio of 309 to 3090 ppm guanidine to 1250 to 2000 ppm phenethyl alcohol. Synergism can be demonstrated when the weight ratio of guanidine to phenethyl alcohol is in the range of 0.15:1 to 12:1.
[0329] Example 22: Investigation of the synergistic interaction between guanidine and phenylpropanol
[0330] Calculation of the synergy index of guanidine and phenylpropanol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0331] Table 22
[0332] Qa: Concentration of guanidine in the mixture showing an endpoint
[0333] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of phenylpropanol in the mixture showing an endpoint QB: Concentration of phenylpropanol as the sole agent showing an endpoint
[0334] Table 22 shows that the optimal synergism, ie, the lowest synergy index (0.79) of a composition of guanidine and phenylpropanol, is at a ratio of 1545 ppm guanidine to 1250 ppm phenylpropanol. Synergism can be demonstrated when the weight ratio of guanidine to phenylpropanol is in the range of 0.4:1 to 6:1.
[0335] Example 23: Investigation of the synergistic interaction between guanidine and benzyl alcohol
[0336] Calculation of the synergy index of guanidine and benzyl alcohol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0337] Table 23
[0338] Qa: Concentration of guanidine in the mixture showing an endpoint
[0339] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of benzyl alcohol in the mixture showing an endpoint QB: Concentration of benzyl alcohol as the sole agent showing an endpoint
[0340] Table 23 shows that the optimal synergism, i.e., the lowest synergy index (0.71) of a composition of guanidine and benzyl alcohol, is at a ratio of 3090 ppm guanidine to 750 ppm benzyl alcohol. Synergism can be demonstrated when the weight ratio of guanidine to benzyl alcohol is in the range of 1:1 to 12:1.
[0341] Example 24: Investigation of the synergistic interaction between guanidine and isopropanol
[0342] Calculation of the synergy index of guanidine and isopropanol with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0343] Table 24
[0344] Qa: Concentration of guanidine in the mixture showing an endpoint
[0345] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of isopropanol in the mixture showing an endpoint QB: Concentration of isopropanol as the sole agent showing an endpoint
[0346] Table 24 shows that the optimal synergism, i.e., the lowest synergy index (0.53) of a guanidine / isopropanol composition, is at a ratio of 309 ppm guanidine to 30,000 ppm isopropanol. Synergism can be demonstrated when the weight ratio of guanidine to isopropanol is in the range of 0.004:1 to 3:1.
[0347] Example 25: Investigation of the synergistic interaction between guanidine and ethylenediaminetetraacetic acid (EDTA). Calculation of the synergy index of guanidine and EDTA with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0348] Table 25 Qa: Concentration of guanidine in the mixture showing an endpoint
[0349] QA: Concentration of guanidine as the sole agent exhibiting an endpoint. Qb: Concentration of EDTA in the mixture exhibiting an endpoint. QB: Concentration of EDTA as the sole agent exhibiting an endpoint. Table 25 shows that the optimal synergism, i.e., the lowest synergy index (0.83) for a guanidine / EDTA composition, is at a ratio of 1545 ppm guanidine to 200 ppm EDTA. Synergism can be demonstrated when the weight ratio of guanidine to EDTA is in the range of 0.6:1 to 37:1.
[0350] Example 26: Investigation of the synergistic interaction between guanidine and (1-hydroxyethylidene)bisphosphonic acid (HEDP)
[0351] Calculation of the synergy index of guanidine and HEDP with respect to Pseudomonas spec.
[0352] DSM 115322 with an incubation time of 48 hours at 30 °C.
[0353] Table 26
[0354] Qa: Concentration of guanidine in the mixture showing an endpoint
[0355] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of HEDP in the mixture showing an endpoint QB: Concentration of HEDP as the sole agent showing an endpoint
[0356] Table 26 shows that the optimal synergism, i.e., the lowest synergy index (0.73) of a guanidine / HEDP composition, is at a ratio of 618 ppm guanidine to 1000 ppm HEDP. Synergism can be demonstrated when the weight ratio of guanidine to HEDP is in the range of 0.6:1 to 1.5:1.
