AGENTS AND METHOD FOR THE PROTECTION OF COATINGS AND WOOD AND OTHER NON-LIVING ORGANIC SUBSTRATES FROM DETERIORATION BY MICRO-ORGANISMS

Abstract: The agents protect coatings and wood and other non-living organic materials, in particular textiles, from deterioration by microorganisms. The agents contain at least one compound of the formula wherein X is nitrogen or a CH group and R₁ is a radikal of the formula or -H-Ar wherein Ar, R and Z are as defined in claim one, or an acid addition salt thereof. The metod provided comprises applying at least one compound as just specified to, or incorporating it in, the material to be protected, in an antimicrobially effective amount.

Description: AGENTS AND METHOD FOR THE PROTECTION OF COATINGS AND OOD AND OTHER NON-LIVING ORGANIC SUBSTRATES FROM DETERIORATION BY MICRO-ORGANISMS The present invention is concerned with agents and a method for the protection of coatings and wood and other non-living organic substrates against deterioration by micro-organisms, as well as with the anti-microbially protected materials. It is known from the literature that many halogenated phenols are used to protect the above-mentioned materials and as germ-killing and conservating agents. See in this connection, for example, U.S. Patent Specifications 3,033,746, 3,062,710, 2,215,596 and 3,41T,1852 British Patent Specification 980,254, Japanese Patent Specifications 29015/63 and 53-26303, German Ausleteschrift 1,160,140, German Offenlegungsschrift 26 07 349, Chemical Reviews, 28, 269 (1941), Journal of the Scientific Research Institute, 48, 38-48 (1954), and Arch. Bioch., 40, 306-309 (1952). The halogenated phenols show either important lacks in their spectrum of activity, are inappropriate for certain substrates, show a too high level of toxicity or an unpleasant odor, are in part difficultly accessible, require a high dose or are for other reasons not or only within limits applicable in practice. For example, pentachlorophenol, which is widely used against mould and- rotting oF textiles and wood shows serious disadvantages, such as a lack of light-fastness and high toxicity. See e.g. in this connection E. Graf and M. Segmuller, Textilveredlung, 12, 496 (1977) and V. Kubelka, M. Popl and J. Mostecky, Chem. Prum., 23, 304 (1973). Further, 1-(4-chlorophenoxy)-1-imidaz-olyl-(1 )-3,3- dimethylbutan-2-one is known from German Offenlegungsschrift 2 600 800 as an antifungal agent for the protection of materials. This agent displays however an unsufficient protecting activity in particular against mouldsand rotting of textiles. Consequently,the objective of the subject invention was to provide coatings and wood and other agents with a higher protecting activity for/non-living organic substrates against deterioration by microorganisms while lacking the disadvantages of the above-cited compounds. I: has now been found that, in order to protect coatings and wood and other non-living organic substriates from deterioration by microorganisms there may successfully be used agents which comprise compounds of the formula EMI2.1 or acid adition salts thereof, wherein X is nitrogen or. a CH group and R1 is a radical of the formula EMI2.2 wherein Z is a group -CH2-CH2-, -CH2-CH2-CH2-, -CH(CH3)-CH(CH3)or -CH2-CH(alkyl)-, wherein said alkyl is a straight or branched C1-C10 alkyl radical; said Ar is a phenyl group which is optionally substituted with 1 to 3 halogens, C C1-C6 alkyl radicals, C1-C6 alkoxy radicals, cyano-, trifluoromethyl- or nitro-groups, a thieny.l-, halothienyl-, naphthalenyl or fluorenyl group; and, said R is C1 -C10 alkyl, cycloalkyl, cycloalkyl-lower alkyl, lower alkenyl, aryl-lower alkyl, arylorj-lower alkyl or a radical of the formula wherein said R0 is C1-C10 alkyl, lower alkenyl, lower alkynyl or aryllower alkyl1 wherein said aryl.radical is phenyl, naphthalenyl or substituted phenyl, wherein said substituted phenyl has 1 to 3 substi- tuents selected from the group consisting of halo, cyano, nitro, phenyl, lower alkyl and lower alkoxy, provided that when two or more substituents are present only one thereof may be cyano, nitro or phenyl. The agents according to the present invention are characterized by containing at least one compound of the formula # as defined above or an acid addition salt thereof. Interesting compounds of formula (I) in accordance with the present invention are those having the formula EMI3.1 wherein X has the above-identified meaning and R'1 is a radical of the formula EMI3.2 wherein Z' is a group -CH2-CH2-, CH2-CH2-CH2-, -CH(CH3)-CH2-, -CH(C2H5)-CH2-, -CH(C3H7)-CH2-, -CH(CH3)-CH(CH3)- or -CH(CH3)-CH(C2H5)-; Ar' is unsubstituted phenyl or phenyl substi tuted with 1 to 3 halogen atoms, preferably chloro atoms, C1-C6- alkyl radicals, C1-C6-alkoxy radicals, cyano or nitro groups; and R' is -C6-alkyl or C3-C4-alkenyloxy. Particularly important are compounds of the formula EMI3.3 wherein X has the above-defined meaning and R'1 is a radical of the formula EMI3.4 wherein R'' is C1-C4 alkyl, C3-C4-lower alkenyloxy, R3 is C1-C3-alkyl and n is 1 or 2. Preferred compounds are those of the formulae EMI4.1 EMI5.1 and The compounds of the formulae (I) to (VIII) which may be used in accordance with the present invention may be prepared according to U.S. Patent Specifications 3,575,999, 3,717,655, 3,636,002, 3,927,017, 4,156,008, 4,079,062, British Patent Specifications 2,026,486 and 2,027,701 and German Offenlegun-gsschrift 27 35 872. Their good activity against human-, animal- and plantpathogenic fungi and yeasts is indicated in the afore-cite-d Patent Specifications.. As "coatinn,n and wood and other nonliving organic substrates" within the ambit of the present invention are considered, for example, oil paints, dispersion paints, lacquers, whitewash, and colored coatings, lacquer films and white coatings obtained by the use of