Compositions containing guanidine and 1,2-benzisothiazoline-3-on

Abstract

The present invention relates to a composition that contains (a) guanidine and / or a salt of guanidine, and (b) 1,2-benzisothiazoline-3-on, and optionally one or more zinc compounds and / or other biocidal active substances. The invention also relates to technical products that contain the composition according to the invention.

Description

[0001] Compositions containing guanidine and l,2-benzisothiazolin-3-one

[0002] The present invention relates to a composition containing (a) guanidine and / or a salt of guanidine and (b) 1,2-benzisothiazolin-3-one, and optionally one or more zinc compounds and / or other biocidal active ingredients. The invention further relates to technical products containing the composition according to the invention.

[0003] Technical products, especially water-based 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 and fungi. If these products are not preservative-free, they can exhibit high bacterial counts just one day after production.

[0004] In order to ensure that these products and, where applicable, the components used in their manufacture meet the hygiene requirements and to ensure the durability of the technical products, so-called biocides are usually added to the products or their components.

[0005] 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.

[0006] 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.

[0007] 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.

[0008] 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.

[0009] 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.

[0010] This object is achieved by the invention by a composition, preferably an aqueous composition, containing: (a) guanidine and / or at least one salt of the non-substituted guanidine and

[0011] (b) l,2-benzisothiazolin-3-one.

[0012] The composition according to the invention has the advantage that the guanidine or its salt, component (a), which is previously unknown as an antimicrobial agent, and the 1,2-benzisothiazolin-3-one, component (b), interact synergistically and can therefore be used in low concentrations when used simultaneously, compared to the low concentrations required for the individual components. As a result, microorganisms contained in the composition due to manufacturing processes, such as bacteria and fungi, are effectively and efficiently inactivated, despite the lower concentrations of components (a) and (b).

[0013] The composition according to the invention contains, as component (a), guanidine and / or at least one salt of unsubstituted guanidine. "At least one salt or at least one further component" in the context of the present invention means that the composition contains a single salt, a single component, or compound, or several, i.e., two, three, four, five, or more salts, components, or compounds.

[0014] For the purposes of the present invention, guanidine and / or a salt of unsubstituted guanidine means that the composition contains, as component (a), guanidine and / or optionally also one or more salts of unsubstituted guanidine. The guanidine is the compound according to the following formula:

[0015] 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, guanidine silicates, formate, acetate or citrate.

[0016] 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.

[0017] As component (b), the composition according to the invention contains 1,2-benzisothiazolin-3-one, which may also be present in the composition in the form of its alkali metal salts. The composition according to the invention therefore contains, as component (b), 1,2-benzisothiazolin-3-one and / or its sodium, potassium, or lithium metal salts, or mixtures thereof.

[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, guanidine, and to the lead structure of component (b), l,2-benzisothiazolin-3-one. Likewise, when determining the stated weight ratios, the content in relation to guanidine, without taking into account any counterion, and the content of l,2-benzisothiazolin-3-one as component (b), without taking into account any counterion, in the composition are used as a basis.

[0019] 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 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 on the basis of the content in relation to the guanidine, without taking into account any counterion, and the content of the 1,2-benzisothiazolin-3-one in the composition.

[0020] The amount of component (a), guanidine and / or its salt contained in the composition according to the invention can vary over wide ranges and is generally in the range from 100 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 amount stated in each case refers to the content of guanidine in the entire composition.

[0021] The amount of component (b), of l,2-benzisothiazolin-3-one and / or its alkali metal salt contained in the composition according to the invention can vary over wide ranges and is generally in the range from 1 to 1,000 ppm, preferably in the range from 10 to 750 ppm, particularly preferably in the range from 25 to 500 ppm, wherein the stated amount in each case relates to the content of l,2-benzisothiazolin-3-one in the entire composition.

[0022] The composition according to the invention is an aqueous composition whose water content can vary widely. Typically, the composition is characterized by a water content of greater than 1 wt.%, preferably greater than 10 wt.%, particularly preferably greater than 20 wt.%, based on the total composition.

