WO2008000797A2 - Microparticules antimicrobiennes - Google Patents

Microparticules antimicrobiennes Download PDF

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Publication number
WO2008000797A2
WO2008000797A2 PCT/EP2007/056493 EP2007056493W WO2008000797A2 WO 2008000797 A2 WO2008000797 A2 WO 2008000797A2 EP 2007056493 W EP2007056493 W EP 2007056493W WO 2008000797 A2 WO2008000797 A2 WO 2008000797A2
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WO
WIPO (PCT)
Prior art keywords
resins
microparticles
active ingredient
antimicrobial
biocidal
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PCT/EP2007/056493
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German (de)
English (en)
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WO2008000797A3 (fr
Inventor
Volker Butz
Rüdiger Baum
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Thor Gmbh
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Publication of WO2008000797A2 publication Critical patent/WO2008000797A2/fr
Publication of WO2008000797A3 publication Critical patent/WO2008000797A3/fr

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    • 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

  • the invention relates to antimicrobial microparticles containing at least one isothiazolinone and optionally one or more other biocides as biocidal active ingredient.
  • the microparticles are formed from an aminoplast resin selected from the group of urea resins, urethane resins, cyan resins, dicyandiamide resins, aniline resins, sulfonamide resins, or a mixture of two or more of these resins.
  • the resins contain the biocidal agent included, which is released from them with a delay.
  • Resin / biocide compositions are known in the art for a variety of applications.
  • such compositions are used in the production of polymer tapes, antimicrobial plastic compositions, for application in plastic articles and in the form of so-called microcapsules in coating compositions.
  • DE 38 83 982 T2 discloses a polymer belt for underground use, comprising at least one layer of thermoplastic, wherein the thermoplastic includes a biocide in an amount sufficient for biocidal activity.
  • the biocide is effectively washed out of the thermoplastic layer and slows growth of microorganisms on the surface of the belt and in the surrounding soil.
  • the layer is selected from a thermoplastic such as polypropylene, polyethylene, ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers or mixtures thereof.
  • microcapsules which are made of polyacrylate derivatives and have pores in the polymer shell. According to this document makes it possible to include in these pores a variety of different substances, such as vitamins or biocides.
  • DE 602 03 757 T2 discloses a composition of a specific biocide and a resin which is suitable for the production of plastic articles.
  • the composition disclosed in this document comprises 1 to 15% by weight of the biocide
  • a resin selected from the group consisting of ethylene-vinyl acetate-carbon monoxide copolymers, styrene
  • butadiene-styrene copolymers styrene-maleic anhydride copolymers, and styrene-methyl methacrylate copolymers and mixtures thereof.
  • Biocides included in a melamine-formaldehyde resin for application in coating compositions, in particular in facade plasters, are known from WO 2004/000953 A1 of the Applicant.
  • granule particles are disclosed which are advantageously designed as microcapsules.
  • the biocides are enclosed in finely dispersed, liquid or solid phase.
  • the wall material of the microcapsules are very different substances in question, namely natural, semi-synthetic and synthetic materials.
  • the materials used for confinement or encapsulation have very different requirements.
  • a basic requirement is that resin and biocidal agent must be compatible with each other; The resin must not react either with its production or in the finished final form, ie the inclusion product, with the enclosed active substance.
  • melamine-formaldehyde resins described as preferred in the aforementioned WO 2004/000953, as is apparent from the examples, have the required compatibility, in particular with isothiazolinones, as well as a good controlled release of the active substance. However, nothing is mentioned in this patent application with regard to the material properties at elevated temperatures.
  • the invention is therefore based on the object of providing further antimicrobial resin / biocidal compositions.
  • resins are to be used which lead to products which have the abovementioned properties (effective entrapment and controlled release and inertness in the entrapment process and storage).
  • the included biocides should be able to be used in a wide variety of applications.
  • antimicrobial microparticles containing as biocidal active ingredient at least one isothiazolinone and optionally one or more other biocides and characterized in that the active ingredient is enclosed in microparticles of an aminoplast resin selected from the group of urea resins, urethane resins, cyan resins, dicyandiamide resins, aniline resins, sulfonamide resins, or a mixture of two or more of these resins is.
  • the resin is an aminoplast resin except for the melamine-formaldehyde resins.
