EP4669108A1 - Compositions synergiques contenant de la guanidine - Google Patents

Compositions synergiques contenant de la guanidine

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Publication number
EP4669108A1
EP4669108A1 EP24706927.1A EP24706927A EP4669108A1 EP 4669108 A1 EP4669108 A1 EP 4669108A1 EP 24706927 A EP24706927 A EP 24706927A EP 4669108 A1 EP4669108 A1 EP 4669108A1
Authority
EP
European Patent Office
Prior art keywords
guanidine
range
salt
ppm
weight ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24706927.1A
Other languages
German (de)
English (en)
Inventor
Thomas Wunder
Roman Grabbe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Thor GmbH
Original Assignee
Thor GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thor GmbH filed Critical Thor GmbH
Publication of EP4669108A1 publication Critical patent/EP4669108A1/fr
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof

Definitions

  • the present invention relates to a composition containing (a) guanidine and/or a salt of non-substituted guanidine and (b) at least one further component selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, octylisothiazolinone,
  • the invention further relates to technical products which contain components (a) and (b) and to the use of the compositions for the container preservation and the preservation of technical products.
  • the invention also relates to the use of (a) guanidine and/or a salt of non-substituted guanidine to improve the antimicrobial effectiveness of one or more compounds selected from the group (b) defined above.
  • aqueous ones such as paints, varnishes, emulsions, detergents and cleaning agents and cosmetic products
  • aqueous ones such as paints, varnishes, emulsions, detergents and cleaning agents and cosmetic products
  • These raw materials and the water used as a solvent are often contaminated with germs such as bacteria, yeasts and fungi. If these products are not preserved during manufacture, they can have high germ counts just one day after production.
  • 3-isothiazolin-3-ones One class of biocides used to preserve aqueous technical products such as paints, plasters, detergents and cleaning agents or glazes, or components of these, are the so-called 3-isothiazolin-3-ones. This class of substances contains very effective antimicrobial compounds with sometimes different profiles of action. Synergistic combinations of different 3-isothiazolin-3-ones are often used to reduce the amount of biocides used. For example, WO 99/08530 A1 proposes the combined use of methylisothiazolin-3-one and l,2-benzisothiazolin-3-one.
  • EP-B 1 030 558 also discloses a synergistic biocide composition containing 2-methylisothiazolin-3-one and 3-iodo-2-propynyl-N-butylcarbamate. This synergistic composition is suitable for combating microorganisms even in low concentrations.
  • biocides are the so-called alkylguanidinium salts and also polyguanidinium salts.
  • medium and long-chain guanidines and biguanidines such as cocospropylenediamine-l,5-bis-guanidinium acetate, bis(guanidinooctyl)amine triacetate, poly(hexamethylene-biguanidine) hydrochloride, di(4'-chlorophenyldiguanido)hexane, chlorhexidine digluconate, chlorhexidine diacetate, have an antimicrobial effect.
  • composition preferably an aqueous composition, containing:
  • CMIT 5-Chloro-2-methyl-4-isothiazolin-3-one
  • MIT 2-Methyl-4-isothiazolin-3-one
  • BIT 1,2-Benzisothiazolin-3-one
  • BBIT N-Butyl -l,2-Benzisothiazolin-3-one
  • MBIT N-Methyl-1,2-Benzisothiazolin-3-one
  • OIT Octylisothiazolinone
  • Bronopol Dibromonitrilopropionamide
  • DBDCB Dibromodicyanobutane
  • IPBC Iodopropynylbutylcarbamate
  • IPBC amino-methyl-propanol
  • AMP amino-ethyl-propanediol
  • MEA monoethanolamine
  • MEA ethylhexylglycerol
  • AEPD amino-ethyl-propanediol
  • MEA monoethanolamine
  • MEA ethy
  • Ethylenediaminetetraacetic acid EDTA
  • HEDP l-hydroxyethylidenebis-phosphonic acid
  • sodium pyrithione sodium pyrithione
  • zinc pyrithione sodium pyrithione
  • oPP o-phenylphenol
  • sorbic acid benzoic acid
  • salicylic acid lactic acid
  • citric acid zinc.
  • composition according to the invention has the advantage that the guanidine or its salt, component (a), which is hitherto unknown as an antimicrobial active ingredient, and the at least one further component from the group given above, group (b), interact synergistically and can therefore be used in low concentrations when used simultaneously, compared to low concentrations in the case of the individual components.
  • at least one further component means that the composition contains a single component or compound selected from the group or several, i.e. two, three, four, five or more components or compounds, from the group.
  • both the amounts of the respective components (a) and (b) and the weight ratios of the components (a) and (b) to one another are specified.
  • the amounts relate in each case to the lead structures, the guanidine, or to the lead structure of component (b).
  • the content in relation to the guanidine, without taking into account any counter ion, and the content of the lead structure of the further component (b), without taking into account any counter ion, in the composition are used as a basis.
  • guanidine and/or a salt of non-substituted guanidine means that the composition contains as active component (a) the guanidine and/or possibly also one or more salts of non-substituted guanidine.
