EP3340795A1 - Composition containing 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least one organic acid and/or the derivatives thereof - Google Patents

Composition containing 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least one organic acid and/or the derivatives thereof

Info

Publication number
EP3340795A1
EP3340795A1 EP16754299.2A EP16754299A EP3340795A1 EP 3340795 A1 EP3340795 A1 EP 3340795A1 EP 16754299 A EP16754299 A EP 16754299A EP 3340795 A1 EP3340795 A1 EP 3340795A1
Authority
EP
European Patent Office
Prior art keywords
derivatives
composition according
dbdcb
acid
composition
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.)
Withdrawn
Application number
EP16754299.2A
Other languages
German (de)
French (fr)
Inventor
Peter Wachtler
Tanja Gerharz
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland 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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP3340795A1 publication Critical patent/EP3340795A1/en
Withdrawn legal-status Critical Current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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts 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
    • A01N2300/00—Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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

Definitions

  • composition containing 1, 2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and / or derivatives thereof
  • DBDCB 1, 2-dibromo-2,4-dicyanobutane
  • the present application relates to compositions comprising 1, 2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and / or derivatives thereof, to processes for producing the compositions of the invention and their use for the protection of industrial materials from attack and destruction by Microorganisms and technical materials containing the compositions according to the invention.
  • DBDCB 1, 2-dibromo-2,4-dicyanobutane
  • DBDCB 1, 2-dibromo-2,4-dicyanobutane
  • Tektamer 38 is a biocidal active ingredient which has long been used in practice for the production of antimicrobially active formulations for controlling material-destroying bacteria, fungi or yeasts, especially in technical preparations It has broad antimicrobial activity against microorganisms such as bacteria, fungi or yeasts and is favorably well tolerated in many products to be protected, but in some applications its effectiveness is not always satisfactory due to the relatively high lipophilicity of DBDCB In such cases, in order to achieve good preservation, use concentrations are required which, in turn, are too high in certain applications, for example for skin compatibility reasons, due to the higher concentrations of sensitizing potential of DBDCB To use the effectiveness of DBDCB even when using smaller quantities.
  • biocidal active ingredients with a good antimicrobial activity against material-destroying bacteria, molds and yeasts are organic acids such as benzoic acid, lactic acid, salicylic acid, sorbic acid or citric acid and their derivatives, which are mainly used in the cosmetics industry.
  • organic acids have weaker antimicrobial activity compared to the biocides used in technical preservation and must therefore, if used as a single product, be used in amounts which can lead to unwanted changes in the properties of the products to be protected (eg thickening, Discoloration, odor changes). Due to the high amounts used, the resulting increased costs result as a further disadvantage.
  • the requirements for a fully comprehensive applicable biocidal product are therefore not met by organic acids as the sole biocidal agent in all applications.
  • EP 1621076B1 describes compositions containing DBDCB and the biocide 2-methyl-3-isothiazolin-3-one (MIT). Since MIT has a strong sensitizing potential, such compositions containing DBDCB and MIT are also not suitable for applications in which improved skin tolerance is particularly important.
  • EP 0098410B1 describes compositions comprising DBDCB and the biocide 1, 2-benzisothiazolin-3-one (BIT). Since BIT also has a strong sensitizing potential, the same problem arises as described in EP 1621076B1.
  • US 5034405A describes compositions containing DBDCB and the biocide mixture 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one (CMIT / MIT). Since the drug mixture CMIT / MIT in turn has a strong sensitizing potential, these compositions are no solution in providing a composition with improved skin tolerance.
  • compositions based on 1,2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and / or derivatives thereof can advantageously overcome the disadvantages of the respective individual components.
  • compositions according to the invention are surprisingly characterized in that they have an unexpectedly high, synergistic increase in activity in specific mixing ratios. It follows that the use levels required for the protection of technical products in the case of the Compositions can be reduced, compared with the necessary concentrations in the case of the respective individual active ingredients, can be reduced. This is extremely advantageous from an economic, ecological and application point of view, as it can achieve the desired improvement in skin compatibility when using DBDCB without sacrificing the quality of preservation.
  • the present invention therefore relates to compositions which are characterized in that they contain 1, 2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and / or derivatives thereof.
  • DBDCB 1, 2-dibromo-2,4-dicyanobutane
  • the relative proportions of DBDCB to the at least one organic acid and / or derivatives thereof in the compositions of this invention can vary over a wide range.
  • the weight ratio of DBDCB to the at least one organic acid and / or derivatives thereof in the composition is 99: 1 to 1:99, more preferably 9: 1 to 1: 9.
  • compositions according to the invention preferably at least 60% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight, even more preferably at least 95% by weight of the sum of DBDCB and at least an organic acid and / or derivatives thereof, based on the total weight of the composition according to the invention, in dissolved form.
  • compositions according to the invention preferably contain at least one organic acid and / or derivatives thereof, which is selected from the group consisting of mono- and polycarboxylic acids and derivatives thereof, more preferably at least one organic acid and / or derivatives thereof, which is selected from the group consisting from benzoic acid, lactic acid, salicylic acid, sorbic acid and citric acid and their derivatives.
  • the derivatives of the at least one organic acid are alkali metal salts.
  • the alkali metal salts of the at least one organic are selected from the group consisting of sodium, potassium and lithium salts.
  • the composition according to the invention contains benzoic acid and / or derivatives thereof as the at least one organic acid and / or its derivatives.
  • the weight ratio of DBDCB to benzoic acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof in the composition of the invention is 9: 1 to 1: 9, more preferably 9: 1 to 6: 4 or 4: 6 to 2. 8
  • the composition according to the invention contains lactic acid and / or derivatives thereof as the at least one organic acid and / or its derivatives.
  • the weight ratio of DBDCB to lactic acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof in the composition of the invention is 9: 1 to 1: 9, more preferably 9: 1 to 6: 4.
  • composition according to the invention contains salicylic acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof.
  • the weight ratio of DBDCB to salicylic acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof in the composition is 9: 1 to 1: 9, more preferably 9: 1 to 3: 7, most preferably 9: 1 to 6: 4 or 5: 4 to 3: 7.
  • Salicylic acid and / or derivatives thereof are particularly preferably used as the at least one organic acid and / or derivatives thereof in the composition according to the invention in the form of a composition SA which is at least 10% by weight, preferably at least 30% by weight, most preferably at least 50 wt .-%, most preferably at least 75 wt .-% salicylic acid and / or derivatives thereof, based on the total weight of the composition SA contains.
  • the composition is Salix Alba extract Sal.
  • Salix Alba extract is an extract from the bark of white willow (Salix alba), which is a species in the genus of willows from the family willow family (Salicaceae).
  • a Salix Alba extract is obtained from the bark of the white willow by methods known to those skilled in the art, preferably by extraction, more preferably by extraction with water and / or ethanol.
  • composition according to the invention contains citric acid and / or derivatives thereof as the at least one organic acid and / or its derivatives.
  • the weight ratio of DBDCB to citric acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof in the composition of the invention is 9: 1 to 1: 9, more preferably 9: 1 to 5: 5, most preferably 9 : 1 to 7: 3.
  • compositions according to the invention may additionally contain no or at least one further biocidal active substance.
  • Preferred further biocidal active substances are the following active substances:
  • IPBC iodopropargyl butyl carbamate
  • OIT 2-n-octylisothiazolin-3-one
  • the weight ratio of the at least one further biocidal active substance to the sum of DBDCB and the at least one organic acid and / or derivatives thereof is preferably 1:40 to 1: 1.
  • compositions according to the invention the sum of the wt .-% of DBDCB and the at least one organic acid and / or derivatives thereof and additionally no or at least one further biocidal active ingredient can be varied within a wide range.
  • the sum of DBDCB, the at least one organic acid and / or derivatives thereof and additionally no or at least one further biocidal active ingredient is preferably from 1 to 80% by weight, particularly preferably from 5 to 60% by weight, based on the total weight of the inventive composition Composition.
  • composition according to the invention may contain no or at least one further additive.
  • composition according to the invention can, depending on their respective physical and / or chemical properties or the specific requirements of the preservation problem to be solved, be carried out either separately in the form of a metered addition of the individual active ingredients, wherein, depending on the present preservation problem, an individual adjustment of the concentration ratio can be made, or the addition of the composition of the invention can be carried out as a finished formulation.
  • the compositions according to the invention are present as finished formulations.
  • compositions according to the invention are particularly preferably in the form of a formulation which is a solution, a dispersion, an emulsion, a suspension, a powder, a foam, a paste, a granulate, an aerosol or a finely encapsulated form in polymeric substances.
  • compositions according to the invention may therefore further contain or not contain at least one auxiliary which is suitable for the preparation of a formulation as a further additive.
  • composition according to the invention preferably contains at least one auxiliary agent as a further additive.
  • composition according to the invention preferably contains at least one auxiliary selected from the group consisting of surfactants, wetting agents, emulsifiers, dispersants, stabilizers, adhesives, thickeners, spreading agents, organic solvents, fragrances, colorants, dedusting agents, buffer substances, buffer systems, pH regulators, solid carriers and water.
  • auxiliary selected from the group consisting of surfactants, wetting agents, emulsifiers, dispersants, stabilizers, adhesives, thickeners, spreading agents, organic solvents, fragrances, colorants, dedusting agents, buffer substances, buffer systems, pH regulators, solid carriers and water.
  • composition according to the invention in which several adjuvants from the above group are selected, these adjuvants are different from one another.
  • the preferred auxiliaries of the present invention are described in greater detail below by way of example:
  • Surfactants such as surfactants.
  • Surfactants may be, for example, nonionic, cationic and amphoteric surfactants, preferably anionic surfactants.
