WO1999008527A1 - Compositions for treating textile and plastic antimicrobial finish, and use of same - Google Patents

Abstract

The invention concerns compositions for treating textile and plastic antimicrobial finish, preferably PVC and woven and nonwoven textiles. Said compositions are in the form of solutions containing 0.1 to 8 % of 2, 3, 5, 6-tetrachloro-4-(methylsulphonyl)-pyridine. Ideally, said active principle is combined with other antimicrobial active principles. In this context, the use of 2, 4, 4'-trichloro-2'-hydroxydiphenylether has yielded excellent results. As a result thereof, the activity spectrum is broadened and the concentration used in the solution is reduced. Besides the antimicrobial finish, said formulation can also yield an acaricidal effect if pyrethroids, preferably 3-phenyoxybenzyyl-(1 R;S)-cis-trans-2.2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropancarboxylate are added thereto. Said formulations are characterised by simple and hygienic dosage and treatment, with low concentration in antimicrobial active principles.

Description

 Compositions for the antimicrobial finishing of textiles and plastics and their use

The invention relates to antimicrobial liquid compositions or formulations with in part additional mite protection for woven and non-woven textiles and plastics and contains 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine in dissolved form as an antimicrobial active ingredient either alone or in combination with other antimicrobial agents such as, for example, 2,4,4 ^' trichloro-2'-hydroxydiphenyl ether and / or acaricidal agents such as 3-phenoxybenzyl- (1 R, S) -cis-trans-2,2-dimethyl -3- (2,2-dichlorovinyl) cyclopropane carboxylate. The formulation also contains other components such as organic solvents. In addition, an emulsifier system consisting of one or more surfactants, such as preferably a poly (ethyleneoxy) nonyiphenyl ether phosphate and a plasticizer, such as preferably a dipropylene glycol dibenzoate, can be included in the formulation.

2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine (CAS number: 13108- 52-6) is manufactured by Zeneca and sold under the names Densil S 25, Densil S 100 and Densil DOP. For the application area of paints as a dry product under the name Densil S 100 and as a 25% suspension in water as Densil S 25. For the application area polyvinyl chloride (PVC) a dispersion with 50% 2,3,5,6-tetrachlor-4 - (methylsulfonyl) pyridine in dioctyl phthalate (DOP) is offered under the name Densil DOP.

The active ingredient 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine has excellent antimicrobial properties against many germs, in particular the product can be regarded as a very potent algicide and fungicide.

However, the following points are disadvantageous in the formulation described above, consisting of 50% 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine suspended in DOP:

- For a good antimicrobial protection of PVC, high concentrations of 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine are required. The range of application recommended by the manufacturer is 0.3 to 1.0% the commercial formulation Densil DOP based on the film weight. This is 0.15 to 0.5% of the active component 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine.

- The germ Pseudomonas aeruginosa ATCC 15442 shows, in the agar diffusion test according to SN 195 920, already in its original state on a PVC film equipped with 0.3% Densil DOP, produced according to DIN 53 775, medium growth. This means that over 10% of the film pattern is covered with the germ. With the addition of 0.5% Densil DOP to a PVC film manufactured according to DIN 53 775, weak growth with the germ can still be determined. This means that up to 10% of the film pattern is covered with the germ. The antimicrobial effect of this pattern is at the limit of effectiveness. Since the germ Pseudomonas aeruginosa attacks the plasticizers in PVC, it is particularly disadvantageous if this germ is not prevented from growing. - If a film, as described, is washed before the antimicrobial test or treated with ultraviolet light, the antimicrobial protection against the germ Pseudomonas aeruginosa ATCC 15442 breaks down into an even higher application concentration. Against the Aspergillus niger EMPA 18 germ (mold), a break-in of the antimicrobial

Effect observed in agar diffusion test.

- Suspensions in handling and conveying are worse than liquid products.

- Suspensions can separate during storage. - Suspensions are more difficult to incorporate homogeneously into a product than dissolved products.