such age.nts; wood products such as timber, lumber, railway sleepers, telephone poles, fences, wood coverings, wicker-work, plywood; particle board, chipboard, joinery, bridges or similar wooden structures, wood products commonly used in housebuilding, or wood pulp used in paper manufacture; joint fillings of tile walls, tiles in polymer.ic materials, paperhangings, hides, leather, artificial leather, bath carpets, shower curtains, technical devices in plastic, glues, mortar as well as walls which are penetrated or fouled by organic materials, and in particular all textiles such as, for example carpets, canvas, awnings, -fishing-nets, ropes and packing materials. Materials which are treated xlith agents according to the invention are protected from mould, rotting, loss of their useful mechanical properties such as resistance to sliding, breaking strength, resistance to shock and shearing strength, or decay of their optical or other useful properties such as odor, surface texture, taste, staining, spot formation caused by the following microorganisms: Asper,gillus species, Penicillium species, Verticillium species, Alternaria species, Rhizopus species; Fusarium species, Mucor species, Paecelomyces species, Saccharomyces species, Trichoderma viride, Cheetomium ylsbosurn, Stachy- botrys atra, Myrothecium verrucaria and Oospora lactis. Special emphasis should be laid on their good activity against moulds such as Aspergillus niger, P-enicillium funiculosum, Trichoderma viride, Alternaria alternata, fungi such as Chaetomium globosum, Trichophyton mentagrophytes, Coriolus versicolor, Coniophora cerebella, Poria- monticola, Merulius (Serpula) lacrymans, and Lenzites trabea, and yeasts such as -Candida albicans and Saccharomyces species. The compounds of formula (I) may be used in accordance with the present invention on their own or in combination with appropriate carriers and/or other additives. Appropriate carriers and additives carl be solid or liquid and correspond to the substances usually used in formulation techniques such as natural or regcnerated inorganic substances solvents, dispersants, emulsifiers, wetting agents, adhesion agents, thickeners or binding agents. The compounds of formula (I) show good solubility in organic solvents and in driving gases for aerosols. The lack of color and odor of the compounds of formula (I) is in this connection of great practical value. The invention further comprises a method of protecting coatings and wood and other non-living organic substrates, characterized in that compounds of formula (I) are incorporated in the materials concerned, or applied to their surface. The following agents according to the invention can be used to apply compounds of formula (I): Solid forms : dusts and wettable powders. Liquid forms : concentrates of the active ingredients in organic solvents or water. In order to prepare solid forms (dusts, wettable powders) the active ingredients are mixed with the solid carriers. As carrier materials may be used, for example, kaolin, talc, bolus, loss, chalk, limestone, chalk gravel, attapulgite, dolomite, diatomaceous earth, precipitated silicic acid, alkaline earth metal silicates, sodium- and potassium aluminum silicates (felspar and mica), calcium- and magnesium sulfate, magnesium oxide, as well as their mixtures with each other. To these mixtures there can also be added stabilizers of the active ingredient and/or non-ionically, anionically and cationically active substances that may for example improve the surface adhesiveness of the active ingredients and/or secure a better wettability (wetting agents) and dispersibility (dispersants) The following substances may, for example, be used: olein/limestone mixture, cellulose derivatives (metylcellulose, carboxymethylcellulose), hydroxyethyleneglycolethers of mono- and dialkyiphenols with 5 to 1 5 ethylene oxide units per molecule and 8 to. 9 carbon atoms in the alkyl radical, ligninsulfonic acids and their alkali and alkaline earth metal salts, polyethyleneglycolethers (carbowax), fatty alcohol polyglycol- ethers with 5 to 20 ethylene oxide units per molecule and 8 to 18 carbon atoms in.the fatty alcohol part, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidone, polyvinylaicohols, urea/- formaldehyde condensation products and latex products. In water dispersible concentrates, i.e. wettable powders-, pastes and emulsifiable concentrates represent agents which can be diluted with water to any desired concentration. They consist of active ingredient, carriers, occasionally stabilizers of the active ingredient, surface active substances and anti-foam agents and occasionally solvents. The wettable powders and pastes are obtained by mixing and grinding the active ingredients with dispersants and powdery carriers in appro priate apparatus to desired homogeneity. The same carriers as indicated above in connection with the solid forms can be used. In many cases it is advantageous to use mixtures of several carriers. As dispersants there can be used, for example, anionic, cationic or nonionic products such as, for example: - sulfated aliphatic alcohols with 8 to 18 carbon atoms in their alkyl chain; e.g.4 suited lauryl alcohol, oleyl alcohol o coco nut oil; - sulfated unsaturated fatty acids or fatty acid lower alkylesters, which in the fatty radical contain 8 to 20 carbon atoms, e.g. oleic acid or ricinoleic acid and oils containing such fatty acids, e.g., ricinus oil; - alkylsulfonates the alkyl chain of which contains 8 to 20 carbon atoms, e.g., dodecylsulfonate; -alkylarylsulfonates with straight or branched alkyl chains having at least 6 carbon atoms, e.g., nonyl- or dodecylbenzenesulfonates or 3,7 -diisobutylnaphthalenesulfonates; - sulfonates of polycarboxylic acid esters, e.g., dioctylsulfo succinate; - alkalI metal, ammonium or amine salts of fatty acids