EP2038473A2

EP2038473A2 - Antimicrobial textile

Info

Publication number: EP2038473A2
Application number: EP07786889A
Authority: EP
Inventors: Volker Butz; Thomas Schiwek
Original assignee: Thor GmbH
Current assignee: Thor GmbH
Priority date: 2006-06-30
Filing date: 2007-06-28
Publication date: 2009-03-25
Also published as: US20090318044A1; BRPI0713948A2; CN101479425A; MX2008016282A; AU2007263697A1; US7700502B2; WO2008000796A2; WO2008000796A3; EP1873300A1; JP2009541610A

Abstract

The invention relates to a textile which is equipped with a biocidal substance. The textile according to the invention is characterized in that 2-n-octyl-4-isothazoline-3-on is contained as the biocidal substance and optionally one or more other biocides, and in that the biocidal substance is embedded in aminoplastic resin microparticles. By embedding the biocidal substance in the microparticles the biocidal substance remains on the textile during drying and condensation while the textile is finished. In practice, the biocidal substance is released only slowly and is not washed out when the textile is exposed to rain or soaked, thereby preventing the biocidal substance from escaping largely already when the textile is finished or preventing it from being washed out from canvas, awnings, filters, tarpaulin, shower curtains and the like after a few downpours.

Description

Antimicrobial textile

The invention relates to a textile antimicrobially finished with at least one biocidal active substance. The biocidal active ingredient is enclosed in a resin based on an aminoplastic. The enclosed biocidal active ingredient is useful as a textile auxiliaries for finishing textiles such as tent fabrics, awnings, covers, shower curtains, nonwovens, filters, carpets and the like.

Most textiles contain microbiologically degradable material. They are either completely or partially made of microbiologically degradable fibers, for example cotton, hemp, flax, linen, viscose, tencel, acetate, silk, wool. Textiles of synthetic fibers, e.g. Polyester, polyacrylonitrile, polyamide, polypropylene, nomex, aramid become microbiologically vulnerable when treated with finishing agents such as e.g. Sizing agents, wetting oils, lubricants, plasticizers, water repellents, antistatic agents, and / or binders or, during use, take up microbiologically degradable material, e.g. organic substances from the environment or soap residues. The infestation of textiles by fungi, algae or bacteria can not only negatively affect the appearance but also the functional properties of the textiles. In addition, unpleasant odor nuisance or a health hazard can be caused by the release of metabolic products.

It is therefore necessary to equip textiles with preservatives, in particular with biocides such as bactericides, fungicides and / or algicides, in order to prevent infestation by microorganisms, eg. As by fungi, such as mold, as well as by bacteria, cyanobacteria, yeasts and algae to prevent or at least minimize. However, when equipping the textile with biocides, difficulties arise concerning both the finishing process as such and equipment-related phenomena.

In the textile industry, high demands are placed on the biocides used for finishing textiles. For example, after finishing, the textiles usually have to be dried at temperatures of 100 to 130 ^° C. and, in order to additionally achieve adequate hydrophobicity, then be treated at temperatures up to 180 ^° C. The high evaporation rate of the biocides often leads to high drug losses. In particular, on the surface of synthetic fibers, such as polyester, polyamide, polypropylene or polyacrylonitrile fibers, drug losses of more than 95% are observed after equipping.

Due to the large surface of the textiles and the small layer thickness of the equipment, the active substance remaining on the textile after finishing is washed out in practice during washing of the textile, for example during irrigation. This is another notable loss of active ingredient. Furthermore, the influence of light can also lead to a decomposition of the biocidal active substances remaining after the finishing.

After equipment has been used, the interaction of certain heavy metal ions, such as iron with certain biocides, such as zinc pyrithione, causes discoloration of the textiles.