2,4,4'-Thchlor-2'-hydroxydiphenyl ether (CAS number: 3380-34-5) has been brought onto the market by the company Ciba Specialty Chemicals under the name Irgasan, depending on the quality, with various names below . The product has excellent antimicrobial values against a large number of bacteria and in some cases quite good values against fungi. The product has found an extremely wide range of technical applications in a wide range of conservation areas. For permanent antimicrobial treatment of plastics. in particular PVC, but also polyurethane, both as foam and in non-foamed form and epoxy resins for special applications, such as in the area of food processing companies, products containing arsenic or heavy metal components are often used. Some of these products have excellent antimicrobial properties. However, these products often cause problems. This over the entire product life cycle due to its other properties such as its toxicological data, the irritant effect, the catalytic properties that are sometimes present, the sometimes high vapor pressures and the associated volatility during processing, up to the final disposal due to the insufficient biodegradability or. the emissions from any combustion.

When using antimicrobial equipment in the textile sector, many parameters have to be observed. In addition to the toxicological properties, the antimicrobial properties, antimicrobially active substances for the application itself must be incorporated into a formulation in such a way that they are sprayed, sprayed, or pulled out using at least one of the customary methods used in finishing textiles, such as padding lazy, on the textile can be applied. The application is usually carried out in an aqueous medium. For an antimicrobial formulation, this practically means that it can be applied from water. Such a formulation must be either soluble or suspendable in water. If it can be suspended, the suspension must be sufficiently stable that it can be applied to textiles in the usual way

Process can be applied. This means that during the entire duration of the technical application, the ingredients of the formulation must not fall out of the bath irreversibly to the extent that a homogeneous application of the antimicrobial formulation is impossible. Such antimicrobial finishing must also not significantly or at least not adversely affect the authenticity of a finished textile. These include light fastness, rub fastness and color fastness. Antimicrobial equipment is also expected to have a certain amount of washing resistance. That means after a few washing processes, Effect against test germs can still be demonstrated. With polyester in particular, this requirement comes up against very narrow limits for practically all products on the market. The possible wash-resistant finishes either work with binder systems, which drastically limit the options available to textile finishers, or they are compounds that react chemically with the textile surface and thereby enable adhesion to the fibers. These products are very often organosilicon compounds. Antimicrobial treatments applied purely physically and without binder systems when finishing polyester fibers are against

Most of the time mold is practically ineffective even in its original state. After the first washing of the antimicrobial finished textile, in the agar diffusion test against Aspergillus niger, strain EMPA 18, normally no further antimycotic effect can be demonstrated.

The object of the invention is compositions or

Provide formulations to permanently soften PVC and other plastics such as polyurethane and epoxy resins, as well as woven and non-woven textiles, without using toxic or environmentally relevant substances that contain arsenic, tin or other heavy metals such as mercury or cadmium. Another object of the present invention is that compositions are used which contain active ingredients in concentrations as low as possible, which achieve a sufficient to excellent protective action against microbes, but which exert the least possible toxicity to mammals. The active ingredients should be easy to dose and optimally distributed during use without losing their long-lasting effect.

It has surprisingly been found that these requirements can be met by compositions which contain 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine in dissolved form.

This task was solved by providing

Compositions for the antimicrobial finishing of woven and non-woven textiles or plastics as defined in the claim 1. The terms “composition” and “formulation” are used synonymously in the present document and mean a preparation of active substance (s) and auxiliary substance (s) with the aim of applying, distributing and unfolding the active substance in a manner that is optimally matched to the particular application enable.

The compositions according to the present invention contain between 0.1 and 8% 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine in dissolved form, in an organic medium consisting of a solvent system which itself consists of a single or several solvents is built up, with or without an emulsifier system, either alone or in combination with other antimicrobial and / or acaricidal or insecticidal active ingredients.

Formulations have been found to be very effective which contain between 0.1 and 7% dissolved 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 0.1 to 10% 2,4,4'-T chlorine Contain -2'-hydroxydiphenyl ether.

Formulations containing between 3 and 6% 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine and 2 to 8% 2,4,4'-trichloro-2'-hydroxydiphenyl ether were optimal.