  • the guanidine is the compound according to the formula shown below:
  • 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 ' is, for example, chloride, carbonate, nitrate, sulfate, thiocyanate, phosphate, hydrogen carbonate, formate, acetate or citrate.
  • 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.
  • the amount of component (a), guanidine and/or its salt contained in the preferably aqueous composition according to the invention can vary over wide ranges and is generally in the range from 100 to 10,000 ppm, preferably in an amount in the range from 200 to 7,500 ppm and particularly preferably in an amount in the range from 300 to 5,000 ppm, wherein the proportion refers to the content of guanidine in the entire aqueous composition.
  • the amount of components (a) and (b) contained in the preferably aqueous composition according to the invention can vary over wide ranges.
  • the composition is characterized in that it contains the guanidine and/or its salt and the at least one further component in a total amount in the range from 0.01% to 10%, preferably in the range from 0.02% to 5% and particularly preferably in the range from 0.03% to 3%, based on the entire composition.
  • the water content in the preferably aqueous composition according to the invention can vary over wide ranges.
  • the composition is usually characterized in that it has a water content of greater than 1% by weight, preferably greater than 10% by weight, particularly preferably greater than 20% by weight, based on the entire composition.
  • the pH of the aqueous composition can vary over wide ranges and is generally in a range from pH 4.5 to pH 12, preferably in the range from pH 5.0 to 11.5, particularly preferably in the range from pH 5.5 to pH 11. The pH can be adjusted to the claimed range using measures familiar to the person skilled in the art.
  • the preferred weight ratios of components (a) to (b) to one another under which a surprisingly good antimicrobial effect can be achieved can, as can be seen from the examples, vary individually.
  • the invention relates to a composition containing guanidine and/or its salt, and 5-chloro-2-methylisothiazolin-3-one.
  • the invention relates to a composition containing guanidine and/or its salt and 5-chloro-2-methylisothiazolin-3-one, in a weight ratio of guanidine and/or its salt to 5-chloro-2-methylisothiazolin-3-one in the range from 62:1 to 9270:1, preferably in the range from 62:1 to 500:1, particularly preferably in the range from 62:1 to 300:1, wherein the weight ratio is determined based on the content in relation to the guanidine, without taking into account any counterion, and the 5-chloro-2-methylisothiazolin-3-one in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and 2-methylisothiazolin-3-one.
  • the invention relates to a composition containing guanidine and/or its salt and 2-methylisothiazolin-3-one, in a weight ratio of guanidine to 2-methylisothiazolin-3-one generally in the range from 10.3:1 to 773:1, preferably in the range from 10.3:1 to 500:1, particularly preferably in the range from 10.3:1 to 300:1, wherein in determining the weight ratio in each case the content in relation to guanidine, without taking into account any counterion, and 2-methylisothiazolin-3-one in the composition is taken as the basis.
  • the invention relates to a composition
  • a composition comprising guanidine and/or its salt and l,2-benzisothiazolin-3-one.
  • the invention relates to a composition containing guanidine and/or its salt and 1,2-benzisothiazolin-3-one, in a weight ratio of guanidine to 1,2-benzisothiazolin-3-one generally in the range from 1.3:1 to 309:1, preferably in the range from 1.3:1 to 200:1, particularly preferably in the range from 1.3:1 to 100:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-benzisothiazolin-3-one in the composition.
  • a weight ratio of guanidine to 1,2-benzisothiazolin-3-one generally in the range from 1.3:1 to 309:1, preferably in the range from 1.3:1 to 200:1, particularly preferably in the range from 1.3:1 to 100:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the
  • the invention relates to a composition
  • a composition comprising guanidine and/or its salt and N-butyl-1,2-benzisothiazolin-3-one.
  • the invention relates to a composition containing guanidine and/or its salt and N-butyl-1,2-benzisothiazolin-3-one, in a weight ratio of guanidine to N-butyl-1,2-benzisothiazolin-3-one generally in the range from 0.52:1 to 309:1, preferably in the range from 0.52:1 to 200:1, particularly preferably in the range from 0.52:1 to 100:1, wherein the weight ratio is determined in each case based on the content in relation to the guanidine, without taking into account any counterion, and the N-butyl-1,2-benzisothiazolin-3-one in the composition.
  • Benzisothiazolin-3-one (MBIT): According to one embodiment, the invention relates to a composition comprising guanidine and/or its salt and N-methyl-1,2-benzisothiazolin-3-one.
  • the invention relates to a composition containing guanidine and N-methyl-1,2-benzisothiazolin-3-one, in a weight ratio of guanidine to N-methyl-1,2-benzisothiazolin-3-one generally in the range from 7.8:1 to 618:1, preferably in the range from 7.8:1 to 400:1, particularly preferably in the range from 7.8:1 to 300:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the N-methyl-1,2-benzisothiazolin-3-one in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and N-octylisothiazolin-3-one.
  • the invention relates to a composition containing guanidine and N-octylisothiazolin-3-one, in a weight ratio of guanidine to N-octylisothiazolin-3-one generally in the range from 1.4:1 to 82:1, preferably in the range from 1.4:1 to 50:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the N-octylisothiazolin-3-one in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and bronopol.
