Compositions containing guanidines and 1, 2-benzisothiazolin-3-ones

Abstract

The present invention relates to a composition comprising (a) a guanidine and / or a guanidine salt and (b) a 1, 2-benzisothiazolin-3-one, and optionally, one or more zinc compounds and / or other biocidally active substances. The invention also relates to an industrial product comprising the composition according to the invention.

Description

[0001] The present invention relates to a composition comprising (a) guanidine and / or a guanidine salt and (b) 1,2-benzisothiazolin-3-one and, optionally, one or more zinc compounds and / or other biocidally active substances. The present invention also relates to an industrial product comprising the composition of the present invention.

[0002] Industrial products, particularly water-based ones such as paints, varnishes, lotions, detergents, and cosmetics, are often produced using natural or biodegradable raw materials. These raw materials and the water used as solvents are often contaminated with microorganisms such as bacteria and fungi. If these products are produced without preservatives, they may already have high microbial counts one day after production.

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

[0004] One class of biocides used for the corrosion protection of water-based industrial products (such as paints, plasters, detergents and cleaning compositions, or glazes) or their components is 3-isothiazolin-3-ones. This substance class includes compounds with very strong antimicrobial activity, which have somewhat different spectrums of action. Synergistic combinations of different 3-isothiazolin-3-ones are often used to reduce the amount of biocide used. For example, WO 99 / 08530 A1 proposes the combined use of methylisothiazolin-3-one and 1,2-benzisothiazolin-3-one.

[0005] EP-B 1 030 558 likewise discloses a synergistic biocidal composition comprising 2-methylisothiazolin-3-one and 3-iodo-2-propynyl N-butylcarbamate. This synergistic composition is suitable for controlling microorganisms even at low concentrations.

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

[0007] The use of such medium-chain and long-chain guanidine compounds with other antimicrobial and / or fungicidal active substances is also known. For example, a known example is the combination with 3-iodo-2-propynyl butylcarbamate or formaldehyde reserves. For example, EP 0 891 710 A1 teaches the combined use of dodecylguanidine hydrochloride and IPBC. However, the use of dodecylguanidine salts for corrosion protection of paint compositions and polymer dispersions has been found to be problematic; for example, incompatibilities in the form of flocculation have been observed when these salts are added.

[0008] In view of the prior art discussed above, there is a need for further compositions, the components of which interact synergistically and can therefore be used in lower concentrations when used simultaneously than would be required in the case of the individual components.

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

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

[0011] (b) 1,2-Benzisothiazolin-3-one.

[0012] The composition of the present invention has the advantage that guanidine or its salt (i.e., component (a)) and 1,2-benzisothiazolin-3-one (i.e., component (b)), which are hitherto unknown antimicrobial active substances, interact synergistically, and therefore can be used at lower concentrations when used together, compared to the lower concentrations of the individual components. Therefore, despite the lower concentrations of components (a) and (b), microorganisms such as bacteria and fungi present in the composition, for example, due to production, are effectively and efficiently inactivated.

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

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

[0015]

[0016] The salt of unsubstituted guanidine or guanidinium salt in the present invention is a guanidine or guanidinium salt of the general formula shown below:

[0017] n Xn-

[0018] wherein n is 1, 2 or 3, and wherein the counterion X n- Examples are chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, guanidine silicate, formate, acetate or citrate.

[0019] In a preferred embodiment of the present invention, the composition of the present invention contains guanidine hydrochloride and / or guanidine carbonate as component (a), and in a particularly preferred embodiment of the present invention, the composition contains guanidine carbonate as component (a).

[0020] As component (b), the composition of the present invention comprises 1,2-benzisothiazolin-3-one, which may also be present in the composition in the form of its alkali metal salt. The composition of the present invention therefore comprises 1,2-benzisothiazolin-3-one and / or its sodium, potassium or lithium metal salt or a mixture thereof as component (b).