Formulations which, in addition to the dissolved 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, contain other antimicrobial active ingredients, such as 3-oxo-1,2-benzisothiazoline, 4-hydroxybenzoic acid methyl ester and 4-hydroxybenzoic acid ethyl ester, have good antimicrobial activity , 4-hydroxybenzoic acid propyl ester, 4-hydroxybenzoic acid butyl ester, 4-hydroxybenzoic acid isobutyl ester, 4-hydroxybenzoic acid benzyl ester, 2-hydroxytoluene, 3-hydroxytoluene, 4-hydroxytoluene, 4-chloro-3-methylphenol, 3-methyl-4- (1-methylethyl) phenol , 4-chloro-5-methyl-2- (1-methylethyl) phenol, bis (3,5,6-thchloro-2-hydroxyphenyl) methane, 2,2 ^* -dihydroxy-5,5'-dichlorodiphenyl monosulfide , N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, benzyloxymethanol, (benzyloxymethoxy) methanol, 5-amino-1, 3-bis (2-ethylhexyl) -5-methylhexahydropyrimidine, 2 -n-octyl-3 (2H) isothiazolone, 4,5-dichloro-2-octyl-3 (2H) -isothiazolone, N- (trichloromethylthio) -4-cyclohexene 1, 2, dιcarboxιmιd, N- (dιchlorofluoromethylthιo) -phenyl-1, 2-dιcarboxιmιd, N-Λlkyl- N, N-dιmethyl-benzylammonιumchlorιd, dichlorobenzyl-dimethyl-alkyl-ammonium chloride, N-hexadecyl-N, N tπmethyl-ammonium bromide, di-n-decyl-dimethyl-ammonium chloride, 1-hexadecyl-pyπdinum chloride, polyhexamethylene-biguanide-hydrochloride, Bιs- (Dιmethylthιocarbamoyl) -dιsulfιd, N, Dιmethylamιno- N '-phenol-chloro , 3,4,4'-Tπchlorcarbanιlιd, zinc naphthenate or zinc octoate

If, in addition to the antimicrobial activity, the formulations are also intended to have activity against house dust mites, formulations which, in addition to the dissolved 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, alone or in combination with other microbial compounds pyrethroids, are suitable Insecticide and / or acanzide included

Formulations which, in addition to the dissolved 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyrin, alone or in combination with other microbial compounds 3-phenoxy-benzyl- (1R , S) -Cιs-trans-2 2-dimethyl-3- (2,2-dιchlorvιnyl) cyclopropanecarboxylate as an acanzide

Typical compositions according to the present invention are solutions which contain 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine alone or in combination with other microbial and / or insecticidal or acantidally active compounds in a phosphoric acid ester in which all three Protons have been replaced by an organic residue, contained in dissolved form

Formulations in which the 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyπdιn and the 2,4,4'-trιchlor-2'-hydroxydiphenyl ether are dissolved in an isopropylated taryl phosphate have proven to be ideal

The aforementioned formulations are used by metering them into plastics, preferably polyvinyl chloride or epoxy resins in concentrations of 0.2 to 5.0%, based on the final weight of the plastic, to the raw mass of the plastic and incorporating them mechanically Takes place, a typical application of a composition according to the _^ present invention based on polyurethane, by 0.2 to 5.0% of the formulation, based on the final weight of the plastic, incorporated, optionally added to the alcohol component before the condensation process and incorporated homogeneously or the melt of the finished plastic can be added

It has turned out to be ideal for solubility and for bath stability if the organic solvent system used contains N-methylpyrrolidone

Because of the minimal emission during application, the low

Toxicity, the high flash point and the ideal solution properties have proven to be ideal that the organic solvent system used additionally contains a polymerized dihydric alcohol, preferably a polyethylene glycol

It has proven ideal both for the bath and for the application of the formulation and on the finished textile that the emulsifier system contains an ethoxylated surfactant, such as preferably a poly (ethyleneoxy) nonylphenyl ether phosphate

It has proven ideal both for the bath and for the application of the formulation and on the finished textile that the emulsifier system contains a plasticizer, such as preferably a dipropylene glycol dibenzoate