  • the wall of the microparticles may comprise one, two or more of the aforementioned resins.
  • said resins for the preparation of the microparticles there is no destruction or inhibition of the active ingredient. After the polymerisation of the resin, no substances are released from it, which over time lead to the destruction or inactivation of the biocidal active substance. Even in the finished polymerized state of the resin no reactions between these and the active ingredient are found.
  • microparticles refers to any type of particle comprising a wall structure and at least one cavity formed by the wall structure.
  • the wall structure in this case contains one or more of the aforementioned resins, preferably one.
  • the cavities formed by the wall structure may be closed or open and contain the biocidal active ingredient and optionally other various excipients. Closed cavities may, for example, be in the form of capsule structures or cell structures, open cavities in the form of pores, channels and the like.
  • the term microparticles may likewise mean a matrix of a resin, the biocidal active ingredient being enclosed in the matrix or being enveloped by it.
  • the term microparticles may refer to so-called microcapsules, in the interior of which the biocidal active ingredient is encapsulated encapsulated.
  • the microparticles have a spherical shape.
  • biocidal agents in the context of the present invention refers to a substance or a mixture of two or more substances with biocidal Effect (biocides). At least one biocide selected from the group of isothiazolinones, including 2-n-octyl-4-isothiazolin-3-one (OIT), 2-methylisothiazolin-3-one (MIT), is present in the biocidic agent , 2-Benzisothiazolin-3-one (BIT), N-alkyl-l, 2-benzisothiazolin-3-one having 1 to 8 C atoms in the alkyl radical, N-methyl-1,2-benzisothiazolin-3-one (N Methyl BIT), N-butyl-1,2-benzisothiazolin-3-one (N-butyl-BIT), 4,5-dichloro-2-n-octylisothiazolin-3-one (DCOIT), 5-chloro 2-methyl-4-isothiazolin-3-one
  • the selection of the isothiazolinone or the depends on the particular desired spectrum of activity of the antimicrobial microparticles of the invention.
  • OIT is preferably used when a fungicidal and algicidal effect is desired.
  • MIT and / or BIT it is preferred to use MIT and / or BIT as the biocidal active ingredient.
  • the microparticles contain one or more isothiazolinones as the biocidal active ingredient and additionally one or more other biocides.
  • the ratio of the isothiazolinone to the other biocide (s) can, in principle, vary and be varied within wide limits, for example in the range from 100: 1 to 1: 100, preferably 50: 1 to 1:50.
  • the isothiazolinone is usually present in amounts of from 10 to 95% by weight, in particular from 20 to 80% by weight, and the other biocides in amounts of from 5 to 90% by weight, in particular from 20 to 80 wt .-%, in each case based on the total amount of contained biocidal active ingredient.
  • the biocidal active ingredient enclosed in the microparticles consists predominantly of one or more isothiazolinones. That is, the trapped biocidal agent as the main component isothiazolinone, preferably in an amount equal to or greater than 50% by weight of isothiazolinone, more preferably in an amount equal to or greater than 70% by weight, especially in an amount equal to or greater than 90 wt .-%, in particular in an amount equal to or greater than 95 wt .-% isothiazolinone, based on the total mass of biocidal active ingredient. In addition, at least one other biocide may be present.
  • the biocidal active ingredient enclosed in the microparticles consists essentially of one or more Isothiazolinones, ie, in addition to at least one isothiazolinone probably still one or more other biocides may be present, but these are present in an amount in which there is no contribution of the respective biocide other than the isothiazolinone to the overall effect of the resulting mixture.
  • the biocidal active ingredient may consist of one or more isothiazolinones as the sole biocide, ie an active substance content of 100% isothiazolinone. In such a case, it is only possible that one or more other ingredients are present without a biocidal effect.
