Compositions containing guanidine and 1,2-benzisothiazolin-3-one

Abstract

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 substances. The present invention also relates to a technical product containing the composition according to the invention.

Description

[Technical Field]

[0001] The present invention relates to compositions comprising (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 substances. The present invention also relates to industrial products comprising the compositions of the present invention. [Background technology]

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

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

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

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

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

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

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

[0009] The present invention provides (a) at least one salt of guanidine and / or unsubstituted guanidine, and (b) 1,2-benzisothiazolin-3-one This object is achieved by a composition, preferably an aqueous composition, comprising:

[0010] The composition of the present invention has the advantage that guanidine or its salt, component (a), and 1,2-benzisothiazolin-3-one, component (b), which have not previously been known as antibacterial active substances, interact synergistically and can therefore be used simultaneously at lower concentrations than the individual components. As a result, microorganisms, such as bacteria and fungi, present in the composition from the time of manufacture are effectively and efficiently inactivated despite the lower concentrations of components (a) and (b). DETAILED DESCRIPTION OF THE INVENTION

[0011] The composition of the present invention contains at least one salt of guanidine and / or unsubstituted guanidine as component (a). In the context of the present invention, "at least one salt or at least one further component" 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 two, three, four, five or more components or two, three, four, five or more compounds.

[0012] For the purposes of the present invention, by salts of guanidine and / or unsubstituted guanidine is meant that the composition also contains one or more salts of guanidine and / or therefore optionally unsubstituted guanidine as component (a). Guanidine has the formula shown below: [ka] is a compound of

[0013] In the context of the present invention, salts of unsubstituted guanidine or guanidine salts are those of the general formula shown below: [ka] (wherein n is 1, 2 or 3; and the counter ion X n- is, for example, chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, bicarbonate, guanidine silicate, formate, acetate or citrate) is a guanidine or guanidinium salt of

[0014] In a preferred embodiment of the invention, the composition of the invention contains guanidine hydrochloride and / or guanidine carbonate as component (a), and in a particularly preferred embodiment of the invention, the composition contains guanidine carbonate as component (a).

[0015] As component (b), the compositions of the present invention comprise 1,2-benzisothiazolin-3-one, which may be present in the composition in the form of its alkali metal salt. Thus, the compositions of the present invention comprise as component (b) 1,2-benzisothiazolin-3-one and / or its sodium, potassium or lithium metal salt or a mixture thereof.

[0016] In the context of the present invention, both the amount of each of components (a) and (b) and the weight ratio of components (a) and (b) to each other are specified. The amounts relate, respectively, to the lead structure, guanidine, or to the lead structure of component (b), 1,2-benzisothiazolin-3-one. The determination of the weight ratio specified is in each case similarly based on the content of guanidine in the composition without any counterion, and on the content of 1,2-benzisothiazolin-3-one as component (b) without any counterion.

[0017] In a preferred embodiment, the present invention relates to a composition comprising guanidine and / or a salt thereof, and 1,2-benzisothiazolin-3-one, in a weight ratio of guanidine to 1,2-benzisothiazolin-3-one in the range from 1.3:1 to 309:1, preferably in the range from 1.3:1 to 200:1, more preferably in the range from 1.3:1 to 100:1, wherein the criteria for determining the weight ratio are in each case the content with respect to guanidine without any counterion in the composition and the 1,2-benzisothiazolin-3-one content.

[0018] The amount of component (a), guanidine and / or salts thereof, present in the compositions of the present invention can vary within wide limits, generally in the range of 100 to 10,000 ppm, preferably in the range of 200 to 7,500 ppm, more preferably in the range of 300 to 5,000 ppm, each specified amount relating to the guanidine content in the total composition.

[0019] The amount of component (b), 1,2-benzisothiazolin-3-one and / or its alkali metal salt, present in the compositions of the present invention can vary over a wide range and is generally in the range of 1 to 1000 ppm, preferably in the range of 10 to 750 ppm, more preferably in the range of 25 to 500 ppm, the amount specified in each case relating to the 1,2-benzisothiazolin-3-one content in the total composition.

[0020] The compositions of the present invention are aqueous compositions, the water content of which can vary over a wide range, and are typically characterized as having a water content of greater than 1% by weight, preferably greater than 10% by weight, and more preferably greater than 20% by weight, based on the total composition.