It is important for the ideally antimicrobial formulation that it contains between 0.1 and 8% 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyrid, 0.1 to 10% 2,4,4 ^' -Tπchlor -2'-hydroxydιphenyl ether and 1 to 30% N-methylpyrrodon, 1-40% polyethylene glycol, preferably with an average molecular weight in the range from 400.5 to 40% poly (ethyleneoxy) nonylphenyl ether phosphate and 5 contains up to 40% dipropylene glycol dibenzoate It is important for the particularly ideal antimicrobial and good _^ administrable formulation to between 2.0 and 5.0% 2,3,5,6-tetrachloro - (methylsulfonyl) -pyrιdιn, 2.0 to 8.0% 2,4,4'-Trιchlor-2'-hydroxydiphenyl ether and 10 to 20% N-methylpyrrolidone, 20-40% polyethylene glycol, preferably with an average molecular mass in the range of 400, 10 to 30% poly (ethyleneoxy) nonylphenyl ether contains phosphate and 20 to 40% dipropylene glycol dibenzoate

If, in addition to the antimicrobial activity, an activity against the Dermatophagoides pteronyssinus, the house dust mite, is to be achieved at the same time, a formulation is particularly preferred which contains between 2.0 and 5.0% 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyrιdιn, 2.0 to 8.0% 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 0.5 to 5% 3-phenoxybenzyl- (1 R, S) -cιs-trans-2,2- dimethyl-3- (2,2-dichlorvιnyl) cyclopropane carboxylate and 10 to 20% N-methylpyrrolidone, 20-40% polyethylene glycol, preferably with an average molecular weight in the range of 400, 10 to 30% poly (ethyleneoxy) - contains nonylphenyl ether phosphate and 20 to 40% dipropylene glycol dibenzoate

In successfully applicable processes for the antimicrobial finishing of woven and non-woven textiles made of natural, synthetic and mixed fibers, the fibers are, based on the weight of the goods, 0.5 to 4%, preferably 0.5 to 3%, for example 1 Treated 5% of a formulation containing between 2.0 and 50% 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyπdιn, 2.0 to 8.0% 2,4,4'-trιchlor- 2'-hydroxydιphenyl ether, 0.5 to 5% 3-phenoxybenzyl- (1 R, S) -cιs-trans-2 2-dimethyl-3- (2,2-dιchlorvιnyl) - cyclopropanecarboxylate and 10 to 20% N-methylpyrrolidone , 20-40%

Contains polyethylene glycol, preferably with an average molecular mass in the range of 400, 10 to 30% poly (ethyleneoxy) nonylphenyl ether phosphate and 20 to 40% dipropylene glycol dibenzoate. The treatment is carried out by suspending 1 to 20% of the composition in water or together with other textile chemicals by padding, taking off, also in the dye bath or by spraying, or in the same concentration range, based on the dry weight of the finished textile, by working into a doctor blade mass and application to the textile by doctoring

The advantages of the formulations according to the invention compared to the formulations described above are - due to the dissolved form, they are very easy to handle during processing. In particular, the formulations are easy to demand and to dose. They can easily be homogeneously mixed into the plastic mass, e.g. PVC plastisol or corresponding individual components of epoxy resins or polyurethane , incorporated - Sufficient to excellent protection against all germs that are in the

Soft PVC area play an important role in the degradation of the plasticizer

- Compared to the microbially highly effective heavy metal compounds, there is, for example, a significant improvement in the hygienic conditions when incorporating them

Formulations in plastics This is because under incorporation conditions the constituents of the formulation according to the invention are practically not volatile

- Very low toxicity to mammals. This is due to the favorable toxicological properties of the active substances themselves and also thanks to the low required concentrations of these substances for good microbial protection

- Good cost / performance ratio of the antimicrobial finishing of plastics, since a broad spectrum of germs can be combated with optimal use concentrations of biologically active material

- Very low application concentrations of antimicrobial substances to achieve an optimal broad antimicrobial spectrum of activity - Optimal antimicrobial values in the agar diffusion test for finished textiles made of cotton, polyester, wool and polyamide - known use of good and low toxicological grade materials in such _^, optimized for the task concentrations that over Warmblutern, but particularly in humans, is expected to not affect - the use of agents that the heat setting on the textiles chemically unchanged and thus survive in known, defined structures