There are effective biocides, which have a low evaporation rate and / or remain largely by irrigation on the textile. In general, however, in this respect satisfactory biocides are less suitable for finishing textiles because of their toxic effects. These include chlorothalonil and in particular the carbendazim classified as carcinogenic. Also skin irritations are to be called as disadvantageous. In the manufacture (e.g., trimming, sewing, etc.) of the antimicrobial textiles, skin contact also occurs with textiles that generally do not come in contact with the human body during intended use.

Due to the volatilization of the active ingredients described above, it is frequently necessary to purchase partially expensive active substances with high minimum inhibitory concentration values (MIC).

Values) to be used in high concentration in order, in spite of the losses of active ingredient in the drying irrigation, to achieve the desired antimicrobial effect for practical purposes, resulting in considerable costs. Furthermore, the high use concentrations and the high losses of biocidal active ingredient during production and use of these products pollute the environment.

Finally, the negative effect of many biocides on the water-repellent effect of the impregnation or coating should be mentioned. The resulting faster wetting with water leads to an accelerated release of the active ingredients. In general, the drug concentration falls below the minimum inhibitory concentration (MIC) of the biocides after only a few irrigation cycles. A long-term effect is therefore no longer present.

The invention is therefore based on the object of providing an antimicrobially finished textile which largely avoids the disadvantages listed above and, in particular, minimizes the escape of the biocidal active ingredient during the finishing. The aim is to reduce the environmental impact and the cost of the equipment of the textile to combat harmful microorganisms and reduce the evaporation rate of the biocidal active ingredient from the finished textile. The antimicrobial effect of the microbicide used for the equipment should be guaranteed for as long as possible.

This object is achieved by providing a textile which is provided with a biocidal active substance, which contains 2-n-octyl-4-isothiazolin-3-one (OIT) as biocidal active substance and furthermore optionally one or more other biocides in which the biocidal active ingredient is enclosed in microparticles of an aminoplast resin, preferably of a melamine-formaldehyde resin.

In the context of the present invention, the term "biocidal active ingredient" denotes the substance or the substance mixture which has the biocidal effect on which the invention is based.The biocidal active ingredient in each case contains OIT, in addition to optionally further active ingredient, as described in more detail below is defined.

In one embodiment of the present invention, the microparticles contain OIT as biocidal active ingredient and additionally one or more other biocides. In principle, the ratio of OIT to the other biocide (s) can vary and be varied within wide limits, for example in the range from 100: 1 to 1: 100, preferred wise 50: 1 to 1:50. According to this embodiment of the invention, the OIT 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.

In another embodiment, the biocidal active ingredient included in the microparticles consists predominantly of OIT. This means that the enclosed biocidal active ingredient as the main constituent OIT, preferably in an amount of equal to or greater than 50 wt .-% OIT, more preferably in an amount of equal to or greater than 70 wt .-%, in particular in an amount equal to or greater than 90 wt .-%, in particular in an amount of equal to or greater than 95 wt .-% OIT, based on the total mass of biocidal active ingredient. In addition, at least one other biocide may be present.

In a further embodiment of the invention, the biocidal active ingredient enclosed in the microparticles consists essentially of OIT, ie, in addition to OIT, one or more other biocides may still be present, but these are present in an amount in which no contribution is made of the particular biocide other than OIT to the total effect of the resulting mixture. Thus, if the biocidal activity of a biocidal active substance (biocide mixture), which apart from OIT has one or more further biocides in subordinate or slight concentration, is not changed compared to the use of OIT alone as sole biocide, this is In connection with the present invention referred to as "substantially consisting".

In another embodiment, the biocidal active ingredient may consist of OIT as the only biocidal active ingredient, ie an active ingredient content of 100% OIT. In such a case, it is only possible that one or more other ingredients are present without a biocidal effect.