[0021] The present invention specifies the amounts of components (a) and (b) and the weight ratios of components (a) and (b) to one another. The amounts relate to the lead structure, i.e., guanidine, or the lead structure of component (b), 1,2-benzisothiazolin-3-one. The specified weight ratios are also determined based on the guanidine content (excluding any counterions) and the 1,2-benzisothiazolin-3-one content (excluding any counterions) of the composition.

[0022] In a preferred embodiment, the present invention relates to a composition containing guanidine and / or its salts and 1,2-benzisothiazolin-3-one in a weight ratio of guanidine to 1,2-benzisothiazolin-3-one within the range of 1.3:1 to 309:1, preferably within the range of 1.3:1 to 200:1, more preferably within the range of 1.3:1 to 100:1, wherein the weight ratio is determined based in each case on the content of guanidine (excluding any counterions) and the content of 1,2-benzisothiazolin-3-one in the composition.

[0023] The amount of component (a), i.e. guanidine and / or its salts, present in the composition according to the invention can vary within wide ranges and is generally in the range from 100 to 10 000 ppm, preferably in the range from 200 to 7500 ppm, more preferably in the range from 300 to 5000 ppm, the amounts specified in each case relating to the guanidine content of the overall composition.

[0024] The amount of component (b), i.e. 1,2-benzisothiazolin-3-one and / or its alkali metal salts, present in the composition of the invention can vary within wide ranges and is generally in the range from 1 to 1000 ppm, preferably in the range from 10 to 750 ppm, more preferably in the range from 25 to 500 ppm, the amounts specified in each case relating to the 1,2-benzisothiazolin-3-one content in the overall composition.

[0025] The composition of the present invention is an aqueous composition whose water content can vary within a wide range. Typically, the composition is characterized in that it has a water content of greater than 1% by weight, preferably greater than 10% by weight, more preferably greater than 20% by weight, based on the entire composition.

[0026] The pH of the composition of the invention can vary within a wide range. In one embodiment of the invention, the composition is characterized in that it has a pH in the range of pH 4.5 to pH 12, preferably in the range of pH 5.0 to pH 11.5, more preferably in the range of pH 5.5 to pH 11. The pH can be adjusted to the claimed range by means of measures familiar to those skilled in the art.

[0027] The composition according to the invention, in particular the aqueous composition, is typically an industrial product, in particular an aqueous industrial product, selected from the group consisting of lignin sulfonates and starch preparations in paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, chalk slurries, mineral slurries, ceramic compounds, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and dispersions, inks, lithographic fluids, thickeners, cosmetics, toiletries, water cycles, woodworking fluids, oil production fluids, paperworking fluids, leather manufacturing fluids, textile manufacturing fluids, drilling oils, hydraulic fluids, cooling lubricants and biocide products. In a preferred embodiment of the invention, the composition is an industrial product, in particular an aqueous industrial product, selected from the group consisting of paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, mineral slurries, pigment pastes and dispersions, detergents and cleaning compositions.

[0028] Component (c) is generally selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, basic zinc carbonate ([ZnCO3]2.[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, dehydrogenated zinc acetate, and zinc carboxylates. In a preferred embodiment of the present invention, component (c) is selected from zinc oxide and zinc carbonate. In a particularly preferred embodiment, component (c) is zinc oxide.

[0029] In this embodiment, the present invention therefore relates in particular to an aqueous composition comprising:

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

[0031] (b) 1,2-benzisothiazolin-3-one, and

[0032] (c) one or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, basic zinc carbonate ([ZnCO3]2.[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, dehydrogenated zinc acetate and zinc carboxylates.

[0033] The composition of the invention in this embodiment in which component (c) is also present has the advantage that the at least one zinc compound, i.e. component (c), interacts synergistically with components (a) and (b) in each case, which means that the content of components (a), (b) and (c) in the composition can be further reduced while maintaining the antimicrobial efficacy.