with 10 to 20 carbon atoms which are indicated as soaps, e.g., colophonium salts; ; -esters of polyalcohols, in particular mono- or diglycerides of fatty -acids with 12 to 18 carbon atoms, e.g., monoglycerides of lauric, stearic or.oleic acid; - acidic esters formed by the reaction oi an organic dicarboxylic acid, such as, e.g., maleic, malonic, oxalic or succinic acid or preferably a polybasic inorganic acid such as phosphoric or in particular sulfuric acid,. with the addition product of I to 60 mol of ethylene oxide and/or propyleno oxide with fatty amine-s, fatty acids, fatty amides or fatty alcohols, each having 8 to 22 carbon atoms or with phenols which are further substituted with at least a C4-C10 alkyl group, -benzyl or phenyl group, or with three- to six-valent alkanols with 3 to 6 carbon atoms; - salts of primary, secondary and tertiary alkylamines, such as hydrochlorides, nitrates, sulfates, allcylsulfates, formates, acetates, lactates and citrates; - salts of the reaction products of C10-C20 fatty acids with di- or polyamines, e.g., the chloride, sulfate, alkylsulfate, acetate, lactate and citrate of stearic acid-N-(ss -aminoethyl)amide or of N-oleoyl-triethylenetetramine; ; -salts of the reaction products of C10-C20 alkyihalogenides with polyalkylenepolyamines, e.g., the chloride, sulfate, alkylsulfate, acetate, lactate and citrate of N-lauryldiethylenetetramine, N octyl- tetraethylenete tramine, N-oc tadecyL-triethvlenetetrafi,ine or N-octadeyl-trimethylenediamine; -salts of addition products of ethyleneoxide with alkylated or acylated di- or polyalkylenepolyamine, e.g., the chloride, sulfate, alkyl sulfate, acetate, lactate, and citrate of N-octadecyl-N,N',N' dioxyethyltrimethylenediamine, N-hexadecyl-N,N',N'-trioxy ethyl-ethylenediamine or N-ocatdecyl-N,N',N'',N''-tetraoxy ethyl-diethylenediamine; ; -quaternized alkylaryl- or aralkylalkylamines, the nitrogen atom of which bears at least one lipophilic radical of 10 to 20 carbon atoms, e.g., lauryl-dimethyl-benzylammonium chloride, cetyl dimethyl-benzylammonium chloride or hexadecyl-trimethyl ammonium bromide; -quaternized pyridines, the N-atom of which bears an alkyl or alkylol radical with 10 to 20 carbon atoms; e.g., laurylpyridinium chloride or sulfate, cetylpyridinium bromide, octadecyloxymethyl lenepyridinium chloride, stearoylaminomethylenepyridinium chlo ride; ; -quaternized imidazolines which are substituted in their 2-position with hydrophobic radicals such as alkyl- or alkylene radicals with 10 to 20 carbon atoms, alkylphenoxymethylene radicals, alkoxymethylene radicals with 10-18 carbon atoms in the alkoxy part, and alkylthiomethylene radicals with 10-18 carbon atoms in the alkylthio part, e.g., 1-hydroxyethyl-1-methyl-2-heptadecenylimidazolinium metosulfate, l-aminoethyl-1-methyl-2-heptadecenyl imidazolinium toluolsulfonate or 1-(#-hydroxyethyldecaoxyethy- lene)-1-methyl-2-heptadecyl imidazolinium methosulfate; - quaternized benzimidazolines, e.g., N-lauryl-N-methyl-benz imidazolinium chloride; ; - quaternized tetrahydropyrimidines, e.g., 1-methyl-1-phenylethyl decaglycolether-2-undecyltetrahydropyridinium methosulfate; - aminooxides such as N-cetyl-N,N-dimethylaminooxide, N-octa decyl-N, N-dioxyethylaminooxide or N-stearyl-N, N-dimethylamino oxide; - addition products of preferably 5 to 80 moles alkyleneoxide, , in particular ethyleneoxide, whereby individual ethyleneoxide units may be replaced by substituted epoxides, such as styryloxide and/ or propyleneoxide, with higher unsaturated or saturated fatty alcohols, fatty acids, fatty amines or fatty amides with 8 to 22 carbon atoms or with phenylphenol or alkylphenols of which the alkyl radical has at least 4 carbon atoms; - condensation products of propyleneoxides, in particular ethylene oxide and/or propyleneoxide; ; and - reaction products of a - to C22-fatty acid with a primary or secondary amaze which is substituted with at least one. hydroxy lower alkyl or lower alkyloxy-lower alkyl radical1 or alkylene- oxide-addition products of these hydroxyalkyl radical containing reaction products, whereby the conversion is effected in such a way that the ratio of the hydroxyalkylamine to the fatty acid can be 1:1 and greater than 1, e.g., 1..1:1 to 2:1. As anti-foaming agents there may be used, for example, silicone oils. The active substances are mixed, ground. and sieved together with the above-indicated additives in such a way that the solid residues have erg a maximal grain size of 0.02 to 0,04 mm in case of wettable powders, and of 0.03 mm in case of pastes. In order to prepare liquid forms suchas solutions, emulsifiable concen trates or pastes, the active ingredients are, in the'appropriate proportions, dissolved or dispersed, ot amulsified, in a solvent or dispersant, which may contain further additives, e.g., dispersants or emulsifiers. The material to be protected which is treated with an agent according e.g. to the invention, should have a content of active ingredient of/from 50 to 20,000 ppm, preferably from 2000 to 15 000 ppm. The agents. according to the invention are preferably used in the form of solutions. For this purpose, one or morc of the active ingredients of formula (I) are dissolved in appropriate organic solvents or solvent mixtures, occasionally in admixture with water. The content of active ingredient in the above -indicatel agent is from 0.01 to 95%, preferably from 0.i to 3% and in particular from 0.2 to 1.55 by weight. The method according to the invention is advantageously cmpl-oyed for the conservation and rot-proof making of wood, coatings natural or other fibres and textiles, thereby the active substances, appl licd to the materials concerned, display thereon a long-lasting activity against harmful rnicroursanisms. The application of these substances can occur before, together with or after treatment of