- Achievement of a sufficient washing permanence of the active ingredients on textiles even without the use of binder systems in the application, especially on polyester

- Articles equipped with the formulation according to the invention can be disposed of without adversely affecting nature, which is attributable to the presence of the formulation in the article of daily use. The examples below explain the invention in more detail, without thereby restricting the scope of protection defined by the appended claims

example 1

Preparation of a typical formulation from 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine and 2,4,4'-trichloro-2'-hydroxydiphenyl ether

90 kg of the isopropylidated tπaryl phosphate (for example a product from the Reofos product range) are introduced and warmed up to 40 to 60 ° C. 5 kg of 2,3,5,6-tetrachloro-4- (methylsulfonyl) are added in succession under stirring. -pyrιdιn and 5 kilograms of 2,4,4'-trιchlor-2'- hydroxydiphenyl ether to The mixture is stirred until the active ingredients are dissolved. If necessary, the solution is clearly filtered and then filled - The contents of the solution can be stored for a long time partially crystallize at room temperature or at lower temperatures. Warming up, ideally with stirring, allows the solution to be completely homogenized again The "minimum inhibitory concentration" (MIC) of this formulation was measured. The values were against Staphylococcus aureus, strain ATCC 6538, with 9.75 ppm, against Aspergillus niger, strain EMPA 18, 313 ppm and against Trichophyton mentagrophytes, strain EMPA 334, 39 ppm

Example 2

Preparation of a typical formulation from 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyrid and 2,4,4'-trichloro-2'-hydroxydiphenyl ether with 3-phenoxybenzyl- (1 R, S) -cιs- trans-2 2-dimethyl-3- (2,2-dichlorovinyl) - cyclopropanecarboxylate 87 kg of the isopropylated tnaryl phosphate (e.g. Reofos

65) are introduced and warmed to 40 to 60 ° C. Under stirring, 5 kg of 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyrid are added in succession, 5 kg of 2,4,4'-trichloro-2 ' -hydroxyphenyl ether and 3 kg of 3-phenoxybenzyl- (1 R, S) -cιs-trans-2 2-dimethyl-3- (2,2-dιchlorvιnyl) -cyclopropane-carboxylate to The mixture is stirred until the active ingredients If necessary, the solution is clearly filtered and then filled - These ingredients of the solution can partially crystallize after long storage at room temperature or at lower temperatures. Discoloration is possible. Warming up, ideally with stirring, allows the solution to be completely homogenized again

Example 3

Incorporation of a typical formulation according to the invention into an epoxy resin

33 grams of epoxy resin, 0.57 grams (1.5%) of the antimicrobial formulation described above and 5 grams of hardener are combined, mixed well and poured into a dish. The resin is left to harden for 48 hours. Diffusion test determines the antimicrobial activity directly with the untreated resin and after a soak for 250 hours at 20 ° C and a water exchange of 15 liters per hour. The antibacterial test against Staphylococcus aureus, strain ATCC 6538, was carried out based on the standard SN 195 920. Both in the original state and after the watering, the samples showed inhibitory zones of at least two millimeters. These are values that are different from any of the other formulations that have been tested and the other active ingredients or combinations of active ingredients than those described in accordance with the invention have only been approximately achieved. With the same application concentration, the antifungal test against Aspergillus niger, strain EMPA 18, showed inhibition zones of a few millimeters both in the original state and after the watering. This effect was by far the best anti-mycotic Effect of all formulations tested

Example 4

Incorporation of a typical formulation according to the invention into PVC plastisol