  • the invention relates to a composition containing guanidine and bronopol, in a weight ratio of guanidine to bronopol generally in the range from 7.8:1 to 824:1, preferably in the range from 7.8:1 to 200:1, particularly preferably in the range from 7.8:1 to 100:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the bronopol in the composition.
  • a weight ratio of guanidine to bronopol generally in the range from 7.8:1 to 824:1, preferably in the range from 7.8:1 to 200:1, particularly preferably in the range from 7.8:1 to 100:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the bronopol in the composition.
  • a weight ratio of guanidine to bronopol generally in the range from 7.8:1 to 824:1, preferably in the range
  • the invention relates to a composition containing guanidine and/or its salt and 2,2-dibromo-3-nitrilopropionamide.
  • the invention relates to a composition containing guanidine and 2,2-dibromo-3-nitrilepropionamide, in a weight ratio of guanidine to 2,2-dibromo-3-nitrilepropionamide, generally in the range from 7.8:1 to 3090:1, preferably in the range from 7.8:1 to 250:1, particularly preferably in the range from 7.8:1 to 100:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 2,2-dibromo-3-nitrilopropionamide in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and dibromodicyanobutane.
  • the invention relates to a composition containing guanidine and dibromodicyanobutane in a weight ratio of guanidine to dibromodicyanobutane, generally in the range from 0.78:1 to 309:1, preferably in the range from 0.8:1 to 200:1, particularly preferably in the range from 0.8:1 to 100:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the N-dibromodicyanobutane in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and iodopropynyl butylcarbamate.
  • the invention relates to a composition containing guanidine and iodopropynyl butylcarbamate in a weight ratio Guanidine to iodopropynyl butylcarbamate, generally in the range from 0.83:1 to 103:1, preferably in the range from 1:1 to 90:1, particularly preferably in the range from 1:1 to 80:1, wherein the weight ratio is determined in each case based on the content in relation to the guanidine, without taking into account any counter ion, and the iodopropynyl butylcarbamate in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and 2-amino-2-methyl-1-propanol.
  • the invention relates to a composition containing guanidine and 2-amino-2-methyl-1-propanol, in a weight ratio of guanidine to 2-amino-2-methyl-1-propanol generally in the range from 0.3:1 to 20:1, preferably in the range from 0.5:1 to 15:1, particularly preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined based on the content in relation to the guanidine, without taking into account any counter ion, and the 2-amino-2-methyl-1-propanol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and 2-amino-1,3-ethylpropanediol.
  • the invention relates to a composition containing guanidine and 2-amino-1,3-ethyl-propanediol, in a weight ratio of guanidine to 2-amino-1,3-ethyl-propanediol generally in the range from 0.2:1 to 15:1, preferably in the range from 0.5:1 to 10:1, particularly preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 2-amino-1,3-ethyl-propanediol in the composition.
  • Synergistic composition containing guanidine and monoethanolamine (MEA) relates to a composition containing guanidine and/or its salt and monoethanolamine.
  • the invention relates to a composition containing guanidine and monoethanolamine, in a weight ratio of guanidine to monoethanolamine generally in the range from 0.2:1 to 30:1, preferably in the range from 0.5:1 to 20:1, particularly preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the monoethanolamine in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and ethylhexylglycerin.
  • the invention relates to a composition containing guanidine and ethylhexylglycerin, in a weight ratio of guanidine to ethylhexylglycerin generally in the range from 0.5:1 to 15:1, preferably in the range from 0.5:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the monoethanolamine in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and hexylglycerin.
  • the invention relates to a composition containing guanidine and hexylglycerin, in a weight ratio of guanidine to hexylglycerin generally in the range from 0.5:1 to 15:1, preferably in the range from 0.5:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the hexylglycerin in the composition.
  • Synergistic composition containing guanidine and 1,2-pentanediol According to one embodiment, the invention relates to a composition containing guanidine and/or its salt and 1,2-pentanediol.
  • the invention relates to a composition containing guanidine and 1,2-pentanediol, in a weight ratio of guanidine to 1,2-pentanediol generally in the range from 0.07:1 to 7.5:1, preferably in the range from 0.1:1 to 7.5:1, particularly preferably in the range from 0.5:1 to 7.5:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-pentanediol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and 1,2-hexanediol.
  • the invention relates to a composition containing guanidine and 1,2-hexanediol, in a weight ratio of guanidine to 1,2-hexanediol generally in the range from 0.06:1 to 15:1, preferably in the range from 0.1:1 to 10:1, particularly preferably in the range from 0.5:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-hexanediol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and 1,2-heptanediol.
  • the invention relates to a composition containing guanidine and 1,2-heptanediol, in a weight ratio of guanidine to 1,2-heptanediol generally in the range from 0.25:1 to 30:1, preferably in the range from 0.5:1 to 20:1, particularly preferably in the range from 0.5:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-heptanediol in the composition.
  • Synergistic composition containing guanidine and 1,2-octanediol Synergistic composition containing guanidine and 1,2-octanediol:
  • the invention relates to a composition containing guanidine and/or its salt and 1,2-octanediol.