[0034] The weight ratios of components (a) to (c) relative to one another can vary within wide ranges. In 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, the weight ratios being determined based in each case on the content as guanidine (excluding any counterions) and the zinc content.

[0035] The amount of component (c), i.e. the at least one zinc compound, present in the composition of the invention can vary within wide ranges and is in the range of 10 to 5000 ppm, preferably in the range of 25 to 2500 ppm, more preferably in the range of 50 to 1000 ppm, in each case based on the zinc content of the composition.

[0036] In a preferred embodiment of the present invention, the composition comprises, as a further component:

[0037] (d) one or more compounds 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-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol and dibromodicyanobutane.

[0038] The composition of the invention in this embodiment in which component (d) is also present has the advantage that the at least one compound 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, phenoxyethanol and dibromodicyanobutane interacts synergistically with component (a), which means that the content of components (a), (b), optionally (c) and (d) in the composition can be further reduced while maintaining antimicrobial efficacy.

[0039] In this embodiment, the present invention therefore relates in particular to an aqueous composition comprising:

[0040] (a) guanidine and / or at least one salt of unsubstituted guanidine,

[0041] (b) 1,2-benzisothiazolin-3-one, optionally:

[0042] (c) one or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, basic zinc carbonate ([ZnCO3]2.[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, zinc dehydroacetate and zinc carboxylates,

[0043] and

[0044] (d) one or more compounds 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-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol and dibromodicyanobutane.

[0045] The amount of component (d) present in the composition of the invention can vary within wide ranges. In a preferred embodiment of the invention, the composition is characterized in that it comprises the following as component (d):

[0046] (d1) phenoxyethanol in an amount ranging from 100 to 10 000 ppm, preferably in an amount ranging from 250 to 7500 ppm, more preferably in an amount ranging from 500 to 5000 ppm, and / or

[0047] (d2) one or more compounds 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-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate and dibromodicyanobutane in a total amount within a range of 1 to 1000 ppm, preferably within a total amount within a range of 1 to 750 ppm, more preferably within a total amount within a range of 1 to 500 ppm.

[0048] In a preferred embodiment of the present invention, the present invention therefore relates in particular to an aqueous composition comprising:

[0049] (a) 100 to 10 000 ppm, preferably 200 to 7500 ppm, more preferably 300 to 5000 ppm of guanidine and / or at least one guanidine salt,

[0050] (b) 1 to 1000 ppm, preferably 10 to 750 ppm, more preferably 25 to 500 ppm of 1,2-benzisothiazolin-3-one,

[0051] (c) 0 to 5000 ppm, preferably 10 to 5000 ppm, more preferably 25 to 2500 ppm, based on the amount of zinc in the composition, of one or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, basic zinc carbonate ([ZnCO3]2.[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, dehydrogenated zinc acetate and zinc carboxylates,

[0052] (d1) 0 to 10 000 ppm, preferably 250 to 7500 ppm, more preferably 500 to 5000 ppm of phenoxyethanol, and

[0053] (d2) 0 to 1000 ppm, preferably 1 to 1000, more preferably 1 to 750 ppm of 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.

[0054] In one embodiment of the present invention, the present invention relates to an aqueous composition comprising:

[0055] (a) 200 to 7500 ppm, more preferably 300 to 5000 ppm, of guanidine and / or at least one guanidine salt,

[0056] (b) 1 to 1000 ppm, preferably 10 to 750 ppm, more preferably 25 to 500 ppm of 1,2-benzisothiazolin-3-one,

[0057] (c) 10 to 5000 ppm, preferably 50 to 1000 ppm, of zinc oxide,

[0058] (d1) 1 to 150 ppm, preferably 2 to 100 ppm, more preferably 5 to 50 ppm of 2-methyl-4-isothiazolin-3-one, and

[0059] (d2) 1 to 100 ppm, preferably 2 to 50 ppm, more preferably 5 to 30 ppm of 5-chloro-2-methyl-4-isothiazolin-3-one.