The PVC plastisol was produced based on the ISO standard 195-X10 1993 (E), i.e. 65 grams of PVC powder (Evipol MP 7764), 5 grams of titanium dioxide, 2 grams of stabilizer (Irgastab BZ 529) and 35 Grams of dioctyl phthalate are added and mixed in a dissolver for between 45 minutes and one hour. 1.5% of the formulation according to the invention and described above are added to this mixture. The mixture is homogenized by stirring, poured onto a release paper to a layer thickness of 1 millimeter and coated for Heated at 170 ° C for 5 minutes. The antimicrobial activity of the film thus produced is tested as described above. After a soak of 720 hours at 20 ° C and a water throughput of 15 liters per hour and after a UV exposure test, the Xenon test 450, after 100, 200 and 400 hours the antimicrobial effect tested. In addition to the germs described above, the antibacterial effect against d en Germ Pseudomonas aeruginosa, strain ATCC 15442 and the antifungal activity against the Streptoverticil germ by waksmann, strain DSM 40464, measured The agar diffusion test for determining the antifungal activity against Aspergillus niger, strain EMPA 18, shows a weak growth of less after watering as 10% of the pattern Against all other germs, the patterns are both after the UV exposure test and after the watering adequate to excellent protection. - After 200 hours of stress in the Xenon Test 450, the Yelowness Index (Yl) increases slightly and the degree of whiteness (CIE) decreases slightly. However, both values change significantly in the test period below the tolerated five units.

Example 5

Example of the preparation of a typical formulation for antimicrobial protection:

40 kg of 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine and 40 kg of 2, 4,4'-thchlor-2'-hydroxydiphenyl ether are stirred into 160 kg of N-methylpyrrolidone at room temperature and dissolved. To this

Mixture is added with stirring 310 kg of 400 polyethylene glycol, 150 kg of poly (ethyleneoxy) nonylphenyl ether phosphate and 300 kg of dipropylene glycol dibenzoate. It is stirred until the solution is homogeneous.

Example e

Example for the production of a typical formulation for antimicrobial protection with simultaneous protection against the house dust mite Dermatophagoides pteronyssinus:

40 kg 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 40 kg 2,4,4'-trichloro-2'-hydroxydiphenyl ether and 20 kg 3-phenoxybenzyl- (1 R, S) -cis -trans-2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate are stirred into 160 kg of N-methylpyrrolidone at room temperature and dissolved. 290 kg of polyethylene glycol 400, 150 kg of poly (ethyleneoxy) nonylphenyl ether phosphate and 300 kg are added to this mixture with stirring

Dipropylene glycol dibenzoate too. It is stirred until the solution is homogeneous. Example 7

Application of the formulation to cotton fabric using the padding process

30 grams of the formulation from Example a) are made up to 1 liter with water with stirring, giving a milky, very fine suspension. This suspension has a pH of 3.1 and is weighted onto cotton gabardme by means of the padding method per square meter of 198 grams, applied in a liquor to tissue ratio of 0.7 to 1

The cloth is dried in the tenter for two minutes at 120 ° C

Example 8

Application of the formulation to polyester using the padding process

The actual application is carried out as described under c). In addition, a wetting agent is advantageously added to the bath during drying

If the padding process is applied to polyester, drying and fixing take place at a much higher temperature. Up to a temperature of 170 ° C, the clamping frame can be fixed for 30 seconds without the antimicrobial values being adversely affected

Example 9

Determination of the washing permanence of the formulation

Textiles made from natural, synthetic or mixed fibers are finished using one of the usual methods, for example by padding with, for example, 1.5% of a formulation as described in Examples a) and b). The finished textile is dried and thermally fixed textile finished in this way, with a liquor ratio of 1 30, for 25 minutes at 40 ° C in tap water, which is mixed with two grams per liter of ECE color fastness test detergent has been washed, rinsed cold for six minutes, spun and dried in the stenter at _^ 80 ° C. The pattern dried in this way is checked for the antimicrobial effect in the agar diffusion test.

Polyester fabric (Trevira, 248 grams per square meter) shows an inhibition zone of 2 millimeters after washing five times in an agar diffusion test against Staphylococcus aureus, strain ATCC 6538.

Against Aspergillus niger, strain EMPA 18, the sample is covered with less than 10% after five washing cycles. This proportion of vegetation is the limit of effectiveness. The same result is achieved against Trichophyton mentagrophytes, strain EMPA 334.

On cotton, the limit of activity against Staphylococcus aureus, strain ATCC 6538, is reached after 20 washing cycles. Against the two fungi, full effect is still achieved after ten wash cycles. The results look practically identical when washing at 60 ° C instead of 40 ° C.