[0357] Example 27: Investigation of the synergistic interaction between guanidine and pyrithione (added in the form of sodium pyrithione). Calculation of the synergistic index of guanidine and pyrithione with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0358] Table 27 Qa: Concentration of guanidine in the mixture showing an endpoint
[0359] QA: Concentration of guanidine as the sole agent exhibiting an endpoint. Qb: Concentration of pyrithione in the mixture exhibiting an endpoint. QB: Concentration of pyrithione as the sole agent exhibiting an endpoint. Table 27 shows that the optimal synergism, i.e., the lowest synergy index (0.70) for a guanidine / pyrithione composition, is at a ratio of 309 ppm guanidine to 85 ppm pyrithione. Synergism can be demonstrated when the weight ratio of guanidine to pyrithione is in the range of 3.6:1 to 180:1.
[0360] Example 28: Investigation of the synergistic interaction between guanidine and o-phenylphenol (oPP) Calculation of the synergy index of guanidine and oPP with respect to Pseudomonas spec.
[0361] DSM 115322 with an incubation time of 48 hours at 30 °C.
[0362] Table 28 Qa: Concentration of guanidine in the mixture showing an endpoint
[0363] QA: Concentration of guanidine as the sole agent showing an endpoint
[0364] Qb: Concentration of oPP in the mixture showing an endpoint
[0365] QB: Concentration of oPP as the sole agent exhibiting an endpoint. Table 28 shows that the optimal synergism, i.e., the lowest synergy index (0.50) of a guanidine / oPP composition, is at a ratio of 1545 ppm guanidine to 250 ppm oPP. Synergism can be demonstrated when the weight ratio of guanidine to oPP is in the range of 0.62:1 to 49:1.
[0366] Example 29: Investigation of the synergistic interaction between guanidine and sorbic acid (added in the form of potassium sorbate)
[0367] Calculation of the synergy index of guanidine and sorbic acid with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0368] Table 29
[0369] Qa: Concentration of guanidine in the mixture showing an endpoint
[0370] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of sorbic acid in the mixture showing an endpoint QB: Concentration of sorbic acid as the sole agent showing an endpoint
[0371] Table 29 shows that the optimal synergism, i.e., the lowest synergy index (0.55) of a composition of guanidine and sorbic acid, is at a ratio of 3090 ppm guanidine to 555 ppm sorbic acid. Synergism can be demonstrated when the weight ratio of guanidine to sorbic acid is in the range of 0.1:1 to 50:1.
[0372] Example 30: Investigation of the synergistic interaction between guanidine and benzoic acid (added in the form of sodium benzoate)
[0373] Calculation of the synergy index of guanidine and benzoic acid with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0374] Table 30
[0375] Qa: Concentration of guanidine in the mixture showing an endpoint
[0376] QA: Concentration of guanidine as the sole agent showing an endpoint
[0377] Qb: Concentration of benzoic acid in the mixture showing an endpoint QB: Concentration of benzoic acid as the sole agent showing an endpoint
[0378] Table 30 shows that the optimal synergism, i.e., the lowest synergy index (0.63) of a guanidine-benzoic acid composition, is at a ratio of 1545 to 4635 ppm guanidine to 840 to 400 ppm benzoic acid. Synergism can be demonstrated when the weight ratio of guanidine to benzoic acid is in the range of 0.25:1 to 88:1.
[0379] Example 31 : Investigation of the synergistic interaction between guanidine and salicylic acid (added in the form of sodium salicylate)
[0380] Calculation of the synergy index of guanidine and salicylic acid with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0381] Table 31
[0382] Qa: Concentration of guanidine in the mixture showing an endpoint
[0383] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of salicylic acid in the mixture showing an endpoint QB: Concentration of salicylic acid as the sole agent showing an endpoint
[0384] Table 31 shows that the optimal synergism, i.e., the lowest synergy index (0.63) of a guanidine-salicylic acid composition, is at a ratio of 1545 to 4635 ppm guanidine to 856 to 428 ppm salicylic acid. Synergism can be demonstrated when the weight ratio of guanidine to salicylic acid is in the range of 0.24:1 to 43:1.