[0060] In a particularly preferred embodiment, the aqueous composition defined above comprises the following components:

[0061] (a) 300 to 10 000 ppm, preferably 500 to 7500 ppm, more preferably 750 to 5000 ppm of guanidine carbonate and / or guanidine hydrochloride.

[0062] The aqueous compositions defined above are aqueous industrial products selected from paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, mineral slurries, pigment slurries and pigment dispersions, detergents and cleaning compositions.

[0063] In a further embodiment of the present invention, the present invention relates to an aqueous composition comprising:

[0064] (a) 200 to 7500 ppm, more preferably 300 to 5000 ppm, of guanidine and / or at least one guanidine salt,

[0065] (b) 1 to 1000 ppm, preferably 10 to 750 ppm, more preferably 25 to 500 ppm of 1,2-benzisothiazolin-3-one,

[0066] (d1) 1 to 150 ppm, preferably 2 to 100 ppm, more preferably 5 to 50 ppm of 2-methyl-4-isothiazolin-3-one, and

[0067] (d2) 1 to 100 ppm, preferably 2 to 50 ppm, more preferably 5 to 30 ppm of 5-chloro-2-methyl-4-isothiazolin-3-one.

[0068] In a particularly preferred embodiment, the aqueous composition defined above comprises the following components:

[0069] (a) 300 to 10 000 ppm, preferably 500 to 7500 ppm, more preferably 750 to 5000 ppm of guanidine carbonate and / or guanidine hydrochloride.

[0070] The aqueous composition defined above is preferably an aqueous industrial product selected from emulsions, latexes, polymer dispersions, pigment dispersions, detergents and cleaning compositions, more preferably an aqueous industrial product selected from emulsions and latexes.

[0071] It is particularly advantageous if the composition of the invention contains as component (d):

[0072] Phenoxyethanol in an amount ranging from 100 to 10 000 ppm, preferably in an amount ranging from 250 to 7500 ppm, more preferably in an amount ranging from 500 to 5000 ppm, and / or

[0073] 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, more preferably in an amount in the range of 30 to 500 ppm, and / or

[0074] Zinc pyrithione in an amount ranging from 10 to 1000 ppm, preferably in an amount ranging from 20 to 750 ppm, more preferably in an amount ranging from 30 to 500 ppm, and / or

[0075] 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, more preferably in an amount in the range of 2 to 50 ppm, and / or

[0076] 2-Methyl-4-isothiazolin-3-one in an amount ranging from 0.5 to 200 ppm, preferably in an amount ranging from 1 to 150 ppm, more preferably in an amount ranging from 2 to 100 ppm, and / or

[0077] N-methyl-1,2-benzisothiazolin-3-one in an amount ranging from 1 to 1000 ppm, preferably in an amount ranging from 2 to 750 ppm, more preferably in an amount ranging from 5 to 500 ppm, and / or

[0078] N-butyl-1,2-benzisothiazolin-3-one in an amount ranging from 5 to 2500 ppm, preferably in an amount ranging from 10 to 2000 ppm, more preferably in an amount ranging from 10 to 1500 ppm, and / or

[0079] Octylisothiazolinone in an amount ranging from 1 to 2500 ppm, preferably in an amount ranging from 5 to 2000 ppm, more preferably in an amount ranging from 10 to 1500 ppm, and / or

[0080] Bronopol in an amount ranging from 1 to 1000 ppm, preferably in an amount ranging from 5 to 750 ppm, more preferably in an amount ranging from 10 to 500 ppm, and / or

[0081] dibromonitrilopropionamide in an amount in the range of 1 to 1000 ppm, preferably in an amount in the range of 5 to 750 ppm, more preferably in an amount in the range of 10 to 500 ppm, and / or

[0082] Iodopropynyl butylcarbamate in an amount ranging from 10 to 5000 ppm, preferably in an amount ranging from 25 to 4500 ppm, more preferably in an amount ranging from 50 to 4000 ppm, and / or

[0083] Dibromodicyanobutane in an amount ranging from 1 to 1000 ppm, preferably in an amount ranging from 5 to 750 ppm, more preferably in an amount ranging from 10 to 500 ppm.