  • one or more other biocides may additionally be used, which may be selected depending on the field of application. Specific examples of such additional biocides are given below:
  • benzyl alcohol 2,4-dichlorobenzyl; 2-phenoxyethanol; 2-Phenoxyethanolhemi- formal, phenylethyl alcohol: 5-bromo-5-nitro-l, 3-dioxane; bronopol; Formaldehyde and formaldehyde depot substances; dimethyloldimethylhydantoin; glyoxal; glutaraldehyde; sorbic acid; benzoic acid; salicylic acid; p-hydroxybenzoic acid esters; chloroacetamide; N-methylolchloroacetamide; Phenols such as p-chloro-m-cresol and o-phenylphenol; N-methylolurea, N, N'-dimethylolurea;benzylformal;4,4-dimethyl-1,3-oxazolidine; 1,3,5-hexahydrotriazine derivatives; Quaternary ammonium compounds such as N-alkyl-N, N-
  • formaldehyde-releasing agent examples include N-formals such as tetramethylol-acetylenediurea; N, N'-dimethylolurea;N-methylol; Wench thylo ldimethylhydantoin; N-methylolchloroacetamide; Reaction products of allantoin; Glycol formals such as ethylene glycol formal and butyl diglycol formal; Benzylformal.
  • biocidal agents are OIT alone or OIT in combination with one or more biocides from the group BIT, N-butyl-BIT, N-methyl-BIT, IPBC, tebuconazole, DCOIT; terbutryn; cyfluthrin; isoproturon; Triclosan and zinc pyrithione.
  • the use of OIT as the sole biocide in the biocidic agent is preferred.
  • a combination of the biocides OIT and BIT is preferred.
  • biocidal active substance used in the microparticles according to the invention contains, in addition to an isothizolinone, further biocides, these further biocides may be contained together with the one isothizolinone as a mixture in the microparticles.
  • microparticles containing only one isothiazolinone are mixed together with microparticles containing the further biocide (s) and this mixture of microparticles is used, for example for the antimicrobial finishing of fabrics.
  • the biocidal active ingredient may also contain other conventional ingredients known to those skilled in the art as additives. These are, for example, thickeners, defoamers, substances for adjusting the pH, fragrances, dispersing aids and coloring or discoloration-preventing substances, complexing agents and stabilizers, for example UV stabilizers.
  • aminoplast resins in the context of the invention are polycondensation products, in particular condensation products of carbonyl compounds, in particular of formaldehyde and compounds containing NH groups, such as, for example, urea (urea resins), urethanes (urethane resins), cyano- and dicyandiamide (cyanogen). or dicyandiamide resins), aromatic Amines (aniline resins) and sulfonamides (sulfonamide resins) to understand.
  • urea resins urethanes
  • cyano- and dicyandiamide cyanogen
  • dicyandiamide resins aromatic Amines
  • aniline resins aniline resins
  • sulfonamides sulfonamide resins
  • the resins used in this invention belong to the aminoplasts, but the melamine-formaldehyde resins listed in WO 2004/000953 A1 mentioned above are not part of the present invention and are expressly excluded.
  • Preferred antimicrobial microparticle materials are urea-formaldehyde resins and dicyandiamide-formaldehyde resins, and particularly preferred materials are urea-formaldehyde resins.
  • urea resins mentioned above are hardenable condensation products of ureas and aldehydes belonging to the family of aminoplasts, in particular these include formaldehyde.
  • formaldehyde For their preparation, urea or substituted ureas are reacted with formaldehyde under mostly alkaline conditions. Hydroxymethyl group-containing oligomers are formed, which are cross-linked under acidic catalysis.
  • formaldehyde it is also possible to use other aldehydes, for example acetaldehyde or glyoxal.
  • Condensates based on modified ureas are also starting materials which can be used in the preparation of the microparticle material in the context of the invention.
  • microparticles containing the biocidal active ingredient may also be formed from two or more of the aforementioned aminoplast resins. In the preparation of the microparticles there is no destruction or inhibition of the biocidal active ingredient.
  • the novel antimicrobial microparticles have been made available, it has been found that only a slight escape of the biocidal active substance from the microparticles can be detected at elevated temperatures. For example, in a thermal treatment over a period of 2 minutes at a temperature of 150 0 C escape of less than about 70%, preferably less than about 50%, more preferably less than 10% of the biocidal agent from the particles to observe. This not only reduces the loss of biocidal active substance, but also the entry into the exhaust air / environment. Despite the inclusion of the biocide in the microparticles, the biocidal activity of the biocidic agent is maintained.
  • biocidal active substance Due to the inclusion of the biocidal active substance in the microparticles, it is advantageously released in a slower (retarding) manner in an aqueous or steam-containing environment. On the one hand, this makes it possible to use smaller amounts of active ingredient and, on the other hand, to achieve considerably longer efficacies.
  • Biocidal agents such as bactericides, fungicides and / or algicides are used in many fields and are used to control bacteria, fungi or algae.