[0023] The pH of the composition according to the invention can vary over a wide range. According to one embodiment of the invention, the composition is characterized in that it has a pH in the range 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.

[0024] The composition, in particular the aqueous composition, according to the present invention is generally a technical, in particular aqueous technical product, which is 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,

[0025] Liquids in paper processing, liquids in leather production,

[0026] Fluids in textile production, drilling and cutting oils, hydraulic

[0027] Liquids, cooling lubricants, and biocidal products. According to a preferred embodiment of the invention, the composition is a technical, particularly aqueous, product selected from the group consisting of coatings, paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, mineral slurries, pigment pastes and pigment dispersions, detergents, and cleaning agents.

[0028] Component (c) is generally selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2'[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate. According to a preferred embodiment of the invention, component (c) is selected from the group consisting of zinc oxide and zinc carbonate; according to a particularly preferred embodiment, component (c) is zinc oxide.

[0029] According to this embodiment, the invention therefore relates to a particularly aqueous composition containing:

[0030] (a) guanidine and / or at least one salt of the unsubstituted guanidine,

[0031] (b) l,2-benzisothiazolin-3-one and

[0032] (c) one or more zinc compounds selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2' [Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate and zinc carboxylate.

[0033] The composition according to the invention according to this embodiment, which further comprises component (c), has the advantage that the at least one zinc compound, component (c), interacts synergistically with components (a) and (b), whereby the content of components (a), (b) and (c) in the composition can be further reduced while maintaining the antimicrobial effectiveness.

[0034] The weight ratio of components (a) to (c) can vary widely. According to a preferred embodiment, the composition according to the invention is characterized in that the weight ratio of (a) to (c) is in the range from 0.77:1 to 12:1, preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined based on the guanidine content, without taking into account any counterion, and the zinc content.

[0035] The amount of component (c), the at least one zinc compound, contained in the composition according to the invention can vary over wide ranges and is in the range from 10 to 5,000 ppm, preferably in the range from 25 to 2,500 ppm, particularly preferably in the range from 50 to 1,000 ppm, in each case based on the content of zinc in the composition.

[0036] According to a preferred embodiment of the invention, the composition contains as a further component:

[0037] (d) one or more compounds selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one,

[0038] Octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynylbutylcarbamate, phenoxyethanol and dibromodicyanobutane.

[0039] The composition according to the invention according to this embodiment, which further comprises component (d), has the advantage that the at least one compound selected from the group consisting of sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-

[0040] Benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol and dibromodicyanobutane, interact synergistically with component (a), whereby the content of components (a), (b), optionally (c) and (d) in the composition can be further reduced while maintaining the antimicrobial efficacy.

[0041] According to this embodiment, the invention therefore relates to a particularly aqueous composition containing:

[0042] (a) guanidine and / or at least one salt of the unsubstituted guanidine,

[0043] (b) l,2-benzisothiazolin-3-one, optionally:

[0044] (c) one or more zinc compounds selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate (ZnCO3]2-[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate and zinc carboxylate, and

[0045] (d) one or more compounds selected from sodium pyrithione,

[0046] Zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol,

[0047] Dibromonitrilopropionamide, iodopropynylbutylcarbamate, phenoxyethanol and dibromodicyanobutane.

[0048] The amount of component (d) contained in the composition according to the invention can vary widely. According to a preferred embodiment of the invention, the composition is characterized in that it contains, as component (d):

[0049] (dl) phenoxyethanol in an amount in the range of 100 to 10,000 ppm, preferably in an amount in the range of 250 to 7,500 ppm, particularly preferably in an amount in the range of 500 to 5,000 ppm and / or

[0050] (d2) one or more compounds selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, and dibromodicyanobutane in a total amount in the range of 1 to 1000 ppm, preferably in a total amount in the range of 1 to 750 ppm and particularly preferably in a total amount in the range of 1 to 500 ppm.