[0385] Example 32: Investigation of the synergistic interaction between guanidine and lactic acid (added in the form of sodium L-lactate)
[0386] Calculation of the synergy index of guanidine and lactic acid with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0387] Table 32
[0388] Qa: Concentration of guanidine in the mixture showing an endpoint
[0389] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of lactic acid in the mixture showing an endpoint QB: Concentration of lactic acid as the sole agent showing an endpoint
[0390] Table 32 shows that the optimal synergism, i.e., the lowest synergy index (0.63) of a guanidine-lactic acid composition, is at a ratio of 4635 to 6180 ppm guanidine to 3974 to 1987 ppm lactic acid. Synergism can be demonstrated when the weight ratio of guanidine to lactic acid is in the range of 0.03:1 to 23:1.
[0391] Example 33: Investigation of the synergistic interaction between guanidine and citric acid (added in the form of trisodium citrate)
[0392] Calculation of the synergy index of guanidine and citric acid with respect to Pseudomonas spec. DSM 115322 during an incubation period of 48 hours at 30 °C.
[0393] Table 33
[0394] Qa: Concentration of guanidine in the mixture showing an endpoint
[0395] QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of citric acid in the mixture showing an endpoint QB: Concentration of citric acid as the sole agent showing an endpoint
[0396] Table 33 shows that the optimal synergism, i.e., the lowest synergy index (0.45) of a guanidine-citric acid composition, is at a ratio of 309 ppm guanidine to 21,983 ppm citric acid. Synergism can be demonstrated when the weight ratio of guanidine to citric acid is in the range of 0.014:1 to 12:1.
[0397] Example 34: Investigation of the synergistic interaction between guanidine and zinc (added in the form of zinc oxide)
[0398] In Example 34, the synergistic interaction between guanidine and a zinc compound (zinc oxide) against microbial attack in an emulsion paint was tested by adding specific amounts of guanidine in the form of guanidine hydrochloride and a zinc compound in the form of zinc oxide, and examining its stability against microbial attack. The tested paint was a emulsion paint based on a styrene acrylate binder (77% PVC, pH 8.8) for interior use, produced in the laboratory without the addition of the usual preservatives.
[0399] The samples were each inoculated several times, a total of three times, with a bacterial cell suspension of the following composition (2% v / w).
[0400] Bacterial mixture A:
[0401] Alcaligenes faecalis NCIMB 13145
[0402] Escherichia coli DSM 13631
[0403] Burkholderia cepacia DSM 9241
[0404] Staphylococcus aureus DSM 799
[0405] Pseudomonas aeruginosa DSM 50071
[0406] Pseudomonas putida DSM 13624
[0407] The cell suspension of bacterial mixture A was prepared by culturing the individual bacteria in liquid culture on a shaker for 24 hours at 30 °C. Müller-Hinton liquid medium served as the bacterial culture medium. After culture, the individual liquid cultures were centrifuged, and the cells were resuspended in physiological saline. To adjust the mixture to a total cell count of 10 9 The individual bacterial suspensions were diluted accordingly before combining with saline solution if necessary. The cell count of the inoculation suspension was determined using the chamber counting method.
[0408] After each inoculation, the microbial contamination of the samples was assessed by determining the number of viable bacteria per g of dye (colony forming units, CFU / g) after 7 days of incubation at 30 °C. The CFU / g was determined at each time point by taking an aliquot (μg) from the previously homogenized sample, a serial decadic dilution series in physiological saline (0.9% NaCl), and the spatula plate method on tryptone soy agar, followed by incubation of the agar plates for 48 hours at 30 °C.
[0409] Example 34 / Table 34: Inoculation with bacterial mixture A, cell count 10 9 / ml
[0410] To demonstrate a synergistic effect between guanidine and zinc, the endpoints of the results after 3 inoculations up to a maximum of 1000 CFU / g were used.
[0411] Example 34 / Table 35
[0412] Qa: Concentration of guanidine in the mixture showing an endpoint
[0413] QA: Concentration of guanidine as the sole agent showing an endpoint
[0414] Qb: Concentration of zinc in the mixture showing an endpoint
[0415] QB: Concentration of zinc as the sole agent showing an endpoint
[0416] Table 35 shows that the optimal synergism, i.e., the lowest synergy index (0.40) of a guanidine-zinc composition, is at a ratio of 618 ppm guanidine to 402 ppm zinc. Synergism can be demonstrated when the weight ratio of guanidine to zinc is in the range of 0.77:1 to 12:1.