For the purposes of the invention, the term textile fibers for textile use, semi-finished and finished textile products, such as threads, yarns, threads, fabrics, knits, woven / knitted fabric, nonwovens, and the like. As well as textile finished goods such as clothing. Preferably, the term textile textile units or subunits of textiles, such as tent fabrics, awnings, umbrellas and sunshades, covers, shower curtains, nonwovens, filters, carpets and the like to understand. The term aminoplast resins in the context of the invention are polycondensation products of carbonyl compounds, in particular of formaldehyde and compounds containing NH groups, for example urea (urea resins), melamine (melamine resins), urethanes (urethane resins) , Cyan and Dicyanamid (cyanide or Dicyanamidharze), aromatic amines (aniline resins) and sulfonamides (sulfonamide resins) to understand, see Römpp, Chemie Lexikon, Thieme Verlag Stuttgart, 9, extended edition, 1995, Volume A -Cl, page 159. Said section of the reference is incorporated by reference into the present application. Preferred materials of the microparticles are melamine, urea and dicyandiamide-formaldehyde resins, particularly preferred materials are melamine-formaldehyde resins.

The urea resins mentioned above are hardenable condensation products of ureas and aldehydes belonging to the aminoplasts, in particular these include formaldehyde. For their preparation, urea or substituted ureas are reacted with formaldehyde in molar excess under mostly alkaline conditions. The result is hydroxymethyl group-containing oligomers, which are cured with crosslinking. Instead of formaldehyde, it is also possible to use other aldehydes, for example acetaldehyde or glyoxal. Condensates based on modified ureas are also useful starting materials in the production of the microparticle material in the context of the invention.

The term melamine resins is to be understood as meaning aminoplast resins in which melamine has been polycondensed under suitable conditions with carbonyl compounds such as aldehydes and ketones, for example formaldehyde, acetaldehyde or glyoxal. For their preparation, melamine is generally reacted with the carbonyl compound in molar excess. Of particular interest in this connection are the polycondensation products of melamine with formaldehyde (melamine-formaldehyde resins) or urea-modified or phenol-modified melamine-formaldehyde resins (melamine-urea-formaldehyde resins, melamine-pheno-1-formaldehyde resins). resins).

The microparticles containing the biocidal active ingredient may also be formed from two or more of the aforementioned aminoplast resins. When selecting the microparticle material, particular care must be taken to ensure that no destruction or inhibition of the biocidal active substance occurs during the preparation. Due to the inclusion of the biocidal active substance in the microparticles, this surprising manner is not or only to a very small extent volatilized or released in the production of the textile during drying and condensation, despite the high temperatures used, while at the same time remaining biocidally active; and he rather remains on the textile, so that it can be used in correspondingly low concentrations. In practical use, the biocidal active ingredient is released only slowed down (retarding). It has been shown in an advantageous manner that the biocidal active substance enclosed in the microparticles is not washed out to a great extent during the irrigation or washing of the textiles equipped therewith, as would have been usual to be expected. On the one hand, according to the invention, on the one hand, smaller amounts of active ingredient can be used for the equipment, and on the other hand, it is possible to achieve considerably longer effective times

According to the present invention, the term 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 aminoplast resins, preferably one. The cavities formed by the wall structure can be closed or open and contain the biocidic active substance and, if appropriate, further different auxiliary substances. 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. For the purposes of the invention, the term microparticles may likewise mean a matrix of an aminoplast resin, wherein the biocidal active ingredient is enclosed in the matrix or enveloped by it. Also, the term microparticles may refer to so-called microcapsules, in the interior of which the biocidal active ingredient is encapsulated encapsulated.

Preferably, the microparticles have a spherical shape. This shape has the advantage of high volume, low surface area, whereby impinging water has a low wetting area. As a result, sprinkling the textiles finished with the microparticles releases only a small portion of the biocidal active substance. This prevents a large proportion of the biocidal active substance from being washed out of the textiles, such as tent fabrics, awnings, tarpaulins, shower curtains, and the like, after a few downpours. The long-term effect of the antimicrobial finish of the textiles is considerably improved. This results in a durable protection of the textiles against microbial attack. The average diameter of microparticles useful for finishing textiles is usually in the range of about 0.5 to about 100 microns, the preferred average diameter is in the range of about 1 to about 10 microns. The size of the microparticles can be determined, for example, under a microscope using a micrometer scale.