[0021] The pH of the compositions of the present invention can vary over a wide range. In one embodiment of the present invention, the compositions are characterized by having a pH in the range of 4.5 to 12, preferably in the range of 5.0 to 11.5, and more preferably in the range of 5.5 to 11. The pH can be adjusted to the ranges set forth in the claims using means well known to those skilled in the art.

[0022] The compositions according to the invention, in particular aqueous compositions, are generally industrial products, in particular aqueous industrial products, selected from the group consisting of lignosulfonate and starch formulations in paints, pigments, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, chalk slurries, mineral slurries, ceramic compounds, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and pigment dispersions, inks, lithography fluids, thickeners, cosmetics, toiletries, water cycle fluids, wood processing fluids, oil production fluids, paper processing fluids, leather manufacturing fluids, textile manufacturing fluids, drilling and cutting oils, hydraulic oils, cooling lubricants and biocidal products. In a preferred embodiment of the present invention, the composition is an industrial product, especially an aqueous industrial product, selected from the group consisting of paints, pigments, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, mineral slurries, pigment pastes and pigment dispersions, detergent and cleaning compositions.

[0023] Component (c) is generally zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3] 2· [Zn(OH)], zinc ascorbate, zinc hydroxide, zinc dehydroacetate and zinc carboxylate. In a preferred embodiment of the present invention, component (c) is selected from the group consisting of zinc oxide and zinc carbonate, and in a particularly preferred embodiment, component (c) is zinc oxide.

[0024] Therefore, in this embodiment, the present invention provides, inter alia: (a) at least one salt of guanidine and / or unsubstituted guanidine; (b) 1,2-benzisothiazolin-3-one, and (c) Zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3] 2· [Zn(OH)2]3), one or more zinc compounds selected from the group consisting of zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate The present invention relates to an aqueous composition comprising:

[0025] 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, component (c), in each case interacts synergistically with components (a) and (b), which means that the content of components (a), (b) and (c) in the composition can be further reduced while maintaining antibacterial efficacy.

[0026] The weight ratio of components (a) to (c) relative to one another can vary over a wide range. In a preferred embodiment, the composition of the invention is characterized in that the weight ratio of (a) to (c) is in the range of 0.77:1 to 12:1, preferably in the range of 1:1 to 10:1, with the proviso that the basis for determining said weight ratio is in each case the content in terms of guanidine, without any counterion, and the zinc content.

[0027] The amount of component (c), the at least one zinc compound, present in the compositions of the present invention can vary over a wide range and in any case will be 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, based on the zinc content of the composition.

[0028] In a preferred embodiment of the present invention, the composition comprises as further component: (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, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol, and dibromodicyanobutane Includes:

[0029] In this embodiment, the composition of the invention, in which component (d) is also present, has the advantage that 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-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), and optionally (c) and (d) in the composition can be further reduced while maintaining antibacterial efficacy.

[0030] Therefore, in this embodiment, the present invention provides, inter alia: (a) at least one salt of guanidine and / or unsubstituted guanidine; (b) 1,2-benzisothiazolin-3-one, optionally (c) Zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3] 2· one or more zinc compounds selected from the group consisting of [Zn(OH)], zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate; and (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, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol, and dibromodicyanobutane The present invention relates to an aqueous composition comprising:

[0031] The amount of component (d) present in the compositions of the present invention can vary over a wide range. In a preferred embodiment of the present invention, the composition contains, as component (d): (d1) phenoxyethanol in an amount ranging from 100 to 10,000 ppm, preferably in an amount ranging from 250 to 7,500 ppm, more preferably in an amount ranging from 500 to 5,000 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-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 more preferably in a total amount in the range of 1 to 500 ppm The present invention is characterized by comprising:

[0032] Therefore, in a preferred embodiment of the present invention, the present invention comprises, in particular: (a) 100 to 10,000 ppm, preferably 200 to 7,500 ppm, more preferably 300 to 5,000 ppm of guanidine and / or at least one salt of guanidine; (b) 1 to 1000 ppm, preferably 10 to 750 ppm, more preferably 25 to 500 ppm of 1,2-benzisothiazolin-3-one; (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 zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3] 2· one or more zinc compounds selected from the group consisting of [Zn(OH)], zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate; (d1) 0 to 10,000 ppm, preferably 250 to 7,500 ppm, more preferably 500 to 5,000 ppm of phenoxyethanol, and (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. The present invention relates to an aqueous composition comprising:

[0033] In one embodiment of the present invention, the present invention provides (a) 200 to 7500 ppm, more preferably 300 to 5000 ppm, of guanidine and / or at least one salt of guanidine; (b) 1 to 1000 ppm, preferably 10 to 750 ppm, more preferably 25 to 500 ppm of 1,2-benzisothiazolin-3-one; (c) 10 to 5000 ppm, preferably 50 to 1000 ppm, of zinc oxide; (d1) 1 to 150 ppm, preferably 2 to 100 ppm, more preferably 5 to 50 ppm of 2-methyl-4-isothiazolin-3-one, and (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 The present invention relates to an aqueous composition comprising: In a particularly preferred embodiment, the aqueous composition defined above comprises as components: (a) 300 to 10,000 ppm, preferably 500 to 7,500 ppm, more preferably 750 to 5,000 ppm of guanidine carbonate and / or guanidine hydrochloride Includes:

[0034] The aqueous compositions defined above are water-based industrial products selected from the group consisting of paints, pigments, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, mineral slurries, pigment pastes and pigment dispersions, detergent and cleaning compositions.

[0035] In a further embodiment of the present invention, the present invention provides (a) 200 to 7500 ppm, more preferably 300 to 5000 ppm, of guanidine and / or at least one salt of guanidine; (b) 1 to 1000 ppm, preferably 10 to 750 ppm, more preferably 25 to 500 ppm of 1,2-benzisothiazolin-3-one; (d1) 1 to 150 ppm, preferably 2 to 100 ppm, more preferably 5 to 50 ppm of 2-methyl-4-isothiazolin-3-one, and (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 The present invention relates to an aqueous composition comprising: In a particularly preferred embodiment, the aqueous composition defined above comprises as components: (a) 300 to 10,000 ppm, preferably 500 to 7,500 ppm, more preferably 750 to 5,000 ppm of guanidine carbonate and / or guanidine hydrochloride Includes:

[0036] The aqueous composition as defined above is preferably an aqueous industrial product selected from the group consisting of emulsions, latexes, polymer dispersions, pigment dispersions, detergent and cleaning compositions, more preferably an aqueous industrial product selected from the group consisting of emulsions and latexes.

[0037] The composition of the present invention comprises, as component (d), Phenoxyethanol in an amount ranging from 100 to 10,000 ppm, preferably in an amount ranging from 250 to 7,500 ppm, more preferably in an amount ranging from 500 to 5,000 ppm, and / or Sodium 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 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 5-chloro-2-methyl-4-isothiazolin-3-one in an amount ranging from 0.5 to 200 ppm, preferably in an amount ranging from 1 to 100 ppm, more preferably in an amount ranging from 2 to 50 ppm, and / or 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 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 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 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 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 dibromonitrilopropionamide 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 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 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. Its inclusion is particularly advantageous.

[0038] This is because it has surprisingly proven advantageous in the context of the present invention if the composition of the present invention, which contains components (a) and (b) and optionally also (c), also contains the above-mentioned component(s) (d) in the amounts specified in each case, thereby achieving a further synergistic increase in the antimicrobial efficacy of the composition of the present invention already possessing components (a) and (b) and optionally also (c). In the context of the present invention, it has also proven to be particularly advantageous when: When phenoxyethanol is present as component (d), the weight ratio of guanidine and / or a salt thereof to phenoxyethanol is in the range of 0.13:1 to 3.6:1, with the proviso that the basis for determining said weight ratio is in each case the content of guanidine in the composition without any counter ions.

[0039] When sodium pyrithione is present as component (d), the weight ratio of guanidine and / or a salt thereof 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, with the proviso that the basis for determining said weight ratio is in each case the content of guanidine in the composition without any counter ion.

[0040] When zinc pyrithione is present as component (d), the weight ratio of guanidine and / or a salt thereof 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, with the proviso that the basis for determining said weight ratio is in each case the content of guanidine in the composition without any counter ion.

[0041] When 5-chloro-2-methyl-4-isothiazolin-3-one is present as component (d), the weight ratio of guanidine and / or a salt thereof 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, and more preferably in the range of 62:1 to 300:1, with the proviso that the basis for determining the weight ratio in each case is the content of guanidine in the composition without any counter ion.