[0417] In the following examples 35 to 38, the synergistic interaction between guanidine and antimicrobial substances against microbial attack was tested using an emulsion paint and a washing or cleaning agent by adding certain amounts of guanidine salts and isothiazolinones to these substances and testing them for their stability against microbial attack:
[0418] The tested paint was a styrene-acrylate-based dispersion paint (77% PVC, pH 8.8) for indoor use, produced in the laboratory without the addition of conventional preservatives. The laundry detergent was a heavy-duty detergent without preservatives (pH 8.1), and the cleaning agent was an all-purpose cleaner without preservatives (pH 7.6), both also produced in the laboratory without the addition of conventional preservatives.
[0419] The paint was treated – individually and in combination – with specific concentrations of guanidinium hydrochloride, benzisothiazolinone (BIT), and a mixture of chloromethylisothiazolinone (CIT) and methylisothiazolinone (MIT). The detergent and cleaning agent were treated with specific concentrations of guanidinium hydrochloride and benzisothiazolinone (BIT).
[0420] The resulting batches of the paint prepared in this way were inoculated with a mixture of different bacterial species (bacterial mixture B), and the batches of the detergent and cleaning agent prepared in this way were inoculated with a yeast mixture.
[0421] Bacterial mixture B:
[0422] Pseudomonas spp. (Pseudomonas oleovorans group) DSM 33933
[0423] Pseudomonas aeruginosa DSM 33935
[0424] Pseudomonas oleovorans DSM 33936
[0425] Pseudomonas spec. DSM 33937
[0426] Pseudomonas aeruginosa DSM 33938
[0427] Yeast mixture:
[0428] Pichia manshurica DSM 12249
[0429] Rhodotorula mucilaginosa DSM 12248
[0430] Candida boidinii DSM 13622
[0431] Candida albicans DSM 1386
[0432] The inoculum was added to the respective sample at each inoculation at 2% (v / w) as a fresh cell suspension in a physiological saline solution (0.9% NaCl). The cell count of the added inoculum for the bacterial mixture A was 10 9 / ml, for the yeast mixture 10 8 / ml, consisting of equal parts of the individual bacterial and yeast strains.
[0433] The cell suspension of the bacterial mixture was prepared by culturing the individual bacteria for 24 hours at 30 °C in liquid culture on a shaker. Müller-Hinton liquid medium served as the bacterial culture medium. After culture, the individual liquid cultures were centrifuged, and the cells were resuspended in physiological saline. To adjust the mixture to a total cell count of 10 9 The individual bacterial suspensions were diluted accordingly before combining with saline solution if necessary. The cell count of the inoculation suspension was determined using the chamber counting method.
[0434] To prepare the cell suspension of the yeast mixture, the yeast strains were grown on Sabouraud glucose agar for 48 hours at 25 °C, and the cell layer was washed off using physiological saline (0.9% NaCl). Further steps were used to adjust the cell count of the inoculation suspension to 10 8 / ml were carried out analogously to the preparation of the bacterial suspension.
[0435] In Examples 35 to 38, the samples were inoculated once with the respective cell suspensions (2% v / w), and the development of the bacteria (bacteria mixture B) or yeasts was monitored using a semi-quantitative evaluation method. The microbial contamination of the inoculated samples was assessed immediately after inoculation on day 1, as well as after 5 additional days of incubation at 30 °C on day 6 (emulsion paint) and after 2 additional days of incubation at 30 °C on day 3 (detergent, cleaning agent). For this purpose, an aliquot was taken from each sample after homogenization using a sterile plastic inoculation loop (10 μl) and spread evenly on agar plates (tryptone soy agar for bacteria, Sabouraud glucose agar for yeasts). The spread agar plates were then incubated for 48 hours at 30 °C (bacteria) or 72 hours at 25 °C (yeast). After incubation, the bacteria or yeast cells grown on the agar plates were analyzed.Yeast colonies were visually assessed and quantified according to the following scheme:.