The textiles are finished in such a way that the antimicrobially finished textile generally has an amount of biocidal active substance, based on the total weight of the textile, of 0.0001% by weight to 0.5% by weight, preferably of 0.01% by weight. to 0.2% by weight, more preferably from 0.05% to 0.15% by weight.

Since there is always only a small concentration of the biocidal active ingredient on the surface of the microparticles and thus on the surface of the textile, the product properties of the textile, such as their hydrophobicity or oleophobicity are not adversely affected.

Furthermore, a long-term effect can be achieved even with lower use concentrations due to the slow release of the biocidal active substance. This has both ecological and economic advantages, since the biocidal active substance is lost only to a small extent during the processing of the textiles and can thus be used in substantially smaller quantities.

The inclusion of the biocidal agent in the microparticles not only has the advantage of the delayed release of the biocidal agent, but the shielding of the biocidal agent through the particle wall has the consequence that this thereby increased stability to UV radiation, elevated temperatures, heavy metal ions and pH values. For example, the duration of action of the biocidal active ingredient, due to a lower rate of decomposition, is considerably prolonged.

Biocides are used in many areas and are used to fight bacteria, fungi or algae. It has long been known to use compounds of the class of 3-isothiazolin-3-ones (which are also referred to as 3-isothiazolones) in such compositions in particular. In this class of substances are very effective biocides with sometimes different Wirkprofϊl. Often, combinations of different 3-isothiazolin-3-ones, or also of one or more 3-isothiaziolin-3-ones, are used with other known biocidal active substances (see below). among others. WO 99/08530 A, EP 0457435 A, EP 0542721 A and WO 02/17716 A). In view of the ever-increasing demands placed on such biocidal compositions, for example with regard to health and environmental protection aspects, the antimicrobial finishing of textiles requires a further development of the known products.

Biocidal active substances enclosed in a melamine-formaldehyde resin for application in coating compositions, in particular in facade plasters, are known from WO 2004/000953 of the applicant. However, this application gives no indication that OIT trapped in an aminoplast resin, preferably in a melamine-formaldehyde resin, is excellent for finishing textiles. The fact that the high temperatures required in the finishing step on the one hand cause only a slight escape of the biocidal active substance from the microparticles is surprising, and the particles release the biocidal active substance to a desired extent after the equipment has been provided after retarding.

As a result of the inclusion of the biocidal active substance in the microparticles based on the aminoplast resin, its release during drying or thermal aftertreatment during the textile finish, as mentioned, is largely prevented. Thus, the antimicrobial textile is characterized in that less than about 70%, preferably less than about 50%, particularly preferably less than 10%, of the biocidal active ingredient escapes during the drying or the thermal after-treatment. This not only reduces the loss of biocidal active substance, but also the entry into the exhaust air / environment. Despite the inclusion of the biocidal active substance in the microparticles, the biocidal activity of the biocidal active substance is retained.

The 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 aminoplast resin and from 0.01 to 95% by weight of the biocidal active substance, preferably from 15 to 60% by weight of the aminoplast Resin and 85 to 40% by weight of the biocidic agent based on the total weight of the aminoplast resin and the biocidic agent.

The known 2-n-octyl-4-isothiazolin-3-one (OIT) has antimicrobial properties which are desirable for the finishing of textiles. To mention here are the fungicidal and algicidal action, which are advantageous for textile use

Complement drug profile. The l, 2-Benzoisothiazolin-3-one (BIT), the very good has bactericidal properties, due to its high water solubility and high volatility at higher temperatures also only partially suitable for textile applications.