  • Suitable anionic surfactants are, for example, alkyl sulfates,
  • alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may each be, for example, between 1 to 10 ethylene oxide or Propylene oxide units, preferably 1 to 3 ethylene oxide units.
  • Suitable examples are sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate and triethanolamine dodecylbenzenesulfonate.
  • Wetting agents such as alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, Polyoxyethylenoctylphenolether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol or Tributylphenyl
  • Emulsifiers such as sodium, potassium and ammonium salts of straight chain aliphatic carboxylic acids of chain length C12-C2 0 , sodium hydroxy-octadecane, sodium, potassium and ammonium salts of hydroxy fatty acids of chain length C12-C2 0 and their sulfation or.
  • alkyl sulfates also known as triethanolamine salts, alkyl (Ci 0 -C 20 ) sulfonates, alkyl (Ci 0 -C 20 ) -aryl sulfonates, dimethyl dialkyl (C 8 -C 8 ) -ammonium chloride, acyl, alkyl -, oleyl and alkyl aryloxethylate and their sulfation, alkali metal salts of sulfosuccinic with aliphatic saturated monohydric alcohols of chain length C 4 - Ci 6 , sulfosuccinic acid 4-esters with polyethylene glycol ethers of monohydric aliphatic alcohols of chain length Ci 0 -Ci 2 (Di Sodium salt), sulfosuccinic acid 4-esters with polyethylene glycol nonylphenyl ether (di-sodium salt), sulfosuccin
  • emulsifiers sodium lauryl sulfate, Sodium lauryl ether sulfate, ethoxylated (3 ethylene oxide groups); the polyethylene glycol (4-20) ethers of oleyl alcohol and the polyethene oxide (4-14) ethers of nonylphenol.
  • Dispersants such as alkylphenol polyglycol ethers.
  • Stabilizers e.g. Cellulose and cellulose derivatives.
  • Adhesives and thickeners such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipid and mineral or vegetable oils.
  • Spreading agents such as isopropyl myristate, polyoxyethylene nonylphenyl ether and polyoxyethylene laurylphenyl ether.
  • Organic solvents such as monohydric or polyhydric alcohols, glycols, esters, ketones or hydrocarbons.
  • Preferred organic solvents are paraffins, mineral and vegetable oils, butanol and glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, particularly preferably glycols, very particularly preferably 1,2-propanediol.
  • Fragrances colorants such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic colorants such as alizarin, azo and metal phthalocyanine colorants and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • inorganic pigments e.g. Iron oxide, titanium oxide, ferrocyan blue and organic colorants such as alizarin, azo and metal phthalocyanine colorants and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • compositions of the invention may contain, for example, in each case 0.01 to 10, preferably 0.1 to 5 wt .-% of buffer substances, buffer systems or pH regulators.
  • Solid carriers such as ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and Silicates.
  • suitable solid carriers for granules are: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corncobs and tobacco rods;
  • composition according to the invention preferably comprises at least one organic solvent as auxiliary, more preferably at least one glycol.
  • composition according to the invention preferably contains from 20 to 99% by weight, more preferably from 40 to 95% by weight, of at least one further additive, based on the total weight of the composition according to the invention.
  • a preferred composition according to the invention contains 10-30% by weight of DBDCB, 10-30% by weight of salix alba extract, which contains at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 50% by weight. , very particularly preferably at least 75 wt .-% salicylic acid and / or derivatives thereof, based on the total weight of the Salix Alba extract, and 40-80 wt .-% of a glycol, preferably 1, 2-propanediol.
  • the invention further relates to a process for the preparation of the composition according to the invention, which comprises mixing DBDCB and the at least one organic acid and / or derivatives thereof optionally with the addition of at least one further biocidal active ingredient and optionally with the addition of at least one further additive.
  • a preferred preparation of the composition according to the invention is characterized in that DBDCB and the at least one organic acid and / or derivatives thereof and at least one further additive, preferably at least one solvent, are mixed together.
  • the invention further relates to the use of the compositions according to the invention for the protection of industrial materials against attack and / or destruction by microorganisms.
  • the compositions according to the invention for the protection of industrial materials against attack and / or destruction by microorganisms.
  • preferred are water-containing functional fluids and water-containing technical products.
  • the use in the following technical materials is mentioned:
  • Starch solutions and syrups or other starch-based products e.g. Printing thickener
  • Polymer dispersions based on e.g. Polyacrylate, polystyrene acrylate, styrene butadiene, polyvinyl acetate, and the like.
  • Mineral oils and mineral oil products such as diesel fuels
  • Wax and clay emulsions Wax and clay emulsions
  • compositions according to the invention are preferably used for protecting detergents and surface-active substances, which are preferably present in dishwashing detergents, liquid detergents, household cleaners and other cleaners.
  • the application concentrations of the mixture to be used according to the invention depend on the type and occurrence of the microorganisms to be controlled, the initial microbial load, the expected storage life of the products to be protected and on the microbiological susceptibility of the components contained in the end products. The optimum amount can be easily determined by preliminary tests and test series in the laboratory in a manner well-known to those skilled in the art.
  • compositions according to the invention are preferably used in the range from 0.01 to 5% by weight, particularly preferably from 0.05 to 1.0% by weight, based on the weight of the material to be protected, for the protection of industrial materials.
  • the invention further relates to technical materials which have been treated with the composition according to the invention. Further, the present invention includes engineering materials containing a composition of the invention.
  • the technical materials containing the composition according to the invention preferably contain these in the range from 0.01 to 5% by weight, particularly preferably from 0.05 to 1.0% by weight, based on the weight of the technical material.
  • the present invention preferably comprises dishwashing detergents, liquid detergents and household cleaners which contain the composition according to the invention.
  • the composition of the invention is effective against microorganisms of various kinds, such as bacteria, molds, yeasts and slime organisms.
  • composition according to the invention has activity:
  • Alcaligenes such as Alcaligenes faecalis, Bacillus such as Bacillus subtilis, Enterobacter such as Enterobacter aerogenes, Escherichia such as Escherichia coli, Proteus such as Proteus vulgaris, Pseudomonas such as Pseudomonas aeruginosa or Pseudomonas fluorescens, Serratia such as Serratia marescens, Staphylococcus such as Staphylococcus aureus.
  • Candida such as Candida albicans, Geotrichum such as Geotrichum candidum, Rhodotorula such as Rhodotorula rubra, Rhodotorula mucilaginosa, Saccharomyces such as Saccharomyces cerevisiae.
  • Acremonium such as Acremonium strictum, Alternaria such as Alternaria tenuis or Alternaria alternata, Aspergillus such as Aspergillus niger, Chaetomium such as Chaetomium globosum, Fusarium such as Fusarium solani, Lentinus such as Lentinus tigrinus, Paecilomyces such as Paecilomyces variotti, Penicillium such as Penicillium glaucum, Trichoderma such as Trichoderma viride.
  • the surprising effect enhancement of the composition according to the invention is exemplified without limitation. Examples
  • composition according to the invention is exemplified below against certain, in particular practical germs such. Pseudomonas aeruginosa, Staphylococcus aureus, Alternaria alternata or Geotrichum candidum.
  • compositions according to the invention can be determined by the following mathematical approach (cf., F. C. Kuli, P. C. Elisman, H. D. Sylwestrowicz, P. K. Mayer, Appl. Microbiol., 9, 1961, p.
  • QA amount of component A, used alone, suppresses the growth of microorganisms
  • Q ⁇ amount of component B, used alone, suppresses the growth of microorganisms.
  • a synergistic index of Sl ⁇ 1 resulting according to the above formula indicates a synergistic effect for the active compound mixture. The lower the Sl, the greater the synergistic effect.
  • compositions according to the invention have a pronounced synergistic action against the test bacterium Staphylococcus aureus.
  • compositions according to the invention have a pronounced synergistic action against the test germ Alternaria alternata in certain concentration ratios.
  • Table 3 (test germ: Geotrichum candidum):
  • compositions according to the invention have a pronounced synergistic action against the test germ Geotrichum candidum in certain concentration ratios.
  • compositions according to the invention have a pronounced synergistic action against the test bacterium Pseudomonas aeruginosa in certain concentration ratios.
  • compositions according to the invention have a pronounced synergistic action against the test germ Alternaria alternata in certain concentration ratios
  • compositions according to the invention have a pronounced synergistic action against the test bacterium Pseudomonas aeruginosa in certain concentration ratios.
  • compositions according to the invention have a pronounced synergistic action against the test germ Alternaria alternata in certain concentration ratios
  • compositions of the invention have in certain concentration ratios a pronounced synergistic action against the test bacterium Bacillus subtilis.
  • Table 9 (Test Germ: Aspergillus brasiliensis):
  • compositions according to the invention have in certain concentration ratios a pronounced synergistic action against the test bacterium Aspergillus brasiliensis.
  • Example 2 Microbiological stress test - Preservation of a rinsing agent
  • the preservative effect of a composition according to the invention comprising DBDCB and Salix alba extract in a hand dishwashing detergent was investigated by means of a microbiological stress test.
  • the Microbiological Stress Test verifies the susceptibility of water-based products to microbial attack and the effects of preservatives.
  • the preservatives are incorporated in defined concentrations in the water-based systems.
  • repeated contamination with microorganisms of a defined type and in defined quantities at weekly intervals is carried out over a test period of 3 to a maximum of 6 weeks. It is determined by germ count determination whether complete kill or at least inhibition of proliferation of the introduced microorganisms occurred in comparison to the unpreserved control sample 2-3 and 7 days after each contamination.
  • germ count determination With knowledge of the microorganism populations prevalent in detergents of the type described here, a mixture of the following microorganism species was used for the test:
  • Bacteria Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus. Pseudomonas putida, Enterobacter gergoviae
  • Yeasts Candida albicans and Rhodotorula rubra.
  • DBDCB B Composition containing 25% by weight Salix Alba extract (containing 80% by weight salicylic acid) and 75% by weight 1,2-propanediol.
  • composition according to the invention comprising DBDCB and Salix Alba extract which contains 80% by weight salicylic acid, a very effective preservation is achieved in spite of a significantly reduced amount of active ingredient compared with the individual active ingredient DBDCB, ie all types of microorganisms used for testing are replaced by the killed mixture according to the invention.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Composition, characterized by containing 1,2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and/or the derivatives thereof.