[0436] The results for examples 35 to 38 are shown in Tables 36 to 39: Example 35 / Table 36:
[0437] Inoculation 2% (w / v) with bacterial mixture B, cell count 10 9 / ml As can be seen from the results presented in Table 36, the synergistic interaction between BIT and guanidine, which was already demonstrated under laboratory conditions, can also be demonstrated in a practical application, in an emulsion paint.
[0438] Example 36 / Table 37:
[0439] Inoculation 2% (w / v) with bacterial mixture B, cell count 10 9 / ml
[0440] As can be seen from the results presented in Table 37, the synergistic interaction between MIT and guanidine, which was already demonstrated under laboratory conditions, can also be demonstrated in a practical application, in an emulsion paint.
[0441] Example 37 / Table 38:
[0442] Inoculation 2% (w / v) with yeast mixture, cell count 10 8 / ml
[0443] As can be seen from the results presented in Table 38, the synergistic interaction between BIT and guanidine, which was already demonstrated under laboratory conditions, can also be demonstrated in a practical application, in a heavy-duty laundry detergent.
[0444] Example 38 / Table 39:
[0445] Inoculation 2% (w / v) with yeast mixture, cell count 10 8 / ml
[0446] As can be seen from the results presented in Table 39, the synergistic interaction between BIT and guanidine, which was already demonstrated under laboratory conditions, can also be demonstrated in a practical application, in a heavy-duty laundry detergent.
Claims
Patent claims 1. Composition containing: (a) guanidine and / or a salt of unsubstituted guanidine 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, octylisothiazolinone, bronopol, dibromonitrilopropionamide, dibromodicyanobutane, iodopropynyl butylcarbamate, aminomethylpropanol, aminoethylpropanediol, monoethanolamine, ethylhexylglycerin, hexylglycerin, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenethyl alcohol, Phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (l-hydroxyethylidene)bisphosphonic acid, Sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid and zinc.
2. Composition according to claim 1, characterized in that the weight ratio of guanidine and / or its salt to 5-chloro-2-methylisothiazolin-3-one is in the range from 62:1 to 9270:1, that the weight ratio of guanidine and / or its salt to 2-methyl-4-isothiazolin-3-one is in the range from 10.3:1 to 773:1, that the weight ratio of guanidine and / or its salt to 1,2-benzisothiazolin-3-one is in the range from 1.3:1 to 309:1, that the weight ratio of guanidine and / or its salt to N-butyl-1,2-benzisothiazolin-3-one is in the range from 0.52:1 to 309:1, that 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, that 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, that the weight ratio of guanidine and / or its salt to bronopol is in the range of 7.8:1 to 824:1, that 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, that the weight ratio of guanidine and / or its salt to Dibromodicyanobutane is in the range of 0.78:1 to 309:1, that the weight ratio of guanidine and / or its salt to iodopropynyl butylcarbamate is in the range of 0.83:1 to 103:1, that 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, that the weight ratio of guanidine and / or its salt to 2-amino-1,3-ethyl-propanediol is in the range of 0.2:1 to 15:1, that the weight ratio of guanidine and / or its salt to Monoethanolamine is in the range of 0.2:1 to 30:1, that the weight ratio of guanidine and / or its salt to Ethylhexylglycerol is in the range of 0.5:1 to 15:1, that the weight ratio of guanidine and / or its salt to hexylglycerol is in the range of 0.5:1 to 15:1, that 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, that the weight ratio of guanidine and / or its salt to 1,2-hexanediol is in the range of 0.06:1 to 15:1, that the weight ratio of guanidine and / or its salt to 1,2-heptanediol is in the range of 0.25:1 to 30:1, that the weight ratio of guanidine and / or its salt to 1,2-octanediol is in the range of 0.2:1 to 6:1, that the weight ratio of guanidine and / or its salt to phenoxyethanol is in the range of 0.13:1 to 3.6:1, that the weight ratio of guanidine and / or its salt to Phenethyl alcohol is in the range of 0.15:1 to 12:1, that the weight ratio of guanidine and / or its salt to phenylpropanol is in the range of 0.4:1 to 6:1, that the weight ratio of guanidine and / or its salt to benzyl alcohol is in the range from 1:1 to 12:1, that the weight ratio of guanidine and / or its salt to isopropanol is in the range from 