The use of the microparticles according to the invention is particularly suitable for the equipment of textiles which are used in the outdoor area, because OIT is a biocide with fungicidal and algicidal action, due to the broad spectrum of activity of OIT. It contains no halogen or heavy metal compounds, is not persistent or accumulable, is not classified as a CMR substance and has a favorable human and ecotoxicological profile. It is therefore generally suitable for the finishing of textiles in terms of its properties. Thus, its use from both the ecological and economic point of view also advantageous because of its advantageous spectrum of action.

For inclusion in the microparticles, in addition to OIT, one or more other biocides can additionally be used, which can 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-dimethylbenzylammonium chloride and di-n-decyldimethylammonium chloride; Cetylpyridinium chloride; diguanidine; polybiguanide; chlorhexidine; l, 2-dibromo-2,4-dicyanobutane; 3,5-dichloro-4-hydroxybenzaldehyde; Ethylenglykolhemiformal; Tetra (hydroxymethyl) phosphonium salts; dichlorophen; 2,2-dibromo-3-nitrilopropionsäureamid; 3-iodo-2-propynyl-N-butylcarbamate; Methyl-N-benzimidazol-2-ylcarbamate; 2,2'-dithio-dibenzoic acid di-N-methyl amide; 2-thiocyanomethylthiobenzothiazole; C-formals such as 2-hydroxymethyl-2-nitro-1, 3-propanediol and 2-bromo-2-nitropropane-1,3-diol; methylene bis; Reaction products of allantoin; 2-methyl-isothiazolin-3-one; N-alkyl-l, 2-benzisothiazolin-3-ones having 1 to 8 carbon atoms in the alkyl radical; N-methyl-l, 2-benzisothiazolin-3-one; N-butyl-1,2-benzisothiazolin-3-one; 4,5-dichloro-2-n-octylisothiazolin-3-one; 4,5-trimethylene-2-methyl isobutyl thiazoline-3-one; 1,2-benzisothiazolin-3-one (BIT); zinc pyrithione; Chlorothalonin; Propiocynazole; tebuconazole; TCMTB; IPBC, terbutryn, cyfluthrin, isoproturon triclosan.

Examples of the formaldehyde releasing agent are N-formals such as tetramethylolacetylenediurea; N, N'-dimethylolurea; N-methylol; Thyl dimethyl dimethylhydanto in; N-methylolchloroacetamide; Reaction products of allantoin; Glycol formals, such as ethylene glycol formal; Butyldiglykolformal; Benzylformal.

According to the invention, preferred biocidal active substances 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 ,

In one embodiment, the use of OIT as the sole biocidic agent is preferred.

In a further embodiment of the invention, a combination of the biocidal active substances OIT and BIT is preferred.

If, in addition to OIT, other biocides are also used in the microparticles according to the invention as biocidal active ingredient, this further biocide may be contained together with the OIT as a mixture in the microparticles. However, it is also possible to mix microparticles containing only OIT with microparticles containing only the further biocide and to apply this mixture of microparticles to the textile.

The microparticles containing the biocidal active substance may additionally contain other customary additives which are customary for the textile application and which are known to the person skilled in the art. These are e.g. Thickeners, defoamers, substances for adjusting the pH, fragrances, dispersing aids and coloring or discoloration-preventing substances, complexing agents and stabilizers such as UV stabilizers.

According to the invention, the microparticles used for finishing textiles preferably do not comprise any harmful solvents. The preferred solvent used in the preparation is water. If, according to a particular embodiment of the invention, further solvents are used in the preparation of the microparticles, these may be polar or nonpolar or mixtures containing polar and non-polar solvents.

In addition to water are to be mentioned as further polar liquid solvent aliphatic alcohols having 1 to 4 carbon atoms, for. For example, ethanol and isopropanol, a glycol, for. Ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol and tripropylene glycol, a glycol ether, e.g. Butyl glycol and butyl diglycol, a glycol ester, eg. Butyl diglycol acetate or 2,2,4-trimethylpentanediol monoisobutyrate, a polyethylene glycol, a polypropylene glycol, N, N-dimethylformamide or a mixture of 2 or more such solvents. The polar liquid solvent is especially water. As nonpolar liquid solvents, e.g. Aromatics, preferably xylene and toluene serve. These may also be used alone or as a mixture of 2 or more such solvents.