The antimicrobial effect on wool and polyamide, when applied using the padding process, is slightly weaker than the effect on polyester.

Claims

Claims: 1 compositions for the antimicrobial finishing of woven and non-woven textiles or plastics, characterized in that they contain between 0.1 and 8% 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyπdιn in dissolved form, in one organic medium, which consists of at least one solvent 2 Composition according to claim 1, characterized in that the organic medium comprises a solvent composition which is composed of a single or more solvents, and optionally contains at least one emulsifier 3 Composition according to claim 1 or 2, characterized in that it contains other antimicrobial and / or akaπzide or insecticidal active ingredients 4 Composition according to claim 2 or 3 for the antimicrobial finishing of woven and non-woven textiles, characterized in that the solvent composition contains N-methylpyrrolidone 5 Composition according to one of claims 2 to 4 for the antimicrobial finishing of woven and non-woven textiles, characterized in that the solvent composition additionally contains a polymerized dihydric alcohol, preferably a polyethylene glycol 6 Composition according to one of claims 2 to 5 for the antimicrobial finishing of woven and non-woven textiles, characterized in that it contains as an emulsifier an ethoxylated surfactant, preferably a poly (ethyleneoxy) nonyl-phenyl ether phosphate 7 Composition according to one of claims 1 to 6 for the antimicrobial finishing of woven and non-woven textiles, thereby characterized in that the emulsifier system contains a plasticizer, such as _^ preferably a dipropylene glycol dibenzoate. 8. Compositions according to one of claims 1 to 7 for the antimicrobial finishing of woven and non-woven textiles, characterized in that they contain between 0.1 and 8% 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 0.1 to 10% 2,4,4'-thchlor-2'-hydroxydiphenyl ether and 1 to 30% N-methylpyrrolidone, 1-40% polyethylene glycol, preferably with an average molecular mass in the range of 400, 5 to 40% poly (ethyleneoxy) nonylphenyl ether phosphate and 5 to 40% dipropylene glycol dibenzoate. 9. Compositions according to one of claims 1 to 8 for the antimicrobial finishing of woven and non-woven textiles, characterized in that they contain between 2.0 and 5.0% 2,3,5,6-tetrachloro-4- (methylsulfonyl) -py din, 2.0 to 8.0% 2,4,4'-thchlor-2'-hydroxydiphenyl ether and 10 to 20% N-methylpyrrolidone, 20-40% polyethylene glycol, preferably with an average molecular mass in the range of 400, Contain 10 to 30% poly (ethyleneoxy) nonylphenyl ether phosphate and 20 to 40% dipropylene glycol dibenzoate. Compositions according to one of Claims 1 to 9 for the antimicrobial finishing of woven and non-woven textiles, characterized in that they contain between 2.0 and 5.0% 2,3,5,6-tetrachloro-4- (methylsulfonyl) -py din, 2.0 to 8.0% 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 0.5 to 5% 3-phenoxybenzyl- (1 R, S) -cis-trans-2,2 -dimethyl-3- (2,2-dichlorovinyl) cyclopropanecarboxylate and 10 to 20% N-methylpyrrolidone, 20-40% polyethylene glycol, preferably with an average molecular mass in the range from 400, 10 to 30% poly (ethyleneoxy) nonylphenyl ether -phosphate and 20 to 40% dipropylene glycol dibenzoate. 11. Composition according to one of claims 1 to 3 for the antimicrobial finishing of plastics, characterized in that it contains between 0.1 and 8%, preferably between 3 and 6% dissolved 2,3,5,6- Tetrachloro-4- (methylsulfonyl) pyridine, 0.1 to 10%, preferably between 2 and 8% 2,4,4'-trichloro-2'-hydroxydiphenyl ether contains. ^ .Composition according to one of claims 1 to 3 and 12 to 13, for the antimicrobial finishing of plastics, characterized in that, in addition to the dissolved 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, they have further antimicrobial active ingredients contains, such as 3-oxo-1, 2-benzisothiazoline, 4-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid ethyl ester, 4-hydroxybenzoic acid propyl ester, 