Description

Zusammensetzung enthaltend 1 ,2-Dibrom-2,4-dicyanobutan (DBDCB) und wenigstens eine organische Säure und/oder deren Derivate  Composition containing 1, 2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and / or derivatives thereof
Gegenstand der vorliegenden Anmeldung sind Zusammensetzungen enthaltend 1 ,2- Dibrom-2,4-dicyanobutan (DBDCB) und wenigstens eine organische Säure und/oder deren Derivate, Verfahren zur Herstellung der erfindungsgemäßen Zusammensetzungen und deren Verwendung zum Schutz technischer Materialien vor Befall und Zerstörung durch Mikroorganismen sowie technische Materialien enthaltend die erfindungsgemäßen Zusammensetzungen. The present application relates to compositions comprising 1, 2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and / or derivatives thereof, to processes for producing the compositions of the invention and their use for the protection of industrial materials from attack and destruction by Microorganisms and technical materials containing the compositions according to the invention.
1 ,2-Dibrom-2,4-dicyanobutan (DBDCB,„Tektamer 38") ist ein seit langem in der Praxis verwendeter biozider Wirkstoff zur Herstellung antimikrobiell wirksamer Formulierungen zur Bekämpfung von materialzerstörenden Bakterien, Pilzen oder Hefen vor allem in technischen Zubereitungen. Dieser Wirkstoff verfügt grundsätzlich über eine breite antimikrobielle Wirkung gegen Mikroorganismen wie Bakterien, Pilze oder Hefen und zeichnet sich vorteilhaft durch eine gute Verträglichkeit in vielen zu schützenden Produkten aus. Allerdings ist die Wirksamkeit in manchen Anwendungen aufgrund der relativ hohen Lipophilie von DBDCB nicht immer zufriedenstellend. Daher sind in solchen Fällen zur Erzielung einer guten Konservierung Einsatzkonzentrationen erforderlich, die wiederum aufgrund des in höheren Konzentrationen sensibilisierenden Potentials von DBDCB in bestimmten Anwendungen aus z.B. Hautverträglichkeitsgründen zu hoch sind. Somit besteht ein Bedürfnis danach, die breite antimikrobielle Wirksamkeit von DBDCB auch bei Einsatz von geringeren Mengen nutzen zu können. Eine weitere Klasse von Biozidwirkstoffen mit einer guten antimikrobiellen Wirksamkeit gegen materialzerstörende Bakterien, Schimmelpilze und Hefen sind organische Säuren wie z.B. Benzoesäure, Milchsäure, Salicylsäure, Sorbinsäure oder Zitronensäure sowie jeweils deren Derivate, welche vor allem in der Kosmetikindustrie eingesetzt werden. Solche organischen Säuren verfügen allerdings über eine im Vergleich zu den standardmäßig in der technischen Konservierung eingesetzten Bioziden schwächere antimikrobielle Wirksamkeit und müssen daher, sofern als Einzelprodukt verwendet, in Mengen eingesetzt werden, die in den zu schützenden Produkten zu ungewollten Eigenschaftsänderungen führen können (z.B. Verdickungen, Verfärbungen, Geruchsveränderungen). Durch die hohen Einsatzmengen ergeben sich als weiterer Nachteil die daraus resultierenden erhöhten Kosten. Die Anforderungen an ein voll umfänglich einsetzbares Biozidprodukt werden daher von organischen Säuren als alleinigem bioziden Wirkstoff nicht in allen Anwendungen erfüllt. 1, 2-dibromo-2,4-dicyanobutane (DBDCB, "Tektamer 38") is a biocidal active ingredient which has long been used in practice for the production of antimicrobially active formulations for controlling material-destroying bacteria, fungi or yeasts, especially in technical preparations It has broad antimicrobial activity against microorganisms such as bacteria, fungi or yeasts and is favorably well tolerated in many products to be protected, but in some applications its effectiveness is not always satisfactory due to the relatively high lipophilicity of DBDCB In such cases, in order to achieve good preservation, use concentrations are required which, in turn, are too high in certain applications, for example for skin compatibility reasons, due to the higher concentrations of sensitizing potential of DBDCB To use the effectiveness of DBDCB even when using smaller quantities. Another class of biocidal active ingredients with a good antimicrobial activity against material-destroying bacteria, molds and yeasts are organic acids such as benzoic acid, lactic acid, salicylic acid, sorbic acid or citric acid and their derivatives, which are mainly used in the cosmetics industry. However, such organic acids have weaker antimicrobial activity compared to the biocides used in technical preservation and must therefore, if used as a single product, be used in amounts which can lead to unwanted changes in the properties of the products to be protected (eg thickening, Discoloration, odor changes). Due to the high amounts used, the resulting increased costs result as a further disadvantage. The requirements for a fully comprehensive applicable biocidal product are therefore not met by organic acids as the sole biocidal agent in all applications.
In EP 1621076B1 sind Zusammensetzungen enthaltend DBDCB und das Biozid 2- Methyl-3-isothiazolin-3-on (MIT) beschrieben. Da MIT ein stark sensibilisierendes Potential aufweist, eignen sich solche Zusammensetzungen enthaltend DBDCB und MIT auch nicht für solche Anwendungen, in denen es besonders auf eine verbesserte Hautverträglichkeit ankommt. In EP 0098410B1 sind Zusammensetzungen enthaltend DBDCB und das Biozid 1 ,2- Benz-isothiazolin-3-οη (BIT) beschrieben. Da auch BIT ein stark sensibilisierendes Potential aufweist, ergibt sich die gleiche Problematik wie unter EP 1621076B1 beschrieben. EP 1621076B1 describes compositions containing DBDCB and the biocide 2-methyl-3-isothiazolin-3-one (MIT). Since MIT has a strong sensitizing potential, such compositions containing DBDCB and MIT are also not suitable for applications in which improved skin tolerance is particularly important. EP 0098410B1 describes compositions comprising DBDCB and the biocide 1, 2-benzisothiazolin-3-one (BIT). Since BIT also has a strong sensitizing potential, the same problem arises as described in EP 1621076B1.
In US 5034405A sind Zusammensetzungen enthaltend DBDCB und das Biozidgemisch 5-Chloro-2-methyl-4-isothiazolin-3-on/ 2-Methyl-4-isothiazolin-3-on (CMIT/MIT) beschrieben. Da auch das Wirkstoffgemisch CMIT/MIT seinerseits ein stark sensibilisierendes Potential aufweist, stellen auch diese Zusammensetzungen keine Lösung hinsichtlich der Bereitstellung einer Zusammensetzung mit verbesserter Hautverträglichkeit dar.  US 5034405A describes compositions containing DBDCB and the biocide mixture 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one (CMIT / MIT). Since the drug mixture CMIT / MIT in turn has a strong sensitizing potential, these compositions are no solution in providing a composition with improved skin tolerance.
Es besteht daher weiterhin ein Bedarf an verbesserten Produktkombinationen, um das an sich gegebene antimikrobielle Wirkspektrum von DBDCB bzw. von organischen Säuren wie z.B. Benzoesäure, Milchsäure, Salicylsäure, Sorbinsäure oder Zitronensäure sowie jeweils deren Derivaten zu verbessern. Ferner soll eine hautverträglichere Produktkombination, verglichen mit DBDCB als alleinigem bioziden Wirkstoff, bereitgestellt werden. There is therefore still a need for improved product combinations to provide the inherent antimicrobial activity spectrum of DBDCB or organic acids such as e.g. Benzoic acid, lactic acid, salicylic acid, sorbic acid or citric acid and their derivatives in each case to improve. Furthermore, a more skin-compatible product combination should be provided, compared with DBDCB as the sole biocidal active ingredient.
Überraschenderweise wurde nun gefunden, dass Zusammensetzungen auf Basis von 1 ,2-Dibrom-2,4-dicyanobutan (DBDCB) und wenigstens einer organischen Säure und/oder deren Derivate die Nachteile der jeweiligen Einzelkomponenten in vorteilhafter Weise überwinden können. Surprisingly, it has now been found that compositions based on 1,2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and / or derivatives thereof can advantageously overcome the disadvantages of the respective individual components.
Darüber hinaus zeichnen sich die erfindungsgemäßen Zusammensetzungen überraschend dadurch aus, dass sie in spezifischen Mischungsverhältnissen eine unerwartet hohe, synergistische Wirkungssteigerung aufweisen. Daraus folgt, dass die zum Schutz technischer Produkte benötigten Einsatzkonzentrationen im Falle der erfindungsge- mäßen Zusammensetzungen, verglichen mit den nötigen Konzentrationen im Falle der jeweiligen Einzelwirkstoffe, herabgesetzt werden können. Dies ist unter ökonomischen, ökologischen und anwendungstechnischen Gesichtspunkten ausgesprochen vorteilhaft, da hierdurch die erwünschte Verbesserung der Hautverträglichkeit beim Einsatz von DBDCB ohne Einbuße der Konservierungsqualität erreicht werden kann. In addition, the compositions according to the invention are surprisingly characterized in that they have an unexpectedly high, synergistic increase in activity in specific mixing ratios. It follows that the use levels required for the protection of technical products in the case of the Compositions can be reduced, compared with the necessary concentrations in the case of the respective individual active ingredients, can be reduced. This is extremely advantageous from an economic, ecological and application point of view, as it can achieve the desired improvement in skin compatibility when using DBDCB without sacrificing the quality of preservation.
Die vorliegende Erfindung betrifft daher Zusammensetzungen, die dadurch gekennzeichnet sind, dass sie 1 ,2-Dibrom-2,4-dicyanobutan (DBDCB) und wenigstens eine organische Säure und/oder deren Derivate enthalten. The present invention therefore relates to compositions which are characterized in that they contain 1, 2-dibromo-2,4-dicyanobutane (DBDCB) and at least one organic acid and / or derivatives thereof.
Die relativen Verhältnisse von DBDCB zu der wenigstens einen organischen Säure und/oder deren Derivaten in den erfindungsgemäßen Zusammensetzungen können über einen weiten Bereich variieren. Bevorzugt ist das Gewichtsverhältnis von DBDCB zu der wenigstens einen organischen Säure und/oder deren Derivaten in der Zusammen- Setzung 99:1 bis 1 :99 , besonders bevorzugt 9:1 bis 1 :9. The relative proportions of DBDCB to the at least one organic acid and / or derivatives thereof in the compositions of this invention can vary over a wide range. Preferably, the weight ratio of DBDCB to the at least one organic acid and / or derivatives thereof in the composition is 99: 1 to 1:99, more preferably 9: 1 to 1: 9.
Des Weiteren liegen in den erfindungsgemäßen Zusammensetzungen bevorzugt wenigstens 60 Gew.-%, besonders bevorzugt wenigstens 80 Gew.-%, ganz besonders bevorzugt wenigstens 90 Gew.-%, noch weiter bevorzugt wenigstens 95 Gew.-% der Summe aus DBDCB und der wenigstens einen organischen Säure und/oder deren Derivaten, bezogen auf das Gesamtgewicht der erfindungsgemäßen Zusammensetzung, in gelöster Form vor. Furthermore, in the compositions according to the invention preferably at least 60% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight, even more preferably at least 95% by weight of the sum of DBDCB and at least an organic acid and / or derivatives thereof, based on the total weight of the composition according to the invention, in dissolved form.
Organische Säuren Organic acids
Die erfindungsgemäßen Zusammensetzungen enthalten bevorzugt wenigstens eine organische Säure und/oder deren Derivate, welche ausgewählt ist aus der Gruppe bestehend aus Mono- und Polycarbonsäuren und deren Derivaten, besonders bevorzugt wenigstens eine organische Säure und/oder deren Derivate, welche ausgewählt ist aus der Gruppe bestehend aus Benzoesäure, Milchsäure, Salicylsäure, Sorbinsäure und Zitronensäure und deren Derivaten. The compositions according to the invention preferably contain at least one organic acid and / or derivatives thereof, which is selected from the group consisting of mono- and polycarboxylic acids and derivatives thereof, more preferably at least one organic acid and / or derivatives thereof, which is selected from the group consisting from benzoic acid, lactic acid, salicylic acid, sorbic acid and citric acid and their derivatives.
Bevorzugt sind die Derivate der wenigstens einen organischen Säure Alkalimetallsalze. Preferably, the derivatives of the at least one organic acid are alkali metal salts.