the materials with other substances, e.g. painting or printing pastes, flame retardantsa softeners, water repellant substances and other finishes. Textiles, wood sad coatings which are treated in this manner are protected from mould and rotting caused by micro organisms -. The application forms of the active ingredients may correspond with usual formulations. Agents for the protection of textiles, wood and coatings should contain the active ingredients in a finely. divided form. For the application there may consequently be used solutions, dispersions, and emulsions of the active ingredients. Aqueous dispersions may for example be derived from pastes or concentrates and may be used in liquid form or as an aerosol. The aqueous solutions, respectively dispersions, appropriately contain tensides (surfactants), for example, anionically active substances, wich as soaps and other carboxylates (e.g. alkali salt of higher fatty acids), derivatives of sulfur-oxyacids (e.g. the sodium salt of dodecylbenzene-sulfonic acid, water-soluble salts of sulfuric acid, monoesters of¯higher alcohols or of their polyglycol- ethers, such as soluble salts of dodecyl-alcohol-sul fate or of dodecyl-alchol polyglycolether-sulfate), derivatives of phosphor-oxyacids (e.g. phosphates), derivatives with an acidic (electrophilic) nitrogen in their hydrophilic radical (e.g. di-sulfine salts) , cationically active tensides, such as amines and their salts (e.g. lauryl-diethylenetriamine) onium compounds, amino-oxides, or non-ionigenic tensides, such as polyhydroxy compounds, tensides on basis of mono- or polysaccharides, higher acetylene glycols, polyglycolethers (e.g. polyglycolethers of higher fatty alcohols, polyglycolethers of higher-alkyl-substituted phenols). At least for textile materials, /the formulation may further contain other usual additives, such as water-soluble perborates, polyphosphates, carbonates, silicates, optical brighteners, softeners, acidic salts such as ammonium or zinc siliconfluoride, or certain organic acids such as oxalic acid and further finishes, e. g., on a basis of synthetic resin or starch. The textile materials c,an, for example be impregnated with hot or cold colored-, bleaching., smoothing- or finishing baths containing. the active substances, whereby different types of textile treatment may be considered, such as the foulard- or stretching treatment. The treatment is appropriately carried out at temperatures from 10 to 100 C, for example, from 10 to 700C, preferably at about room temperature. In view of their good solubility in organic solvents the active substances are also well suited for application in non-aqueous mediums. The materials to be protected can thereby easily be impregnated with the solutions. As organic solvents there may be used aliphatic and aromatic hydrocarbons, their chlorinated derivatives, acid amides, rr,ineral oils, alcohols, ethers, glycolethers, such as, for example, methylenechloride, propyleneglycol, methoxyethanol, ethoxyethanol, N, N -dimethylformamide on their own or as mixtures with each other, to which there may be added dispersants (e.g., emulsifiers such as sulfurated ricinus oil, fatty alcohol sulfates etc.) and/or other additives. Compositions for treatment contain, depending on their purpose of use, from 0.1 to 50 g, preferably from 1 to 30 g of active substance per liter. As textiles-, which are treated, respectively protected, there are primarily considered fibres of natural origin, such as cellulose containing fibres, e.g., cotton, or polypeptide containing fibers, e.g., wool or silk, but also synthetic fibers, such as those on basis of polyamide, polyacrilonitrile or polyester, or mixtures of such fibers. The amount of active ingredient applied to the textile substances is preferably at least 2000 ppm relative to the material. In general, the textiles are sufficiently protected from deterioratiorL by microorganisms with an amount of 50 to 20, 000, preferably 2,000 to 15,000 pprn of the active substance. In the treatment of'textiles according to the invention1 there m-ay at the: same time be used a water-epellent agent. As such may be mentioned e.g. parafin emulsions, zircon- or aluminium salt-parain emulsions, melamin resins, modified melamin resins and polysiloxanes. By combining the subject compounds with surface-active, in particalar wash-active substances there are obtained detergents with excellent activity against microorganisms, in particular fungi. Said detergents can occur in any desired form) e.g., liquid, pasty, solid, flocky or granular. For this purpose, the active substances can be incorporated in aqueous formulations which contain one, or a mixture of two or more, of the above tensides. Their antimicrobial activity is fully retained thereby. The content of active ingredient in detergents, calculated by weight, is in general from 0.1 to 20%, mostly from 0.1 to 3%. Aqueous preparations of such detergents, which contain the active substances can, for example, be used for the antimicrobial treatment of textiles, wood or coatings. They are also suitable for the antimicrobial cleaning in the food and beverages industry, e.g., in breweries, dairies, cheese factories, stables and abattoirs. The method of the invention can further be used to protect the most different surfaces from deterioration by microorganisms. In particular should be mentioned in this respect, the treatment of leather, skins and hides. It is however also possible to protect with the method ot the invention' vessels in which any technical materials are stored, floors, walls and equipment of stables, abattoirs, fruit stores, incubators etc. affected by organic materials. The equipment or surfaces are, depending on their shape, sprayed (e.g. with o spray), brushed or steeped, or dipped, with the solution or dispersion being used. As organic