  • the invention relates to a composition containing guanidine and 1,2-octanediol, in a weight ratio of guanidine to 1,2-octanediol generally in the range from 0.2:1 to 6:1, preferably in the range from 0.5:1 to 6:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the 1,2-octanediol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and phenoxyethanol.
  • the invention relates to a composition containing guanidine and phenoxyethanol in a weight ratio of guanidine to phenoxyethanol generally in the range from 0.13:1 to 3.6:1, preferably in the range from 0.3:1 to 3.6:1, particularly preferably in the range from 0.5:1 to 3.6:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the phenoxyethanol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and phenethyl alcohol.
  • the invention relates to a composition containing guanidine and phenethyl alcohol in a weight ratio of guanidine to phenethyl alcohol generally in the range from 0.15:1 to 12:1, preferably in the range from 0.3:1 to 12:1, particularly preferably in the range from 0.5:1 to 12:1, wherein in determining the weight ratio, the content in relation to the guanidine, without Taking into account any counterion and the phenoxyethanol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and phenylpropanol.
  • the invention relates to a composition containing guanidine and phenylpropanol in a weight ratio of guanidine to phenylpropanol, generally in the range from 0.4:1 to 6:1, preferably in the range from 0.5:1 to 6:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the phenoxyethanol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and benzyl alcohol.
  • the invention relates to a composition containing guanidine and benzyl alcohol in a weight ratio of guanidine to benzyl alcohol generally in the range from 1:1 to 12:1, preferably in the range from 1:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the benzyl alcohol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and isopropanol.
  • the invention relates to a composition containing guanidine and isopropanol in a weight ratio of guanidine to isopropanol generally in the range of 0.004:1 to 3:1, preferably in the range of 0.01:1 to 3:1, particularly preferably 0.1 to 3:1, wherein in determining the
  • the invention relates to a composition
  • a composition comprising guanidine and/or its salt and ethylenediaminetetraacetic acid and/or its salt(s).
  • the invention relates to a composition containing guanidine and ethylenediaminetetraacetic acid, in a weight ratio of guanidine to ethylenediaminetetraacetic acid generally in the range from 0.6:1 to 37:1, preferably in the range from 0.6:1 to 20:1, particularly preferably 0.6:1 to 15:1, wherein the weight ratio is determined in each case based on the content in relation to the guanidine, without taking into account any counterion, and the ethylenediaminetetraacetic acid in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and (l-hydroxyethylidene)bis-phosphonic acid and/or its salt(s).
  • the invention relates to a composition containing guanidine and (l-hydroxyethylidene)bis-phosphonic acid, in a weight ratio of guanidine to (l-hydroxyethylidene)bis-phosphonic acid generally in the range from 0.6:1 to 1.5:1, preferably in the range from 0.6:1 to 1:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the (1-hydroxyethylidene)bis-phosphonic acid in the composition.
  • Synergistic composition containing guanidine and sodium pyrithione According to one embodiment, the invention relates to a composition containing guanidine and/or its salt and sodium pyrithione.
  • the invention relates to a composition containing guanidine and sodium pyrithione, in a weight ratio of guanidine to sodium pyrithione generally in the range from 3.6:1 to 180:1, preferably in the range from 3.6:1 to 100:1, particularly preferably 3.6:1 to 50:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the sodium pyrithione in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and zinc pyrithione.
  • the invention relates to a composition containing guanidine and zinc pyrithione, in a weight ratio of guanidine to zinc pyrithione generally in the range from 3.6:1 to 180:1, preferably in the range from 3.6:1 to 100:1, particularly preferably 3.6:1 to 50:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the zinc pyrithione in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and o-phenylphenol.
  • the invention relates to a composition containing guanidine and o-phenylphenol, in a weight ratio of guanidine to o-phenylphenol generally in the range from 0.62:1 to 49:1, preferably in the range from 0.62:1 to 40:1, particularly preferably 0.62:1 to 30:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the o-phenylphenol in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and sorbic acid and/or its salt(s).
  • the invention relates to a composition containing guanidine and sorbic acid in a weight ratio of guanidine to sorbic acid generally in the range from 0.1:1 to 50:1, preferably in the range from 0.25:1 to 40:1, particularly preferably 0.25:1 to 30:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counter ion, and the sorbic acid in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and benzoic acid and/or its salt(s).
  • the invention relates to a composition containing guanidine and benzoic acid in a weight ratio of guanidine to benzoic acid generally in the range from 0.25:1 to 88:1, preferably in the range from 0.25:1 to 50:1, particularly preferably 0.25:1 to 30:1, wherein the weight ratio is determined in each case on the basis of the content in relation to the guanidine, without taking into account any counterion, and the benzoic acid in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and salicylic acid and/or its salt(s).
  • the invention relates to a composition containing guanidine and salicylic acid in a weight ratio of guanidine to salicylic acid generally in the range from 0.24:1 to 43:1, preferably in the range from 0.24:1 to 30:1, wherein in determining the weight ratio, the content in relation to to the guanidine, without taking into account any counter ion, and the salicylic acid in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and lactic acid and/or its salt(s).