According to a preferred embodiment of the invention, the microparticles are anchored on the textiles by means of a finish (for example polymer dispersions, amino resins, melamine-formaldehyde resins, paraffin emulsions, fluorocarbon emulsions, silicone emulsions). The finish is an impregnating liquid which is applied to textile threads or textiles by spraying, dipping or coating. The finishing of the textiles with the microparticles can thus be carried out in one operation with the application of the finish. The attachment of reactive groups on the surface or a reactive anchoring of the microparticles with the textile fibers is not necessary here.

Furthermore, the microparticles can be physically bound to the fibers of the textiles by means of a polymer. The polymer coating is usually a coating of polymers such as polyacrylates, polyvinyl acetate, polyesters, polyvinyl alcohols, polyurethanes, and mixtures thereof. The polymer is preferably used as a dispersion during application.

According to a further embodiment of the invention, a chemical anchoring of the microparticles according to the invention with the surface of the textiles is carried out. Since the surface of the microparticles has reactive groups, such as amino, hydroxyl and methylol groups (CH ₂ -OH), it is possible to use these with the aid of a suitable reactive binder, for example an isocyanate, in particular a protected or blocked one Isocyanates permanently anchored to the textile surface. By appropriate choice of monomer ratio in the production of the aminoplast resin, for example, the ratio of formaldehyde to melamine in the melamine-formaldehyde resins, it is possible to influence the type and number of reactive groups. For example, an excess of melamine causes an increased presence of amino groups.

Due to the chemical anchoring of the microparticles according to the invention, a good washing permanence of the textiles can be achieved.

The invention further relates to the use of the active ingredient 2-n-octyl-4-isothiazolin-3-one and optionally one or more other biocides containing microparticles based on an aminoplast resin for the protection of textiles against microorganism infestation.

According to a further embodiment of the invention, in the context of the invention, the term textile may also be a filter or fleece, preferably an air filter equipped with the 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. In particular, such equipped filters are suitable for use in ventilation systems or air conditioning systems 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 it losing its antimicrobial activity. It has been found to be particularly effective in this embodiment of the invention when the biocidal active ingredient is a mixture of OIT and BIT. The advantage of this biocidal active ingredient is on the one hand that OIT effectively prevents the infestation of the filter by algae and fungi and BIT the attack by bacteria.

In the microparticles according to the invention, the biocidal active ingredient is preferably enclosed in finely dispersed, liquid or solid phase, more preferably in the preparation of the microparticles the biocidal active substance is introduced in an aqueous medium.

Numerous methods are known for the preparation of these microparticles, see for example CA. Finch, R. Bodmeier, Microencapsulation, Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition 2001, VoI 21 Electronic Release, page 733 to 749. Depending on the desired wall thickness, the appropriate method can be selected in each case. The said pages of the reference are incorporated by reference into the present application.

The preparation of the preferably used melamine-formaldehyde microparticles comprises the use of melamine-formaldehyde precondensates which are water-soluble and from which melamine-formaldehyde-resin microparticles are prepared from the aqueous phase. The manufacturing process has several advantages, such as, in addition to inexpensive compared to other possible polymerization process starting materials and the environmentally friendly use of water as a preferred solvent. If the enclosed or encapsulated biocidal active ingredients are not readily water-soluble, as an alternative, the partial substitution of the solvent used in the process, water, with water-miscible organic solvents can be carried out.

In the preparation of the 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. To set the acidic environment serve inorganic and / or organic acids such as hydrochloric acid, phosphoric acid and citric acid.