[0051] According to a preferred embodiment of the invention, the invention therefore relates to a particularly aqueous composition containing:

[0052] (a) 100 to 10,000 ppm, preferably 200 to 7,500 ppm, particularly preferably 300 to 5,000 ppm of guanidine and / or at least one salt of guanidine,

[0053] (b) 1 to 1,000 ppm, preferably 10 to 750 ppm, particularly preferably 25 to 500 ppm, of 1,2-benzisothiazolin-3-one,

[0054] (c) 0 to 5,000 ppm, preferably 10 to 5,000 ppm, particularly preferably 25 to 2,500 ppm, based on the amount of zinc in the composition, of one or more zinc compounds selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2' [Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate and zinc carboxylate,

[0055] (dl) 0 to 10,000 ppm, preferably 250 to 7,500 ppm, particularly preferably 500 to 5,000 ppm phenoxyethanol, and

[0056] (d2) 0 to 1000 ppm, preferably 1 to 1,000, particularly preferably 1 to 750 ppm of one or more compound(s) selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, and dibromodicyanobutane.

[0057] According to one embodiment of the invention, the invention relates to an aqueous composition containing:

[0058] (a) 200 to 7,500 ppm, particularly preferably 300 to 5,000 ppm of guanidine and / or at least one salt of guanidine,

[0059] (b) 1 to 1,000 ppm, preferably 10 to 750 ppm, particularly preferably 25 to 500 ppm, of 1,2-benzisothiazolin-3-one,

[0060] (c) 10 to 5,000 ppm, preferably 50 to 1,000 ppm zinc oxide,

[0061] (dl) 1 to 150 ppm, preferably 2 to 100 ppm, particularly preferably 5 to 50 ppm of 2-methyl-4-isothiazolin-3-one and (d2) 1 to 100 ppm, preferably 2 to 50 ppm, particularly preferably 5 to 30 ppm of 5-chloro-

[0062] 2-methyl-4-isothiazolin-3-one.

[0063] According to a particularly preferred embodiment, the above-defined aqueous composition contains as component:

[0064] (a) 300 to 10,000 ppm, preferably 500 to 7,500 ppm, particularly preferably 750 to

[0065] 5,000 ppm guanidine carbonate and / or guanidine hydrochloride.

[0066] The aqueous composition defined above is an aqueous technical product selected from the group consisting of coatings, paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, mineral slurries, pigment pastes and pigment dispersions, detergents and cleaning agents.

[0067] According to a further embodiment of the invention, the invention relates to an aqueous composition containing:

[0068] (a) 200 to 7,500 ppm, particularly preferably 300 to 5,000 ppm of guanidine and / or at least one salt of guanidine,

[0069] (b) 1 to 1,000 ppm, preferably 10 to 750 ppm, particularly preferably 25 to 500 ppm, of 1,2-benzisothiazolin-3-one,

[0070] (dl) 1 to 150 ppm, preferably 2 to 100 ppm, particularly preferably 5 to 50 ppm of 2-methyl-4-isothiazolin-3-one and

[0071] (d2) 1 to 100 ppm, preferably 2 to 50 ppm, particularly preferably 5 to 30 ppm of 5-chloro-

[0072] 2-methyl-4-isothiazolin-3 -one.

[0073] According to a particularly preferred embodiment, the above-defined aqueous composition contains as component:

[0074] (a) 300 to 10,000 ppm, preferably 500 to 7,500 ppm, particularly preferably 750 to

[0075] 5,000 ppm guanidine carbonate and / or guanidine hydrochloride. The aqueous composition defined above is preferably an aqueous technical product selected from the group consisting of emulsions, latices, polymer dispersions, pigment dispersions, detergents, and cleaning agents; more preferably, it is an aqueous technical product selected from the group consisting of emulsions and latices.