[0084] This is because it has been found surprisingly advantageous in the present invention that the composition according to the invention comprising components (a) and (b) and optionally also (c) comprises the above-listed component (d) in the amounts specified in each case. This allows for a further synergistic increase in the antimicrobial efficacy of the composition according to the invention which already comprises components (a) and (b) and optionally also (c).

[0085] It has also been found to be particularly advantageous in the context of the present invention that:

[0086] In the case of the presence of phenoxyethanol as component (d), the weight ratio of guanidine and / or its salts to phenoxyethanol is in the range from 0.13:1 to 3.6:1, wherein the weight ratio is determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0087] 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 of 3.6:1 to 180:1, preferably in the range of 3.6:1 to 100:1, more preferably in the range of 3.6:1 to 50:1, wherein the weight ratio is determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0088] 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 of 3.6:1 to 180:1, preferably in the range of 3.6:1 to 100:1, more preferably in the range of 3.6:1 to 50:1, wherein the weight ratio is determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0089] 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 of 62:1 to 9270:1, preferably in the range of 62:1 to 500:1, more preferably in the range of 62:1 to 300:1, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0090] 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 of 10.3:1 to 773:1, preferably in the range of 10.3:1 to 500:1, more preferably in the range of 10.3:1 to 300:1, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0091] 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 salts to N-methyl-1,2-benzisothiazolin-3-one is in the range of 7.8:1 to 618:1, preferably in the range of 7.8:1 to 400:1, more preferably in the range of 7.8:1 to 300:1, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0092] 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 salts to N-butyl-1,2-benzisothiazolin-3-one is in the range of 0.52:1 to 309:1, preferably in the range of 0.52:1 to 200:1, more preferably in the range of 0.52:1 to 100:1, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0093] In the case of the presence of octylisothiazolinone as component (d), the weight ratio of guanidine and / or its salts 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, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0094] 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 of 7.8:1 to 824:1, preferably in the range of 7.8:1 to 200:1, more preferably in the range of 7.8:1 to 100:1, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0095] In the case of the presence of dibromonitrilopropionamide as component (d), the weight ratio of guanidine and / or its salts to 2,2-dibromo-3-nitrilopropionamide is in the range of 7.8:1 to 3090:1, preferably in the range of 7.8:1 to 250:1, more preferably in the range of 7.8:1 to 100:1, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0096] 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 of 0.83:1 to 103:1, preferably in the range of 1:1 to 90:1, more preferably in the range of 1:1 to 80:1, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0097] 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, more preferably in the range from 0.8:1 to 100:1, the weight ratio being determined based in each case on the content of guanidine in the composition, excluding any counterions.

[0098] This is because it has been found surprisingly advantageous in the present invention that component (a), i.e. guanidine and / or its salt, and component (d) specified above are in a defined synergistic ratio with one another. This allows a further synergistic increase in the antimicrobial efficacy of the composition of the invention which already contains components (a) and (b) and optionally also (c).

[0099] In a further embodiment, the present invention relates to the use of (a) guanidine and / or a salt of unsubstituted guanidine to improve the antimicrobial efficacy of (b) 1,2-benzisothiazolin-3-one.

[0100] From the examples given below it can be inferred that the use of guanidine or its salts, which was hitherto unknown as antimicrobial active substance, leads to a surprising synergistic increase in the effect of 1,2-benzisothiazolin-3-one.