  • the invention relates to a composition containing guanidine and lactic acid, in a weight ratio of guanidine to lactic acid generally in the range from 0.03:1 to 23:1, preferably in the range from 0.03:1 to 10:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the lactic acid in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and citric acid and/or its salt(s).
  • the invention relates to a composition containing guanidine and citric acid in a weight ratio of guanidine to citric acid in the range from 1:0.014 to 12:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and the citric acid in the composition.
  • the invention relates to a composition containing guanidine and/or its salt and zinc.
  • the zinc is provided by at least one zinc compound that serves as a zinc source.
  • the zinc compound is preferably selected from the group consisting of zinc oxide, zinc chloride, zinc sulfate, zinc phosphate, zinc carbonate, zinc ascorbate, zinc dehydroacetate, zinc hydroxide and zinc carboxylate.
  • the zinc compound is selected from the group, consisting of zinc oxide, zinc chloride and zinc carbonate.
  • the zinc is particularly preferably provided by zinc oxide or incorporated into the composition.
  • the invention relates to a composition containing guanidine and zinc in a weight ratio of guanidine to zinc in the range of 0.77:1 to 12:1, preferably 1:1 to 12:1, wherein the weight ratio is determined on the basis of the content in relation to the guanidine, without taking into account any counterion, and in relation to the zinc ion.
  • the composition according to the invention is characterized in that the weight ratio of guanidine and/or its salt to 5-chloro-2-methylisothiazolin-3-one is in the range from 62:1 to 9270:1, that the weight ratio of guanidine and/or its salt to 2-methyl-4-isothiazolin-3-one is in the range from 10.3:1 to 773:1, that the weight ratio of guanidine and/or its salt to 1,2-benzisothiazolin-3-one is in the range from 1.3:1 to 309:1, that the weight ratio of guanidine and/or its salt to N-butyl-1,2-benzisothiazolin-3-one is in the range from 0.52:1 to 309:1, that the weight ratio of guanidine and/or its salt to N-methyl-1,2- Benzisothiazolin-3-one is in the range from 7.8:1 to 618:1, that the weight ratio of guanidine and/or its salt
  • the aqueous composition is characterized in that it is a technical product selected from the group consisting of: lignosulfonates and starch preparation in paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions, chalk slurries, mineral slurries, ceramic Masses, adhesives, fragrances, casein-containing products, starch-containing products, bitumen emulsions, surfactant solutions, fuels, detergents, cleaning agents, pigment pastes and pigment dispersions, inks, lithographic fluids, thickeners, cosmetic products, toiletries, water circuits, fluids in wood processing, fluids in petroleum production, fluids in paper processing, fluids in leather production, fluids in textile production, drilling and cutting oils, hydraulic fluids, cooling lubricants and biocidal products.
  • lignosulfonates and starch preparation in paints, varnishes, glazes and plasters, emulsions, latices, polymer dispersions,
  • the content of components (a) and (b) in the technical products defined above can vary over a wide range depending on the intended use and is usually determined by the person skilled in the art of biocides.
  • the concentration ranges given below give the person skilled in the art an indication of the amounts to be used in each case:
  • the amount of component (a), guanidine and/or its salt contained in the technical products can vary over wide ranges and is generally in the range from 100 to 10,000 ppm, preferably in an amount in the range from 200 to 7,500 ppm and particularly preferably in an amount in the range from 300 to 5,000 ppm, wherein the proportion refers to the content of guanidine in the entire technical product.
  • the amount of component (b) contained in the technical products can also vary over wide ranges:
  • CIT 5-chloro-2-methyl-4-isothiazolin-3-one
  • component (b) it is generally present in the aqueous composition or the technical product in an amount in the range from 0.5 to 200 ppm, preferably in an amount from 5 to 100 ppm, particularly preferably in an amount from 10 to 50 ppm, especially preferably in an amount from 15 to 30 ppm.
  • MIT 2-methyl-4-isothiazolin-3-one
  • component (b) it is generally present in the aqueous composition or the technical product in an amount in the range from 0.5 to 200 ppm, preferably in an amount from 1 to 150 ppm, particularly preferably in an amount from 5 to 125 ppm, especially preferably in an amount from 10 to 100 ppm.
  • l,2-benzisothiazolin-3-one is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 500 ppm, preferably in an amount from 5 to 500 ppm, particularly preferably in an amount from 10 to 500 ppm.
  • N-butyl-1,2-benzisothiazolin-3-one (BBIT) is present as component (b), this is generally contained in the aqueous composition or the technical product in an amount in the range from 5 to 2,500 ppm, preferably in an amount from 10 to 2,000 ppm, particularly preferably in an amount from 10 to 1,500 ppm.
  • N-methyl-1,2-benzisothiazolin-3-one is present as component (b), this is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 500 ppm, preferably in an amount from 5 to 500 ppm, particularly preferably in an amount from 10 to 1,000 ppm.
  • octylisothiazolinone (OIT) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 2,500 ppm, preferably in an amount from 5 to 2,000 ppm, particularly preferably in an amount from 10 to 1,500 ppm.
  • bronopol is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 1,000 ppm, preferably in an amount from 5 to 750 ppm, particularly preferably in an amount from 10 to 500 ppm.