solvents there may, for example, be cited water-immiscible solvents such as, lower alcohols (e.g. ethanol, methanol), ethlene- glycolmonomethylether or monoethylethe preferably there is applied such an amount. of the agent according to the invention that1 after the application, the equipment etc. beards 0.01 to 50 g/mê of the active substance. The method of the invention can also be applied in the cellulose and paper industry. In particular in order to prevent slime formation by microorganisms in apparatus which are used in the manufacture of paper. For this purpose, the active substance is added either to the paper mass or to the water circuit, optinally in admixture with known antibiotics. The method of the invention can also be applied in an analogous form in other industrial plants where destruction by microorganisms can be expected. The amount of active ingredient usually has to be at least 50 ppm, in practice about 100 to 10.000 ppm and preferably 200'to 5000 ppm. When added to water circuits a concentration of 50 ppm is often sufficient. The compounds of formula (I) are also suited for the protection of non-living organic materials such as glues, binders, textile additives, respectively refining agents, printing pastes or technical formed tions in general. They may further be used to prevent and destroy fungal infections in animal oils, fats and emulsions sucn as cutting oils and drilling oils. Softeners, filling ups (e.g. on basis of polyvinyl alcohol or starch may be protected. Also plastics of any kind, e.g. polyamides, polycarbonates, polyesters, polyvinyl chloride, polyolefins or polyvinyl alcohol can advantageously be protected from deterioration by bacteria and fungi. When softeners are used it is advan tageous to dissolve or disperse the activc substance in the softener and add it to the plastic. In order to suit the purpose care should be taken that the distribution in the plastic is as homogenous gs possible. The thus obtained plastics can be used to make useful objects o± any kind, such as for example foodmats, shower-curtains, seats, gratings in swiming pools, wall coverings, tennis-court pavements, etc. The active substances are also excellently suited for the treatment of carpets against fungal infection, in particular to warrant the useful properties of the carpets, but also as a preventive measure to combat fungi of the-feet; and for incorporation in waxes and polishes which then have antimicrobial actions when ysed on floors and-furniture. carpet treaLment the carpets can be treated in the same manner as the above-cited textile substrates, or the active substances are incor-porated in a carpet-shampoo or carpet-treating agent at a concentration of 0.1 to 5% and then display their action when the carpets are treated. In the method of the invention, the active substances can also be used in combination with other antimicrobial agents, whereby an increased activity is . often achieved. As antimicrobial,agents, which may be used in combination with the compounds of formula, I there may 5e considered compounds of the following- classes: : Phenol derivatives such as 3, 5-dichlorophcnol, 2, 5-dichlorophenol, 3, 5-dibromophenol, 2, 5-dibromophenol1 2, 5-(resp. 3, 5)-dichloro-4- bromophenol, 3,4,5-trichlorophenol, chlorinated hydroxydiphenylethers such as, for example, 2-hydroxy-3,2',4'-trichlorodiphenylether, ph enyl- phenol, 4-chloro-2-phenylphenol, 4-chloro-2-benzylphenol, dichlorophene, hexachlorophene; aldehydes such as formaldehyde, glutaraldehyde, salicylaldehyde; alcohols such as phenoxyethanol; antimicrobially active carboxylic acids and their derivatives; organometallic compounds such as tributyltin compounds; iodine compounds such as iodophores, iodonium compounds; mono-, di- and polyamines such as dodecylamine or 1,10-di(n-heptyl)-1,10-diaminodecane; quaternary ammonium compounds such as benzyl-dimthyldodecylammonium chloride, dimethyldodecylammonium chloride, benzyl-di(2-hydroxyethyl)dodecylammonium chloride; sulfonium- and phosphonium compound; mercapto compounds as-well as their alkali, alkaline earth and heavy metal'salts such as 2-mercaptopyridine-N-oxide and its sodium and zinc salt, 3-mercaptopyridazin-2-oxide, 2-mercapto-quinoxaline-1-oxide, 2-mercaptoquinoxaline-di-N-oxide, as well as the symmetrical disuijides of said mercapto compounds; ureas such as tribromo- or trichloroca-barllide, dichloro-trifluoromethyl-diphenylurea; tribromosalicylanilide;2-bromo 2-nitro-1,3-dihydroxypropane; dichlorobenzoxazolon; chlorohexidine; isothia- and benzisothiazolone derivatives. The following Examples illustrate the invention. In the Examples, the compounds tested are the above-identified Compounds IV, VI, VII, VIII and IX, unless otherwise indicated. Example T Testing of fungicidal activity of the active substances by the agarincorporation test: Of the compounds of formula(I)there is made each time a 5% stock solution in ethyleneglycol monomethylether. From this stock solution there is prepared a dilution series wherein the concentrations differ each time by a factor of 10. 