[0101] In a preferred embodiment of the present invention, the present invention further relates to: (a) the use of 100 to 10 000 ppm, preferably 200 to 7500 ppm, more preferably 300 to 5000 ppm of guanidine and / or at least one guanidine salt for improving the antimicrobial efficacy of an aqueous composition comprising:

[0102] (a) 100 to 10 000 ppm, preferably 200 to 7500 ppm, more preferably 300 to 5000 ppm of guanidine and / or at least one guanidine salt,

[0103] (b) 1 to 1000 ppm, preferably 10 to 750 ppm, more preferably 25 to 500 ppm of 1,2-benzisothiazolin-3-one,

[0104] (c) 0 to 5000 ppm, preferably 10 to 5000 ppm, more preferably 25 to 2500 ppm, based on the amount of zinc in the composition, of one or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, basic zinc carbonate ([ZnCO3]2.[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, dehydrogenated zinc acetate and zinc carboxylates,

[0105] (d1) 0 to 10,000 ppm, preferably 100 to 10,000 ppm, more preferably 250 to 7,500 ppm, most preferably 500 to 5,000 ppm of phenoxyethanol, and

[0106] (d2) 0 to 1000 ppm, preferably 1 to 1000, more preferably 1 to 750 ppm of 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.

[0107] The present invention further provides a process for producing an aqueous composition according to the invention, which comprises mixing the components defined above.

[0108] The following examples are used to further illustrate the present invention:

[0109] Study of synergistic interactions

[0110] The synergistic interaction of the combination of guanidine (added as guanidine hydrochloride) and 1,2-benzothiazolin-3-one (BIT) was examined.

[0111] The test organism used was from Pseudomonas sp. Pseudomonas spec. Gram-negative bacterial species of DSM 115322. For this purpose, mixtures with different concentrations of the corresponding active substances were prepared and tested for their effect on Pseudomonas. 6 The test was performed at a cell density of 10 microorganisms / ml.

[0112] The culture was run in microplates at 30°C for 48 hours. After 48 hours, the batches were assessed for turbidity caused by growth and the optical density was also determined photometrically. In this way, the minimum inhibitory concentration (MIC) of the two active substances was determined individually and in combination.

[0113] The synergistic effect that occurs is expressed numerically by calculating the synergy index (SI). The calculation is performed according to the standard method of FC Kull et al., Applied Microbiology, Vol. 9 (1961), p. 538.

[0114] This involves calculating the Synergy Index (SI) via the following formula:

[0115] Synergy Index SI = Q a / Q A + Q b / Q B

[0116] Q a = Concentration of component A in mixture A + B

[0117] Q A = Concentration of Component A as the sole biocide

[0118] Q b = Concentration of component B in the mixture A + B

[0119] Q B = Concentration of Component B as the sole biocide

[0120] If the synergy index is greater than 1, this means that there is an antagonistic effect. If the value of the synergy index is 1, this means that the effects of the two biocides / compounds are additive. If the value of the synergy index is less than 1, this means that there is a synergistic effect of the two biocides / compounds.

[0121] Embodiment 1:Study on the synergistic interaction between guanidine and 1,2-benzisothiazolin-3-one (BIT)

[0122] At 30 °C for 48 h, the effect of guanidine and BIT on Pseudomonas spec. Calculation of the synergy index of DSM 115322.

[0123] Table 1

[0124]

[0125] Qa: Concentration of guanidine in the mixture indicating the endpoint

[0126] QA: Concentration of guanidine as the sole reagent to indicate endpoint

[0127] Qb: BIT concentration in the mixture showing the endpoint

[0128] QB: Concentration of BIT as the only reagent that indicates the endpoint

[0129] Table 1 shows that the best synergistic effect of the combination of guanidine and BIT, i.e., the lowest synergistic index (0.67), is at a ratio of 3090 ppm guanidine / 100 ppm BIT. The synergistic effect can be confirmed when the weight ratio of guanidine to BIT is in the range of 1.3:1 to 309:1.

[0130] In the following Examples 2 to 4, the synergistic interaction of guanidine and benzisothiazolinone (BIT) against microbial infestation was investigated using latex paints and detergent or cleaning compositions by adding specific amounts of guanidine salts and benzisothiazolinone and examining their stability against microbial infestation:

[0131] The paint tested was a latex paint based on a styrene-acrylate binder for interior use (PVC 77%, pH 8.8), manufactured in the laboratory without the addition of common preservatives.