[0042] When 2-methyl-4-isothiazolin-3-one is present as component (d), the weight ratio of guanidine and / or a salt thereof 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, and more preferably in the range of 10.3:1 to 300:1, with the proviso that the basis for determining the weight ratio in each case is the content of guanidine in the composition without any counter ion.

[0043] When N-methyl-1,2-benzisothiazolin-3-one is present as component (d), the weight ratio of guanidine and / or a salt thereof 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, with the proviso that the basis for determining said weight ratio in each case is the content of guanidine in the composition without any counter ion.

[0044] When N-butyl-1,2-benzisothiazolin-3-one is present as component (d), the weight ratio of guanidine and / or a salt thereof 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, and more preferably in the range of 0.52:1 to 100:1, with the proviso that the basis for determining the weight ratio in each case is the content of guanidine in the composition without any counter ion.

[0045] When octylisothiazolinone is present as component (d), 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, preferably in the range of 1.4:1 to 50:1, with the proviso that the basis for determining said weight ratio is in each case the content of guanidine in the composition without any counterion.

[0046] When bronopol is present as component (d), the weight ratio of guanidine and / or a salt thereof 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, with the proviso that the basis for determining said weight ratio in each case is the content of guanidine in the composition without any counter ion.

[0047] When dibromonitrilopropionamide is present as component (d), the weight ratio of guanidine and / or a salt thereof to 2,2-dibromo-3-nitrilopropionamide is in the range of 7.8:1 to 3090:1, preferably in the range of 7.8:1 to 250:1, more preferably in the range of 7.8:1 to 100:1, with the proviso that the basis for determining said weight ratio is in each case the content of guanidine in the composition without any counterion.

[0048] When iodopropynyl butylcarbamate is present as component (d), the weight ratio of guanidine and / or a salt thereof to iodopropynyl butylcarbamate is in the range of 0.83:1 to 103:1, preferably in the range of 1:1 to 90:1, and more preferably in the range of 1:1 to 80:1, with the proviso that the basis for determining said weight ratio is in each case the content of guanidine in the composition without any counter ion.

[0049] When dibromodicyanobutane is present as component (d), the weight ratio of guanidine and / or a salt thereof to dibromodicyanobutane is in the range of 0.78:1 to 309:1, preferably in the range of 0.8:1 to 200:1, more preferably in the range of 0.8:1 to 100:1, with the proviso that the basis for determining said weight ratio is in each case the content of guanidine in the composition without any counter ion.

[0050] This is because, in the context of the present invention, it has been found to be surprisingly advantageous when component (a), guanidine and / or its salts, and the above-specified component(s) (d) are in a defined synergistic ratio relative to one another, which allows achieving a further synergistic increase in the antibacterial efficacy of the composition of the present invention already possessing components (a) and (b) and optionally also (c).

[0051] In a further embodiment, the present invention relates to the use of (a) a salt of guanidine and / or unsubstituted guanidine for improving the antibacterial efficacy of (b) 1,2-benzisothiazolin-3-one.

[0052] As can be seen from the examples presented below, the use of guanidine or its salts, which have not been known as antibacterial active substances until now, causes a surprising synergistic increase in the effect of 1,2-benzisothiazolin-3-one.

[0053] In a preferred embodiment of the present invention, the present invention further comprises: (a) 100 to 10,000 ppm, preferably 200 to 7,500 ppm, more preferably 300 to 5,000 ppm of guanidine and / or at least one salt of guanidine; (b) 1 to 1000 ppm, preferably 10 to 750 ppm, more preferably 25 to 500 ppm of 1,2-benzisothiazolin-3-one; (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 zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc hydroxycarbonate ([ZnCO3] 2· one or more zinc compounds selected from the group consisting of [Zn(OH)], zinc ascorbate, zinc hydroxide, zinc dehydroacetate, and zinc carboxylate; (d1) phenoxyethanol in a concentration of 0 to 10,000 ppm, preferably 100 to 10,000 ppm, more preferably 250 to 7,500 ppm, and most preferably 500 to 5,000 ppm, and (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. The present invention relates to the use of (a) 100 to 10,000 ppm, preferably 200 to 7,500 ppm, more preferably 300 to 5,000 ppm of guanidine and / or at least one salt of guanidine for improving the antibacterial efficacy of an aqueous composition containing the compound.