Bevorzugt sind die Alkalimetallsalze der wenigstens einen organischen ausgewählt aus der Gruppe bestehend aus Natrium-, Kalium- und Lithiumsalzen. In einer bevorzugten Ausführungsform enthält die erfindungsgemäße Zusammensetzung Benzoesäure und/oder deren Derivate als die wenigstens eine organische Säure und/oder deren Derivate. Bevorzugt ist das Gewichtsverhältnis von DBDCB zu Benzoesäure und/oder deren Derivaten als die wenigstens eine organische Säure und/oder deren Derivaten in der erfindungsgemäßen Zusammensetzung 9:1 bis 1 :9 , besonders bevorzugt 9:1 bis 6:4 oder 4:6 bis 2:8. In einer weiteren bevorzugten Ausführungsform enthält die erfindungsgemäße Zusammensetzung Milchsäure und/oder deren Derivate als die wenigstens eine organische Säure und/oder deren Derivate. Preferably, the alkali metal salts of the at least one organic are selected from the group consisting of sodium, potassium and lithium salts. In a preferred embodiment, the composition according to the invention contains benzoic acid and / or derivatives thereof as the at least one organic acid and / or its derivatives. Preferably, the weight ratio of DBDCB to benzoic acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof in the composition of the invention is 9: 1 to 1: 9, more preferably 9: 1 to 6: 4 or 4: 6 to 2. 8 In a further preferred embodiment, the composition according to the invention contains lactic acid and / or derivatives thereof as the at least one organic acid and / or its derivatives.
Bevorzugt ist das Gewichtsverhältnis von DBDCB zu Milchsäure und/oder deren Derivaten als die wenigstens eine organische Säure und/oder deren Derivaten in der erfindungsgemäßen Zusammensetzung 9:1 bis 1 : 9 , besonders bevorzugt 9:1 bis 6:4. Preferably, the weight ratio of DBDCB to lactic acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof in the composition of the invention is 9: 1 to 1: 9, more preferably 9: 1 to 6: 4.
In einer anderen bevorzugten Ausführungsform enthält die erfindungsgemäße Zusammensetzung Salicylsäure und/oder deren Derivate als die wenigstens eine organische Säure und/oder deren Derivate. In another preferred embodiment, the composition according to the invention contains salicylic acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof.
Bevorzugt ist das Gewichtsverhältnis von DBDCB zu Salicylsäure und/oder deren Derivaten als die wenigstens eine organische Säure und/oder deren Derivaten in der Zusammensetzung 9:1 bis 1 : 9, besonders bevorzugt 9 :1 bis 3:7, ganz besonders bevorzugt 9:1 bis 6:4 oder 5:4 bis 3:7. Preferably, the weight ratio of DBDCB to salicylic acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof in the composition is 9: 1 to 1: 9, more preferably 9: 1 to 3: 7, most preferably 9: 1 to 6: 4 or 5: 4 to 3: 7.
Besonders bevorzugt wird Salicylsäure und/oder deren Derivate als die wenigstens eine organische Säure und/oder deren Derivate in der erfindungsgemäßen Zusammensetzung in Form einer Zusammensetzung SA eingesetzt, welche wenigstens 10 Gew.-%, bevorzugt wenigstens 30 Gew.-%, besonders bevorzugt weigstens 50 Gew.-%, ganz besonders bevorzugt wenigstens 75 Gew.-% Salicylsäure und/oder deren Derivate, bezogen auf das Gesamtgewicht der Zusammensetzung SA, enthält. Salicylic acid and / or derivatives thereof are particularly preferably used as the at least one organic acid and / or derivatives thereof in the composition according to the invention in the form of a composition SA which is at least 10% by weight, preferably at least 30% by weight, most preferably at least 50 wt .-%, most preferably at least 75 wt .-% salicylic acid and / or derivatives thereof, based on the total weight of the composition SA contains.
In einer ganz besonders bevorzugten Ausführungsform ist die Zusammensetzung SA Salix Alba-Extrakt. Salix Alba-Extrakt ist ein Extrakt aus der Rinde der Silberweide (Salix alba), welche eine Pflanzenart in der Gattung der Weiden aus der Familie der Weidengewächse (Salicaceae) ist. Ein Salix Alba-Extrakt wird durch dem Fachmann bekannte Verfahren aus der Rinde der Silberweide gewonnen, bevorzugt durch Extraktion, besonders bevorzugt durch Extraktion mit Wasser und/oder Ethanol. In a most preferred embodiment, the composition is Salix Alba extract Sal. Salix Alba extract is an extract from the bark of white willow (Salix alba), which is a species in the genus of willows from the family willow family (Salicaceae). A Salix Alba extract is obtained from the bark of the white willow by methods known to those skilled in the art, preferably by extraction, more preferably by extraction with water and / or ethanol.
In einer anderen bevorzugten Ausführungsform enthält die erfindungsgemäße Zusammensetzung Zitronensäure und/oder deren Derivate als die wenigstens eine organische Säure und/oder deren Derivate. In another preferred embodiment, the composition according to the invention contains citric acid and / or derivatives thereof as the at least one organic acid and / or its derivatives.
Bevorzugt ist das Gewichtsverhältnis von DBDCB zu Zitronensäure und/oder deren Derivaten als die wenigstens eine organische Säure und/oder deren Derivaten in der erfindungsgemäßen Zusammensetzung 9:1 bis 1 :9 , besonders bevorzugt 9:1 bis 5:5, ganz besonders bevorzugt 9:1 bis 7:3. Preferably, the weight ratio of DBDCB to citric acid and / or derivatives thereof as the at least one organic acid and / or derivatives thereof in the composition of the invention is 9: 1 to 1: 9, more preferably 9: 1 to 5: 5, most preferably 9 : 1 to 7: 3.
Weitere biozide Wirkstoffe Other biocidal agents
Die erfindungsgemäßen Zusammensetzungen können neben DBDCB und der wenigstens einen organischen Säure und/oder deren Derivaten zusätzlich keinen oder wenigstens einen weiteren bioziden Wirkstoff enthalten. In addition to DBDCB and the at least one organic acid and / or derivatives thereof, the compositions according to the invention may additionally contain no or at least one further biocidal active substance.
Als bevorzugte weitere biozide Wirkstoffe seien die folgenden Wirkstoffe genannt: Preferred further biocidal active substances are the following active substances:
1 ,2-Benzisothiazol-3(2H)-on (BIT) 1, 2-Benzisothiazol-3 (2H) -one (BIT)
Benzylalkohol benzyl alcohol
Benzylhemiformal Benzylhemiformal
2-Bromo-2-nitropropan-1 3-diol (Bronopol)  2-bromo-2-nitropropane-1,3-diol (bronopol)
5-Chloro-2-methyl-4-isothiazolin-3-on / 2-Methyl-4-isothiazolin-3-on (CM IT/M IT)  5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one (CM IT / M IT)
2,2-Dibromo-3-nitrilopropionamid (DBNPA)  2,2-dibromo-3-nitrilopropionamide (DBNPA)
Diazolidinylharnstoff  diazolidinyl
3,3-Dimethylol-5,5-dimethylhydantoin (DMDMH) 3,3-Dimethylol-5,5-dimethylhydantoin (DMDMH)
Dichlorbenzylalkohol  dichlorobenzyl
Di-decyl-di-methyl-ammoniumchlorid  Di-decyl-di-methyl ammonium chloride
Dimethylolhydantoin  Dimethylolhydantoin
Dodecylguanidinhydrochlorid  dodecylguanidine
Imidazolidinylharnstoff imidazolidinyl
lodpropargylbutylcarbamat (IPBC) 2-n-Octylisothiazolin-3-on (OIT) iodopropargyl butyl carbamate (IPBC) 2-n-octylisothiazolin-3-one (OIT)
Phenoxyethanol phenoxyethanol
Phenoxypropanol phenoxy
Phenylethylalkohol phenylethyl
o-Phenyl-phenol (OPP) o-phenyl-phenol (OPP)
Poly(hexamethylenebiguanide) hydrochloride (PHMB)  Poly (hexamethylene biguanide) hydrochloride (PHMB)
Tetramethylolacetylendiharnstoff (TMAD) Tetramethylolacetylenediurea (TMAD)
Das Gewichtsverhältnis des wenigstens einen weiteren bioziden Wirkstoffs zu der Summe von DBDCB und der wenigstens einen organischen Säure und/oder deren Derivaten ist bevorzugt 1 : 40 bis 1 : 1 . The weight ratio of the at least one further biocidal active substance to the sum of DBDCB and the at least one organic acid and / or derivatives thereof is preferably 1:40 to 1: 1.
In den erfindungsgemäßen Zusammensetzungen kann die Summe der Gew.-% von DBDCB und der wenigstens einen organischen Säure und/oder deren Derivaten und des zusätzlich keinen oder wenigstens einen weiteren bioziden Wirkstoffs in einem breiten Bereich variiert werden. In the compositions according to the invention, the sum of the wt .-% of DBDCB and the at least one organic acid and / or derivatives thereof and additionally no or at least one further biocidal active ingredient can be varied within a wide range.
Bevorzugt beträgt die Summe von DBDCB, der wenigstens einen organischen Säure und/oder deren Derivaten und des zusätzlich keinen oder wenigstens einen weiteren bioziden Wirkstoffs 1 bis 80 Gew.-%, besonders bevorzugt 5 bis 60 Gew.%, bezogen auf das Gesamtgewicht der erfindungsgemäßen Zusammensetzung. The sum of DBDCB, the at least one organic acid and / or derivatives thereof and additionally no or at least one further biocidal active ingredient is preferably from 1 to 80% by weight, particularly preferably from 5 to 60% by weight, based on the total weight of the inventive composition Composition.
Weitere Zusatzstoffe Die erfindungsgemäße Zusammensetzung kann keinen oder wenigstens einen weiteren Zusatzstoff enthalten. Other additives The composition according to the invention may contain no or at least one further additive.
Die Applikation der erfindungsgemäßen Zusammensetzung kann, in Abhängigkeit von ihren jeweiligen physikalischen und/oder chemischen Eigenschaften bzw. den spezifi- sehen Erfordernissen des zu lösenden Konservierungsproblems, entweder separat in Form einer Zudosierung der Einzelwirkstoffe erfolgen, wobei je nach vorliegendem Konservierungsproblem eine individuelle Einstellung des Konzentrationsverhältnisses vorgenommen werden kann, oder die Zudosierung der erfindungsgemäßen Zusammensetzung kann als fertige Formulierung erfolgen. Bevorzugt liegen die erfindungsgemäßen Zusammensetzungen als fertige Formulierungen vor. The application of the composition according to the invention can, depending on their respective physical and / or chemical properties or the specific requirements of the preservation problem to be solved, be carried out either separately in the form of a metered addition of the individual active ingredients, wherein, depending on the present preservation problem, an individual adjustment of the concentration ratio can be made, or the addition of the composition of the invention can be carried out as a finished formulation. Preferably, the compositions according to the invention are present as finished formulations.
Besonders bevorzugt liegen die erfindungsgemäßen Zusammensetzungen als Formu- lierung vor, die eine Lösung, eine Dispersion, eine Emulsion, eine Suspension, ein Pulver, ein Schaum, eine Paste, ein Granulat, Aerosol oder eine feinstverkapselte Form in polymeren Stoffen ist. The compositions according to the invention are particularly preferably in the form of a formulation which is a solution, a dispersion, an emulsion, a suspension, a powder, a foam, a paste, a granulate, an aerosol or a finely encapsulated form in polymeric substances.
Die erfindungsgemäßen Zusammensetzungen können daher weiterhin wenigstens ein Hilfsmittel, das geeignet zur Herstellung einer Formulierung ist, als weiteren Zusatzstoff enthalten oder nicht enthalten. The compositions according to the invention may therefore further contain or not contain at least one auxiliary which is suitable for the preparation of a formulation as a further additive.
Bevorzugt enthält die erfindungsgemäße Zusammensetzung wenigstens ein Hilfsmittel als weiteren Zusatzstoff. The composition according to the invention preferably contains at least one auxiliary agent as a further additive.
Bevorzugt enthält die erfindungsgemäße Zusammensetzung wenigstens ein Hilfsmittel ausgewählt aus der Gruppe bestehend aus grenzflächenaktive Stoffe, Benetzungsmittel, Emulgatoren, Dispergiermittel, Stabilisatoren, Haftmittel, Verdicker, Spreitmittel, organische Lösungsmittel, Duftstoffe, Farbmittel, Entstaubungsmittel, Puffersubstanzen, Puffersysteme, pH-Wert-Regulatoren, feste Trägerstoffe und Wasser. The composition according to the invention preferably contains at least one auxiliary selected from the group consisting of surfactants, wetting agents, emulsifiers, dispersants, stabilizers, adhesives, thickeners, spreading agents, organic solvents, fragrances, colorants, dedusting agents, buffer substances, buffer systems, pH regulators, solid carriers and water.
In einer bevorzugten erfindungsgemäßen Zusammensetzung, in der mehrere Hilfsmittel aus obiger Gruppe ausgewählt sind, sind diese Hilfsmittel voneinander verschieden. Im Folgenden sind die bevorzugten Hilfsmittel der vorliegenden Erfindung beispielhaft näher ausgeführt: In a preferred composition according to the invention, in which several adjuvants from the above group are selected, these adjuvants are different from one another. The preferred auxiliaries of the present invention are described in greater detail below by way of example:
Grenzflächenaktive Stoffe, wie beispielsweise Tenside. Tenside können beispielsweise nichtionische, kationische und amphotere Tenside, vorzugsweise anionische Tenside sein. Geeignete anionische Tenside sind beispielsweise Alkylsulfate,Surfactants, such as surfactants. Surfactants may be, for example, nonionic, cationic and amphoteric surfactants, preferably anionic surfactants. Suitable anionic surfactants are, for example, alkyl sulfates,
Alkylethersulfate, Alkylarylsulfonate, Alkylsuccinate, Alkylsulfosuccinate, N-Alkoyl- sarkosinate, Acyltaurate, Acylisethionate, Alkylphosphate, Alkyletherphosphate, Alkylethercarboxylate, Alpha-Olefinsulfonate, insbesondere die Alkali- und Erdalkalimetallsalze, z.B. Natrium, Kalium, Magnesium, Calcium, sowie Ammonium- und Triethanolamin-Salze. Die Alkylethersulfate, Alkyletherphosphate und Alkylethercarboxylate können jeweils beispielsweise zwischen 1 bis 10 Ethylenoxid- oder Propylenoxid-Einheiten, bevorzugt 1 bis 3 Ethylenoxideinheiten aufweisen. Geeignet sind zum Beispiel Natriumlaurylsulfat, Ammoniumlaurylsulfat, Natriumlauryl- ethersulfat, Ammoniumlaurylethersulfat, Natriumlaurylsarkosinat, Natriumoleyl- succinat, Ammoniumlaurylsulfosuccinat, Natriumdodecylbenzolsulfonat, Triethanol- amindodecyl-benzolsulfonat. Alkyl ether sulfates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, in particular the alkali and alkaline earth metal salts, for example sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may each be, for example, between 1 to 10 ethylene oxide or Propylene oxide units, preferably 1 to 3 ethylene oxide units. Suitable examples are sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate and triethanolamine dodecylbenzenesulfonate.
Benetzungsmittel, wie beispielsweise Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutyl- naphthalinsulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether-und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta-und Octadecanole oder Fettalkoholglycolethern, Kondensationsprodukte von sulfonier- tem Naphthalin und seinen Derivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethylenoctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenol- oder Tributylphenylpolyglycolether, Alkylarylpolyetheralkohole, Isotri- decylalkohol, Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxy- ethylenalkylether oder Polyoxypropylen, Laurylalkoholpolyglycoletheracetat, Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose. Wetting agents, such as alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, Polyoxyethylenoctylphenolether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol or Tributylphenylpolyglycolether, Alkylarylpolyetheralkohole, Isotri- decylalkohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkylether or Polyoxypropylene, Laurylalkoholpolyglycoletheracetat, sorbitol esters, Lignin-Sulphatablaugen or methylcellulose.
Emulgatoren, wie beispielsweise Natrium-, Kalium- und Ammoniumsalze von gradkettigen aliphatischen Carbonsäuren der Kettenlänge C12-C20, Natriumhydroxy- octadecansulfonat, Natrium-, Kalium- und Ammoniumsalze von Hydroxyfettsäuren der Kettenlänge C12-C20 und deren Sulfierungs-bzw. Acetylierungsprodukte, Alkyl- sulfate, auch als Triethanolaminsalze, Alkyl-(Ci0-C20)-sulfonate, Alkyl(Ci0-C20)-aryl- sulfonate, Dimethyldialkyl(C8-Ci8)-ammoniumchlorid, Acyl-, Alkyl-, Oleyl-und Alkyl- aryloxethylate und ihre Sulfierungsprodukte, Alkalisalze der Sulfobernstein- säureester mit aliphatischen gesättigten einwertigen Alkoholen der Kettenlänge C4- Ci6, Sulfobernsteinsäure-4-Ester mit Polyethylenglykolethern von einwertigen aliphatischen Alkoholen der Kettenlänge Ci0-Ci2 (Di-Natriumsalz), Sulfobernsteinsäure-4- Ester mit Polyethylenglykolnonylphenylether (Di-Natriumsalz), Sulfobernsteinsäure bis-cyclohexylester (Natriumsalz), Ligninsulfonsäure sowie deren Calcium-, Magnesium-, Natrium-und Ammoniumsalze, Polyoxyethylen-sorbitanmonooleat mit 20 Ethylenoxidgruppen, Harzsäuren, hydrierte und dehydrierte Harzsäuren sowie deren Alkalisalze, dodecyliertes Diphenyletherdisulfonsaures Natrium sowie Copolymere aus Ethylenoxyd und Propylenoxyd mit einem Mindestgehalt von 10 Gew.-% Ethylenoxid. Vorzugsweise werden als Emulgatoren verwendet: Natriumlaurylsulfat, Natriumlaurylethersulfat, ethoxyliert (3 Ethylenoxidgruppen); die Polyethylenglykol(4- 20)ether des Oleylalkohols sowie die Polyethenoxid-(4-14)ether von Nonylphenol. Emulsifiers, such as sodium, potassium and ammonium salts of straight chain aliphatic carboxylic acids of chain length C12-C2 0 , sodium hydroxy-octadecane, sodium, potassium and ammonium salts of hydroxy fatty acids of chain length C12-C2 0 and their sulfation or. Acetylation products, alkyl sulfates, also known as triethanolamine salts, alkyl (Ci 0 -C 20 ) sulfonates, alkyl (Ci 0 -C 20 ) -aryl sulfonates, dimethyl dialkyl (C 8 -C 8 ) -ammonium chloride, acyl, alkyl -, oleyl and alkyl aryloxethylate and their sulfation, alkali metal salts of sulfosuccinic with aliphatic saturated monohydric alcohols of chain length C 4 - Ci 6 , sulfosuccinic acid 4-esters with polyethylene glycol ethers of monohydric aliphatic alcohols of chain length Ci 0 -Ci 2 (Di Sodium salt), sulfosuccinic acid 4-esters with polyethylene glycol nonylphenyl ether (di-sodium salt), sulfosuccinic acid bis-cyclohexylester (sodium salt), lignin sulfonic acid and its calcium, magnesium, sodium and ammonium salts, polyoxyethylene sorbitan monooleate with 20 ethylene oxide groups, resin acids, hydrogenated and Dehydrated resin acids and their alkali salts, dodecylated Diphenyletherdisulfonsaures sodium and copolymers of ethylene oxide and propylene oxide with a mind estgehalt of 10 wt .-% ethylene oxide. Preferably used as emulsifiers: sodium lauryl sulfate, Sodium lauryl ether sulfate, ethoxylated (3 ethylene oxide groups); the polyethylene glycol (4-20) ethers of oleyl alcohol and the polyethene oxide (4-14) ethers of nonylphenol.
Dispergiermittel, wie beispielsweise Alkylphenolpolyglycolether. Dispersants, such as alkylphenol polyglycol ethers.
Stabilisatoren, wie z.B. Cellulose und Cellulosederivate. Stabilizers, e.g. Cellulose and cellulose derivatives.
Haftmittel und Verdicker, wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummi- arabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipid sowie mineralische oder pflanzliche Öle. Adhesives and thickeners, such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipid and mineral or vegetable oils.
Spreitmittel, wie beispielsweise Isopropylmyristat, Polyoxyethylennonylphenylether und Polyoxyethylenlaurylphenylether. Spreading agents such as isopropyl myristate, polyoxyethylene nonylphenyl ether and polyoxyethylene laurylphenyl ether.
Organische Lösungsmittel, wie beispielsweise ein- oder mehrwertige Alkohole, Glykole, Ester, Ketone oder Kohlenwasserstoffe. Bevorzugte organische Lösungsmittel sind Paraffine, mineralische und pflanzliche Öle, Butanol und Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, besonders bevorzugt Glykole, ganz besonders bevorzugt 1 ,2- Propandiol. Organic solvents, such as monohydric or polyhydric alcohols, glycols, esters, ketones or hydrocarbons. Preferred organic solvents are paraffins, mineral and vegetable oils, butanol and glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, particularly preferably glycols, very particularly preferably 1,2-propanediol.
Duftstoffe, Farbmittel, wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbmittel, wie Alizarin-, Azo- und Metallphthalo- cyaninfarbmittel und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink. Fragrances, colorants such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic colorants such as alizarin, azo and metal phthalocyanine colorants and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Puffersubstanzen, Puffersysteme oder pH-Wert-Regulatoren. Die erfindungsgemäßen Zusammensetzungen können dabei beispielsweise jeweils 0,01 bis 10, vorzugsweise 0,1 bis 5 Gew.-% an Puffersubstanzen, Puffersystemen oder pH- Wert-Regulatoren enthalten. Buffer substances, buffer systems or pH regulators. The compositions of the invention may contain, for example, in each case 0.01 to 10, preferably 0.1 to 5 wt .-% of buffer substances, buffer systems or pH regulators.
Feste Trägerstoffe wie beispielsweise natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde sowie synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate. Als feste Trägerstoffe insbesondere für Granulate sind beispielsweise geeignet: gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokos- nußschalen, Maiskolben und Tabakstangen; Solid carriers such as ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and Silicates. Examples of suitable solid carriers for granules are: broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corncobs and tobacco rods;
Wasser. Water.
Bevorzugt enthält die erfindungsgemäße Zusammensetzung wenigstens ein organisches Lösungsmittel als Hilfsmittel, besonders bevorzugt wenigstens ein Glykol. The composition according to the invention preferably comprises at least one organic solvent as auxiliary, more preferably at least one glycol.
In der erfindungsgemäßen Zusammensetzung sind bevorzugt 20-99 Gew.% besonders bevorzugt 40 bis 95 Gew.% wenigstens eines weiteren Zusatzstoffes enthalten, bezogen auf das Gesamtgewicht der erfindungsgemäßen Zusammensetzung. The composition according to the invention preferably contains from 20 to 99% by weight, more preferably from 40 to 95% by weight, of at least one further additive, based on the total weight of the composition according to the invention.
Eine bevorzugte erfindungsgemäße Zusammensetzung enthält 10-30 Gew.-% DBDCB, 10-30 Gew.-% Salix Alba-Extrakt, welcher wenigstens 10 Gew.-%, bevorzugt wenigstens 30 Gew.-%, besonders bevorzugt wenigstens 50 Gew.-%, ganz besonders bevorzugt wenigstens 75 Gew.-% Salicylsäure und/oder deren Derivate, bezogen auf das Gesamtgewicht des Salix Alba-Extraktes, und 40-80 Gew.-% eines Glykols, bevorzugt 1 ,2-Propandiol enthält. A preferred composition according to the invention contains 10-30% by weight of DBDCB, 10-30% by weight of salix alba extract, which contains at least 10% by weight, preferably at least 30% by weight, particularly preferably at least 50% by weight. , very particularly preferably at least 75 wt .-% salicylic acid and / or derivatives thereof, based on the total weight of the Salix Alba extract, and 40-80 wt .-% of a glycol, preferably 1, 2-propanediol.
Herstellung Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung der erfindungsgemäßen Zusammensetzung, dadurch gekennzeichnet, dass man DBDCB und die wenigstens eine organische Säure und/oder deren Derivate gegebenenfalls unter Zugabe wenigstens eines weiteren bioziden Wirkstoffs und gegebenenfalls unter Zugabe wenigstens eines weiteren Zusatzstoffes, miteinander vermischt. The invention further relates to a process for the preparation of the composition according to the invention, which comprises mixing DBDCB and the at least one organic acid and / or derivatives thereof optionally with the addition of at least one further biocidal active ingredient and optionally with the addition of at least one further additive.
Eine bevorzugte Herstellung der erfindungsgemäßen Zusammensetzung ist dadurch gekennzeichnet, dass man DBDCB und die wenigstens eine organische Säure und/oder deren Derivate sowie wenigstens einen weiteren Zusatzstoff, bevorzugt wenigstens ein Lösungsmittel, miteinander vermischt. Es gelten für die erfindungsgemäße Herstellung die obigen Angaben bezüglich der weiteren bioziden Wirkstoffe, der Zusatzstoffe und Hilfsmittel analog. A preferred preparation of the composition according to the invention is characterized in that DBDCB and the at least one organic acid and / or derivatives thereof and at least one further additive, preferably at least one solvent, are mixed together. The above statements regarding the further biocidal active substances, the additives and auxiliaries apply analogously to the preparation according to the invention.
Verwendung use
Die Erfindung betrifft weiterhin die Verwendung der erfindungsgemäßen Zusammensetzungen zum Schutz von technischen Materialien vor Befall und/oder Zerstörung durch Mikroorganismen. Bevorzugt sind als technische Materialien, die unter Verwendung der erfindungsgemäßen Zusammensetzungen vor Befall und/oder Zerstörung durch Mikroorganismen geschützt werden sollen, wasserhaltige funktionelle Flüssigkeiten und wasserhaltige technische Produkte zu nennen. Beispielhaft, jedoch ohne zu limitieren, sei die Verwendung in folgenden technischen Materialien genannt: The invention further relates to the use of the compositions according to the invention for the protection of industrial materials against attack and / or destruction by microorganisms. As technical materials which are to be protected against attack and / or destruction by microorganisms using the compositions according to the invention, preferred are water-containing functional fluids and water-containing technical products. By way of example, but without limiting, the use in the following technical materials is mentioned:
Anstrichmittel, Farben, Putze und sonstige Beschichtungsmittel Paints, paints, plasters and other coating agents
Stärkelösungen und -slurrys oder andere auf Basis von Stärke hergestellte Produkte wie z.B. Druckverdicker  Starch solutions and syrups or other starch-based products, e.g. Printing thickener
Slurrys anderer Rohstoffe wie Farbpigmente (z.B. Eisenoxidpigmente, Rußpigmente, Titandioxidpigmente) oder Slurrys von anorganischen Füllstoffen und Pigmenten wie Kaolin, Calciumcarbonat, Gips, Bentonit, Magnesium Silikate, Smectid oder Talkum. Bauchemische Produkte wie Betonadditive beispielsweise auf Basis von Melasse, Ligninsulfonat oder Polyacrylaten, Bituimenemulsionen oder Fugendichtungsmassen Slurries of other raw materials such as color pigments (for example iron oxide pigments, carbon black pigments, titanium dioxide pigments) or slurries of inorganic fillers and pigments such as kaolin, calcium carbonate, gypsum, bentonite, magnesium silicates, smectide or talcum. Building chemical products such as concrete additives, for example, based on molasses, lignosulfonate or polyacrylates, Bituimenemulsionen or jointing compounds
Leime oder Klebstoffe auf Basis der bekannten tierischen, pflanzlichen oder synthetischen Rohstoffe Glues or adhesives based on the known animal, vegetable or synthetic raw materials
Polymerdispersionen auf Basis von z.B. Polyacrylat, Polystyrolacrylat, Styrolbutadien, Polyvinylacetat u.a.  Polymer dispersions based on e.g. Polyacrylate, polystyrene acrylate, styrene butadiene, polyvinyl acetate, and the like.
- Spülmittel, flüssige Waschmittel und Haushaltsreiniger für den technischen und Haushaltsbedarf - Detergents, liquid detergents and household cleaners for technical and household needs
Mineralöle und Mineralölprodukte (wie z.B. Dieselkraftstoffe)  Mineral oils and mineral oil products (such as diesel fuels)
Kühlschmierstoffe zur Metallverarbeitung auf Basis von Mineralöl-haltigen, halbsynthetischen oder synthetischen Konzentraten  Metalworking cooling lubricants based on mineral oil-containing, semi-synthetic or synthetic concentrates
- Hilfsmittel für die Leder-, Textil- oder photochemische Industrie Vor- und Zwischenprodukte der chemischen Industrie, z.B. bei der Farbstoffproduktion und -lagerung - Auxiliaries for the leather, textile or photochemical industry Pre and intermediate products of the chemical industry, eg in dye production and storage
Tinten oder Tuschen  Inks or inks
Wachs und Tonemulsionen  Wax and clay emulsions
Bevorzugt werden die erfindungsgemäßen Zusammensetzungen zum Schutz von Detergentien und oberflächenaktiven Stoffen, die bevorzugt in Spülmitteln, flüssigen Waschmitteln, Haushaltsreinigern und sonstigen Reinigern enthalten sind, verwendet. Die Anwendungskonzentrationen der erfindungsgemäß zu verwendenden erfindungsgemäßen Mischung richten sich nach der Art und dem Vorkommen der zu bekämpfenden Mikroorganismen, der mikrobiellen Ausgangsbelastung, der zu erwartenden Lagerdauer der zu schützenden Produkte sowie nach der mikrobiologischen Anfälligkeit der in den Endprodukten enthaltenen Komponenten. Die optimale Einsatzmenge kann durch Vorversuche und Testreihen im Labor in einer dem Fachmann hinlänglich bekannten Weise einfach ermittelt werden. The compositions according to the invention are preferably used for protecting detergents and surface-active substances, which are preferably present in dishwashing detergents, liquid detergents, household cleaners and other cleaners. The application concentrations of the mixture to be used according to the invention depend on the type and occurrence of the microorganisms to be controlled, the initial microbial load, the expected storage life of the products to be protected and on the microbiological susceptibility of the components contained in the end products. The optimum amount can be easily determined by preliminary tests and test series in the laboratory in a manner well-known to those skilled in the art.
Bevorzugt werden die erfindungsgemäßen Zusammensetzungen im Bereich von 0,01 bis 5 Gew.-%, besonders bevorzugt von 0,05 bis 1 ,0 Gew.-%, bezogen auf das Gewicht des zu schützenden Materials, zum Schutz von technischen Materialien eingesetzt. The compositions according to the invention are preferably used in the range from 0.01 to 5% by weight, particularly preferably from 0.05 to 1.0% by weight, based on the weight of the material to be protected, for the protection of industrial materials.
Die Erfindung betrifft weiterhin technische Materialien, die mit der erfindungsgemäßen Zusammensetzung behandelt wurden. Weiter umfasst die vorliegende Erfindung technische Materialien, die eine erfindungsgemäße Zusammensetzung enthalten. The invention further relates to technical materials which have been treated with the composition according to the invention. Further, the present invention includes engineering materials containing a composition of the invention.
Bevorzugt enthalten die technischen Materialien, die die erfindungsgemäße Zusammensetzung enthalten, diese im Bereich von 0,01 bis 5 Gew.-%, besonders bevorzugt von 0,05 bis 1 ,0 Gew.-%, bezogen auf das Gewicht des technischen Materials. The technical materials containing the composition according to the invention preferably contain these in the range from 0.01 to 5% by weight, particularly preferably from 0.05 to 1.0% by weight, based on the weight of the technical material.
Es gelten für die technischen Materialien die obigen beispielhaft genannten technischen Materialien analog. Bevorzugt umfasst die vorliegende Erfindung als technische Materialien Spülmittel, flüssige Waschmittel und Haushaltsreiniger, welche die erfindungsgemäße Zusammensetzung enthalten. Die erfindungsgemäße Zusammensetzung ist wirksam gegen Mikroorganismen der verschiedensten Art, wie z.B. Bakterien, Schimmelpilze, Hefen sowie Schleimorganismen. The above-mentioned exemplary technical materials apply analogously to the technical materials. As technical materials, the present invention preferably comprises dishwashing detergents, liquid detergents and household cleaners which contain the composition according to the invention. The composition of the invention is effective against microorganisms of various kinds, such as bacteria, molds, yeasts and slime organisms.
Beispielhaft, jedoch ohne zu limitieren, seien die folgenden Arten genannt, gegen die die erfindungsgemäße Zusammensetzung Wirksamkeit aufweist: By way of example, but without limitation, the following types are mentioned against which the composition according to the invention has activity:
Bakterien: Bacteria:
Alcaligenes wie Alcaligenes faecalis, Bacillus wie Bacillus subtilis, Enterobacter wie Enterobacter aerogenes, Escherichia wie Escherichia coli, Proteus wie Proteus vulgaris, Pseudomonas wie Pseudomonas aeruginosa oder Pseudomonas fluorescens, Serratia wie Serratia marescens, Staphylococcus wie Staphylococcus aureus.  Alcaligenes such as Alcaligenes faecalis, Bacillus such as Bacillus subtilis, Enterobacter such as Enterobacter aerogenes, Escherichia such as Escherichia coli, Proteus such as Proteus vulgaris, Pseudomonas such as Pseudomonas aeruginosa or Pseudomonas fluorescens, Serratia such as Serratia marescens, Staphylococcus such as Staphylococcus aureus.
Hefen: yeast:
Candida wie Candida albicans, Geotrichum wie Geotrichum candidum, Rhodotorula wie Rhodotorula rubra, Rhodotorula mucilaginosa, Saccharomyces wie Saccharomyces cerevisiae.  Candida such as Candida albicans, Geotrichum such as Geotrichum candidum, Rhodotorula such as Rhodotorula rubra, Rhodotorula mucilaginosa, Saccharomyces such as Saccharomyces cerevisiae.
Pilze: mushrooms:
Acremonium wie Acremonium strictum, Alternaria wie Alternaria tenuis oder Alternaria alternata, Aspergillus wie Aspergillus niger, Chaetomium wie Chaetomium globosum, Fusarium wie Fusarium solani, Lentinus wie Lentinus tigrinus, Paecilomyces wie Paecilomyces variotti, Penicillium wie Penicillium glaucum, Trichoderma wie Trichoderma viride. In den nachfolgenden Beispielen wird die überraschende Wirkungsverstärkung der erfindungsgemäßen Zusammensetzung beispielhaft, ohne zu limitieren, dokumentiert. Beispiele Acremonium such as Acremonium strictum, Alternaria such as Alternaria tenuis or Alternaria alternata, Aspergillus such as Aspergillus niger, Chaetomium such as Chaetomium globosum, Fusarium such as Fusarium solani, Lentinus such as Lentinus tigrinus, Paecilomyces such as Paecilomyces variotti, Penicillium such as Penicillium glaucum, Trichoderma such as Trichoderma viride. In the following examples, the surprising effect enhancement of the composition according to the invention is exemplified without limitation. Examples
Der Synergismus der erfindungsgemäßen Zusammensetzung wird im Folgenden beispielhaft gegen bestimmte, insbesondere praxisrelevante Keime wie z.B. Pseudomonas aeruginosa, Staphylococcus aureus, Alternaria alternata oder Geotrichum candidum gezeigt. The synergism of the composition according to the invention is exemplified below against certain, in particular practical germs such. Pseudomonas aeruginosa, Staphylococcus aureus, Alternaria alternata or Geotrichum candidum.
Der gefundene Synergismus der erfindungsgemäßen Zusammensetzungen lässt sich über folgenden mathematischen Ansatz ermitteln (vgl. F.C. Kuli, P.C. Elisman, H.D. Sylwestrowicz, P.K. Mayer, Appl. Microbiol. 9, 1961 , S. 538: The synergism found for the compositions according to the invention can be determined by the following mathematical approach (cf., F. C. Kuli, P. C. Elisman, H. D. Sylwestrowicz, P. K. Mayer, Appl. Microbiol., 9, 1961, p.
synergistischer Index (Sl) synergistic index (SI)
QA QB wobei gilt:  QA QB where:
Qa = Menge Komponente A in der Wirkstoffmischung, die den gewünschten Q a = amount of component A in the active ingredient mixture containing the desired
Effekt, d.h. kein mikrobielles Wachstum, erzielt,  Effect, i. no microbial growth, achieved,
QA = Menge Komponente A, die allein eingesetzt, das Wachstum der Mikroorganismen unterdrückt, QA = amount of component A, used alone, suppresses the growth of microorganisms,
Qb = Menge Komponente B in der Wirkstoffmischung, die den gewünschten  Qb = amount of component B in the active ingredient mixture containing the desired
Effekt, d.h. kein mikrobielles Wachstum, erzielt,  Effect, i. no microbial growth, achieved,
und and
Qß = Menge Komponente B, die allein eingesetzt, das Wachstum der Mikroorganismen unterdrückt. Qβ = amount of component B, used alone, suppresses the growth of microorganisms.
Ein gemäß obiger Formel resultierender synergistischer Index von Sl <1 zeigt für die Wirkstoffmischung einen synergistischen Effekt an. Je geringer der Sl ist, desto größer ist der synergistische Effekt. A synergistic index of Sl <1 resulting according to the above formula indicates a synergistic effect for the active compound mixture. The lower the Sl, the greater the synergistic effect.
Beispielhaft, ohne zu limitieren, wird anhand der nachfolgenden Beispiele und Berechnungen die synergistische Wirkungsverstärkung erläutert. Beispiel 1 By way of example, without limiting, the synergistic effect enhancement is explained on the basis of the following examples and calculations. example 1
Mit verschiedenen Testkeimen wurden die minimalen Hemmkonzentration ermittelt und darauf basierend anhand der Formel von F.C. Kuli et. al. die Synergieeffekte der aufgeführten erfindungsgemäßen Zusammensetzungen berechnet. With different test germs, the minimum inhibitory concentration was determined and based on the formula of F.C. Kuli et. al. calculated the synergy effects of the listed compositions of the invention.
Zusammensetzungen enthaltend DBDCB und Zitronensäure Compositions containing DBDCB and citric acid
Tabelle 1 (Testkeim: Staphylococcus aureus): Table 1 (Test Germ: Staphylococcus aureus):
(Testkeim: Staphylococcus aureus => QA = 50 ppm DBDCB, QB = 3001 ppm Zitronensäure) (Test germ: Staphylococcus aureus => Q A = 50 ppm DBDCB, Q B = 3001 ppm citric acid)
Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrationsverhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Staphylococcus aureus auf. In certain concentration ratios, the compositions according to the invention have a pronounced synergistic action against the test bacterium Staphylococcus aureus.
Tabelle 2 (Testkeim: Alternaria alternata): Table 2 (Test Germ: Alternaria alternata):