[0132] The detergent was a preservative-free heavy-duty laundry detergent (pH 8.1), and the cleaning composition was a preservative-free all-purpose detergent (pH 7.6). Each was also made in the laboratory without the addition of commonly found preservatives.

[0133] program:

[0134] To each paint were added—alone and in combination—specific concentrations of guanidine hydrochloride and benzisothiazolinone (BIT). Detergents and cleaning compositions were mixed with specific concentrations of guanidine hydrochloride and benzisothiazolinone (BIT).

[0135] The resulting batches of paints thus prepared were inoculated with a mixture of various bacteria; batches of detergent and cleaning compositions thus prepared were inoculated with a mixture of yeasts.

[0136] Bacterial mixture:

[0137] Pseudomonas spp. (Pseudomonas oleovorans group) DSM 33933

[0138] Pseudomonas aeruginosa DSM 33935

[0139] Pseudomonas oleovorans DSM 33936

[0140] Pseudomonas spec. DSM 33937

[0141] Pseudomonas aeruginosa DSM 33938

[0142] Yeast mixture:

[0143] Pichia manshurica DSM 12249

[0144] Rhodotorula mucilaginosa DSM 12248

[0145] Candida boidinii DSM 13622

[0146] Candida albicans DSM 1386

[0147] In each inoculation, the inoculum was added to the respective sample at 2% (v / w) as a fresh cell suspension in physiological saline solution (0.9% NaCl). The cell count of the added inoculum was 10 in the case of the bacterial mixture. 9 / ml, in the case of yeast mixtures 10 8 / ml, consisting of a single bacterial or yeast strain in aliquots.

[0148] A cell suspension of the bacterial mixture was prepared by culturing each bacterium in a liquid culture on a shaker at 30°C for 24 hours. The growth medium used for the bacteria was Müller-Hinton liquid medium. After the incubation, each liquid culture was centrifuged and the cells were resuspended in a physiological saline solution. In order to adjust the mixture to 10 9 The total cell count of each bacterial suspension was determined by chamber counting in each case.

[0149] A cell suspension of the yeast mixture was prepared by growing the yeast on Sabouraud dextrose-agar at 25°C for 48 hours and washing the cell lawn with physiological saline solution (0.9% NaCl). 8 The remaining steps for cell counting of the inoculum suspension of 100 μg / ml are carried out analogously to the preparation of the bacterial suspension.

[0150] In Examples 2 to 4, samples were inoculated once with the respective cell suspension (2% v / w), and the evolution of bacteria or yeasts was followed using a semiquantitative evaluation method. Microbial infestation was assessed in each of the inoculated samples at the following times: immediately after inoculation on day 1, and after a further incubation of 5 days at 30°C (for latex paints), or on day 3 after a further incubation of 2 days at 30°C (for detergents, cleaning compositions). To do this, a 10 µl aliquot was removed from each sample using a sterile plastic inoculating loop after homogenization and streaked evenly onto agar plates (tryptone soy agar for bacteria, Sabouraud dextrose agar for yeasts). The streaked agar plates were then incubated at 30°C for 48 hours (for bacteria) or at 25°C for 72 hours (for yeasts). After incubation, the bacterial or yeast colonies growing on the agar plates were visually assessed and quantified according to the following protocol:

[0151]

[0152] The results of Examples 2 to 4 are shown in Tables 2 to 4:

[0153] Example 2 / Table 2 :

[0154] Inoculate 2% (w / v) of the bacterial mixture and count 10 cells. 9 / ml

[0155]

[0156] From the results shown in Table 2, it can be inferred that the synergistic interaction between BIT and guanidine that has been demonstrated above under laboratory conditions can also be confirmed in practical applications in latex paints.