  • plastics or paints are provided with bactericides, fungicides and / or algicides to prevent infestation by microorganisms, eg. As by fungi, such as mold, as well as by bacteria, cyanobacteria, yeasts and algae partially or completely.
  • fungi such as mold
  • bacteria cyanobacteria, yeasts and algae partially or completely.
  • Microcapsules in the interior of which biocides are included, are described in WO 2004/000953 of the applicant as already mentioned above. Some embodiments are shown below.
  • Preferred natural materials for the wall of the microcapsules disclosed in WO 2004/000953 are gum arabic, agar, agarose, maltodextrin, sodium alginate, calcium alginate, dextran, fats, fatty acids, cetyl alcohol, milk solids, molasses, gelatin, gluten, albumin, shellac, starches Caseinates, stearinates, sucrose and waxes such as beeswax, carnauba wax and spermaceti wax.
  • Preferred semisynthetic materials for the microcapsule wall are cellulose acetate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose nitrate, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose phthalate, methylcellulose, sodium carboxymethylcellulose, hydrogenated tallow, myristyl alcohol, glycerol mono- or dipalmitate, hydrogenated castor oil, glyceryl mono- or tristearates and 12-hydroxystearyl alcohol.
  • preferred synthetic materials for the microcapsule wall are formaldehyde-melamine resins, acrylic polymers and copolymers, such as polyacrylamide, polyalkyl cyanoacrylate, and poly (ethylene vinyl acetate), aluminum monostearate, carboxyvinyl polymers, polyamides, poly (methylvinyl ether maleic anhydride), poly ( adipinyl-L-lysine), polycarbonates, polyterephthalamide, poly (vinyl terephthalate), poly (terephthaloyl-L-lysine), polyaryl sulfones, poly (methyl methacrylate), poly ( ⁇ -L-lysine), polyaryl sulfones, poly ( methylmethacrylate), poly ( ⁇ -caprolactone), polyvinylpyrrolidone, polymethylsiloxane, polyoxyethylenes, polyesters, polyglycolic acid, polylactic acid and its copolymers, polyglutamic acid, polylys
  • the particularly preferred wall materials of the microcapsules disclosed in WO 2004/000953 are formaldehyde-melamine resins.
  • WO 2004/000953 refers to numerous known methods, such as CA. Finch, R. Bodmeier, Microencapsulation, Ullmann's Encyclopaedia of Industrial Chemistry, 6th Edition 2001, Electronic Release). Depending on the biocide used and the wall material of the microcapsules to be used in each case the appropriate method can be selected.
  • microcapsules have a size in the range of 30 to 40 microns.
  • the biocidal agent is included in these microcapsules.
  • preferred fungicides are isothiazolinones, carbamates, pyrithiones, aldehydes, ketones, quinones, amines, amidines, guanidines, hydrazo and azo compounds, aromatic carbonitriles, quinoxalines, imidazoles, triazoles, pyrimidines, triazines, halogenated and nitrated alcohols and Phenols, perhaloalkyl mercaptan derivatives, phosphoric and phosphonic acid esters, tetrahydro-l, 3,5-thiadiazinethionones, thio- and isothiocyanates, thiophenes, antibiotics and herbal active substances.
  • fungicides are methyl-1H-benzimidazol-2-ylcarbamate (carbendazim), 2-pyridinethiol-1-oxide-zinc (zinc), pyrithione), 2-n-octylisothiazolin-3-one (OIT), 4,5-dichloroisothiazolin-3-one (DCOIT) and 3-iodo-2-propynyl-N-butylcarbamate (IPBC).
  • carbendazim 2-pyridinethiol-1-oxide-zinc
  • pyrithione 2-n-octylisothiazolin-3-one
  • OIT 2-n-octylisothiazolin-3-one
  • DCOIT 4,5-dichloroisothiazolin-3-one
  • IPBC 3-iodo-2-propynyl-N-butylcarbamate
  • algicides within the scope of WO 2004/000953 are triazines, N, N-dimethylureas and uracils.
  • Specific examples of well-suited algicides are N 2 -t-butyl-N 4 -ethyl-6-methylthio-l, 3,5-triazine-2,4-diyldiamine (terbutryn), 2-chloro
  • inclusion of water-soluble isothiazolinones such as MIT, CIT, BIT, and N-methyl-BIT in the microparticles of the present invention enables their use as film preservatives for preserving plastics and the like.