(Testkeim: Alternaria alternata => QA = 25 ppm DBDCB, QB = 3001 ppm Zitronensäure) (Test germ: Alternaria alternata => Q A = 25 ppm DBDCB, Q B = 3001 ppm citric acid)
Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrations- Verhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Alternaria alternata auf. Tabelle 3 (Testkeim: Geotrichum candidum): The compositions according to the invention have a pronounced synergistic action against the test germ Alternaria alternata in certain concentration ratios. Table 3 (test germ: Geotrichum candidum):
(Testkeim: Geotrichum candidum => QA = 100 ppm DBDCB, QB = 3001 ppm Zitronensäure) (Test germ: Geotrichum candidum => Q A = 100 ppm DBDCB, Q B = 3001 ppm citric acid)
Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrationsverhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Geotrichum candidum auf. The compositions according to the invention have a pronounced synergistic action against the test germ Geotrichum candidum in certain concentration ratios.
Zusammensetzungen enthaltend DBDCB und Milchsäure Compositions containing DBDCB and lactic acid
Tabelle 4 (Testkeim: Pseudomonas aeruginosa): Table 4 (Test germ: Pseudomonas aeruginosa):
(Testkeim: Pseudomonas aeruginosa => QA = 500 ppm DBDCB, QB = 3001 ppm Milchsäure) (Test germ: Pseudomonas aeruginosa => Q A = 500 ppm DBDCB, Q B = 3001 ppm lactic acid)
Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrationsverhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Pseudomonas aeruginosa auf. The compositions according to the invention have a pronounced synergistic action against the test bacterium Pseudomonas aeruginosa in certain concentration ratios.
Tabelle 5 (Testkeim: Alternaria alternata): Table 5 (Test germ: Alternaria alternata):
DBDCB : Milchsäure  DBDCB: lactic acid
Nr. Qa DBDCB [ppm] Qb Milchsäure [ppm] Sl No. Q a DBDCB [ppm] Q b Lactic acid [ppm] Sl
[Gew.-%/ Gew.-%]  [% By weight /% by weight]
1 9:1 22,5 2,5 0,90 1 9: 1 22.5 2.5 0.90
2 8:2 20 5 0,802 8: 2 20 5 0.80
3 7:3 17,5 7,5 0,703 7: 3 17.5 7.5 0.70
4 6:4 15 10 0,60 DBDCB : Milchsäure 4 6: 4 15 10 0.60 DBDCB: lactic acid
Nr. Qa DBDCB [ppm] Qb Milchsäure [ppm] Sl No. Q a DBDCB [ppm] Q b Lactic acid [ppm] Sl
[Gew.-%/ Gew.-%]  [% By weight /% by weight]
5 5:5 12,5 12,5 0,50 5 5: 5 12.5 12.5 0.50
6 4:6 10 15 0,406 4: 6 10 15 0.40
7 3:7 15 35 0,617 3: 7 15 35 0.61
8 2:8 15 60 0,628 2: 8 15 60 0.62
9 1 :9 10 90 0,439 1: 9 10 90 0.43
(Testkeim: Alternaria alternata => QA = 25 ppm DBDCB, QB = 3001 ppm Milchsäure) (Test germ: Alternaria alternata => Q A = 25 ppm DBDCB, Q B = 3001 ppm lactic acid)
Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrationsverhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Alternaria alternata auf The compositions according to the invention have a pronounced synergistic action against the test germ Alternaria alternata in certain concentration ratios
Zusammensetzungen enthaltend DBDCB und Salicyl Compositions containing DBDCB and salicyl
Tabelle 6 (Testkeim: Pseudomonas aeruginosa): Table 6 (Test germ: Pseudomonas aeruginosa):
(Testkeim: Pseudomonas aeruginosa QA = 250 ppm DBDCB, QB = 3001 ppm Salicylsäure) (Test germ: Pseudomonas aeruginosa Q A = 250 ppm DBDCB, Q B = 3001 ppm salicylic acid)
Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrationsverhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Pseudomonas aeruginosa auf. The compositions according to the invention have a pronounced synergistic action against the test bacterium Pseudomonas aeruginosa in certain concentration ratios.
Tabelle 7 (Testkeim: Alternaria alternata): Table 7 (Test germ: Alternaria alternata):
Nr. DBDCB : Salicylsäure Qa DBDCB [ppm] Qb Salicylsäure Sl No. DBDCB: salicylic acid Q a DBDCB [ppm] Q b salicylic acid Sl
[Gew.-%/ Gew.-%] [ppm]  [Wt% / wt%] [ppm]
1 9:1 22,5 2,5 0,91 1 9: 1 22.5 2.5 0.91
2 8:2 20 5 0,81 Nr. DBDCB : Salicylsäure Qa DBDCB [ppm] Qb Salicylsäure Sl 2 8: 2 20 5 0.81 No. DBDCB: salicylic acid Q a DBDCB [ppm] Q b salicylic acid Sl
[Gew.-%/ Gew.-%] [ppm]  [Wt% / wt%] [ppm]
3 7:3 17,5 7,5 0,72 3 7: 3 17.5 7.5 0.72
4 4:6 20 30 0,864 4: 6 20 30 0.86
5 3:7 15 35 0,675 3: 7 15 35 0.67
6 2:8 15 60 0,726 2: 8 15 60 0.72
(Testkeim: Alternaria alternata => QA = 25 ppm DBDCB, QB = 500 ppm Salicylsäure) (Test germ: Alternaria alternata => Q A = 25 ppm DBDCB, Q B = 500 ppm salicylic acid)
Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrationsverhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Alternaria alternata auf The compositions according to the invention have a pronounced synergistic action against the test germ Alternaria alternata in certain concentration ratios
Zusammensetzungen enthaltend DBDCB und Benzoesäure Compositions containing DBDCB and benzoic acid
Tabelle 8 (Testkeim: Bacillus subtilis): Table 8 (Test Germ: Bacillus subtilis):
(QA = 25 ppm DBDCB, QB = 3000 ppm Benzoesäure) (Q A = 25 ppm DBDCB, Q B = 3000 ppm benzoic acid)
Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrationsverhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Bacillus subtilis auf. Tabelle 9 (Testkeim: Aspergillus brasiliensis): The compositions of the invention have in certain concentration ratios a pronounced synergistic action against the test bacterium Bacillus subtilis. Table 9 (Test Germ: Aspergillus brasiliensis):
250 ppm DBDCB, QB = 1000 ppm Benzoesäure) Die erfindungsgemäßen Zusammensetzungen weisen in bestimmten Konzentrationsverhältnissen eine ausgeprägte synergistische Wirkung gegen den Testkeim Aspergillus brasiliensis. 250 ppm DBDCB, Q B = 1000 ppm benzoic acid) The compositions according to the invention have in certain concentration ratios a pronounced synergistic action against the test bacterium Aspergillus brasiliensis.
Beispiel 2: Mikrobiologischer Belastungstest - Konservierung eines Spülmittels Example 2: Microbiological stress test - Preservation of a rinsing agent
Untersucht wurde die konservierende Wirkung einer erfindungsgemäßen Zusammensetzung enthaltend DBDCB und Salix Alba-Extrakt in einem Handspülmittel mit Hilfe eines mikrobiologischen Belastungstests. Mit dem mikrobiologischen Belastungstest wird die Anfälligkeit wasserbasierter Produkte gegen mikrobiellen Befall und die Wirkung von Konservierungsmitteln überprüft. Hierzu werden die Konservierungsmittel in definierten Konzentrationen in die wasserbasierten Systeme eingearbeitet. Nach Abschluss der Vorarbeiten erfolgt über einen Versuchszeitraum von 3 bis maximal 6 Wochen eine wiederholte Kontamination mit Mikroorganis- men definierter Art und in definierten Mengen im wöchentlichen Abstand. 2-3 und 7 Tage nach jeder Kontamination wird durch Keimzahlbestimmung festgestellt, ob vollständige Abtötung oder zumindest Vermehrungshemmung der eingebrachten Mikroorganismen im Vergleich zur nicht konservierten Kontrollprobe eingetreten ist. In Kenntnis der in Detergentien der hier beschriebenen Art vorherrschenden Mikroorganismen-Populationen wurde für den Versuch ein Gemisch der folgenden Mikroorganismenarten für die Prüfung eingesetzt: The preservative effect of a composition according to the invention comprising DBDCB and Salix alba extract in a hand dishwashing detergent was investigated by means of a microbiological stress test. The Microbiological Stress Test verifies the susceptibility of water-based products to microbial attack and the effects of preservatives. For this purpose, the preservatives are incorporated in defined concentrations in the water-based systems. After completion of the preliminary work, repeated contamination with microorganisms of a defined type and in defined quantities at weekly intervals is carried out over a test period of 3 to a maximum of 6 weeks. It is determined by germ count determination whether complete kill or at least inhibition of proliferation of the introduced microorganisms occurred in comparison to the unpreserved control sample 2-3 and 7 days after each contamination. With knowledge of the microorganism populations prevalent in detergents of the type described here, a mixture of the following microorganism species was used for the test:
Bakterien: Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus. Pseudomonas putida, Enterobacter gergoviae Bacteria: Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus. Pseudomonas putida, Enterobacter gergoviae
Schimmelpilze: Acremonium strictum, Aspergillus niger und Geotrichum candidum. Molds: Acremonium strictum, Aspergillus niger and Geotrichum candidum.
Hefen: Candida albicans und Rhodotorula rubra. Yeasts: Candida albicans and Rhodotorula rubra.
Eine sehr gute Wirksamkeit wird erreicht, wenn in den konservierten Proben eine vollständige Abtötung (auf 0 Bakterien bzw. auf 0 Schimmel- bzw. Hefezellen pro/g) der eingebrachten Mikroorganismen erfolgt (Bewertung 3 = sehr gut). A very good effectiveness is achieved if in the preserved samples a complete kill (on 0 bacteria or on 0 mold or yeast cells per / g) of the introduced microorganisms takes place (evaluation 3 = very good).
Eine gute Wirksamkeit liegt dann vor, wenn in den konservierten Proben im Vergleich zur unkonservierten Probe (sogenannte Nullprobe) ein stark reduziertes Mikrobenniveau beobachtet wird (auf 103 - 101 Bakterien bzw. auf 102 - 101 Schimmel- bzw. Hefezellen pro/g) (Bewertung 2 = gut). A good efficacy is present when a much reduced level of microbes is observed in the preserved samples compared to the unpreserved sample (so-called blank sample) (on 10 3 - 10 1 bacteria or on 10 2 - 10 1 mold or yeast cells per / g) (rating 2 = good).
Eine mäßige Wirksamkeit liegt dann vor, wenn im Vergleich zur unkonservierten Probe ein leicht reduziertes Mikrobenniveau beobachtet wird (auf 104 - 103 Bakterien bzw. auf 103 - 102 Schimmel- bzw. Hefezellen pro/g) (Bewertung 1 = mäßig) . A moderate efficacy is present when compared to the unpreserved sample a slightly reduced level of microbes is observed (on 10 4 - 10 3 bacteria or on 10 3 - 10 2 mold or yeast cells per / g) (rating 1 = moderate) ,
Eine mangelhafte Wirksamkeit liegt dann vor, wenn im Vergleich zur unkonservierten Probe keine oder eine nur geringfügige Reduktion des Mikrobenniveaus beobachtet wird (auf ein Restniveau von mindestens 105 Bakterien bzw. 104 Schimmel- bzw. Hefezellen pro/g) (Bewertung 0 = mangelhaft). Die erzielten Ergebnisse sind in Tabelle 10 ange- geben. A poor efficacy is present when compared to the unpreserved sample no or a slight reduction in the microbial level is observed (to a residual level of at least 10 5 bacteria or 10 4 mold or yeast cells per / g) (rating 0 = deficient ). The results obtained are shown in Table 10.
Folgende Zusammensetzungen wurden in den in Tabelle 10 dargestellten Versuchen eingesetzt: The following compositions were used in the experiments shown in Table 10:
A: DBDCB B: Zusammensetzung enthaltend 25 Gew.-% Salix Alba-Extrakt (der 80 Gew.-% Salicylsäure enthält) und 75 Gew.-% 1 ,2-Propandiol. A: DBDCB B: Composition containing 25% by weight Salix Alba extract (containing 80% by weight salicylic acid) and 75% by weight 1,2-propanediol.
C: Zusammensetzung enthaltend 20 Gew.-% DBDCB, 20 Gew.-% Salix Alba-Extrakt (der 80 Gew.-% Salicylsäure enthält) und 60 Gew.-% 1 ,2-PropandiolC: Composition containing 20% by weight of DBDCB, 20% by weight of Salix Alba extract (containing 80% by weight of salicylic acid) and 60% by weight of 1,2-propanediol
(erfindungsgemäß). (Invention).
Tabelle 10: Wirksamkeit der Biozide in einem Handspülmittel, ermittelt jeweils 1 Woche nach Keimzugabe Table 10: Effectiveness of the biocides in a hand dishwashing detergent, determined in each case 1 week after germ addition
(B = Bakterien, S = Schimmelpilze, H = Hefen) (B = bacteria, S = molds, H = yeasts)
3 = sehr gute Wirksamkeit 3 = very good effectiveness
2 = gute Wirksamkeit 2 = good effectiveness
1 = mäßige Wirksamkeit 1 = moderate effectiveness
0 = mangelhafte Wirksamkeit Durch Zugabe einer erfindungsgemäßen Zusammensetzung enthaltend DBDCB und Salix Alba-Extrakt, welcher 80 Gew.-% Salicylsäure enthält, wird trotz deutlich herabgesetzter Wirkstoff menge gegenüber dem Einzelwirkstoff DBDCB eine sehr gut wirksame Konservierung erzielt, d.h. alle zur Prüfung eingesetzten Mikroorganismen- arten werden durch die erfindungsgemäße Mischung abgetötet. 0 = poor effectiveness By adding a composition according to the invention comprising DBDCB and Salix Alba extract which contains 80% by weight salicylic acid, a very effective preservation is achieved in spite of a significantly reduced amount of active ingredient compared with the individual active ingredient DBDCB, ie all types of microorganisms used for testing are replaced by the killed mixture according to the invention.