[0157] Example 3 / Table 3:

[0158] Inoculate with 2% (w / v) yeast mixture and count 10 cells 8 / ml

[0159]

[0160] From the results shown in Table 3, it can be inferred that the synergistic interaction between BIT and guanidine that has been demonstrated above under laboratory conditions can also be confirmed in practical application in heavy-duty laundry detergents.

[0161] Example 4 / Table 4:

[0162] Inoculate with 2% (w / v) yeast mixture and count 10 cells 8 / ml

[0163]

[0164] From the results shown in Table 4, it can be inferred that the synergistic interaction between BIT and guanidine that has been demonstrated above under laboratory conditions can also be confirmed in practical application in heavy-duty laundry detergents.

Claims

1. A composition comprising: (a) guanidine and / or at least one guanidine salt, and (b) 1,2-Benzisothiazolin-3-one.

2. The composition according to claim 1, characterized in that The guanidine salt present is guanidine hydrochloride and / or guanidine carbonate.

3. The 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 weight ratio being determined based in each case on the content calculated as guanidine.

4. The composition according to any one of claims 1 to 3, further comprising: (c) one or more zinc compounds selected from zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, basic zinc carbonate ([ZnCO3]2.[Zn(OH)2]3), zinc ascorbate, zinc hydroxide, dehydrogenated zinc acetate and zinc carboxylates.

5. The composition according to any 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 weight ratio being determined based in each case on the contents calculated as guanidine and zinc.

6. The composition according to any one of claims 1 to 4, further comprising: (d) one or more compounds 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-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol and dibromodicyanobutane.

7. The composition according to any one of claims 1 to 6, characterized in that The composition is an industrial product selected from the group consisting of lignin sulfonate and starch preparations in paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, chalk slurries, mineral slurries, ceramic compounds, adhesives, fragrances, casein-containing products, starch-containing products, asphalt emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment slurries and pigment dispersions, inks, lithographic fluids, thickeners, cosmetics, toiletries, water circulation, woodworking fluids, oil extraction fluids, paperworking fluids, leather manufacturing fluids, textile manufacturing fluids, drilling oils, hydraulic fluids, cooling lubricants and biocide products.

8. The composition according to any one of claims 1 to 7, characterized in that It has a pH in the range of pH 4.5 to pH 12.

9. The composition according to any one of claims 1 to 8, characterized in that The composition contains: component (a) in an amount ranging from 100 to 10 000 ppm, based on the amount of guanidine in the composition, and Component (b), in an amount ranging from 1 ppm to 1000 ppm.

10. The composition according to any one of claims 4 to 8, characterized in that The composition contains: Component (c) in an amount ranging from 10 to 5000 ppm, based on the amount of zinc in the composition.

11. The composition according to any one of claims 6 to 10, characterized in that The composition contains the following components: (d1) phenoxyethanol in an amount ranging from 100 to 10 000 ppm, and / or (d2) one or more compounds 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-benzothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate and dibromodicyanobutane in a total amount within a range of 1 to 1000 ppm.

12. The composition according to any one of claims 1 to 11, characterized in that It has a water content of greater than 10% by weight.

13. An aqueous composition selected from paints, stains, varnishes, glazes and plasters, emulsions, latexes, polymer dispersions, mineral slurries, pigment slurries and pigment dispersions, detergents and cleaning compositions, comprising: (a) 200 to 7500 ppm of guanidine and / or at least one guanidine salt, (b) 1 to 1000 ppm of 1,2-benzisothiazolin-3-one, (c) 10 to 5000 ppm of zinc oxide, (d1) 1 to 150 ppm of 2-methyl-4-isothiazolin-3-one, and (d2) 1 to 100 ppm of 5-chloro-2-methyl-4-isothiazolin-3-one.

14. Use of (a) guanidine and / or a salt of unsubstituted guanidine for improving the antimicrobial efficacy of (b) 1,2-benzisothiazolin-3-one.

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