[0054] The present invention further provides a method for preparing the aqueous composition of the present invention, which comprises mixing the ingredients defined above. [Example]

[0055] The following examples serve to further illustrate the present invention:

[0056] Study of synergistic interactions The combination of guanidine (added in the form of guanidine hydrochloride) and 1,2-benzothiazolin-3-one (BIT) was examined for their synergistic interaction.

[0057] The test organism used was a Gram-negative bacterial species from the group of Pseudomonads, Pseudomonas spec. DSM 115322. For this purpose, mixtures with different concentrations of the respective active substances were prepared and their effect on Pseudomonads was tested. The test was carried out at 10 per ml 6 Microbial cell density was determined in Mueller-Hinton broth (MHB).

[0058] Incubation was carried out in microplates at 30°C for 48 hours. After 48 hours, the batches were evaluated for turbidity resulting from growth and the optical density was determined photometrically. In this way, the minimum inhibitory concentrations (MICs) of the two active substances were determined individually and in combination.

[0059] The resulting synergistic effect was quantified by calculating the synergy index (SI). The calculation was performed according to the standard method of F.C. Kull et al., Applied Microbiology, vol. 9 (1961), p. 538.

[0060] This involves calculating the synergy index (SI) according to the following formula:

number

[0061] If the synergy index is greater than 1, this means that there is antagonism. If the synergy index assumes a value of 1, this means that the effects of the two biocides / compounds are additive. If the synergy index assumes a value less than 1, this means that there is a synergistic effect between the two biocides / compounds.

[0062] Example 1: Study of the synergistic interaction of guanidine and 1,2-benzisothiazolin-3-one (BIT) Calculation of synergy index of guanidine and BIT for Pseudomonas sp. DSM 115322 at 30°C and 48 h incubation time.

[0063] [Table 1]

[0064] Table 1 shows that the optimal synergistic effect of the guanidine and BIT composition, i.e., the lowest synergy index (0.67), is obtained at a ratio of 3090 ppm guanidine to 100 ppm BIT. Synergistic effect can be demonstrated when the weight ratio of guanidine to BIT ranges from 1.3:1 to 309:1.

[0065] In the following Examples 2-4, the synergistic interaction of guanidine and benzisothiazolinone (BIT) with respect to microbial infestation was investigated using emulsion paints and detergent or cleaning compositions by adding specific amounts of guanidine salts and benzisothiazolinone and testing their stability against microbial infestation:

[0066] The paint tested was an emulsion paint based on a styrene acrylate binder (PVC 77%, pH 8.8) for indoor use, manufactured in the laboratory without the addition of conventional preservatives.

[0067] 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 similarly prepared in the laboratory without the addition of additional conventional preservatives.

[0068] procedure: To each paint, specific concentrations of guanidinium hydrochloride and benzisothiazolinone (BIT) were added - individually and in combination. Detergent and cleaning compositions were mixed with specific concentrations of guanidinium hydrochloride and benzisothiazolinone (BIT).

[0069] The resulting batches of paints thus prepared were inoculated with a mixture of different bacteria; the batches of detergent and cleaning compositions thus prepared were inoculated with a yeast mixture.

[0070] Bacterial mixture: Pseudomonas spp. (Pseudomonas oleovorans group) DSM 33933 Pseudomonas aeruginosa DSM 33935 Pseudomonas oleovorans DSM 33936 Pseudomonas spec. DSM 33937 Pseudomonas aeruginosa DSM 33938

[0071] Yeast mixture: Pichia manshurica DSM 12249 Rhodotorula mucilaginosa DSM 12248 Candida boidinii DSM 13622 Candida albicans DSM 1386

[0072] The inoculum was added to each sample as a fresh cell suspension in saline (0.9% NaCl) at 2% (v / w) for each inoculum. The cell count of the added inoculum was determined by the bacterial mixture being 10 9 / ml and the yeast mixture was 10 8 / ml and consisted of equal parts of individual bacterial or yeast strains.

[0073] Cell suspensions of the bacterial mixture were produced by growing individual bacteria in liquid culture on a shaker at 30°C for 24 h. The growth medium used for the bacteria was Mueller-Hinton liquid medium. After growth, the individual liquid cultures were centrifuged and the cells were resuspended in saline. The mixture was then diluted to 100 ml. 9 To adjust the total cell count to 100 / ml, the individual bacterial suspensions were diluted accordingly, if necessary, before being combined with saline. The cell number of the inoculum was determined each time by chamber counting.