The microparticles can be prepared in the apparatuses customary for condensation polymerizations. These include stirred tanks, stirred tank cascades, autoclaves, tubular reactors and kneaders. The reaction is carried out, for example, in stirred tanks equipped with an armature, blade, impeller, dissolver or multistage pulse counterstirrer. Particularly suitable are apparatuses that allow the direct isolation of the product following the polymerization, such as. B. paddle dryer. The obtained suspensions can be dried directly in evaporators, such as belt dryers, paddle dryers, spray dryers or fluid bed dryers. But you can also cut off by filtration or centrifugation, the majority of the water.

As starting material for the preferably used melamine-formaldehyde resins, on the one hand, etherified melamine-formaldehyde condensates obtainable, preferably with small amounts of vegetable free formaldehyde such as Quecodur DM 70 (available from THOR GmbH). Furthermore, the melamine-formaldehyde resin may also be prepared by polycondensation of melamine and formaldehyde in the presence of the biocidic agent by techniques known to those skilled in the art, such as by reaction between melamine and formaldehyde at a molar ratio of 1 to 6 parts of formaldehyde to one part of melamine ,

The reaction is preferably carried out in aqueous solution. Depending on the wall thickness and the desired amount of biocidal active substance in the finished microparticles, the concentration of the prepolymer in the aqueous solution can be varied over a wide range. Most preferably, the prepolymer is supplied or formed such that the prepolymer concentration is from about 1 to about 70 weight percent, preferably from about 5 to about 50 weight percent.

In addition to the abovementioned aminoplast resins, the microparticles according to the invention may contain further substances which are generally known and customary depending on the intended use. These include on the one hand corresponding binders and film formers, such as polyacrylates, polystyrene or silicone resins, on the other hand, known auxiliaries, such as pigments; Fillers such as calcium carbonate, talc, kaolins, silicates, pyrrugic silica and / or zeolites; Solvents; Thickeners such as polysaccharides and / or cellulose ethers; defoamers; plasticizers; Dispersants such as phosphates and / or acrylates; Emulsifiers such as fatty alcohol ethoxylates, EO / PO block polymers and / or sulfonates; Stabilizers such as UV stabilizers, dyes or discoloration-preventing substances.

The polycondensation of the aminoplast 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.

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 controlled release of the biocidic agent. The following examples are illustrative of both the methods and the product of the present invention, but are not intended to be in any way limiting or defining them.

The preparation examples illustrate the preparation of microparticles in which the biocidal active ingredient is included.

Preparation example

Using the following materials, microparticles of melamine-formaldehyde were prepared in which the biocidal active ingredient 2-n-octyl-4-isothiazolin-3-one was included.

Substances used Quantities [gl

Water 430.00

polyacrylate

(Coatex BR 3, Dimed Company) 1.50

Gum arabic 0,60

Silicone antifoam

(Aspumit AP, Thor GmbH) 0.30

OIT 60.00

Hydrochloric acid 1% 46,10

Melamine-formaldehyde resin

(Quecodur DM 70, Thor GmbH) 85.00

623.50

To prepare the microparticles, the water was initially charged with the melamine resin. In it were stirred in polyacrylate, gum arabic, silicone defoamer and the 2-n-octyl-4-isothiazolin-3-one. The resulting mixture was heated to 90 ⁰ C and added dropwise over 1 h hydrochloric acid to a pH of 4. Subsequently, the mixture was stirred for 2 h at the same temperature.

The contained mixture contained the desired microparticles in which the biocidal active ingredient is included. Example 1 and Comparative Example 1

The following examples and comparative examples demonstrate the effect of the trapped OIT. For this purpose, textiles which are equipped with the microparticles according to the invention are compared with textiles which are equipped with dispersed OIT.

In order to investigate the effect of the fabric according to the invention, various textile samples having a size of 40 × 40 cm were impregnated in each case 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 OIT , As finishing aid, 30 g / l of Quecophob GAR (fluorocarbon resin, Fa THOR GmbH) were added. The swatches were subsequently squeezed off on a Foulardwalze, dried one minute at 120 ⁰ C and condenses at 150 ⁰ C for one minute. Before drying, the overlay was determined and used to calculate the theoretical drug concentration.