  • the water-soluble active substances enclosed in the microparticles are protected from attack by water and only released from the microparticle by retarding.
  • microparticles according to the invention then have a good effect according to the invention when they contain from 5 to 99.99% by weight of the resin and from 0.01 to 95% by weight of the biocidal active ingredient, preferably from 15 to 60% by weight of the resin and to 40% by weight of the biocidal agent, based on the total weight of the resin and the biocidic agent.
  • the average diameter of the antimicrobial microparticles provided is in the range of about 0.5 ⁇ m to about 100 ⁇ m, the preferred mean diameter in one embodiment is in the range of 10 to 40 ⁇ m, and in another embodiment in the range of about 1 ⁇ m to about 10 microns.
  • the size of the microparticles can be determined, for example, under a microscope using a micrometer scale.
  • the biocidal active ingredient is enclosed in a finely dispersed, liquid or solid phase; it is particularly preferred during the preparation of the microparticles for the biocidal active substance to be introduced into the microparticles in an aqueous medium.
  • the preparation of the microparticles according to the invention preferably comprises the use of so-called precondensates which are water-soluble and from which the antimicrobial microparticles are prepared from the aqueous phase.
  • the manufacturing process has several advantages, for example, in addition to other possible ones
  • a polar and / or non-polar liquid solvent can be used.
  • polar liquid solvents aliphatic alcohols having 1 to 4 carbon atoms, eg.
  • ethanol and isopropanol a glycol, for.
  • the polar liquid solvent is especially water.
  • nonpolar liquid solvents can serve, for example, aromatics, preferably xylene and toluene. These may also be used alone or as a mixture of 2 or more such solvents.
  • microparticles according to the invention preference is given to starting from an aqueous suspension of the biocidal active substance or active substance mixture using water as solvent.
  • the microparticles according to the invention are preferably prepared with stirring in an acidic medium.
  • acidic medium serve inorganic and / or organic acids such as hydrochloric acid, phosphoric acid and citric acid.
  • the microparticles can be prepared in conventional apparatus for condensation polymerizations. These include stirred tanks, stirred tank cascades, autoclaves, tube reactors and kneaders.
  • the reaction is carried out, for example, in stirred tanks equipped with an anchor, blade, impeller, dissolver or multistage pulse countercurrent stirrer.
  • apparatuses that allow the direct isolation of the product following the polymerization such as. B. paddle dryer.
  • the resulting suspensions can be dried directly in evaporators, such as belt dryers, paddle dryers, spray dryers or fluidized bed dryers. But you can also cut off by filtration or centrifugation, the majority of the water.
  • the resin As the starting material for the resin, on the one hand, known etherified precondensates known to those skilled in the art are used. Furthermore, however, the resin can also be prepared in the presence of the biocidal active ingredient from the educts by techniques known in the art, such as by reaction between urea and formaldehyde.
  • the reaction is preferably carried out in aqueous solution.
  • concentration of the precondensate in the aqueous solution can be varied over a wide range.
  • the precondensate is supplied or formed such that the precondensate concentration is from about 1 to about 70 weight percent, preferably from about 5 to about 50 weight percent.
  • the microparticles according to the invention may contain other substances which are generally known and customary depending on the intended use.
  • suitable binders and film formers such as polyacrylates, polystyrene acrylates or silicone resins
  • auxiliaries such as pigments
  • Fillers such as calcium carbonate, talc, kaolins, silicates, fumed silica and / or zeolites
  • Solvents such as calcium carbonate, talc, kaolins, silicates, fumed silica and / or zeolites
  • Solvents such as polysaccharides and / or cellulose ethers
  • defoamers such as polysaccharides and / or cellulose ethers
  • defoamers such as polysaccharides and / or cellulose ethers
  • defoamers such as polysaccharides and / or cellulose ethers
  • defoamers such as polysaccharides and / or cellulose ethers
  • defoamers such as polysaccharides and / or cellulose ethers
  • defoamers such as
  • the condensation polymerization of the resin may be carried out anywhere within the range of about 20 to about 95 ° C., preferably between about 50 and 80 ° C.
  • the reaction will generally be completed within a few hours, although the reaction at high temperature may be completed within a few minutes.