0.004:1 to 3:1, that the weight ratio of guanidine and / or its salt to ethylenediaminetetraacetic acid is in the range from 0.6:1 to 37:1, that the weight ratio of guanidine and / or its salt to (1-hydroxyethylidene)bisphosphonic acid is in the range from 0.6:1 to 1.5:1, that the weight ratio of guanidine and / or its salt to sodium pyrithione is in the range from 3.6:1 to 180:1, that the weight ratio of guanidine and / or its salt to zinc pyrithione is in the range from 3.6:1 to 180:1, that the weight ratio of guanidine and / or its salt to o-phenylphenol is in the range of 0.62:1 to 49:1, that 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,that the weight ratio of guanidine and / or its salt to benzoic acid and / or its salt is in the range from 0.25:1 to 88:1, that the weight ratio of guanidine and / or its salt to salicylic acid and / or its salt is in the range from 0.24:1 to 43:1, that the weight ratio of guanidine and / or its salt to lactic acid and / or its salt is in the range from 0.03:1 to 23:1, that the weight ratio of guanidine and / or its salt to citric acid and / or its salt is in the range from 0.014:1 to 12:1, that the weight ratio of guanidine and / or its salt to zinc is in the range from 0.77:1 to 12:1, wherein in determining the weight ratio, the content in relation to the guanidine or the further component, without taking into account any counterion, in the composition is used as a basis., 3. Composition according to claim 1 or 2, characterized in that it contains the guanidine and / or its salt, as well as the at least one further component in a total amount in the range of 0.01% to 10%, preferably in the range of 0.02% to 5% and particularly preferably in the range of 0.03% to 3%, based on the total composition.
4. Composition according to one of claims 1 to 3, characterized in that it contains the guanidine and / or its salt in an amount in the range of 100 to 10,000 ppm, preferably in an amount in the range of 200 to 7,500 ppm, particularly preferably in an amount in the range of 300 to 5,000 ppm, wherein the proportion relates to the content of guanidine in the entire composition.
5. Composition according to one of claims 1 to 4, characterized in that the composition: - in the presence of 5-chloro-2-methyl-4-isothiazolin-3-one as a further component, this is contained in an amount in the range of 0.5 to 200 ppm, - in the presence of 2-methyl-4-isothiazolin-3-one as a further component, this is contained in an amount in the range of 0.5 to 200 ppm, - in the presence of l,2-benzisothiazolin-3-one as a further component, this is contained in an amount in the range of 1 to 500 ppm, - in the presence of N-butyl-l,2-benzisothiazolin-3-one as an additional Component, this in an amount in the range of 5 to 2,500 ppm, - in the presence of N-methyl-l,2-benzisothiazolin-3-one as further Component, this in an amount in the range of 1 to 500 ppm, - in the presence of octylisothiazolinone as a further component, this is contained in an amount in the range of 1 to 2,500 ppm, - in the case of Bronopol as an additional component, this contains an amount in the range of 1 to 1,000 ppm, - in the presence of dibromonitrilopropionamide as a further component, this contains an amount in the range of 1 to 1,000 ppm, - in the presence of dibromodicyanobutane as a further component, it contains this in an amount in the range of 1 to 1,000 ppm, - in the presence of iodopropynyl butylcarbamate as a further component, this contains an amount in the range of 10 to 5,000 ppm, - in the presence of aminomethylpropanol as a further component, it contains this in an amount in the range of 10 to 10,000 ppm, - in the presence of aminoethylpropanediol as a further component, this contains an amount in the range of 10 to 10,000 ppm, - in the presence of monoethanolamine as an additional component, this contains an amount of 25 to 7,500 ppm, - in the presence of ethylhexylglycerol as a further component, this contains an amount in the range of 10 to 10,000 ppm, - in the presence of hexylglycerol as an additional component, this contains an amount in the range of 10 to 10,000 ppm, - in the presence of 1,2-pentanediol as a further component, this contains an amount in the range of 10 to 10,000 ppm, - in the presence of 1,2-hexanediol as a further component, this contains an amount in the range of 10 to 10,000 ppm, - in the presence of 1,2-heptanediol as a further component, this contains an amount in the range of 10 to 10,000 ppm, - in the presence of 1,2-octanediol as a further