[0076] It is particularly advantageous if the composition according to the invention contains as component(s) (d):

[0077] Phenoxyethanol in an amount in the range of 100 to 10,000 ppm, preferably in an amount in the range of 250 to 7,500 ppm, particularly preferably in an amount in the range of 500 to 5,000 ppm and / or

[0078] Sodium pyrithione in an amount in the range of 10 to 1000 ppm, preferably in an amount in the range of 20 to 750 ppm, particularly preferably in an amount in the range of 30 to 500 ppm and / or

[0079] Zinc pyrithione in an amount in the range of 10 to 1000 ppm, preferably in an amount in the range of 20 to 750 ppm, particularly preferably in an amount in the range of 30 to 500 ppm and / or

[0080] 5-chloro-2-methyl-4-isothiazolin-3-one in an amount in the range of 0.5 to 200 ppm, preferably in an amount in the range of 1 to 100 ppm, particularly preferably in an amount in the range of 2 to 50 ppm and / or

[0081] 2-methyl-4-isothiazolin-3-one in an amount in the range of 0.5 to 200 ppm, preferably in an amount in the range of 1 to 150 ppm, particularly preferably in an amount in the range of 2 to 100 ppm, and / or

[0082] N-methyl-l,2-benzisothiazolin-3-one in an amount in the range of 1 to 1000 ppm, preferably in an amount in the range of 2 to 750 ppm, particularly preferably in an amount in the range of 5 to 500 ppm and / or

[0083] N-butyl-l,2-benzisothiazolin-3-one in an amount in the range of 5 to 2,500 ppm, preferably in an amount in the range of 10 to 2,000 ppm, particularly preferably in an amount in the range of 10 to 1,500 ppm and / or

[0084] Octylisothiazolinone in an amount in the range of 1 to 2,500 ppm, preferably in an amount in the range of 5 to 2,000 ppm, particularly preferably in an amount in the range of 10 to 1,500 ppm and / or Bronopol in an amount in the range of 1 to 1,000 ppm, preferably in an amount in the range of 5 to 750 ppm, particularly preferably in an amount in the range of 10 to 500 ppm and / or

[0085] Dibromonitrilopropionamide in an amount in the range of 1 to 1,000 ppm, preferably in an amount in the range of 5 to 750 ppm, particularly preferably in an amount in the range of 10 to 500 ppm and / or iodopropynyl butylcarbamate in an amount in the range of 10 to 5,000 ppm, preferably in an amount in the range of 25 to 4,500 ppm, particularly preferably in an amount in the range of 50 to 4,000 ppm and / or

[0086] Dibromodicyanobutane in an amount in the range of 1 to 1,000 ppm, preferably in an amount in the range of 5 to 750 ppm, particularly preferably in an amount in the range of 10 to 500 ppm.

[0087] In the context of the invention, it has been found to be surprisingly advantageous if the composition according to the invention, which contains components (a) and (b) and optionally also (c), contains the above-mentioned component(s) (d) in the respective amounts specified. This can achieve a further synergistic increase in the antimicrobial efficacy of the composition according to the invention, which already contains components (a) and (b) and optionally also (c).

[0088] In the context of the present invention, it has also been found to be particularly advantageous if:

[0089] In the case of the presence of phenoxyethanol as component (d), the weight ratio of guanidine and / or its salt to phenoxyethanol is in the range of 0.13:1 to 3.6:1, wherein the weight ratio is determined in each case based on the content in relation to the guanidine, without taking into account any counterion in the composition.

[0090] In the case of the presence of sodium pyrithione as component (d), the weight ratio of guanidine and / or its salt to sodium pyrithione is in the range from 3.6:1 to 180:1, preferably in the range from 3.6:1 to 100:1, particularly preferably in the range from 3.6:1 to 50:1, wherein the content in relation to the guanidine is used as the basis for determining the weight ratio, without taking into account any counterion in the composition.

[0091] In the case of the presence of zinc pyrithione as component (d), the weight ratio of guanidine and / or its salt to zinc pyrithione is in the range from 3.6:1 to 180:1, preferably in the range from 3.6:1 to 100:1, particularly preferably in the range from 3.6:1 to 50:1, wherein the content in relation to the guanidine is used as the basis for determining the weight ratio, without taking into account any counterion in the composition.