4-hydroxybenzoic acid butyl ester, 4-hydroxybenzoic acid isobutyl ester, 4-hydroxybenzoic acid benzylol, 4-hydroxytoluene, 2-hydroxytoluene -Chlor-3-methylphenol, 3-methyl-4- (1-methylethyl) phenol, 4-chloro-5-methyl-2- (1-methylethyl) phenol, bis- (3,5,6-trichloro- 2-hydroxyphenyl) methane, 2,2'-dihydroxy-5,5'-dichlorodiphenyl monosulfide, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, benzyloxymethanol, (benzyloxymethoxy) methanol, 5 -Amino-1,3-bis- (2-ethylhexyl) -5-methylhexahydropyrimidine, 2-n-octyl-3 (2H) isothiazolone, 4,5-dichloro-2-octyl-3 (2H) -isothiazolone, N- (Trichloromethy lthio) -4-cyclohexene-1, 2, dicarboximide, N- (dichlorofluoromethylthio) phenyl-1, 2-dicarboximide, N-alkyl-N, N-dimethyl-benzylammonium chloride, dichlorobenzyl-dimethyl-alkyl-ammonium chloride, N-hexadecyl -N, N, Nt methyl-ammonium bromide, di-n-decyl-dimethyl-ammonium chloride, 1-hexadecyl-pyhdinum chloride, polyhexamethylene biguanide hydrochloride, bis (dimethylthiocarbamoyl) disulfide, N. Dimethylamino-N '(fluorodichloromethylthio) - N'-phenyl sulfamide, zinc naphthenate or zinc octoate. 13. Composition according to one of claims 1 to 3 and 12 to 14, for the antimicrobial finishing of plastics, characterized in that, in addition to the dissolved 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine alone or in Combination with other microbial compounds pyrethroids than Contains acaricide. H. Composition according to one of claims 1 to 3 and 12 to 15, for the antimicrobial finishing of plastics, characterized in that, in addition to the dissolved 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, alone or in Combination with other microbial compounds 3-phenoxybenzyl- (1 R; S) -cis-trans-2,2-dimethyl-3- (2,2-dichlorovinyl) - Cyclopropanecarboxylate pure or as a mixture of the ice and trans compound as an acaricide. ^ .Composition according to one of claims 1 to 3 and 12 to 16, for the antimicrobial finishing of plastics, characterized in that 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine alone or in combination with other microbial and / or insecticidal or acaricidal compounds are dissolved in a phosphoric acid ester in which all three protons have been replaced by an organic radical. 16. Compositions according to one of claims 1 to 3 and 12 to 17, for the antimicrobial finishing of plastics, characterized in that the 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyhdin and the 2,4, 4'-trichloro-2'-hydroxydiphenyl ether are dissolved in an isopropylated triaryl phosphate. 17. A method for the antimicrobial finishing of woven and non-woven textiles made of natural, synthetic and mixed fibers, characterized in that, based on the weight of the goods, they are treated with 0.5 to 4% of a composition according to one of claims 1 to 10, wherein it is suspended in a proportion of 1 to 20% in water, the textiles are loaded alone or together with other textile chemicals by padding, undressing, also in the dye bath or by spraying, respectively. in the same concentration range, based on the dry weight of the finished textile, by incorporation into a doctor blade mass and application to the textile by doctoring. 18. The method according to claim 17, characterized in that a composition according to claim 9 or 10 is used. 19. A method for the antimicrobial finishing of plastics, characterized in that a composition according to one of claims 1 to 3 and 12 to 18 in plastics in concentrations of 0.2 to 5.0%, based on the final weight of the plastic, metered in and is incorporated. 20. The method according to claim 19, characterized in that polyvinyl chloride or epoxy resins are given an antimicrobial treatment by metering the composition into the raw mass of the plastic and incorporating it mechanically. 21. The method according to claim 19, characterized in that polyurethane is equipped by 0.2 to 5.0% of the composition, based on the final weight of the plastic, optionally added to the alcohol component before the condensation process and incorporated homogeneously or the melt of the finished Plastic can be added.