component, this is contained in an amount in the range of 10 to 10,000 ppm, - in the presence of phenoxyethanol as a further component, it contains this in an amount in the range of 10 to 10,000 ppm, - in the presence of phenethyl alcohol as a further component, it contains this in an amount in the range of 10 to 10,000 ppm, - in the presence of phenylpropanol as a further component, it contains this in an amount in the range of 10 to 10,000 ppm, - in the presence of benzyl alcohol as a further component, it contains this in an amount in the range of 10 to 10,000 ppm, - in the presence of isopropanol as an additional component, it contains this in an amount in the range of 10 to 30,000 ppm, - in the presence of ethylenediaminetetraacetic acid as a further component, this contains an amount in the range of 10 to 10,000 ppm, - in the presence of (l-hydroxyethylidene)bisphosphonic acid as a further component, this contains an amount in the range of 10 to 10,000 ppm, - in the presence of sodium pyrithione as an additional component, this contains an amount in the range of 1 to 2,500 ppm, - in the presence of zinc pyrithione as an additional component, this contains an amount in the range of 1 to 2,500 ppm, - in the presence of o-phenylphenol as a further component, it contains this in an amount in the range of 1 to 10,000 ppm, - if sorbic acid is present as an additional component, it contains this in an amount in the range of 1 to 10,000 ppm, - if benzoic acid is present as an additional component, it contains this in an amount in the range of 1 to 10,000 ppm, - in the presence of salicylic acid as an additional component, this contains an amount in the range of 1 to 10,000 ppm, - if lactic acid is present as an additional component, it contains this in an amount in the range of 1 to 50,000 ppm, - in the presence of citric acid as a further component, it contains this in an amount in the range of 1 to 100,000 ppm, and - if zinc is present as an additional component, this is contained in an amount in the range of 10 to 5,000 ppm.
6. Composition according to one of claims 1 to 5, characterized in that it has a water content of greater than 1% by weight.
7. Composition according to one of claims 1 to 6, characterized in that it has a pH in the range of pH 3.5 to pH 12.
8. Composition according to one of claims 1 to 7, characterized in that it contains guanidine hydrochloride and / or guanidine carbonate as guanidine salt.
9. Composition according to one of claims 1 to 9, characterized in that the composition is a technical product selected from the group consisting of: Lignosulfonates and starch preparations in coatings, paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, chalk slurries, mineral slurries, ceramic masses, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning agents, pigment pastes and pigment dispersions, inks, lithographic fluids, thickeners, cosmetic products, toiletries, water cycles, fluids in wood processing, fluids in petroleum production, fluids in paper processing, fluids in leather production, fluids in textile production, 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 container preservation.
11. Use of the composition according to any one of claims 1 to 8 for the preservation of technical products selected from the group consisting of lignin sulfonates and starch preparations in paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, chalk slurries, mineral slurries, ceramic masses, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning agents, pigment pastes and pigment dispersions, inks, lithographic fluids, thickeners, cosmetic products, toiletries, water circuits, fluids in wood processing, fluids in petroleum production, fluids in paper processing, fluids in leather production, fluids in textile production, drilling and cutting oils, hydraulic fluids and cooling lubricants.
12. The use of: (a) guanidine and / or a salt of unsubstituted guanidine to improve the antimicrobial activity of one or more compounds selected from the group (b) 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, iodopropynylbutylcarbamate, amino-methyl-propanol, amino-ethyl-propanediol, monoethanolamine, ethylhexylglycerin, Hexylglycerol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phenoxyethanol, phenethyl alcohol, phenylpropanol, benzyl alcohol, isopropanol, ethylenediaminetetraacetic acid, (1-Hy droxyethyl lidene)bis-phosphonic acid, Sodium pyrithione, zinc pyrithione, o-phenylphenol, sorbic acid, benzoic acid, salicylic acid, lactic acid, citric acid and zinc.