  • DBNPA dibromonitrilopropionamide
  • DBDCB dibromodicyanobutane
  • IPBC iodopropynyl butyl carbamate
  • aminomethylpropanol (AMP) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 25 to 7,500 ppm, particularly preferably in an amount from 50 to 5,000 ppm.
  • AEPD aminoethylpropanediol
  • component (b) If monoethanolamine (MEA) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 25 to 7,500 ppm, particularly preferably in an amount from 50 to 5,000 ppm. If ethylhexylglycerol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • MEA monoethanolamine
  • hexylglycerol is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range 10 to 10,000 ppm, preferably in an amount of 50 to 7,500 ppm, particularly preferably in an amount of 100 to 5,000 ppm.
  • 1,2-pentanediol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • 1,2-hexanediol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • 1,2-heptanediol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • 1,2-octanediol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • phenoxyethanol is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • phenethyl alcohol is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • phenylpropanol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • benzyl alcohol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • isopropanol is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 10 to 30,000 ppm, preferably in an amount from 50 to 20,000 ppm, particularly preferably in an amount from 100 to 15,000 ppm.
  • ethylenediaminetetraacetic acid is present as component (b), it is generally contained in the aqueous composition or the technical product preserved product in an amount in the range of 10 to 10,000 ppm, preferably in an amount of 50 to 7,500 ppm, particularly preferably in an amount of 100 to 5,000 ppm.
  • EDTA ethylenediaminetetraacetic acid
  • component (b) If (l-hydroxyethylidene)bisphosphonic acid (HEDP) is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 10 to 10,000 ppm, preferably in an amount from 50 to 7,500 ppm, particularly preferably in an amount from 100 to 5,000 ppm.
  • HEDP (l-hydroxyethylidene)bisphosphonic acid
  • sodium pyrithione is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 2,500 ppm, preferably in an amount from 5 to 1,500 ppm, particularly preferably in an amount from 10 to 1,000 ppm.
  • zinc pyrithione is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 2,500 ppm, preferably in an amount from 5 to 1,500 ppm, particularly preferably in an amount from 10 to 1,000 ppm.
  • o-phenylphenol is present as component (b), it is generally present in the aqueous composition or the technical product in an amount in the range from 1 to 10,000 ppm, preferably in an amount from 10 to 5,000 ppm, particularly preferably in an amount from 25 to 2,500 ppm, especially preferably in an amount from 50 to 1,500 ppm.
  • sorbic acid is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 10,000 ppm, preferably in an amount from 5 to 7,500 ppm, particularly preferably in an amount from 10 to 5,000 ppm.
  • benzoic acid is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 10,000 ppm, preferably in an amount from 5 to 7,500 ppm, particularly preferably in an amount from 10 to 5,000 ppm.
  • salicylic acid is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 10,000 ppm, preferably in an amount from 5 to 7,500 ppm, particularly preferably in an amount from 10 to 5,000 ppm.
  • lactic acid is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 50,000 ppm, preferably in an amount from 5 to 25,000 ppm, particularly preferably in an amount from 10 to 15,000 ppm.
  • citric acid is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 1 to 100,000 ppm, preferably in an amount from 5 to 50,000 ppm, particularly preferably in an amount from 10 to 25,000 ppm.
  • zinc is present as component (b), it is generally contained in the aqueous composition or the technical product in an amount in the range from 10 to 5,000 ppm, preferably in an amount from 25 to 2,500 ppm, preferably in an amount from 50 to 1,000 ppm, particularly preferably in an amount from 100 to 500 ppm.
  • the present invention further relates to the use of the above-defined, preferably aqueous compositions for the preservation of containers, or the use for the preservation of technical products selected from the group consisting of lignin sulfonates and starch preparations in 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 liquids, thickeners, cosmetic products, toiletries, water circuits, liquids in wood processing, liquids in petroleum production, liquids in paper processing, Fluids in leather production, fluids in textile production, drilling and cutting oils, hydraulic fluids and cooling lubricants.
  • technical products selected from the group consisting of lignin sulfonates and starch preparations in
  • the present invention relates to the use of:
  • guanidine or its salt which is not known to date as an antimicrobial active ingredient, leads to a surprising synergistic increase in the effect of at least one further component from the group (b) given above.
  • the at least one biocidal active component from group (b) can be used in significantly low concentrations in the presence of guanidine.
  • the amounts of components (a) and (b) used can vary over a wide range and are, for example, in the range from 0.01% to 10%, preferably in the range from 0.02% to 5% and particularly preferably in the range from 0.03% to 3%, based on the total composition in which the components are contained.
  • 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 and/or the weight ratio of guanidine and/or its salt to 2-methyl-4-isothiazolin-3-one is in the range from 10.3:1 to 773:1, and/or the weight ratio of guanidine and/or its salt to l,2-benzisothiazolin-3-one is in the range from 1.3:1 to 309:1 and/or the weight ratio of guanidine and/or its salt to N-butyl-1,2-benzisothiazolin-3-one is in the range from 0.52:1 to 309:1 and/or the weight ratio of guanidine and/or its salt to N-methyl-1,2-benzisothiazolin-3-one is in the range from 7.8:1 to 618:1 and/or the weight ratio of guan
  • Gram-negative bacterial species from the group of pseudomonads Pseudomonas putida DSM 115323 and Pseudomonas spec. DSM 115322, were used as test organisms. For this purpose, mixtures with different concentrations of the respective active ingredients were prepared and their effect on the pseudomonads was tested. The test was carried out in Müller-Hinton broth MHB with a cell density of 10 6 germs per ml. When organic acids were used as a combination partner for the guanidine, the pH of MHB was adjusted to 5.5.