  • microparticles Once the microparticles are formed, they can be stored as dispersions and used or filtered as dried particles. In any form, the particles are useful and effective in the sustained release of the biocide.
  • microparticles according to the invention are particularly suitable for the preservation of films.
  • they are added in the desired amount to a system, for example a paint or a coating composition for coating building walls, a lacquer, a glaze, an adhesive and prevent the growth of fungi, algae and / or bacteria depending on the selected biocidal active ingredient.
  • the antimicrobial microparticles are furthermore suitable as constituents of a coating composition for coating building walls, if these are contained, for example, in a plaster.
  • the antimicrobial microparticles are used for permanent preservation of wood against microbial infestation.
  • the biocidal active substance OIT is suitable for effective protection of the wood against attack by algae and fungi.
  • Another important aspect of the invention relates to the equipping of textiles with the microparticles according to the invention.
  • textiles according to the present invention fibers for textile use, semi-finished and finished semi-finished products, such as yarns, fabrics and finished textile goods such as clothing to understand.
  • textile textile units or subunits of textiles such as tent fabrics, awnings, covers, shower curtains, fleeces, filters, fish nets, carpets and the like to understand.
  • the biocidal active substance in the microparticles As a result of the inclusion of the biocidal active substance in the microparticles, it is released (retarded) in an advantageous manner during the drying or during the irrigation or washing of the textiles equipped therewith.
  • the microparticles according to the invention are particularly suitable for this application, since the high temperatures required during the finishing step on the one hand cause only a slight escape of the biocidal active substance from the microparticles, but release the active ingredient to the desired extent after the equipment has been provided.
  • fish nets are protected with the microparticles according to the invention using the active ingredient DCOIT against the infestation of algae.
  • rinse and wipes can be equipped with the microparticles and thus effectively protect against microbial infestation.
  • the antimicrobial microparticles according to the invention are used to equip a filter, preferably an air filter.
  • the filter comprises a textile, in particular a nonwoven fabric and microparticles, in which the biocidal active substance is enclosed.
  • the filter material is in this case equipped with the microparticles according to the invention to prevent the growth of fungi, algae and bacteria in the filter at least largely.
  • the thus equipped filters are suitable for use in air conditioning systems, as well as in exhaust air and supply air systems.
  • such equipped filters are suitable for use in ventilation systems or air conditioners in slaughterhouses, since the equipment of the filter material with the microparticles according to the invention makes it possible to wash out the filter without this thereby losing its antimicrobial activity.
  • biocidal active ingredient is a mixture of OIT and BIT.
  • OIT effective the infestation of algae and fungi and BIT prevents the infestation of the filter by bacteria.
  • microparticles were prepared from urea-formaldehyde, which included the biocidal active ingredient 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT).
  • DCOIT biocidal active ingredient
  • the water was initially charged with the formalin solution and the urea at pH 7.5. After stirring for 10 minutes, the polyacrylate, gum arabic, silicone defoamer, sodium citrate and the 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one were stirred. The resulting mixture was adjusted to pH 6.2 with sodium hydroxide or hydrochloric acid and heated to 70 0 C. Thereafter, hydrochloric acid was added dropwise over a period of one hour to a pH of 4. Subsequently, the mixture was stirred for 2 hours at the same temperature. The contained mixture contained the desired microparticles in which the biocidal active ingredient is included.
  • various textile samples having a size of 40 ⁇ 40 cm were each impregnated in aqueous liquors with 30 g / l of a composition containing about 10% microparticles or a corresponding amount of a comparison product with conventionally dispersed DCOIT.
  • 30 g / l of Quecophob GAR fluorocarbon resin, Fa THOR GmbH
  • the swatches were subsequently squeezed off on a Foulardwalze, dried one minute at 120 0 C and cured at 150 0 C for one minute. Before drying, the overlay was determined and used to calculate the theoretical drug concentration.
  • Table 1 Results of the Example and Comparative Example for Loss of Active Substance in the Drying of Textiles.
  • Table 2 Results of the example and comparative example of loss of active ingredient in the washing of textiles.
  • Example 3 The polyester samples prepared according to Example 1 and Comparative Example 1 were tested for their fungi-inhibiting properties according to DIN 53931. The results are shown in Table 3.