[0074] A cell suspension of the yeast mixture was produced by growing yeast on Sabouraud dextrose agar for 48 hours at 25°C and washing off the cell lawn with saline (0.9% NaCl). 8 Further steps for determining cell counts / ml were performed similar to the production of bacterial suspensions.

[0075] In Examples 2 to 4, the samples were inoculated once with the respective cell suspension (2% v / w), and bacterial or yeast growth was then followed by a semi-quantitative evaluation method. The inoculated samples were evaluated for microbial spread on the first day immediately after inoculation and on the sixth day after an additional 5 days of incubation at 30°C (emulsion paints), or on the third day after an additional 2 days of incubation at 30°C (detergents, cleaning compositions). For this purpose, aliquots were taken from each sample after homogenization using a sterile plastic inoculation loop (10 μl) and uniformly streaked onto agar plates (tryptone soy agar for bacteria, Sabouraud dextrose agar for yeast). The streaked agar plates were then incubated at 30°C for 48 hours (bacteria) or at 25°C for 72 hours (yeast). After incubation, bacterial or yeast colonies grown on the agar plates were visually evaluated and quantified according to the following scheme:

[0076] TIFF2026505253000005.tif80149

[0077] The results of Examples 2-4 are shown in Tables 2-4:

[0078] Example 2 / Table 2: [Table 2]

[0079] As can be inferred from the results shown in Table 2, the synergistic interaction of BIT and guanidine already demonstrated under the above laboratory conditions can also be demonstrated in practical applications in emulsion paints.

[0080] Example 3 / Table 3: [Table 3]

[0081] As can be inferred from the results shown in Table 3, the synergistic interaction of BIT and guanidine already demonstrated under the above laboratory conditions can also be demonstrated in practical applications in heavy-duty laundry detergents.

[0082] Example 4 / Table 4: [Table 4] As can be inferred from the results shown in Table 4, the synergistic interaction of BIT and guanidine already demonstrated under the above laboratory conditions can also be demonstrated in practical applications in heavy-duty laundry detergents.

Claims

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

2. 2. A composition according to claim 1, characterized in that the guanidine salts present are guanidine hydrochloride and / or guanidine carbonate.

3. 3. Composition according to claim 1 or 2, characterized in that the weight ratio of (a) to (b) ranges from 1.3:1 to 309:1, with the criterion in determining said weight ratio being in each case the content in relation to guanidine.

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

5. 5. Composition according to any one of claims 1 to 4, characterized in that the weight ratio of (a) to (c) ranges from 0.77:1 to 12:1, with the criterion in determining said weight ratio being in each case the contents with respect to guanidine and zinc.

6. (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, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, phenoxyethanol, and dibromodicyanobutane The composition of any one of claims 1 to 4, further comprising:

7. 7. The composition according to any one of claims 1 to 6, characterized in that it is an industrial product selected from the group consisting of lignosulfonate and starch formulations in paints, pigments, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, chalk slurries, ore slurries, ceramic compounds, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning compositions, pigment pastes and pigment dispersions, inks, lithography fluids, thickeners, cosmetics, toiletries, water cycles, wood processing fluids, petroleum production fluids, paper processing fluids, leather manufacturing fluids, textile manufacturing fluids, drilling and cutting oils, hydraulic oils, cooling lubricants, and biocidal products.

8. A composition according to any one of claims 1 to 7, characterized in that it has a pH ranging from pH 4.5 to pH 12.

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

10. 9. The composition according to claim 4, wherein the component (c) is contained in an amount ranging from 10 to 5000 ppm based on the amount of zinc in the composition.

11. The composition comprises: (d1) phenoxyethanol in an amount ranging from 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-1,2-benzothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromonitrilopropionamide, iodopropynyl butylcarbamate, and dibromodicyanobutane in a total amount ranging from 1 to 1000 ppm. The composition according to any one of claims 6 to 10, comprising:

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

13. 1. An aqueous composition selected from the group consisting of paints, pigments, varnishes, glazes and primers, emulsions, latexes, polymer dispersions, mineral slurries, pigment pastes and pigment dispersions, detergent and cleaning compositions, comprising: (a) 200 to 7500 ppm of guanidine and / or at least one salt of guanidine; (b) 1 to 1000 ppm of 1,2-benzisothiazolin-3-one; (c) 10 to 5000 ppm 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 A composition comprising:

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

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