  • the synergism that occurred was numerically represented by calculating the synergy index (SI).
  • the calculation was carried out according to the standard method of FC Kull et al., Applied Microbiology, Vol. 9 (1961), p. 538. There, the synergy index (SI) is calculated using the following formula:
  • synergy index has a value of more than 1, this means that antagonism exists. If the synergy index has a value of 1, this means that the effects of the two biocides/compounds are additive. If the synergy index has a value of less than 1, this means that there is synergism between the two biocides/compounds.
  • Qa Concentration of guanidine in the mixture showing an endpoint QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of BIT in the mixture showing an endpoint QB: Concentration of BIT as the sole agent showing an endpoint
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of BBIT in the mixture showing an endpoint
  • QB Concentration of BBIT as the sole agent showing an endpoint
  • Qa Concentration of guanidine in the mixture showing an endpoint QA: Concentration of guanidine as the sole agent showing an endpoint Qb: Concentration of MBIT in the mixture showing an endpoint QB: Concentration of MBIT as the sole agent showing an endpoint
  • the optimal synergism ie the lowest synergy index (0.87) of a composition of guanidine and OIT is at a ratio of 618 to 1590 ppm guanidine to 200 to 175 ppm OIT. Synergism can be demonstrated when the weight ratio of guanidine to OIT is in the range of 1.4:1 to 82:1.
  • the optimal synergism ie the lowest synergy index (0.77) of a composition of guanidine and bronopol is at a ratio of 1545 ppm guanidine to 15 ppm bronopol. Synergism can be demonstrated when the weight ratio of guanidine to bronopol is in the range of 7.8:1 to 824:1.
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of IPBC in the mixture showing an endpoint
  • QB Concentration of IPBC as the sole agent showing an endpoint
  • the optimal synergism ie the lowest synergy index (0.73) of a composition of guanidine and AEPD is at a ratio of 3090 ppm guanidine to 2000 ppm AEPD. Synergism can be demonstrated when the weight ratio of guanidine to AEPD is in the range of 0.2:1 to 15:1.
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of hexylglycerol in the mixture showing an endpoint
  • QB Concentration of hexylglycerol as the sole agent showing an endpoint
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of 1,2-hexanediol in the mixture showing an endpoint
  • QB Concentration of 1,2-hexanediol as the sole agent showing an endpoint
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of 1,2-heptanediol in the mixture showing an endpoint
  • QB Concentration of 1,2-heptanediol as the sole agent showing an endpoint
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of phenoxyethanol in the mixture showing an endpoint
  • QB Concentration of phenoxyethanol as the sole agent showing an endpoint
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of phenylpropanol in the mixture showing an endpoint
  • QB Concentration of phenylpropanol as the sole agent showing an endpoint
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of benzyl alcohol in the mixture showing an endpoint
  • QB Concentration of benzyl alcohol as the sole agent showing an endpoint
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of isopropanol in the mixture showing an endpoint
  • QB Concentration of isopropanol as the sole agent showing an endpoint
  • Example 25 Investigation of the synergistic interaction between guanidine and ethylenediaminetetraacetic acid (EDTA) Calculation of the synergy index of guanidine and EDTA with respect to Pseudomonas spec. DSM 115322 with an incubation time of 48 hours at 30 °C.
  • EDTA ethylenediaminetetraacetic acid
  • Example 27 Investigation of the synergistic interaction between guanidine and pyrithione (added in the form of sodium pyrithione) Calculation of the synergy index of guanidine and pyrithione with respect to Pseudomonas spec. DSM 115322 with an incubation time of 48 hours at 30 °C.
  • Example 28 Investigation of the synergistic interaction between guanidine and o-phenylphenol (oPP) Calculation of the synergy index of guanidine and oPP with respect to Pseudomonas spec.
  • Example 29 Investigation of the synergistic interaction between guanidine and sorbic acid (added in the form of potassium sorbate)
  • the optimal synergism ie the lowest synergy index (0.55) of a composition of guanidine and sorbic acid is at a ratio of 3090 ppm guanidine to 555 ppm sorbic acid. Synergism can be demonstrated if the weight ratio of guanidine to sorbic acid is in the range of 0.1:1 to 50:1.