  • Textile samples finished with DCOIT included show excellent antifungal properties. These antifungal properties are still present even after the washing of the textiles.
  • Emulsifier (Hostapur SAS 60) 0.40
  • the water was initially charged with the formalin solution, the polyacrylate, the gum arabic, the citric acid, the emulsifier and the 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT).
  • DCOIT 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one
  • the resulting mixture was adjusted with hydrochloric acid to a pH of 2.0 and heated to 70 0 C. Now a 25% urea solution was added dropwise over 2 hours and stirred for 10 h.
  • the contained mixture contained the desired microparticles in which the biocidal active ingredient is included. These microparticles prepared according to Preparation Example 2 were used in Examples 4, 5 and 6.
  • Table 4 Results of the example and comparative example of loss of active ingredient in the drying of textiles.
  • Table 5 Results of the example and comparative example of loss of active ingredient in the washing of textiles.
  • Example 6 and Comparative Example 6 The polyester samples prepared according to Example 4 and Comparative Example 4 were examined for their fungi-inhibiting properties according to DIN 53931. The results are shown in Table 6.
  • Textile samples finished with DCOIT included show excellent antifungal properties. These antifungal properties are still present even after the washing of the textiles.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Microparticules antimicrobiennes qui contiennent au moins une isothiazolinone et éventuellement un ou plusieurs autres biocides en tant que principe actif biocide. Le principe actif biocide est enfermé dans une résine aminoplaste choisie dans le groupe constitué par les résines d'urée, les résines d'uréthanne, les résines cyan, les résines de dicyandiamide, les résines d'aniline, les résines sulfonamide ou un mélange de deux de ces résines ou plus, et est libéré de ce mélange de manière retardée.
PCT/EP2007/056493 2006-06-30 2007-06-28 Microparticules antimicrobiennes WO2008000797A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200610030705 DE102006030705A1 (de) 2006-06-30 2006-06-30 Antimikrobielle Mikropartikel
DE102006030705.4 2006-06-30

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US20120322839A1 (en) * 2011-06-17 2012-12-20 Patrick Thomas Felder Aqueous dispersions
EP2801256A1 (fr) 2013-05-08 2014-11-12 LANXESS Deutschland GmbH Microcapsules contenant un agent algicide et un polymère mélamine-formaldéhyde
EP2157862B1 (fr) 2007-06-05 2016-03-30 THOR GmbH Composition biocide contenant du glutaraldehyde et au moins une isothiazolinone
WO2017095335A1 (fr) * 2015-11-30 2017-06-08 Aquafil S.P.A. Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche
US10212935B2 (en) 2014-02-27 2019-02-26 Lanxess Deutschland Gmbh Biocidic microcapsules
EP3669654A1 (fr) 2018-12-18 2020-06-24 LANXESS Deutschland GmbH Microcapsules comprenant oit en combinaison avec propiconazol et/ou ipbc

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Publication number Priority date Publication date Assignee Title
EP2157862B1 (fr) 2007-06-05 2016-03-30 THOR GmbH Composition biocide contenant du glutaraldehyde et au moins une isothiazolinone
WO2010121606A2 (fr) 2009-04-24 2010-10-28 Chemische Werke Kluthe Gmbh Procédé, formulations et produit pour le traitement biocide d'un agent de lubrification réfrigérant
DE102010018312A1 (de) 2009-04-24 2010-11-04 Chemische Werke Kluthe Gmbh Verfahren und Erzeugnis für die biozide Behandlung eines Kühlschmierstoffs
US20120322839A1 (en) * 2011-06-17 2012-12-20 Patrick Thomas Felder Aqueous dispersions
EP2801256A1 (fr) 2013-05-08 2014-11-12 LANXESS Deutschland GmbH Microcapsules contenant un agent algicide et un polymère mélamine-formaldéhyde
US10212935B2 (en) 2014-02-27 2019-02-26 Lanxess Deutschland Gmbh Biocidic microcapsules
WO2017095335A1 (fr) * 2015-11-30 2017-06-08 Aquafil S.P.A. Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche
EP3669654A1 (fr) 2018-12-18 2020-06-24 LANXESS Deutschland GmbH Microcapsules comprenant oit en combinaison avec propiconazol et/ou ipbc
WO2020126967A1 (fr) 2018-12-18 2020-06-25 Lanxess Deutschland Gmbh Microcapsules

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