0.3 ml oi the thus obtained solutions are brought into sterile Petri dishes and mixed with 1 5 ml of hot liquid nutrient medium (mycophil-agar). The nutrient mediums then contain 1000, 100, 10, I and 0.1 ppm of the active substance. After solidification of t:e plates there is dropped thereon with a F"a'steur pipette or an inoculation device- a germ suspension of Asp gillus tiger ATCC 6275. The incubation time is 3 to 4 days.at 2,30C. Thereafter it is stated at which concentration of the active substance growth of the germs can still be observed. The compounds tested show a good activity against Aspergillus niger. Example II, The compounds o± formula (I)'are dissolved each time in an appropriate organic solvent (ethyleneglycol monoethyletherj. The three different textile substrates listed below are steeped therein and sub sequently squeezed between two layers of aluminum film and thereafter dried in air. The squeezing pressure is set such that 1000 ppm of the active substance remain on the tissue. The following are used in the test: 1. Lixiviated and bleached reinforced cotton of weight 121 g/mê 2. Fixed and bleached polyamide staple-fibres of weight 140g/mê. 3. Fixed and bleached polyester dacron staple-fibres of weight 130 g/mê The substrates are tested according to the agar-diffusion test (modified AATCC-test method 90, 1970) against the 3 test organisms listed below Candida albicans ATTC 10259 Trichophyton mentagrophytes ATCC 9533 Aspergillus niger ATCC 6275 The test plates consist of a double layered agar, i. e. of a ground layer of non-inoculated nutrient medium and a cover layer of an inoculated nutrient medium (Mycophil-agar). After solidification of the inoculated cover layer there are put thereon rounds of 20 mm diameter of the treated substrates. The plates ino culated with Candida albicans are incubated for 24 hours at 3 70C, and those inoculated with Trichophyton mentagrophytes and Aspergillus niger for 3 to 5 days'at 28 C The growth inhibiting action is'evaluated thereafter on basis of the resulting inhibition zone on the plate. When an inhibition zone is lacking, the growth under the test object is also evaluated. The compounds of formula (I), tested in this manner, show i.fl com binat n with the substrates used a good activity against the micro- orga. sms tested. Example III The active substances, dissolved in ethyleneglycolaminoethylether, are applied, by Foulard, to different textiles such as, cotton, polyester/- cotton. There is applied a concentration of the active substance of 0. 6% relative to the tissue. Sterile plastic disks are thereafter filled with nutrient medium, such as cellulose, resp. oaks-malt agar. After solidification of the agar, the plates are inoculated with a spore suspension (germ number about 1 x 105/ml), Test microorganisms are: Trichoderma viride ATCC 8678 Chaetomium globosum ATCC 6205 Penicillium funiculosum ATCC 9644 Aspergillus niger ATCC 6275. Textile rounds of 40 mm diameter are subsequently put on the plates, wich are then incubated for 2 weeks at 290 # 100. At the final evaluation there is only qualitatively examined whether the textile rounds are grown by test organisms. The compounds of formulae (IV) to (X) show an excellent activity in this test. Example IV Foulard application from 2 Foulard formulations. First Foulard formulation. 5.7 g/l of active ingredient dissolved in ethyleneglycolmonoethylether. Substrate: bleached cotton cretonne of 210 g/mê Liquid uptake: 70%'-. 1 passage through Peter-Vertical-Foulard and subsequent drying at 80 C during 5 minutes. Then follows the second Foulard treatment. Second Foulard formulation. 150g/l water repellent agent (e.g. a 35% zirconium paraffine emul sion) 1.5 mg/I of acetic acid 80%. Liquid uptake: 70%. 1 passage through Peter-Vertical-Foulard and subsequent drying at 1200C during 90 seconds. Thereafter the substrate is conditioned for 18 hours at room temperature. Out of the treated tissue are punched rounds of 40 mm diameter which are further processed as in example III. The compounds of formulae IV to X show an excellent activity in this anti-fungal test. Example V The active substance is applied each time in ethyleneglycoi monoethyl- ether to cotton by the Foulard process in such a way that the active substance is present in a concentration of 1. 55 by weight of the substrate. The treated tissue is cut in 10 strips (10 x 2.5 cm) and these are buried obliquely in plates filled with compost soil. After storage for 2, respectively 4 weeks at 29 C and 97% relative humidity, the test strips are dug up, rinsed with cold water and dried. The tissue samples, treated with compounds (US) to (X) show in this rotting test a clearly better resistance against attack by micro- organisms living in the soil. This is evaluated on basis of a rent-resistance test. Example VI The following mixture is rolled for 20 minutes at 1500C betwee: laminated ro'llers. 100.00 g polyvinylchloride. 19.20 g di(2-ethylhexylphthalate) 27. 00 g di(2 -ethylhexylcbacate). 1.50 g Ba/Cd-laurate 0.25 g stearic acid 3.10 g of a compound of formula (I). The distance between the rollers is adjusted such that there are formed 1 mm thick films which are subsequently pressed for 20 minutes at 165 to 170 C at 1400 kg/cmê. In order to investigate the activity against fungi there are punched rounds of 10 mm diameter which are put on Mycophil-agar plates, previously inoculated with Aspergillus niger ATCC 6275. Thereafter the plates are incubated for 3 to 5 days at 28 C. In all cases a prononced inhibition of fungal growth is observed under the rounds. Example VII Emulsifiable concentrates: The following substances are used to prepare a 25% emulsifiable concentrate: 25 parts of active ingredient 2.5 parts of epoxidized vegetable oil 10 parts of an alkylarylsulfonate/fatty alcohol -polyglyc ole the r mixture 5 parts of N, N-dimethyliorrnamide 57.5 parts of xylene. From such concentrates there can be prepared ernulsions with any desired concentration by dilution with water. Example VIII A3 oil-soluble concentrate is- prepared by mixing the following substances: 20 parts of active substance 40 parts of ethyleneglycol monoethylether 10 parts of N,N-dimethylformamide 30 parts of xylene To this concentrate there is admixed. a cutting oil, in a concentration of 0.1%. Protection from microbiological deterloration is obtained thereby. Example IX A wettable powder is obtained by mixing the following substances: 55 parts of active substance 3 parts of polyethyleneoxide. 