[0092] In the case of the presence of 5-chloro-2-methyl-4-isothiazolin-3-one as component (d), 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, 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 is used in each case to determine the weight ratio, without taking into account any counterion in the composition.

[0093] In the case of the presence of 2-methyl-4-isothiazolin-3-one as component (d), the weight ratio of guanidine and / or its salt to 2-methylisothiazolin-3-one is 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 content in relation to the guanidine is used as the basis for determining the weight ratio, without taking into account any counterion in the composition.

[0094] In the case of the presence of N-methyl-1,2-benzisothiazolin-3-one as component (d), the weight ratio of guanidine and / or its salt to N-methyl-1,2-benzisothiazolin-3-one is 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 content in relation to the guanidine is used as the basis for determining the weight ratio, without taking into account any counterion in the composition.

[0095] In the case of the presence of N-butyl-1,2-benzisothiazolin-3-one as component (d), 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, 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 content in relation to the guanidine is used as the basis for determining the weight ratio, without taking into account any counterion in the composition.

[0096] In the case of the presence of octylisothiazolinone as component (d), the weight ratio of guanidine and / or its salt to N-octylisothiazolin-3-one is 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 in each case on the basis of the content in relation to the guanidine, without taking into account any counterion in the composition.

[0097] In the case of the presence of bronopol as component (d), the weight ratio of guanidine and / or its salt to bronopol is 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 in each case on the basis of the content in relation to the guanidine, without taking into account any counterion in the composition.

[0098] In the case of the presence of dibromonitrilopropionamide as component (d), the weight ratio of guanidine and / or its salt to 2,2-dibromo-3-nitrilepropionamide is 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 is used as the basis for determining the weight ratio, without taking into account any counterion in the composition.

[0099] In the case of the presence of iodopropynyl butylcarbamate as component (d), the weight ratio of guanidine and / or its salt to iodopropynyl butylcarbamate is 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 content in relation to the guanidine, without taking into account any counterion, in the composition is used as the basis for determining the weight ratio.

[0100] In the case of the presence of dibromodicyanobutane as component (d), the weight ratio of guanidine and / or its salt to dibromodicyanobutane is 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 content in relation to the guanidine is used as the basis for determining the weight ratio, without taking into account any counterion in the composition.

[0101] In the context of the invention, it has been found to be surprisingly advantageous if component (a), the guanidine and / or its salt, and the above-mentioned component(s) (d) are present in the specified synergistic ratios to one another. This allows a further synergistic increase in the antimicrobial efficacy of the composition according to the invention, which already contains components (a) and (b) and optionally also (c), to be achieved.

[0102] According to a further embodiment, the present invention relates to the use of:

[0103] (a) Guanidine and / or a salt of unsubstituted guanidine to improve the antimicrobial efficacy of

[0104] (b) l,2-benzisothiazolin-3-one.

[0105] 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 agent, leads to a surprising synergistic increase in the effect of l,2-benzisothiazolin-3-one.

[0106] According to a preferred embodiment of the invention, the invention further relates to the use of:

[0107] (a) 100 to 10,000 ppm, preferably 200 to 7,500 ppm, particularly preferably 300 to 5,000 ppm of guanidine and / or at least one salt of guanidine, for improving the antimicrobial activity of an aqueous composition containing:

[0108] (a) 100 to 10,000 ppm, preferably 200 to 7,500 ppm, particularly preferably 300 to

[0109] 5000 ppm guanidine and / or at least one salt of guanidine, (b) 1 to 1,000 ppm, preferably 10 to 750 ppm, particularly preferably 25 to 500 ppm, 1,2-benzisothiazolin-3-one,

[0110] (c) 0 to 5,000, preferably 10 to 5,000 ppm, particularly preferably 25 to 2,500 ppm, based on the amount of zinc in the composition, of one or more zinc compounds selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2' [Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate and zinc carboxylate,

[0111] (dl) 0 to 10,000 ppm, preferably 100 to 10,000 ppm, particularly preferably 250 to 7,500 ppm, very particularly preferably 500 to 5,000 ppm of phenoxyethanol, and

[0112] (d2) 0 to 1000 ppm, preferably 1 to 1000, particularly preferably 1 to 750 ppm of one or more compound(s) selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, and dibromodicyanobutane.