Samples were subsequently taken from the impregnated substances and analyzed for their active ingredient concentration by means of HPLC. The results obtained are shown in Table 1.

Table 1: Results of the example and the comparative example for loss of active ingredient in the drying of textiles.

Example 2 and Comparative Example 2

Furthermore, some of the textile samples patterned according to the example were watered for a period of 24 hours and then tested for their active ingredient content. Table 2 lists the drug concentrations before and after the wash.

Table 2: Results of the Example and the Comparative Example for Loss of Active Substance in the Wetting of Textiles.

The values listed in Tables 1 and 2 clearly show the advantage of the inclusion according to the invention of the active ingredient in the microparticles. In the case of the textile which is provided with enclosed or encapsulated OIT, considerably more active substance can be detected after the thermal aftertreatment and washing than in the textile which has been conventionally finished. On the basis of the above test results, it can be seen that the inclusion of the biocidal active substance reduces the loss of biocidal active substance and the entry into the exhaust air / environment and, moreover, significantly more active substance remains on the textiles.

Example 3 and Comparative Example 3

The polyester samples prepared according to Example 1 and Comparative Example were examined for their fungi-inhibiting properties according to DIN 53931. The results are shown in Table 3.

Table 3: Results of the Example and Comparative Example of the Fungal Inhibiting Effect of the Encapsulated OIT. The evaluation scheme for DIN 53931 (fungi-inhibiting test) is shown below.

Flächenbewuchs 00 The whole plate free of fouling

0 Yield formation (non-contaminated zone in the vicinity of the sample) mold resistant (0) The fungus is equipped to grow up to the sample

1 sample only overgrown

2 Sample overgrown (less than 25%) 3 Sample surface with single colonies overgrown not mold resistant

(25% to 75%)

4 sample surface overgrown (75% and more, but not the whole surface)

5 sample surface completely covered (100%)

The trapped OIT textile samples show excellent antifungal properties. These antifungal properties are still present even after the washing of the textiles.

Claims

claims

1. textile provided with a biocidal active ingredient, characterized in that it contains as biocidic active ingredient 2-n-octyl-4-isothiazolin-3-one and optionally one or more other biocides, wherein the biocidal active ingredient in microparticles from an aminoplast Resin is included.

2. A textile according to claim 1, characterized in that the microparticles 5 to 99.99 wt .-% of the aminoplast resin and 0.01 to 95 wt .-% of the biocidal active ingredient, based on the total weight of the aminoplast resin and biocidal agent.

3. A textile according to any one of claims 1 or 2, characterized in that the amount of biocidal agent, based on the total weight of the textile, 0.0001

Wt .-% to 0.5 wt .-% is.

4. A textile according to any one of claims 1 to 3, characterized in that the aminoplast resin is selected from the group of melamine, urea, cyanogen and dicyandiamide-formaldehyde resins or a mixture of two or more of these resins.

5. A textile according to any one of claims 1 to 4, characterized in that the aminoplast resin is a melamine-formaldehyde resin.

6. Textile according to one of claims 1 to 3, characterized in that the aminoplast resin is a melamine-urea-formaldehyde resin or a melamine-phenol-formaldehyde resin.

7. A textile according to any one of claims 1 to 3, characterized in that the aminoplast resin is formed from a compound containing NH groups and acetaldehyde or glyoxal.

8. A textile according to any one of claims 1 to 7, characterized in that the microparticles have an average diameter of about 0.5 to about 100 microns.

9. Textile according to one of claims 1 to 7, characterized in that the microparticles have an average diameter of about 1 to 10 microns.

10. Use of the biocidal active ingredient 2-n-octyl-4-isothiazolin-3-one and optionally one or more other biocides containing microparticles based on an aminoplast resin for the protection of textiles against microorganism infestation.