5 parts of 'ligninsulfonic acrid 20 parts of diatomaceous earth t7 parts of clay. The powder is suspended in water and can be sprayed on surfaces in order to inhibit fungal growth. Example X The concentrate, prepared according to Example VII is diluted 10 to 100 fold with water and added to the water circuit in a machine for paper manu- facture in such an amount that the concentration of the active substance is from 20 to 200 ppm. The slime formation which otherwise occurs is actively suppressed thereby. Example NI Of the compounds of formula (I) there is d each tie a 5 stock solution in ethyleneglycolmonomethylether. From this stock solution there is prepared a dilution series wherein the concentrations differ each time by a factor of 10. 0.3 ml of the thus obtained solutions are brought into sterile Petri dishes and mixed with 15 ml of hot liquid nutrient medium (yeast-malt-agar; oska-malt-agar, Sabouraud-maltose-agar). The nutrient medium then contains 1000, 100, 10, 1 or 0.1 ppm of active sub-stance. After solidification of the plates thee is dropped thereon with a Pasteur pipette or an inoculation device a germ suspension of the following organisms: Poria placenta EMPA 229 Serpula lacrymans EMPA 342 Coniophora puteana EMPA 62 Glucophyllum trabeum EMPA 100 Aureobasideum pullulans EMPA 316 Sclerophoma pityophila EMPA 315 The incubation time is 3 to 4 days at 28 C. Thereafter it is stated at which concentration of the active substance growth of the germs can still be observed. The compounds tested show a good fungistatic activity against these test fungi. Example XII (Wood rut test) The active substance is dissolved in an appropriate organic solvent. The wood to be protected is treated by the dipping technique (European norm 113). Such concentration has to be chosen that 1 to 3 kg of active substance is available per m of wood. The treated wood is buried for 12 to 16 weeks in a compost soil at 29 + 100C and 97 of relative air humidity. Thereafter the wood is washed in cold water and dried. The treated wood shows a much better protection against attack by microorganisms living in the soil than untrea-ted- wood. Example XIII (Brown rot test) Pinus sylvestris wood blocks of 5x2.5x0.5 cm were autoclaved for 20 minutes, subsequently dried for 19.5 hours at 100-1100C, allowed to cool in a desiccator and weighed (initial dry weight). One ml of 0.125% solution of the test compound in a 1/1 met.hanol/wate-r mixture is equally distributed over the wood block so that the final concentration in the wood is 2 kg a.i./m . Blocks treated with water and with 1/1 methanol/water are included as controls. The blocks are allowed to dry in a laminar flow chamber. Evaporation of the solvent is performed in an oven at 500C for 3 hours. The blocks are then transferred onto rralt-aga- Petri dishes which have been inoculated 8 days before with Coniophora puteana. Two blocks, treated with the same concentration of active ingredient are placed on a small stainless steel frarn'e in the ?etri drsh to allow contact with the aerial mycelium of the fungus and to avoid contact with the agar medium. The blocks are exposed to fungal attack for 8 weeks at 25 C. They are then freed f-om adhering mycelium, oven-dried for 19. O hours at 100 110 C and dried. In the following table are given mean results obtained on 4 blocks. EMI25.1 <tb> Treatment <SEP> mean <SEP> weight <SEP> loss <SEP> in <SEP> % <tb> 1. <SEP> water <SEP> 28.05 <tb> 2. <SEP> 1/1 <SEP> methanol/water <SEP> 30.45 <tb> 3. <SEP> compound <SEP> (V) <SEP> 2Kg/m <SEP> 14.15 <tb> 4. <SEP> compound <SEP> (VI) <SEP> 2 <SEP> kg/m3 <SEP> 2.03 <tb> Example XIV (white rot test) Fagus sylvatica wood blocks of 5 X 2 X 0.6 cm are oven-dried for 18 hours, cooled in a desiccator and weighed. The test blocks are laid down in a Petri dish bottom and placed in a vacuum desiccator. Pressure is reduced to 40 mbar with a suction p=p. The blocks are impregnated with a test solution comprising 3000 or 1500 ppm of the active substance in 50% aqueous methanol through a tube leading to the Petri dish. When the blocks are well-co-vered vacuum is released, the Petri dish is removed tram the desiccator and left for two hours in order to saturate the blocks. Control blocks are treated in the same manner with 50% aqueous methanol. The blocks are tamponed with filter paper, weighed and the amount of test compound taken up is calculated Four blocks are used for each compound and concentration. The blocks are then sterilized by treating then 3 times for S minutes with steam of about 100 C. Six days after treatment the blocks are transferred to malt-agar Petro dishes which have been inoculated 20 days before with Corioluls versicolor. Two blocks, one .treated and one control, are placed on a stainless steel frame in the Petri dish The test blocks are exposed to fungal attack for 8 weeks at 25 C. E order to avoid desiccation the Petri' dishes are put tpgether in a plastic bag. The blocks are scored visually according to the following score system. score 0 = no attack. score 1 = slight attack. score 2 = moderate attack. score 3 = severe attack. The blocks are freed from adhering mycelium, oven-dried for 18 hours at 100-110 C, allowed to cool in n desiccator and weighed. The mean results obtained on 4 blocks each time are given in the following table. EMI26.1 <tb> <SEP> Treatment <SEP> Conc. <SEP> a.i. <SEP> in <SEP> Kg/m <SEP> wood <SEP> Weight <SEP> loss <SEP> in <SEP> % <SEP> visual <SEP> score <tb> 1.Compound <SEP> (V) <SEP> 1.93 <SEP> 0 <SEP> 0 <tb> <SEP> 3000 <SEP> ppm <tb> <SEP> control <SEP> 17 <SEP> 3 <tb> <SEP> 2.Compound(V) <SEP> 0.93 <SEP> 0 <SEP> 0 <tb> <SEP> 1500 <SEP> ppm <tb> control <SEP> - <SEP> 19 <SEP> 3 <tb> <SEP> 3.Compound <SEP> (VI) <SEP> 1.85 <SEP> 0 <SEP> 0 <tb> <SEP> 3000 <SEP> ppm <tb> <SEP> control <SEP> 20 <SEP> 3 <tb> <SEP> 4.Compound <SEP> (VI) <SEP> 0.96 <SEP> 0 <SEP> 0 <tb> <SEP> 1500 <SEP> ppm <tb> <SEP> control <SEP> - <SEP> 16 <SEP> 3 <tb>