[0113] The present invention further relates to a process for preparing the aqueous compositions according to the invention, comprising mixing the components defined above.

[0114] The following examples serve to further illustrate the present invention:

[0115] Investigation of the synergistic interaction

[0116] A combination of guanidine (added in the form of guanidine hydrochloride) and l,2-benzisothiazolin-3-one (BIT) was investigated for their synergistic interaction.

[0117] A Gram-negative bacterial species from the Pseudomonad group, Pseudomonas spec. DSM 115322, was used as the test organism. Mixtures with different concentrations of the respective active ingredients were prepared and tested for their effect on Pseudomonads. The tests were carried out in Müller-Hinton Broth (MHB) with a cell density of 10 6 Germs per ml.

[0118] 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.

[0119] 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.

[0120] There, the synergy index (SI) is calculated using the following formula:

[0121] Synergy index SI = Q3 / QA + Qb / Qß

[0122] Q a = Concentration of component A in the mixture A + B

[0123] QA = Concentration of component A as the sole biocide

[0124] Qb = Concentration of component B in the mixture A + B

[0125] QB = Concentration of component B as sole biocide

[0126] 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. Example 1: Investigation of the synergistic interaction between guanidine and l,2-benzisothiazolin-3-one (BIT)

[0127] 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.

[0128] Table 1

[0129] Qa: Concentration of guanidine in the mixture showing an endpoint

[0130] QA: Concentration of guanidine as the sole agent showing an endpoint

[0131] Qb: Concentration of BIT in the mixture showing an endpoint

[0132] QB: Concentration of BIT as the sole agent showing an endpoint

[0133] Table 1 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.

[0134] In the following examples 2 to 4, the synergistic interaction between guanidine and benzisothiazolinone (BIT) against microbial attack was tested using an emulsion paint and a washing or cleaning agent by adding certain amounts of guanidine salts and benzisothiazolinone to these and testing them for their stability against microbial attack: The tested paint was an emulsion paint based on styrene acrylate (PVK 77%, pH 8.8) for interior use, produced in the laboratory without the addition of the otherwise usual preservatives.

[0135] The 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), each also produced in the laboratory without the addition of the usual conventional preservatives.

[0136] Procedure:

[0137] The paint was treated with specific concentrations of guanidinium hydrochloride and benzisothiazolinone (BIT)—both individually and in combination. The detergent and cleaning agent were treated with specific concentrations of guanidinium hydrochloride and benzisothiazolinone (BIT).

[0138] The resulting batches of the prepared paint were inoculated with a mixture of various bacteria, and the batches of the prepared detergent and cleaning agent were inoculated with a yeast mixture.

[0139] Bacterial mixture:

[0140] Pseudomonas spp. (Pseudomonas oleovorans group) DSM 33933

[0141] Pseudomonas aeruginosa DSM 33935

[0142] Pseudomonas oleovorans DSM 33936

[0143] Pseudomonas spec. DSM 33937

[0144] Pseudomonas aeruginosa DSM 33938

[0145] Yeast mixture:

[0146] Pichia manshurica DSM 12249

[0147] Rhodotorula mucilaginosa DSM 12248

[0148] Candida boidinii DSM 13622

[0149] Candida albicans DSM 1386

[0150] 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 was 10 9 / ml, for the yeast mixture 10 8 / ml, consisting of equal parts of the individual bacterial and yeast strains.

[0151] 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.

[0152] To prepare the cell suspension of the yeast mixture, the yeasts 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.