  • Qb Concentration of benzoic acid in the mixture showing an endpoint
  • QB Concentration of benzoic acid as the sole agent showing an endpoint
  • Example 31 Investigation of the synergistic interaction between guanidine and salicylic acid (added in the form of sodium salicylate)
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of salicylic acid in the mixture showing an endpoint
  • QB Concentration of salicylic acid as the sole agent showing an endpoint
  • Example 33 Investigation of the synergistic interaction between guanidine and citric acid (added in the form of trisodium citrate)
  • QA Concentration of guanidine as the sole agent showing an endpoint
  • Qb Concentration of citric acid in the mixture showing an endpoint
  • QB Concentration of citric acid as the sole agent showing an endpoint
  • Example 34 the synergistic interaction between guanidine and a zinc compound (zinc oxide) against microbial attack in an emulsion paint was tested by adding certain amounts of guanidine in the form of guanidine hydrochloride and a zinc compound in the form of zinc oxide to the paint and examining its stability against microbial attack.
  • the paint tested was an emulsion paint based on styrene acrylate (PVK 77%, pH 8.8) for interior use, manufactured in the laboratory without the addition of the usual preservatives.
  • the samples were each inoculated three times with a bacterial cell suspension of the following composition (2% v/w).
  • the cell suspension of the bacterial mixture A was prepared by culturing the individual bacteria for 24 hours at 30 °C in liquid culture on a shaker. Müller-Hinton liquid medium was used as the medium for culturing the bacteria. After cultivation, the individual liquid cultures were centrifuged and the cells resuspended in physiological saline. To adjust the mixture to a total cell count of 10 9 /ml, the individual bacterial suspensions were diluted accordingly before combining with saline if necessary. The cell count of the inoculation suspension was determined using the chamber counting method.
  • the microbial contamination of the samples was assessed after 7 days of incubation at 30 °C by determining the number of viable bacteria per gram of paint (colony forming units, CFU/g).
  • CFU/g colony forming units
  • the determination of the CFU/g at each time point was carried out by taking an aliquot (lg) from the previously homogenized sample, a serial decadic dilution series in physiological saline solution (0.9% NaCl) and spatula plate method on tryptone soy agar, with subsequent incubation of the agar plates for 48 h at 30 °C.
  • the paint tested was a dispersion 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.
  • 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 manufactured in the laboratory, without the addition of the usual conventional preservatives.
  • the paint was mixed - individually and in combination - with certain concentrations of guanidinium hydrochloride, benzisothiazolinone (BIT), and a mixture of chloromethylisothiazolinone (CIT) and methylisothiazolinone (MIT).
  • the detergent and cleaning agent were mixed with certain concentrations of guanidinium hydrochloride and benzisothiazolinone (BIT).
  • the resulting batches of the paint prepared in this way were inoculated with a mixture of different bacterial species (bacterial mixture B), and the batches of the detergent and cleaning agent prepared in this way were inoculated with a yeast mixture.
  • Bacterial mixture B is Bacterial mixture B:
  • 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 was 10 9 /ml for the bacterial mixture A, the yeast mixture 10 8 /ml, consisting of equal parts of the individual bacterial and yeast strains.
  • 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 was used as the medium for culturing the bacteria. After cultivation, the individual liquid cultures were centrifuged and the cells resuspended in physiological saline solution. To adjust the mixture to a total cell count of 10 9 /ml, 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.
  • the yeast strains were grown on Sabouraud glucose agar for 48 hours at 25 °C and the cell layer was washed down using physiological saline solution (0.9% NaCl). Further steps to adjust the cell count of the inoculation suspension to 10 8 /ml were carried out analogously to the preparation of the bacterial suspension.
  • the samples were inoculated once with the respective cell suspensions (2% v/w) and the development of the bacteria (bacteria mixture B) or yeasts was monitored using a semi-quantitative evaluation method.
  • the microbial contamination of the inoculated samples was assessed directly after inoculation on day 1 and after 5 further days of incubation at 30 °C on day 6 (emulsion paint) or after 2 further days of incubation at 30 °C on day 3 (detergent, cleaning agent).

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Abstract

La présente invention concerne une composition, contenant (a) de la guanidine et/ou un sel de la guanidine non substituée, et (b) au moins un autre composant, choisi dans le groupe constitué de 5-chloro-2-méthyl-4-isothiazolin-3-one, 2-méthyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-butyl-1,2-benzisothiazolin-3-one, N-méthyl-1,2-benzisothiazolin-3-one, octylisothiazolinone, bronopol, dibromnitrilopropion amide, dibromodicyanobutane, butylcarbamate d'iodpropinyle, amino-méthyl-propanol, amino-éthyl-propanediol, monoéthanolamine, éthylhexylglycérine, hexylglycérine, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, phénoxyéthanol, alcool phénéthylique, phénylpropanol, alcool benzylique, isopropanol, acide éthylènediaminetétraacétique, acide (1-hydroxy éthylidène) bis-phosphonique, pyrithione de sodium, pyrithione de zinc, o-phénylphénol, acide sorbique, acide benzoïque, acide salicylique, acide lactique, acide citrique et zinc. L'invention concerne en outre des produits techniques qui contiennent les composants (a) et (b), et l'utilisation des compositions pour la conservation de récipients et la conservation de produits techniques. L'invention concerne également l'utilisation de (a) la guanidine et/ou d'un sel de la guanidine non substituée pour améliorer l'efficacité antimicrobienne d'un ou de plusieurs composés, choisis dans le groupe (b) mentionné ci-dessus.
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