Claims: CLAINS: coatings and wood and other 1. An agent for the protection of/non-living organic substrates from deterioration by microorganisms which comprises carrier material and as an active ingredient an antimi,crobially effective amount of at least one compound selected from the group consisting of an azole derivative having the formula EMI27.1 and the organic and inorganic acid addition salts thereof wherein: : X is a member selected from the group consisting of N and CH and R1 is a member selected from the group consisting 0± the radicals EMI27.2 whe-rein said Z is a member selected from the group consisting of -CH2-CH2-, -CH2-CH2-CH2-, -CH(CH3)-, and -CH2 CH(alkyl)-, wherein said alkyl is a straight or branched alkyl radical with 1 to 10 carbon atoms; said Ar is a member selected from the group consisting of phenyl, substituted phenyl, thienyl, halothienyl, naphthalenyl and fluorenyl, wherein said substituted phenyl has from 1 to 3 substituens selected from the group consisting of halo, C1-C6-alkyl, C1-C6-alkoxy, cyano, tri:fluoromethyl and nitro; and said R is S member selected from the group consisting of C1-C10-alkyl, cycloalkyl, cycloalkyl-lower alkyl, lower alkenyl, aryl-lower alkyl', aryloxy-lower alkyl and a radical -O-R0 wherein said R0 is selected from the group consisting of C1-C10 alkyl, lower alkenyl, lower alkynyl and aryl-lower alkyl, wherein said aryl radical is selected from the group consisting of phenyl, naphthalenyl and substituted phenyl, the latter havin; 1 to 3 substituents selected from the group consisting of halo, cyano, nitro, phezyl, lower alkyl and lower alkoxy, provided that when two or more substituents are present only one thereof may be cyano, nitro or phenyl. 2 An agent according to claim 1 wherein said azole derivative has the formula EMI28.1 wherein: X is a member selected from the group consisting of N and CH; R1' is a member selected from the group consisting of the radicals EMI28.2 wherein said Z' is a member selected from the group consisting of -CH2-CH2-, -CH2-CH2-CH2-, -CH(CH3)-CH2-, -CH(C2H5)-CH2-, -CH(C3H7)-CH2-, -CH(CH3)-CH(CH3)-and -CH(CH3)-CH(C2H5); said Ar is phenyl optionally substituted with 1 to 3 substituents selected from the group consisting of halo, C1 -C6- alkyl, C1-C6-alkoxy, cyano ind nitro and R' is C1-C 6-alkyl or C3-C4- alkenyloxy. 3. An agent according to claim 2 wherein said azole derivative has the formula EMI28.3 wherein X is a mem-ber selected from the group consisting of N and C; and .R" is a member selected from the group consisting of the radicals EMI28.4 and EMI28.5 wherein said R'' is selected from the group consisting of C1-C4alkyl and C3-C4-lower alkenyloxy, said R3 is hydrogen or C1-C3-alkyl and n is -me integer 1 or 2. 4. An agent according to claim 3 wherein said atone derivative is 1-[2-(2,4-dichlorophenyl)-4-methyl-1,3-dioxolan-2-ylmethyl]1H-1,2,4-triazole. 5. - An agent according to claim 3 wherein said azole derivative is 1-[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-ylmethyl]-1H 1,2, 4-triazole. 6. An agent according to claim 3 wherein said azole derivative is 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2ylmethyl]-1H-1,2,4-triazole. 7. An agent accoding to claim 3 wherein said azole derivative is 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H 1,2, 4-triazole. 8. An agent according to claim 3 wherein said azole derivative is 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole. 9. An agent according to claim 3 wherein said azole derivative 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylmethyl]-1Himidazole. 10. An agent according to claim 3 wherein said azole derivative is 1-(ss-allyloxy-2,4-dichlorophenethyl)imidazole. 11. An agent according to/claims/to 10 for the protection of nonliving organic substrates from deterioration by fungi. 12. An agent according to any of claims 1 to 11 comprising from 0.1 to 10% of at least one compound of formula (I) as defined in claim 1, by weight. 13. A method cf protecting coatings and wood and other non-living organic substrates from deterioration by micro organisms which cornpriscs applying to thein, or incorporating in them, an antimicrobially effective amount of at least one compound of the formula (I) as defined in any of Claims 1 to 10. 14. A method according to Claim 13 for the protection of textiles as non-living organic substrates. 15. A method according to Claim 13 or 14 for the protection cf textile substrates consisting of cotton polyamide, polyacrylonitrile or polyester 16. A method according to Claim 13 for the protection of wood. 17. A method according to Claim 13, 14, 15 or 16 wherein from 50 to 20,000 ppm of at least one compound of the formula (I) as defined in any of Claims 1 to 10 are applied to or incorporated in the material to be protected. 18. Antimicrobially protected coatings or wood or other non-living organic substrates containing from 50 to 20,000 ppm of at least one compound of the formula (I) as defined in any of Claims 1 to 10. 19. An antiseptic detergent comprising a detergent material and as an a active ingredient an antimicrobially effective amount of at least one compound of the formula (I) as defined in any of Claims 1 to 10. 20. An antiseptic detergent comprising a detergent material and as an active ingredient from 0.1 to 20% by weight of at least one compound of the formula (I) as defined in any of Claims 1 to 10. 21. An antiseptic detergent comprising a detergent material and inactive ingredients from 0.1 to 5% by weight of at least one compound of the formula (I) as defined in any of Claims 1 to 10.

Inventors: BELLUS, DANIEL, DUYTSCHAEVER, BENEDIKT DOMIEN M., MUNTWYLER, RENE, SCHARER, MAX, VAN GESTEL, JOZEF FRANS E.
Applicants: JANSSEN PHARMACEUTICA N.V.
Application year: 1981
Main classification: A01N43
IPC codes: D06M101, D21H21, D06M13, B27K3, D06M16, A01N43, C09D5