[0153] In Examples 2 to 4, the samples were inoculated once with the respective cell suspensions (2% v / w), and the development of the bacteria 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 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 (yeasts). After incubation, the bacterial or yeast colonies grown on the agar plates were visually assessed and quantified according to the following scheme:

[0154] The results for examples 2 to 4 are shown in Tables 2 to 4: Example 2 / Table 2:

[0155] Inoculation 2% (w / v) with a bacterial mixture, cell count 10 9 / ml As can be seen from the results presented in Table 2, 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.

[0156] Example 3 / Table 3:

[0157] Inoculation 2% (w / v) with a yeast mixture, cell count 10 8 / ml

[0158] As can be seen from the results presented in Table 3, the synergistic interaction between BIT and guanidine, already demonstrated under laboratory conditions, can also be demonstrated in a practical application, in a heavy-duty laundry detergent. Example 4 / Table 4:

[0159] Inoculation 2% (w / v) with yeast mixture, cell count 10 8 / ml As can be seen from the results presented in Table 4, 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 at least one salt of guanidine and (b) l,2-benzisothiazolin-3-one.

2. Composition according to claim 1, characterized in that it contains guanidine hydrochloride and / or guanidine carbonate as guanidine salt.

3. Composition according to claim 1 or 2, characterized in that the weight ratio of (a) to (b) is in the range from 1.3:1 to 309:1, the content in relation to the guanidine being used as the basis for determining the weight ratio.

4. Composition according to any one of claims 1 to 3, further comprising: (c) one or more zinc compounds selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3]2' [Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate and zinc carboxylate.

5. Composition according to one of claims 1 to 4, characterized in that the weight ratio of (a) to (c) is in the range from 0.77:1 to 12:1, the content in relation to the guanidine and zinc being used as the basis for determining the weight ratio.

6. Composition according to any one of claims 1 to 4, further comprising: (d) one or more compounds selected from sodium pyrithione, Zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-l,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, Dibromonitrilopropionamide, iodopropynylbutylcarbamate, phenoxyethanol and dibromodicyanobutane.

7. Composition according to one of claims 1 to 6, 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.

8. Composition according to one of claims 1 to 7, characterized in that it has a pH value in the range of pH 4.5 to pH 12.

9. Composition according to one of claims 1 to 8, characterized in that it comprises the components: (a) in an amount in the range of 100 to 10,000 ppm, based on the amount of guanidine in the composition, and (b) in an amount in the range of 1 ppm to 1000 ppm.

10. Composition according to one of claims 4 to 8, characterized in that it comprises the component: (c) in an amount ranging from 10 to 5,000 ppm, based on the amount of zinc in the composition.

11. Composition according to one of claims 6 to 10, characterized in that it comprises the component: (dl) Phenoxyethanol in an amount in the range of 100 to 10,000 ppm and / or (d2) one or more compounds selected from sodium pyrithione, zinc pyrithione, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-methyl-l,2-benzisothiazolin-3-one, N-butyl-l,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, Dibromonitrilopropionamide, iodopropynylbutylcarbamate, and Contains dibromodicyanobutane in a total amount in the range of 1 to 1000 ppm.

12. Composition according to one of claims 1 to 11, characterized in that it has a water content of greater than 10% by weight.

13. Aqueous composition selected from the group consisting of coatings, paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, mineral slurries, pigment pastes and pigment dispersions, detergents and cleaning agents, containing: (a) 200 to 7,500 ppm guanidine and / or at least one salt of guanidine, (b) 1 to 1,000 ppm l,2-benzisothiazolin-3-one, (c) 10 to 5,000 ppm zinc oxide, (dl) 1 to 150 ppm 2-methyl-4-isothiazolin-3-one and (d2) 1 to 100 ppm 5-chloro-2-methyl-4-isothiazolin-3-one.

14. The use of: (a) Guanidine and / or a salt of unsubstituted guanidine to improve the antimicrobial efficacy of (b) l,2-benzisothiazolin-3-one.

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