Claims

Patentansprüche claims
Zusammensetzung, dadurch gekennzeichnet, dass sie 1 ,2-Dibrom-2,4-dicyano- butan (DBDCB) und wenigstens eine organische Säure und/oder deren Derivate enthält. Composition, characterized in that it contains 1, 2-dibromo-2,4-dicyano-butane (DBDCB) and at least one organic acid and / or derivatives thereof.
Zusammensetzung gemäß Anspruch 1 , dadurch gekennzeichnet, dass das Gewichtsverhältnis von DBDCB zu der wenigstens einen organischen Säure und/oder deren Derivaten in der Zusammensetzung 99:1 bis 1 : 99, bevorzugt 9 :1 bis 1 :9 beträgt. Composition according to Claim 1, characterized in that the weight ratio of DBDCB to the at least one organic acid and / or derivatives thereof in the composition is 99: 1 to 1:99, preferably 9: 1 to 1: 9.
Zusammensetzung gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass die wenigstens eine organische Säure und/oder deren Derivate ausgewählt ist aus der Gruppe bestehend aus Mono- und Polycarbonsäuren und deren Derivaten, bevorzugt ausgewählt aus der Gruppe bestehend aus Benzoesäure, Milchsäure, Salicylsäure, Sorbinsäure und Zitronensäure und deren Derivaten. Composition according to one of claims 1 or 2, characterized in that the at least one organic acid and / or derivatives thereof is selected from the group consisting of mono- and polycarboxylic acids and derivatives thereof, preferably selected from the group consisting of benzoic acid, lactic acid, salicylic acid , Sorbic acid and citric acid and their derivatives.
Zusammensetzung gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die wenigstens eine organische Säure und/oder deren Derivate Salicylsäure und/oder deren Derivate ist und in Form einer Zusammensetzung SA eingesetzt wird, welche wenigstens 10 Gew.-%, bevorzugt wenigstens 30 Gew.-%, besonders bevorzugt weigstens 50 Gew.-%, ganz besonders bevorzugt wenigstens 75 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung SA, Salicylsäure und/oder deren Derivate enthält. Composition according to any one of Claims 1 to 3, characterized in that the at least one organic acid and / or derivatives thereof is salicylic acid and / or derivatives thereof and is used in the form of a composition SA containing at least 10% by weight, preferably at least 30% Wt .-%, particularly preferably at least 50 wt .-%, most preferably at least 75 wt .-%, based on the total weight of the composition SA, salicylic acid and / or derivatives thereof.
Zusammensetzung gemäß Anspruch 4, dadurch gekennzeichnet, dass die Zusammensetzung SA ein Salix Alba-Extrakt ist. Composition according to claim 4, characterized in that the composition SA is a salix alba extract.
Zusammensetzung gemäß Anspruch 5, dadurch gekennzeichnet, dass der SalixComposition according to Claim 5, characterized in that the Salix
Alba-Extrakt durch Extraktion aus der Rinde der Silberweide gewonnen wird, bevorzugt durch Extraktion mit Wasser und/oder Ethanol. Zusammensetzung gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass wenigstens ein weiterer biozider Wirkstoff enthalten ist. Alba extract is obtained by extraction from the bark of white willow, preferably by extraction with water and / or ethanol. Composition according to any one of Claims 1 to 6, characterized in that at least one further biocidal active substance is present.
Zusammensetzung gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Summe von DBDCB, der wenigstens einen organischen Säure und/oder deren Derivaten und des zusätzlich keinen oder wenigstens einen weiteren bioziden Wirkstoffs 1 bis 80 Gew.-%, bevorzugt 5 bis 60 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, beträgt. A composition according to any one of claims 1 to 7, characterized in that the sum of DBDCB, the at least one organic acid and / or derivatives thereof and additionally no or at least one further biocidal active substance is 1 to 80% by weight, preferably 5 to 60% by weight, based on the total weight of the Composition, is.
9. Zusammensetzung gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Derivate der wenigstens einen organischen Säure Alkalimetallsalze sind, bevorzugt ausgewählt aus der Gruppe bestehend aus Natrium-, Kalium- und Lithiumsalzen. 9. A composition according to any one of claims 1 to 8, characterized in that the derivatives of the at least one organic acid are alkali metal salts, preferably selected from the group consisting of sodium, potassium and lithium salts.
10 Zusammensetzung gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass wenigstens ein weiterer Zusatzstoff enthalten ist, bevorzugt ausgewählt aus der Gruppe bestehend aus grenzflächenaktive Stoffe, Benetzungsmittel, Emulgatoren, Dispergiermittel, Stabilisatoren, Haftmittel, Verdicker, Spreitmittel, organische Lösungsmittel, Duftstoffe, Farbmittel, Entstaubungsmittel, Puffersubstanzen, Puffersysteme, pH-Wert-Regulatoren, feste Trägerstoffe und Wasser, besonders bevorzugt wenigstens ein organisches Lösungsmittel, ganz besonders bevorzugt wenigstens ein Glykol. A composition according to any one of claims 1 to 9, characterized in that it contains at least one further additive, preferably selected from the group consisting of surfactants, wetting agents, emulsifiers, dispersants, stabilizers, adhesives, thickeners, spreading agents, organic solvents, fragrances, Colorants, dedusting agents, buffer substances, buffer systems, pH regulators, solid carriers and water, more preferably at least one organic solvent, most preferably at least one glycol.
1 1 Zusammensetzung gemäß 10, dadurch gekennzeichnet, dass 20 bis 99 Gew.%, bevorzugt 40 bis 95 Gew.-%, wenigstens eines weiteren Zusatzstoffes enthalten sind, bezogen auf das Gesamtgewicht der Zusammensetzung. 1 1 Composition according to 10, characterized in that 20 to 99 wt.%, Preferably 40 to 95 wt .-%, of at least one further additive are contained, based on the total weight of the composition.
12 Verfahren zur Herstellung der Zusammensetzung gemäß einem der Ansprüche 1 bis 1 1 , dadurch gekennzeichnet, dass man DBDCB und wenigstens eine organische Säure und/oder deren Derivate, gegebenenfalls unter Zugabe wenigstens eines weiteren bioziden Wirkstoffs und gegebenenfalls unter Zugabe wenigstens eines weiteren Zusatzstoffes, miteinander vermischt. 12 A process for the preparation of the composition according to any one of claims 1 to 1 1, characterized in that DBDCB and at least one organic acid and / or derivatives thereof, optionally with the addition of at least one further biocidal active ingredient and optionally with the addition of at least one further additive with each other mixed.
13. Verwendung der Zusammensetzung gemäß einem der Ansprüche 1 bis 1 1 zum Schutz von technischen Materialien vor Befall und/oder Zerstörung durch Mikroorganismen. 13. Use of the composition according to any one of claims 1 to 1 1 for the protection of industrial materials from attack and / or destruction by microorganisms.
14. Technische Materialien, dadurch gekennzeichnet, dass sie mit einer Zusammensetzung gemäß einem der Ansprüche 1 bis 1 1 behandelt wurden. 14. Technical materials, characterized in that they have been treated with a composition according to any one of claims 1 to 1 1.
15. Technische Materialien enthaltend eine Zusammensetzung gemäß einem Ansprüche 1 bis 1 1 . 15. Technical materials containing a composition according to any one of claims 1 to 1 1.
EP16754299.2A 2015-08-24 2016-08-23 Composition containing 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least one organic acid and/or the derivatives thereof Withdrawn EP3340795A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15182206.1A EP3135112A1 (en) 2015-08-24 2015-08-24 Compositions comprising 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least an organic acid and/or derivatives thereof
PCT/EP2016/069844 WO2017032756A1 (en) 2015-08-24 2016-08-23 Composition containing 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least one organic acid and/or the derivatives thereof

Publications (1)

Publication Number Publication Date
EP3340795A1 true EP3340795A1 (en) 2018-07-04

Family

ID=54056076

Family Applications (2)

Application Number Title Priority Date Filing Date
EP15182206.1A Withdrawn EP3135112A1 (en) 2015-08-24 2015-08-24 Compositions comprising 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least an organic acid and/or derivatives thereof
EP16754299.2A Withdrawn EP3340795A1 (en) 2015-08-24 2016-08-23 Composition containing 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least one organic acid and/or the derivatives thereof

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP15182206.1A Withdrawn EP3135112A1 (en) 2015-08-24 2015-08-24 Compositions comprising 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least an organic acid and/or derivatives thereof

Country Status (3)

Country Link
US (1) US20190008147A1 (en)
EP (2) EP3135112A1 (en)
WO (1) WO2017032756A1 (en)

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3361289D1 (en) 1982-06-21 1986-01-02 Merck & Co Inc Synergistic antimicrobial combination
US4830657A (en) * 1982-06-21 1989-05-16 Calgon Corporation Synergistic antimicrobial combination
US5034405A (en) 1985-03-27 1991-07-23 Calgon Corporation Admixtures of 2-bromo-2-bromomethyl-glutaronitrile, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one
AU6306594A (en) * 1994-05-12 1995-11-23 R & C Products Pty Limited Liquid dishwashing composition
AUPN396295A0 (en) * 1995-07-03 1995-07-27 R & C Products Pty Limited Ironing aid
US5641808A (en) * 1995-09-01 1997-06-24 Calgon Corporation Synergistic antimicrobial composition of 1,2-dibromo-2,4-dicyanobutane and esters of parahydroxybenzoic acid
DE19625982A1 (en) * 1996-06-28 1998-01-02 Wella Ag Cosmetic agent for hair treatment with dendrimers
DE19627931A1 (en) * 1996-07-11 1998-01-22 Care Full Colours Kosmetik Pro Lipstick
EP1525797A3 (en) 2002-01-31 2005-05-11 Rohm And Haas Company Synergistic microbicidal combination
WO2003086335A1 (en) * 2002-04-08 2003-10-23 Purac Biochem B.V. Hair care composition for restoring the elasticity of hair
CN102948417A (en) * 2012-06-07 2013-03-06 江西正邦生物化工股份有限公司 Bromothalonil water dispersible granule and preparation method thereof

Also Published As

Publication number Publication date
EP3135112A1 (en) 2017-03-01
US20190008147A1 (en) 2019-01-10
WO2017032756A1 (en) 2017-03-02

Similar Documents

Publication Publication Date Title
DE69033037T2 (en) Synergetic microbicidal combinations
DE68925801T2 (en) Biocidal compositions
EP1315419B1 (en) Synergetic biocidal composition comprising 2-methylisothiazoline-3-on
WO2007026004A2 (en) Synergetic silver-containing biocide composition
EP3038468B1 (en) Microbicidal agents
DE102007051006A1 (en) Stable, synergistic mixtures
EP3439473B1 (en) Synergetic biocidal compositions containing 5-chloro-2-methyl-isothiazolin-3-one
WO2011147558A1 (en) Synergistic biocide composition containing at least three biocide components
WO2006074788A2 (en) Antimicrobial solid matter preparations
EP1937062B1 (en) Active substance mixtures comprising opp and amines, microbicidal agents
EP0383005A1 (en) Preservative for systems or products with an aqueous phase
DE60311486T2 (en) STABLE SYNERGISTIC ANTIMICROBIAL COMPOSITIONS FROM ALDEHYDE DONATORS AND DESHYDRATE ACIDS WITH LOW CONTENT OF FREE FORMALDEHYDE
EP2272348A1 (en) Biocidal agent
EP2213166A1 (en) Biocidal compounds containing 2-methylisothiazolin-3-one and a haloalkylsulfone
EP3182825B1 (en) Composition comprising 1,2-dibrom-2,4-dicyanobutane (dbdcb) and zinc pyrithione (zpt)
EP0068442B1 (en) Agent, its application and process for combating phytopathogenic fungi and bacteria
EP1259110B1 (en) Microbicidal agent
EP3340795A1 (en) Composition containing 1,2-dibromo-2,4-dicyanobutane (dbdcb) and at least one organic acid and/or the derivatives thereof
DE10340829A1 (en) Low-salt or salt-free microbicidal composition based on isothiazolone derivatives and pyrion disulfide
EP2157862B1 (en) Biocide composition containing glutaraldehyde and at least one isothiazolinone
WO2017174180A1 (en) Synergetic biocidal compositions comprising 5-chlorine-2-methylisothiazolin-3-one
DE10318366A1 (en) Microbicidal agents
DE69712891T2 (en) Synergistic antimicrobial composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20180326

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20180731